2013 Teme

MINISTRY OF NATIONAL EDUCATION
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THE ANNALS OF
DUNAREA DE JOS UNIVERSITY
OF GALATI
Fascicle IX
METALLURGY AND MATERIALS SCIENCE
YEAR XXXI (XXXVI),

November 2013, SPECIAL ISSUE
ISSN 1453-083X
2013
GALATI UNIVERSITY PRESS
EDITORIAL BOARD
EDITOR-IN-CHIEF
Prof. Marian BORDEI - Dunarea de Jos University of Galati, Romania
EXECUTIVE EDITOR
PhD. Marius BODOR - Dunarea de Jos University of Galati, Romania
PRESIDENT OF HONOUR
Prof. Nicolae CANANAU - Dunarea de Jos University of Galati, Romania
SCIENTIFIC ADVISORY COMMITTEE

Lecturer Stefan BALTA - Dunarea de Jos University of Galati, Romania
Prof. Lidia BENEA - Dunarea de Jos University of Galati, Romania
Acad. Prof. Ion BOSTAN - Technical University of Moldova, Moldova Republic
Prof. Bart Van der BRUGGEN - Katholieke Universiteit Leuven, Belgium
Prof. Francisco Manuel BRAZ FERNANDES - New University of Lisbon Caparica, Portugal
Acad. Prof. Valeriu CANTSER - Academy of Moldova Republic, Moldova Republic
Prof. Anisoara CIOCAN - Dunarea de Jos University of Galati, Romania
Lecturer Alina CIUBOTARIU - Dunarea de Jos University of Galati, Romania
Prof. Alexandru CHIRIAC - Dunarea de Jos University of Galati, Romania
Assoc. Prof. Stela CONSTANTINESCU - Dunarea de Jos University of Galati, Romania
Assoc. Prof. Viorel DRAGAN - Dunarea de Jos University of Galati, Romania
Prof. Valeriu DULGHERU - Technical University of Moldova, Moldova Republic
Prof. Jean Bernard GUILLOT - cole Centrale Paris, France
Assoc. Prof. Gheorghe GURAU - Dunarea de Jos University of Galati, Romania
Prof. Iulian IONITA - Gheorghe Asachi Technical University Iasi, Romania
Prof. Philippe MARCUS - cole Nationale Suprieure de Chimie de Paris, France
Prof. Vasile MARINA - Technical University of Moldova, Moldova Republic
Prof. Rodrigo MARTINS - NOVA University of Lisbon, Portugal
Prof. Strul MOISA - Ben Gurion University of the Negev, Israel
Prof. Daniel MUNTEANU - Transilvania University of Brasov, Romania
Prof. Viorel MUNTEANU - Dunarea de Jos University of Galati, Romania
Prof. Viorica MUSAT - Dunarea de Jos University of Galati, Romania
Prof. Maria NICOLAE - Politehnica University Bucuresti, Romania
Prof. Petre Stelian NITA - Dunarea de Jos University of Galati, Romania
Prof. Florentina POTECASU - Dunarea de Jos University of Galati, Romania
Assoc. Prof. Octavian POTECASU - Dunarea de Jos University of Galati, Romania
Prof. Cristian PREDESCU - Politehnica University Bucuresti, Romania
Prof. Iulian RIPOSAN - Politehnica University Bucuresti, Romania
Prof. Antonio de SAJA - University of Valladolid, Spain
Prof. Wolfgang SAND - Duisburg-Essen University Duisburg Germany
Prof. Ion SANDU - Al. I. Cuza University of Iasi, Romania
Prof. Georgios SAVAIDIS - Aristotle University of Thessaloniki, Greece
Prof. Elisabeta VASILESCU - Dunarea de Jos University of Galati, Romania
Prof. Ioan VIDA-SIMITI - Technical University of Cluj Napoca, Romania
Prof. Mircea Horia TIEREAN - Transilvania University of Brasov, Romania
Assoc. Prof. Petrica VIZUREANU - Gheorghe Asachi Technical University Iasi, Romania
Prof. Maria VLAD - Dunarea de Jos University of Galati, Romania
Prof. Franois WENGER - cole Centrale Paris, France
EDITING SECRETARY
Lecturer Stefan BALTA - Dunarea de Jos University of Galati, Romania
PhD. Marius BODOR - Dunarea de Jos University of Galati, Romania
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THE ANNALS OF DUNAREA DE JOS UNIVERSITY OF GALATI.

FASCICLE IX. METALLURGY AND MATERIALS SCIENCE
SPECIAL ISSUE 2013, ISSN 1453 083X
FA
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Table of Content
1.
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20.
Raluca Maria FLOREA, Oana BLTESCU, Ioan CARCEA - Aluminium

Alloys Matrix Composites Formed by "in Situ" Reaction.......................................... 7
Liviu GURAU, Carmela GURAU - Properties Improvement of Micro Alloyed
Carbon Steel by High Deformation Degree................................................................ 13
Mihai AXINTE, Manuela-Cristina PERJU, Carmen NEJNERU, Ctlin Andrei
UGUI - Unconventionally Microstructure Behaviour Analysis for W1.8507......... 18
Denisa Elena ANCA, Elena PANCIU, Mihai CHISAMERA - The Influence of
Modifying Potential on the Graphite Morphology in the Superficial Layer of the
Iron Castings Sulphur and Oxygen Additions Effect............................................... 23
Petre Stelian NITA - Model to Evaluate Occurrence of Instability at Steel-Slag
Interface During Steel Desulphurization Process....................................................... 28
Lucica ORAC, Stela CONSTANTINESCU - Corrosion Resistance of the
Composites Cu-Mo Obtained by Electrochemical Method........................................ 32
Mihaela MARIN, Florentina POTECAU, Elena DRUGESCU, Octavian
POTECAU - Researches Regarding the Effect of Steam Oxidation on
Microstructure and Wear Behavior of Sintered Alloys............................................... 38
Elena PANCIU, Denisa Elena ANCA, Mihai CHISAMERA - Influence of Silicon
on the Phase Quantities Resulted on the Grey Cast Iron Solidification...................... 42
Ionu TIRBU, Petric VIZUREANU, Ramona CIMPOEU - Titanium Based
Alloys Chemical Surface Functionalization................................................................ 49
Irina VLCIU, Maria NICOLAE, Avram NICOLAE - Methods of Recovery at the
Renewable Energy Sources From Blast Furnaces...................................................
54
Drago-Cristian ACHIEI, Petric VIZUREANU, Viorel GRANCEA - Studies on
the Modification of Properties by Heat Treatments of Steel Rul2.............................. 58
Marian NEACU, Doru HANGANU - Thermomechanical Process Optimization
Treatment Using an Aluminum Alloy Gradient Method............................................ 62
Simona BOICIUC, Petric ALEXANDRU - Research on the Production of
Sintered Powder 410................................................................................................... 67
Gheorghe BULUC, Iulia FLOREA, Ioan CARCEA - A Short Overview of High
Entropy Alloys............................................................................................................ 74
Ion PALAMARCIUC, Dan Gelu GALUC, Drago Cristian ACHIEI Corrosion Analysis of a Stainless Steel Fuel Pipe...................................................... 77
Carmen-Penelopi PAPADATU - Aspects Regarding the Influence of Tribologycal
Factors on the Superficial Layers of Steels Treated with Plasma Nitriding Applied
after Thermo-Magnetic Regimes................................................................................ 81
Iulia FLOREA, Gheorghe BULUC, Ioan CARCEA - High Entropy Alloys
Obtained by Induction Melt Method........................................................................... 88
Manuela-Cristina PERJU, Carmen NEJNERU, Petric VIZUREANU, Mihai
AXINTE, Drago-Cristian ACHIEI - Studies on Layer-Material Interface at
Deposition by Impulse Electrical Discharge Method................................................. 92
Mirabela Georgiana MINCIUN, Petric VIZUREANU, Alina Adriana MINEA,
Drago Cristian ACHIEI - Engineering Biocompatible Implant Surface................ 97
Anisoara CIOCAN, Simion BALINT, Vasile BASLIU - Problems of Recycling
Process for Used Aluminum Beverage Cans.............................................................. 100
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21. Stefan DRAGOMIR, Marian BORDEI - Use the Eco-Friendly Propulsion with
Compressed air in the Place of those with Fossil Fuels..............................................
22. Vasilica-Viorica (CORCOOI) TONI, Maria VLAD, Gelu MOVILEANU Characterization of Dusts and Slurries from Iron and Steel Industry in Terms of
Chemical Composition, Morphology and Physical Properties...................................
23. Beatrice TUDOR, Anioara CIOCAN, Catalin ZAHARIA - Air Pollutant
Emissions from the Basic Oxygen Furnaces Sector of Integrated Steel Plant and the
Abatement Measures Available............................................................................
24. Cristina Madalina DRAGAN, Mircea Viorel DRAGAN - Investigating Offshore
Wind Farms Connetions..............................................................................................
25. Stela CONSTANTINESCU - Studies of Environmental Risk For Total Suspended.
26. Anisoara CIOCAN, Tamara RADU - Impact of Waste Dump from the Integrated
Steel Mill Plant on Environmental Factors.................................................................
27. Stefan DRAGOMIR, Maria VLAD - Low Energy Consumption of an Modern
Ecological Habitat.......................................................................................................
28. Liliana ONEL - Biomass as Main Renewable Source for Biofuels............................
29. Octavian POTECASU, Florin Bogdan MARIN - Cooling System Design Based on
Thermal Storage for Public Transport Bus.................................................................
30. Tamara RADU, Maria VLAD, Gelu MOVILEANU - Environmental Risk
Management in a Siderurgical Slag Dump.................................................................
31. Gheorghe FLOREA, Florin Bogdan MARIN - 3D Face Modeling Technique from
Uncalibrated Images....................................................................................................
32. Beatrice TUDOR, Anisoara CIOCAN - Research Regarding the Safety Work in the
Continuous Casting Machine................................................................................
33. Raluca Anamaria CRISTACHE, Ion SANDU, Viorica VASILACHE, Ioana
HUTANU, Liliana NICA, Anamaria BUDU - The Study of Dendrochronology as
an Archeometryc Method for Characterizing Old Wooden Artifacts
34. Denisa C. M. SIMONESCU, C. CAPATINA, E. PARASCHIV, V. PUNESCU Polyoxovanadate Na2(NH4)4[V10O28].10H2O Thermal Behaviour........................
35. Carmen-Penelopi PAPADATU - Communicative Tools Used to World Wide
Promotion of Industrial Products................................................................................
36. Petronela SPIRIDON, Ion SANDU, Viorica VASILACHE, Irina Crina Anca
SANDU - Contributions Concerning Integrated Scientific Conservation of Cultural
and Natural Heritage...................................................................................................
37. Gh. FLOREA, L. D.DRAGOMIRESCU, L. PARASCHIV, E. PARASCHIV Materials and Techniquesshaping them into Art........................................................
38. Ana-Maria BUDU, Silvea PRUTEANU, Viorica VASILACHE, Ion SANDU Investigation Methods and Techniques for Analysis of Panel Paintings State of
Conservation................................................................................................................
39. Adrian LEOPA, Daniela TRIFAN - Quantification of Atmospheric Pollution by
Qualitative Analysis of Precipitation as Snow............................................................
40. Marcel BULARDA, Ionel IVAN, Daniela TRIFAN, Ioan VIINESCU - Testing
Some Technological Solutions Aligned to Natural Condition in Ameliorating Rice
Paddies..........................................................................................................................
41. Gheorghe FLOREA, Camelia NEAGU-COGLNICEANU, Irinel NEAGUCOGLNICEANU - Recycling Method for Flat and Container Glass.......................
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42. Ioan VIINESCU, Marcel BULARDA, Daniela TRIFAN - Groundwater

Exploitation by Ground-Irrigation on Agricultural Territories from the Big Island of
Braila.............................................................................................................................
43. Mariana Carmen BURTEA, Anca SERBAN, Gheorghe CANTEMIR - Study on the
Chemical Parameters of Polluted Groundwater in Some Areas of Brila County.......
44. Dorin EFTIMIE, Aurel CIUREA - Methods of Obtaining Bioplastic.........................
45. Gelu MOVILEANU, Maria VLAD, Tamara RADU, Stefan DRAGOMIR Research Concerning the Impact of the Pollution on Water and Soil Resources from
Danube Delta................................................................................................................
46. Carmen DEBELEAC - Inventory Activity of Machines Used on Construction Sites
for Environmental Emissions Evaluation.....................................................................
47. Ovidiu DIMA - Study On the use of Natural Ecological Materials for Construction
and Insulation of Buildings Reeds.............................................................................
48. Dorin EFTIMIE, Dumitru POPA - Sawdust Recycling Technology in Insulation
Boards Manufacturing..................................................................................................
49. Anca ERBAN, Adrian LEOPA - The Experimental Analysis of Ultrasonic
Treatment Efficiency of Wastewaters from Fish Farms...............................................
50. Gabriela Alina CIOROMELE, Aurel CIUREA, Nicoleta AXINTI - The Impact of
Agricultural Pesticides on the Environment.................................................................
51. Ioan VIINESCU, Daniela TRIFAN, Marcel BULARDA - Studies Regarding Soil
and Groundwater Resources from the Big Island of Braila..........................................
52. Stefania IONESCU, Adrian LEOPA - The Experimental Method of Investigation
and Diagnosis of Humidity In Structural Elements of Heritage Buildings..................
53. Dorin EFTIMIE, Aurel CIUREA - Decontamination of Polluted Soil by
Composting Oil with the Help of Mushrooms.............................................................
54. Marcel BULARDA, Ioan IVAN, Ioan VIINESCU, Daniela TRIFAN - Research
on Water Evacuation Reuse in Rice Padding on Ameliorative Salty Soils Being
Improved.......................................................................................................................
55. Carmen DEBELEAC - Corellations Between Operating Modes and Environmental
Emissions of Non-Road Machines at Construction Sites.............................................
56. Lucica BALINT, Doru MATEI, Simion Ioan BALINT - Environmental Risk at
Urban Wastewater Treatment...
57. Aurel CIUREA, Marian BORDEI, Mariana Carmen BURTEA - Research
Concerning Heavy Metal Pollution of Soil and Vegetation in the Areas Bordering
to the Deallocated Factory of Heavy Equipments
58. Mariana Carmen BURTEA, Aurel CIUREA, Luxia RNOVEANU - The
Influence of Arid Climatic Conditions on the Degradation of Soils in the N-E
Romanian Plain.............................................................................................................
59 Elisabeta VASILESCU, Vlad Gabriel VASILESCU - Studies on the
Biocompatibility of Titanium Based Alloys Used in Oral Implantology.....................
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ALUMINIUM ALLOYS MATRIX COMPOSITES FORMED BY

"IN SITU" REACTION
Raluca Maria FLOREA, Oana BLTESCU, Ioan CARCEA
Gheorghe Asachi Technical University of Iai, Faculty of Materials
email: raluca.m_florea@yahoo.com
ABSTRACT
In this paper characteristics of an AlMg/AlN composite produced in-situ
and processed in a flowing N2 atmosphere is investigated. Some critical parameters
such as the manufacturing process temperature, the percentage of the magnesium
consumed, the flowing reactive gas flow and the time for completing the
manufacturing are considered as variables for the parametric investigation.
Moreover, the effect of different amount of Mg employed has been also investigated,
since Mg acts as a catalyst at the surface both for the gas/liquid and solid/liquid
systems
KEYWORDS: Al, alloys, AlN, gas injection, in situ, Mg
1. Introduction
2. Experimental procedure
Aluminium-Magnesium alloys are attractive

engineering materials because of their low density,
along with other beneficial properties such as good
damping capacity, excellent castability, and superior
machinability.
However, compared with other metallic
materials, Al-Mg alloys have lower strength,
especially at elevated temperatures.
Aluminium-Magnesium matrix composites
reinforced with various hard particles have been
widely studied to further improve the mechanical
properties of magnesium alloys.
Although these composites are most commonly
prepared by stir casting, squeeze casting, or powder
metallurgy [13], the more recently developed in situ
synthesis process is considered an attractive
alternative to the existing processes.
The attractiveness of this alternative lies in that
the fine particles produced are more compatible with
the matrix and their distribution throughout the matrix
is more uniform.
The formation of AlN in this system is favored
by the high concentration of Al in the molten system,
and was assisted by the existence of magnesium [4].
This communication presents the results of a
recent investigation on in situ forming hard AlN
particles in an Aluminium-Magnesium alloy by
addition of N2 reactive gas into molten matrix during
the melting process.
Experimental procedure for obtaining composite

materials such AlMg / AlN is based on the "in-situ"
technique and consist of introduction of reactive gas
(nitrium) into the melt (AlMg alloy melt).
Reinforcing particles (AlN) are formed from the
reaction between molten metal and bubbling gas.
Table 1. Experimental parameters

Composite
material
type
AlMg15/
AlN
AlMg10/
AlN
AlMg15/
AlN
Temper
a-ture,
C
1000
Mg
Procent
a-ge
%gr.
15
Gas
flow
l/mi
n.
0,6
Bubbling
time,
min.
360
1000
10
0,6
360
1000
10
0,6
360
Table 1 presents the material and process

parameters that have been tested in experiments on
the formation of "in situ" AlN reinforcement
particles. The experiments have been carried out in an
enclosed reaction chamber heated from outside by a
vertical tube furnace (Figure 1). The aluminum
alloy(260 g, 99,9% pure Al and 99,9%pure Mg ) has
been introduced in an alumina crucible (3), which has
been placed in a graphite larger crucible (2), inside a
closed box melting chamber (1) made out of high
grade stainless steel.
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The entire assembly has been introduced into the

furnace (8) supported by an L-shape frame (7) which
also holds the closed box supporting and adjustable

pillar (4).
a)
b)
EDAX ZAF Quantification (Standardless)
Element Normalized
SEC Table : User D:
EDAX\HAP_05EG.sec
Elem Wt % At % K-Ratio Z
A
F
------------------------------------------------------------MgK 4.93 5.25 0.0277 1.0284 0.8641 1.0638
AlK 95.07 94.75 0.8670 0.9991 0.8939 1.0000
Total 100.00 100.00
Fig. 1. Experimental installation. 1) melting

chamber, 2) graphite crucible, 3) alumina
crucible, 4) adjustable pillar, 5) insulation lid, 6)
frame base, 7) L-shape frame, 8) furnace [5]
c:\edax32\genesis\genspc.spc
Label :
Acquisition Time : 09:29:01 Date : 30-Jan-2013
kV: 30.00 Tilt: 0.00 Take-off: 34.91 AmpT: 102.4
Det Type:SUTW, Sapphire Res: 130.53 Lsec: 21
c)
3. Results and discution
Fig. 2. a) SEM analysis to highlight the general

appearance of the AlMg5/AlN composite;
b) EDX qualitative analysis on the composite
matrix;
c) EDX quantitative analysis performed on the
composite matrix
3.1. SEM/EDS Microstructure of

AlMg5/AlN composite
The microstructure of the AlMg5/AlN
composite samples consists of primary aluminium
grains with isolated particles distributed in the matrix,
as shown in Figure 2a.
The figure 2a showed the general composite
microstructure, qualitative (Figure 2b) and
quantitative analysis (Figure 2c).
The composition of the isolated particles (SEM

images in Figure 3a) was analyzed by EDS. The
results revealed that these particles containe mainly
AlN, along with a small amount of Al and Mg
oxidies, as shown in Figure 3b.
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Element Normalized
SEC Table : User D
A
F
------------------------------------------------------------MgK 9.82 10.61 0.0734 1.0269 0.8703 1.0502
AlK 90.18 89.39 0.6909 0.9977 0.7513 1.0000
Total 100.00 100.00
Label :
Acquisition Time : 09:57:48 Date : 04-Feb-2013
c)
a)
b)
Fig. 3. a) SEM image in order to identify microcompound formed . In the Al- Mg matrix (1)
mixed precipitates (2) appear along magnesium
and aluminum oxides (3) and small submicron
precipitates groups (4) of AlNp under
quantitative EDX detection limit; b) EDX
qualitative analysis reveals that most of the
compounds formed are based Al- N.

matrix;
composite matrix
The SEM micrographs for the AlMg10/AlN
composite samples are shown in Figure 4. Compared
to the AlMg5/AlN composite samples, a greater
amount of particles were formed with significant
segregation. The particles, (Figure 5) had irregular
shapes with a maximum size of a few microns. The
EDS analysis showed that the composition of these
particles is similar to that of the particles in the
AlMg5/AlN samples.

AlMg10/AlN composite
a)
a)
NK
b)
b)
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Element Normalized
SEC Table : User D
A
F
------------------------------------------------------------N K 10.46 13.61 0.0139 1.0496 0.1768 1.0011
O K 3.87 4.51 0.0534 1.0425 0.2143 1.0011
MgK 9.94 10.48 0.0474 1.0050 0.5532 1.0219
AlK 75.82 71.4 0.3219 0.9765 0.5543 1.0000
Total 100.00 100.00
a)
D:\18 february 2013 edax\P2 zona5.spc
Label :
c)
Fig. 5. a) SEM image of the composite matrix

identifying individual precipitates with
prismatic/platelet shape with size of a few
microns;
b) EDX qualitative analysis that identifies the
atomic species that are found with 1 and 2 in
5a);
c) EDX quantitative analysis highlights the
existence in matrix of AlN precipitates with
small amounts of Mg and Al oxides
b)
Element Normalized
SEC Table : User D
A
F
------------------------------------------------------------MgK 14.87 15.88 0.0976 1.0261 0.8777 1.0453
AlK 85.63 84.12 0.6247 0.9970 0.6991 1.0000
Total 100.00 100.00

AlMg15/AlN composite
The microstructure of the AlMg15/AlN
composite has been investigated using an optical
microscope and EDS/SEM. The SEM micrographs of
the sample are given in Figure 6. The figure 6a
showed the general composite microstructure,
qualitative (Figure 6b) and quantitative analysis
(Figure 6c).
According to Figure 7 are present intergranular
precipitates formed from particles of defined
compounds Al8Mg5 and intermetallic phases such
Al12Mg17, small areas of oxides (3) and micron sized
dispersed phase of AlN (4) of gray colour harder to
spot in the array.
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Label :
c)

matrix;
composite matrix

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Fig. 8. Change in percentage of AlN particles

with composite type: AlMg5/AlN, AlMg10/AlN
and AlMg5/AlN
a)
SEM microscopy images taken by the three

kinds of composite materials confirm a good
distribution of the reinforcing particles in the matrix
aluminum alloy . SEM analysis of the composite in
these tests were performed and the surface of the
agglomerates of particles eds. It was found that
agglomerates containing AlN and small amounts of
oxides of magnesium and aluminum.
Figure 8 shows the change in percentage of AlN
particles with composite type: AlMg5/AlN,
AlMg10/AlN and AlMg5/AlN.
NK
OK
b)
4. Conclusions
c)
Fig. 7. a) SEM image of the alloy renders the

overall layout of the array , the small separation
of fragile metal compounds (1) and oxides place
in preference to the boundaries of the primary
grain (2);
b ) EDX qualitative analysis that identifies
atomic species that are found in crystallite
associated and identified in SEM image (Figure
7a));
c) Quantitative analysis (EDX) which highlights
the existence of nitride -type AlN in matrix
precipitated together with small quantities of Mg
and Al oxides
The experiments made have corroborated that

the reaction between liquid aluminium alloys and
nitrogen may lead to the formation of AlN phases,
and the presence of Mg in the matrix speeds up the
reaction intensity.
The high Mg concentration in the Al-Mg alloys
improved the nitridation reaction, which resulted in a
high nitride growth rate. AlN is the major phase
exists in the final product besides MgO, -Al2O3,
MgAl2O4 and residual Al.
The presence of the oxide phases indicated the
existence of O2 content threshold in the nitriding
atmosphere. A lower heating rate means a longer
reaction period is required, thus allowed more
conversion of Al to AlN to form Al/AlN composite.
Acknowledgement
This paper was realised with the support of
POSDRU CUANTUMDOC Doctoral studies for
european performances in research and inovation
ID79407 project funded by the European Social
Found and Romanian Government.
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References
[1]. H. Z. Ye, X. Y. Liu, Ben Luan, In situ synthesis of AlN
particles in MgAl alloy by Mg3N2 addition, Materials Letters, 58
(2004), 2361 2364.
[2]. M. Dyzia, J. O. Eleziona, Aluminium matrix composites
reinforced with AlN particles formed by in situ reaction, Archives
of Materials Science and Engineering, Volume 31, Issue (1May
2008), Pages 17-20.
[3]. Jingzhong Zhaoa, Jiqiang Gao, Zhihao Jin, Preparation of

AlN matrix composites using an infiltration and reaction approach,
Materials Chemistry and Physics, 97 (2006), 506510.
[4]. Zheng Xinhe, Wang Qun, Zhou Meiling, Li Chunguo,
Thermodynamics and kinetics analysis of in-situ synthesizing AlN,
Science in China (Series E), Vol. 45, No. 3 (2002), 249-254.
[5]. V. Soare, D. Mitrica, P. Moldovan, I. Carcea, Method and
system for obtaining aluminum alloys matrix and reinforcement of
carbide particles composite material through the in situ process,
Patent no. A2010 00835 (15.09.2010).
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PROPERTIES IMPROVEMENT OF MICRO ALLOYED CARBON

STEEL BY HIGH DEFORMATION DEGREE
Liviu GURAU, Carmela GURAU
Dunarea de Jos University of Galati
email: carmela.gurau@ugal.ro
ABSTRACT
The effect of severe plastic deformation via High Pressure Torsion (HPT) on
microstructure, and mechanical characteristics of the micro alloyed carbon steel
alloys was investigated. The effects of microstructural refinement samples subjected
to high deformation degrees relieve the formation of ultrafine grains and also dense
structures. In trials is used, a modified technique of HPT, at high speed. Processing
shape memory alloys by HPT, is ideally suited for the production of the very small
parts with excellent resistant properties. Severe deformation parameters like force,
pressure, number of rotation, time of torsion, were determined to obtain thin carbon
steel discs. This type of severe plastic deformation generates large plastic
deformation similar to other methods, causing changes in mechanical properties
and structure. An alloy subjected to this severe plastic deformation, reduces its
grain size due to the fragmentation the microstructure by compression and rotation.
The specimens exhibits not too different localized shearing contributes to uniformity
deformation between center of specimen and periphery, like in classic HPT. In this
specific high speed technology, deformation unevenness on diameter is greatly
diminished. Polycrystalline samples of micro alloyed carbon steel, were studied
before and after severe deformation. Microstructural analysis was done on the
cross-sectional diameter and transversal section. The analyses of hardness tests
also were done.
KEYWORDS: severe plastic deformation, high pressure torsion, low carbon
steel
1. Introduction
Bulk nanocrystalline carbon microalloyed steel.
The materials with UFG ultra fine grains or
nanocrystalline microstructures may be fabricated
using two different approaches. The first approaches
are referring at methods starting from individual
atoms, the second approaches are starting with
samples being conventional micrometer coarse grain
size and refine the grain size to at least the 100 nm
level [1-4]. There are now several possible procedures
for processing these bulk solids but all procedures
rely upon the imposition of heavy straining and thus
upon the introduction of a very high dislocation
density [2]. Since these processes introduce severe
plastic deformation (SPD) into the materials, it is
convenient to describe all of these operations using
the general term SPD processing. Several processes
are now available to obtain nanograins in bulk
materials including high-pressure torsion (HPT) [1].
These three procedures are fundamentally different
but they each produce exceptional grain refinement to

at least the submicrometer level. This paper is
concerned refine grains size of carbon microalloyed
steel using high speed HPT. The samples are
subjected to a compressive force and concurrent
torsion straining, reduces its structure size due to the
fragmentation the microstructure by pressure and
rotation. Processing by HPT is ideally suited for the
production of the very small parts needed in
applications that required high resistant.
2. Material and procedures

2.1. Samples
The as-received material was a commercially
available hot-rolled S420-steel thick sheet. Samples
about of 8X6 mm3 were machined parallel to the
transverse direction of the plate.
The samples were subjected to room
temperature high speed HPT process using alumina
lubrication. The samples were deformed at the initial
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pressure of 20, 30, and 50 MPa. The deformation

force was applied after heating in system on the
strength of friction between sample and die. The
samples were cooled in air. The dimension of discs
diameters obtained was between 11 to 34 mm and
thickness varied between 1.18 to 0.31 mm.
2.2. High Pressure Torsion method

High pressure torsion was applied on steel
specimens using a home made machine. In this paper
is presented the results obtained using an original
severe plastic deformation HPT process. High
Pressure Torsion metal forming process in this
original method is produced at high speed.
Nanostructuring occurs at high temperatures
generated in system by friction. The friction appears
by rotation pistons.
The superior piston rotates at 1800 rpm.
Between the upper piston and the sample there takes
place an intense friction process provoked because of
the high pressure applied on the inferior piston. The
inferior punch hydraulically driven induces in
specimen pressure around 1GPa.
Unlike the classic HPT, which even for very
small samples dimensions, is necessary a large
amount of deformation time, the severe deformation
in high speed HPT, takes place in seconds. Severe
deformation parameters like force, pressure, number
of rotation, time of torsion, were determined to obtain

thin carbon steel discs.
2.3. Investigation equipment

The optical microscopy study has been carried
out using a microscope Olimpus BX45 with digital
image resolution at higher magnifications. The
samples surface have been metallographically
prepared and etched with 4% Nital solution.
Electronic micrographs were recorded using a
Zeiss scanning electron microscope (SEM) coupled
with an EDX detector.
The hardness Vickers has been carried out using
a hardness testing machine 5 kgf load.
3. Results and discutions

3.1. Characterization of starting
microalloyed low carbon steel
Scientific interest in the last decade is going to
obtain ultrafine and nanocrystalline materials, carbon
steel being one of the choices. Processing by high
speed HPT it can be obtain small parts needed in
applications that required high resistant, quickly,
easily and with improved mechanical characteristics.
The bulk chemical analysis of the received material is
presented in Table 1.
Table 1
3.2. Severe deformation process parameters

for obtaining ultrafine structures
These deformation degrees were calculated like
in classic deformation process from equation:
=ln (hi / hf)
(1)
where hi is initial height and hf is final height after

deformation.
The effective strain in case of classic HPT
procces, is shown as a function of the equivalent von
Mises strain, vM, and the evolution of microstructure
refinement evolution is controlled only by equivalent
plastic stain [2].
h
r h0
2N r h0 (2)
r
= ln
+ ln 0 = ln
2
h
h
h
h2
= ln
where: r is the radius of the disc, N is the number of

revolutions and h0 and h denote the initial and final
thickness of the sample respectively.
The estimate of number of revolution is
imprecise and requires further study. In this paper we
use the logarithmic degree of deformation obtained
from the equation based on the classic plastic
deformation.
The degrees of deformation obtained after
severe plastic deformation by HPT method are
ranging 1.2 to 3.07.
Although cold plastic deformation occurs at
room temperature, the heating process appears a
phenomenon, the red colors of the sample caused by
friction. The sample color and temperature
estimation, allows us to say that the distortion can
occur in intercritic domain austenitic and ferritic
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phases (A + F) or above critical point Ac3.

Experiments were conducted by changing size of the
applied force.
The samples were cooled in air. But the discs
are very thin and the cooling rate is higher than the
balance, and foils are cooled relatively quickly.
Refining takes place by shearing and sliding of
crystalline grains of grain boundaries simultaneously

in compact blocks. Numerical data were obtained
from Hottinger Spider 8 acquisition system (time in
second and micrometer/meter- signal, corrected with
constant transducer to achieved force in Newton).
The acquisition sample rate was set at 60 Hz.
Plots HPT motor parameters are shown in figure 1.
Fig. 1. HPT motor parameters

Variation of force in the HPT process shows one
plateau at 30 MPa during severe plastic deformation,
few seconds.
3.3. Optical microscopy

Initial sample structure is hot rolled with feritopearlitic structure. Mostly basic mass of the sample
was found polygonal ferrite grain structure. The
ferrite grains are approximately equal size. They are
accompanied by soft strings, fine grain black pearl,
arranged in linear arrays. At the ferrite grain
boundaries appear tertiary cementite and other
carbides of accompanying elements. The average of

ferrite grains are 10-12 m (Fig. 2a).
As the application an advanced degree of
deformation, occurs a process of refining the initial
ferrite grain. This process occurs by shearing strength
subsequent under high pressure concomitantly with
rotating. In surface the structure are dense with
concentric flow lines (Fig. 2b).
The ferrite grains are very fine and elongated in
white color, to a variable mass become black.
In transversal section it can be observed more
pseudoperlite and coagulation of precipitate (Fig. 2c).
Figure. 2. OM low carbon steel in (a) hot rolled state, and subjected to hsHPT with logarithmic
strain =0.16: (b) longitudinal crosssection, (c) transversal crosssection
3.4. Scanning electron microscopy

As the application of a more advanced degree of
deformation occurs a process of refining the initial
ferrite grain. The degree of refining can reach until
the nanometer-scale structure of the sample. In this

case the grain boundaries are observed only
concentric flow lines.
In figure 3 it can be observed the SEM
micrographs at different magnification.
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Fig. 3. SEM micrographs low carbon steel after hsHPT with =3.07 logarithmic strain longitudinal
crosssection densely aspect and concentric flow lines at magnification increasingly higher
SEM micrographs in longitudinal cross section
of sample with =3.07, until 10000x magnification
reveals only concentric flow lines and densely aspect.
This microstructural aspect is specific to
nanostructured alloys.
3.5. Scanning electron microscopy

The EDS spectra confirmed the chemical
homogeneity and the fact that the flow lines raised,
are rich in Cr and Ni (Fig. 4).
Fig. 4. EDS spectra. HPTed at =2.9
3.5. Hardness tests

The hardness tests results for low carbon steel
discs samples after severe plastic deformation was
done in longitudinal section along diameter.
The samples were subjected to room
temperature HPT process, at initial pressure at 30
MPa. In system appeared friction and heating induced
by friction, uneven on diameter especially in
longitudinal section. This was reflected by changed
hardness values. The hardness values varied along
radius between 503 MPa in center and 597 MPa at
periphery. The neuniformity of deformation is less
than in classic HPT. The results is a reason for
application of process in case of other alloys. The
specimen that has got highest hardness (601 MPa)
was produced in condition of deformation with 3.07
deformation degree and had the smallest thickness
0.31 mm. This result is in correlation with ultra fine
structures.
There was a significant refinement of the crystalline

grain by the procedure described for obtaining
ultrafine size. Refining takes place by shearing and
sliding of crystalline grains of grain boundaries
simultaneously in compact blocks. The specimen that
has got highest hardness (601 MPa) was produced in
condition of deformation with 3.07 deformation
degree and had the smallest thickness 0.31 mm. This
result is in correlation with ultra fine structures.
Results obtained by this method allow further
research to obtain such products do NEMS
nanostructured by high speed HPT with much
improved properties. It is well known that UFG or
NC structures are correlated with combination good
resistance properties concomitantly with improving
the plasticity. The results obtained by high, speed
HPT in case of carbon steel, can be used for the disc
or ring elements, up to 35-40mm, which require very
good resistance and good plasticity properties.
Acknowledgement
4. Conclusions
It was described a process of severe deformation
by high speed HPT process for low-carbon steel.
This paper was financially supported by

UEFISCDI through contract 144, project PN.II-PTPCCA-2011-3.1-0174
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References
[1]. Alexander P. Zhilyaev, Terence G. Langdon, Using highpressure torsion for metal processing: Fundamentals and
applications, Progress in Materials Science, 53, (2008), p. 893
979.
[2]. Valiev R. Z., Langdon T. G., Prog Mater. Sci., 2006; 51, 881.
[3]. Saito Y., Tsuji N., Utsunomiya H., Sakai T., Hong R. G.,
Scripta Mater, 1998, 39, 1221.
[4]. Mahesh K. K., et al., Stability of thermal-induced phase
transformations in the severely deformed equiatomic Ni-Ti alloys,
Journal Of Materials Science, Volume: 47, Issue: 16.
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UNCONVENTIONALLY MICROSTRUCTURE BEHAVIOUR

ANALYSIS FOR W1.8507
Mihai AXINTE, Manuela-Cristina PERJU, Carmen NEJNERU,
Ctlin Andrei UGUI
Gheorghe Asachi Technical University from Iai, Romnia, Faculty of Material Science and Engineering
email: mihai.axinte@gmail.com
ABSTRACT
The The local properties of the material, rather than the bulk, mechanical
properties are important for microstructure behaviour on different loads. In this
paper we analyzed the displacement and the deformation of grains and grain
boundaries in a virtual application, with the processing tools offered by OOF2
software, in order to study the microstructural changes that occurs on stamping
W.18507 nitriding steel.
KEYWORDS: finite elements analysis, indenter, OOF2, elastic modulus,
hardeness
1. Introduction
The finite elements analysis software use a
homogeneous material micro model, and do not take
into account the fact that the metal is composed of
grains with different properties. This is due the fact
that are used for the analysis of large structures in
relation to the size of metal microstructure [7].
Therefore, microstructural changes occurring in
different applications cannot be identified, otherwise
than using a specialized program with object-oriented
analysis technique that is a true picture of
microstructure. In this paper we continued the work
started in the studies prom the paper [6], with a
comparing analyzes for the displacement and the
deformation of grains and grain boundaries in a
virtual application on two microstructures, first is
untreated and second is plasma nitrided.
Nanoindentation and microindentation test has
been established as an important tool for the
mechanical characterization of materials onthe
submicron scale [2]. Such a test is usually conducted
using instrumented machines with which indenter
load, P, and indenter displacement, h, can be
continuously and simultaneously recorded during
indenter loading and unloading. The unloading data
are then analyzed to yield the hardness, H, and the
Youngs modulus, E. Although nanoindentation test
has been widely employed during the past decades to
measure the mechanical properties for numerous
materials [1], little attention has been paid to the
effect of microstructural inhomogeneity on the
reproducibility of the nanoindentation data. In fact,
when being examined at the submicron scale, any

polycrystalline should be considered to be
inhomogeneous [3]. Thus, one can expect that, when
being indented at different positions, or to different
depth at the same position, of the specimen surface,
the response of the test material to indentation may be
different due mainly to the fact that the indentationinduced deformation (and fracture) is dominated
mainly by the local, rather than the bulk, mechanical
properties.
The loaddisplacement (Ph) curves obtained in
the studies of Jianghong Gong et al. [1], presents a
very interesting feature that the coefficient of
variation of hmax exhibits a decreasing tendency with
increasing peak load. This seems to be an indirect
support for the above analysis. As the peak load
increases, the indenter penetration depth increases
and the indentation zone of influence expands. As a
result, the indentation zone of influence would feel
more microstructural features and the effect of
microstructural inhomogeneity would weaken [1].
Hardness being a considerable property of
materials, its measurement has of long been a
preoccupation and concern for metallurgists.
Measurement of hardness of a material consists of
applying a high static load on an indenter of known
geometry and an optical microscope to measure the
print area left in the material.
Hardness is determined by the marked projected
area of the indenter and the peak load applied during
the test.
Atomic-scale indentation of thin films and
nanostructured materials is an effective experimental
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technique for the analysis of material properties. This

technique consists of pushing a sharp tip made of a
hard material, usually diamond, into a matrix/sub
strate material under investigation and measuring the
loading force as a function of indentation depth.
Material properties of the matrix are then evaluated
from the analysis of a resultant load-indentation curve
and the properties of the tip as well as the plastic
behavior of the substrate material.
By numerical calculation of the load
displacement curves, the mechanical properties,
Youngs modulus and hardness can be obtained from
nano-indentation test. Today; scientists are also using
molecular dynamic (MD) models for finding
mechanical properties of such materials [5]. Also,
surface-based properties such as hardness are difficult
to calculate using these techniques. It is the aim of
this study to find a less expensive but still accurate
way to obtain the elastic and surface properties of
reinforced nanocomposites. Many studies have been
already conducted to simulate the nano-indentation
test using the finite element method [8], some of them
will be addressed in the next paragraphs [2].
researches are part of studies concerning plasma

nitriding. The steel was subject to martensitic
quenching and high tempering. Further, the sample
was subjected to chemical treatment plasma nitriding
with the following parameters: time T=7 hours,
pressure P=5 torri, cathode voltage Uk= 460V,
cathode intensity Ik= 0.1 A, treatment temperature
T=520 C.
For finite element analysis a few micrographs
were recorded. They were recorded in the same area,
in the section of the sample. These ones are
representative microstructure images for the sample
and are obtained on the PMT 3 microhardness gauge
device. We have used the Vickers microhardness
values for the microstructural elements from these
micrographs.
Chemical composition for the used sample
material is presented in table 1 and was determined
with the spectrometer Foundry Masters from the
Technologies and Equipments for Materials
Processing Department, Faculty of Materials Science
and Engineering from Iai.
Table 1. Chemical composition

for W1.8507 steel
2. Method
There are two general approaches for modeling
materials properties, with complex microstructures.
The first is to use approximations by medium fields
and to calculate the medium properties for a statistic
representative microstructure. The second is to
accurately model the specific microstructure (or a set
of microstructures), using all the geometric available
data [7].
For this microstructure, finite element analysis
on an oriented object technique was used to analyze
the microstructure. We have used OOF2 software [7],
developed by the prodigious NIST association, an
application which is running on a Linux platform,
using the Python programming language, one of the
few existing programs for finite element analysis of
the microstructure.
OOF2 takes a non-reductionist, brute force
approach, but in a user-friendly way. The user starts
with a digitized image of the microstructure and
builds a data structure on top of it. All the data plus
any that can be inferred by the user is employed.
Tools are provided to allow the user to graphically
select features in the microstructural image and
specify their properties. For OOF2, the microstructure
is a data structure composed of image and property
data [6].
For the experiment we have used samples made
from steel type W1.8507 DIN 7210, equivalent with
steel grade 38CrMoAl09 from STAS 791/88. We
have used this steel because is the only one romanian
steel made especially for nitriding, and these
Elem.
Perc
%
Elem.
Perc
%
Fe
95.4
C
0.503
Cr
1.49
S
Cr
0.296 1.49
Mo
0.127
Ni
0.122
Al
1.17
Cu
W
Ti
0.122 0.065 0.016
We have assigned properties as determined by

microhardness test, differentiated for ferrite and
pearlite microstructure constituents, for treatead and
untreated constituents. We have used micro hardness
values for pearlite from the micro hardness
micrographs. An example is presented in figure 1. In
the micrographs from the image, obtained on the
PMT3 microhardness gauge, we can see two kind of
grains, white grains, meaning ferritic ones, and dark
colored ones, of pearlitic type.
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Example of
ferritic grain
50m
Example of
pearlitic grain
Fig. 1. Micrographs used in virtual test and

finite element analysis: a) diamond-pyramid
hardness footprint for pearlite constituent
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We have started from a digitized image, twodimensional microstructure and we have built up a
data structure, understood by the program. We have
used different tools to define the structure, to select
graphically the pixels from the structure image, and to
specify their properties. Finally, for the OOF2
program, the microstructure has become a set of data
consisting of images and properties. After that we
have fulfilled several filter applications preparatory
for easier pixels picture selection.
We have assigned material properties to the
groups of pixels, previously completed, including
color, but in the same we have accomplished the
structural mapping. When properties are created, they
are chosen from a list (tree). The properties can be
parameterized, copied named or/and saved for future
utilization. Also new properties can be added to this
tree [7].
The first step was the selection of pixels
corresponding to ferrite (white and light grey pixels)
and pearlite (black and dark grey pixels). In figure 2
is presented the boundary of the ferrite grains during
pixel selection.
Then we started to construct the skeleton,

meaning the geometric elements of the mesh. In
OOF2, a Skeleton is in essence a discretized
geometric representation of the Microstructure. One
Microstructure can contain several skeletons,
meaning different placement of the vertices and
edges. One skeleton can generate several Meshes,
allowing different tests on the same geometry [7].
Fig. 3. Map representation of the material

microstructure and skeleton discretization in the
first phase
Then we refined the skeleton edges through
various methods in order to approximate better the
previously created mapping. In figure 3 is presented
the first phase of the discretization, followed by an
automated discretization, figure 4, then an manual
refining of the skeleton boundaries, to fit as well as
possible the contour edges, figure 5.
Fig 2. The boundary of the ferrite grains during

pixel selection
Thus we consider the displacement in plane with
the obtained micrograph. Figure 3 presents the
studied microstructure after we assign materials to the
pixels. The mechanic properties for the materials are:
the pearlitic grains Young modulus E = 4.6x1011
[N/m2] and Poisson ratio = 0.27. Properties for
ferritic grains are Young modulus E=2.0x1011 [N/m2]
and Poisson ratio = 0.291.
Also, for the material, we assigned isotropic
properties. The Dirichlet boundary conditions were
applied to the lower limit, with displacement settings
on the x and y axes (x=0, y=0), and the lateral
limits were constrained only to the horizontal
displacement, x=0.
Figure 3 shows the materials map for the
microstructure in figure 2 where each pixel was
colored by the property Color assigned to the
Material.
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Fig. 4. Map representation with automated

refined skeleton edges
Fig. 5. Map representation with manual refined

skeleton edges
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In the next stage we determined what types of

loads operate on the microstructure. This is a
displacement caused by pressing with a punch tool,
with a 30 units travel along the y axis. By several
tests was observed that the Vickers pyramid
penetration corresponds to a of 30 units displacement
in OOF2 on pearlitic constituents, the same as the
layer considered in virtual test.
Boundary conditions were activated for each
one of the sides, the lower ones and the lateral ones
and were activated by checking the option. Boundary
conditions values were set in the same menu, as it
shows in Fig. 8.
Boundary conditions were set to the lower limit,
limiting the displacement on the x and y axes (x=0,
y=0), and the lateral limits were set only for
horizontal displacement (x=0). Also, the boundary
conditions for the reference surface, where the punch
tool will act will have the following values (x=0,
y=-30) [6].
In figure 7 is shown the displacement

comparison
between
nontreated
sample
corresponding to the virtual stamp test for nitrided
sample. The mechanic properties for the materials for
the pearlitic grains are: Young elasticity modulus for
nitrided pearlite is 5,8e+11[N/m2], and for nitrided
ferrite is 2,7e+11[N/m2], Poisson ratio = 0.27 values
obtained with microindenter CETR UMT Multispecimen test systems.
3. Results and discussion

We launched the solver running finite element
analysis to obtain local deformations. Finally, we
conducted analysis displacement fields for the
deformed microstructure. Using the same micrograph
give us the possibility to compare the behavior on
virtual displacement for the same microstructure, for
both phases: treated and untreated.
Fig. 7. Elements displacement on virtual stamp

test for nontreated sample corresponding to the
virtual stamp test for nitrided sample
After shape analysis of the displacement areas, a
certain irregularity is observed in their perfect circular
shape. This is due to the different properties of the
materials in the microstructure. The homogeneity
factor of the materials is involved in the analysis. The
displacement and deformation of each element from
the mesh is made according to the deformations
produced on assigned materials.
4. Summary and conclusions
Fig. 6. Elements displacement on virtual stamp

test for nitrided sample [6]
In the image from figure 6 are highlighted the
displacement fields of material for complete
deformation. The green mesh is the structural mesh
before applying deformation. On the layer in the
background the displacements fields are displayed
after applying deformation. The radial deformation
propagation is observed.
In this paper we have analyzed the displacement

and the deformation of grains and grain boundaries in
a virtual application by stamping 38MoCrAl09
STAS791/88 steel, (equivalent with W.18507, DIN
17210-69 type 34CrAlMo5).
The displacement inside the material and the
final shape were analyzed, using OOF2 software, and
the following conclusions were obtained:
1. The displacement is overtaken by the pealitic
grains, the ferritic ones are more influenced by the
deformation, due to the fact that the maximum yield
point is lower, in the end they will deform.
2. Comparing the positioning for the
displacement fields we can assume that due to high
degree of maximal local deformation, compared to
the reduced degree of local deformation, the risk of
breaking is higher on treated than the treated sample.
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3. Being part of current research area, fully

growing, object oriented finite element analysis and
finite element analysis on microstructure OOF2 is a
very useful and powerful tool, for the researchers in
the materials science domain.
References
[1]. Jianghong Gong, Zhijian Peng, Hezhuo Miao, Analysis of
the nanoindentation loaddisplacement curves measured on highpurity fine-grained alumina, Journal of the European Ceramic
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[2]. Nima Nouri, Saeed Ziaei-Rad, Sara Adibi, Fathollah
Karimzadeh, Fabrication and mechanical property prediction of
carbon nanotube reinforced Aluminum nanocomposites, Materials
and
Design,
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doi:
10.1016/j.matdes.2011.07.047.
[3]. Oliver W. C., Pharr G. M., An improved technique for
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[4]. Nix, W. D., Elastic and plastic properties of thin films on
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[5]. Fischer-Cripps, A. C., Analysis of instrumented indentation
test data for functionally graded materials, Surf. Coat. Technol.
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[6]. Nejneru Carmen, Axinte Mihai, Perju Manuela-Cristina,
Object Oriented Finite Element Analysis on Microstructure for
W1.8507, Applied Mechanics and Materials, vol. 371 (2013) pp
358-362,
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[7]. A. C. E. Reid, R. C. Lua, E. R. Garcia, V. R. Coffman, S. A.
Langer, Modeling Microstructures with OOF2, International
Journal of Materials and Product Technology, 2009, Vol. 35, No.
3/4, pp. 361 373.
[8]. V. dOtreppe, M. Mengoni, R. Boman, J. P. Ponthot,
Image-based Finite Element Mesh Generation for Microstructures,
Fifth International Conference on Advanced Computational
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THE INFLUENCE OF MODIFYING POTENTIAL ON THE GRAPHITE

MORPHOLOGY IN THE SUPERFICIAL LAYER OF THE IRON
CASTINGS SULPHUR AND OXYGEN ADDITIONS EFFECT
*Denisa Elena ANCA, Elena PANCIU,
**
Mihai CHISAMERA
POLITEHNICA University of Bucharest, 313, Spl. Independentei, RO-060042, Bucharest, Romania

emails: denisa_elena_anca@yahoo.com; elenapanciu@yahoo.com; mchisamera@hotmail.com
*corresponding author; **PhD coordinator
ABSTRACT
The main objectiv of this experimental reserch is a comparative analysis of
sulphur and oxygen effects on the graphite morphology in the superficial layer at
different iron melt modifying potential (residual Mg content). For the experiment,
three irons with different modifying potential (0.0014, 0.0213 and 0.033 wt %
residual Mg content respectively) were developed. After Ca-Ba inoculation, the
three irons were additionaly treated by stoichiometric equivalent additions of
sulphur and oxygen as FeS2 and Fe2O3 respectively. Both FeS2 and Fe2O3 sources
were placed on the bottom of standard Quik-Cup moulds, usualy used for iron melt
thermal analysis. The effect of sulphur and oxygen at different modifying potential
on the graphite morphology in the superficial layer was evaluated by graphite
nodularity and graphite shape factors, but also by degenerated graphite thickness.
The experimental results show a much stronger degenerative effect of the sulphur
by comparing with stoichiometric equivalent oxygen addition while the oxygen
exerts an inoculant and a lower degenerative effect on graphite morphology in the
superficial layer.
KEYWORDS: modifying potential, graphite morphology, superficial layer,
sulphur, oxygen
1. Introduction
The surface layer of a casting has, in most cases,
a microstructure and associated properties that are
different than those in the bulk of the casting.
Because of the larger undercooling at the mold/metal
interface, and of chemical reactions between the
metal and the atmosphere or the molding material,
microstructural differences between the surface layer
and the bulk of the casting will occur. This abnormal
surface layer may be present in any casting thickness.
However, it becomes most critical for thin wall
castings, where it could occupy more than 10% of the
total thickness. In ductile and compacted graphite
irons, solidified with thin wall, the formation of an
abnormal structure in the surface layer and its
detrimental effect on mechanical properties has been
documented over the years [2-8].
The graphite degeneration layer can by viewed
as a layer of lamellar graphite witch favors the crack
propagation. In gray iron, there is only a small
difference between the graphite degeneration layer
and the bulk structure, as graphite is lamellar at the

surface as well as in the bulk. Mg depletion and
solidification kinetics effects were suggested as the
main formation mechanism for the graphite
degeneration [9-11].
Mg reaction with oxygen and/or sulfur causes
Mg depletion in the iron at the proximity of the mold
wall, resulting in graphite degeneration. Large
undercooling at the mold/metal interface favors
solidification of austenite dendrites that reject
magnesium at the solidification front. This results in
low Mg and lamellar graphite structure close to the
mold/metal interface with a high nodularity zone
further inside.
To a more deep understanding the graphite
degeneration phenomenon in the superficial layer of
the iron castings present work is mainly focused to
evaluate the influence of sulfur and oxygen on the
graphite morphology in the superficial layer at
different iron melt modifying potential.
In this reason, three irons with different
modifying potential were developed. After the Mg
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treatment and CaBaFeSi inoculation, the iron melt

was poured into standard Quik-Cup molds where
FeS2 or Fe2O3 were previously added on the bottom
of the cups as sources of S and O respectivelly. The
metalographic samples were drawn for structure
analysis.
The base irons were prepared by induction
melting using a 10 kg neutral crucible induction
furnace, at 8000 Hz frequency. As charge materials
for the three iron heats, 64 wt%, 60 wt% and 60 wt%
high purity pig iron respectively and 34 wt%, 40 wt%
and 40 wt% grey iron scrap respectively were used
while for iron melt chemical correction, high purity
carburiser (>98 wt% C) and foundrygrade FeSi (75
wt% Si) were added [1].
The thermal regim of iron melts processing was
as follows: superheating temperature Ts=1550 oC;
Mg-treatment temperature- Tm=1530 oC; pouring
temperature- Tp=1350 oC.
The tehnical schedule of the experimental
researce program is presented in fig.1.
FeSiCaMgRE (6 wt% and 8 wt% Mg
respectively and 1.1 wt% RE) alloy as nodulizer was
used (1.5 wt%, 1.5 wt% and 2 wt% addition) while,
for inoculation, CaBaFeSi75 (0.5 wt% addition for all
three cases). The inoculated Mg-treated irons were
poured in standard Quik-Cup resine molds [1] where
FeS2 or Fe2O3 as sulphur and oxygen sources
respectively were placed.
For metallographic analysis the cup samples
were drawn [1].
Graphite nodularity was made in accordance
with ISO 945 norm [12] after a previously
metallographic preparation [1].
The main graphite shape factors analyzed are:
circularity, sphericity, elongation and aspect ratio [1].
Graphite morphology analysis was made by
using a professional automat image analyzer using
both the standard cast iron modulus and particle
analysis software.
The thickness of the surface layer was evaluated
according to the schematic fig. 2.a. with 100 m
between measurements. The measured thickness of
the surface layer as an average. The structure in
surface layer was analized according to the schematic
in fig. 2.b. along 23 analysis direction, the distance
between points in the same direction is the 0.13 mm.
The analysis in the layer was made a depth about 1.9
mm, including the superficial layer, the transition
zone and the healthy in the vicinity of degenerate
graphite. The average level of the structure
parameters was calculated.

The chemical compositions of inoculated irons
(before S/O additions) show different levels of the
active elements (Mg, Ce, La). The three irons have a
slight hypereutectic position and a low level of
harmful elements (Ti, Pb, Sn, As, Te) - Table 1.
Both graphite nodularity and graphite shape
factors were changed in the surface layer, depending
on the residual magnesium content and S/O additions.
It is clear that the degenerated layer thickness is
greater for lower magnesium content.
The lowest nodularity was recorded for iron I
(gray iron). There is only a small difference between
the graphite shape factors in gray iron because the
graphite is almost lamellar over the all sample
surface.
As fig. 4 shows the strongest effect of sulphur
addition both on graphite morphology and thickness
of degenerated layer was recorded on the medium
modifying potential that is iron II (0.0213 wt.%
residual Mg).
By sulphur addition both the nodularity and
shapes factors were changed and graphite was
degenerated to lamellar structure over all surface
(total graphite degeneration).
On a higher modifying potential (0.033 wt%
Mgres,) the same sulphur additions have determined a
lower but visible graphite decompactizing effect in
superficial layer (iron III).
No visible effects were recorded on a very low
modifying potential (iron I).
Oxygen addition had no a decompactizing effect
but contrary the graphite nodularity shows a slight
increasing given the inoculated iron more visible on
VG structure (iron II-fig.3, table 2).
The effect of S/O added may be put into
connection with the different chemical reactions the
two elements involve into the iron melt during its
solidification [1].
So, the O added in the iron melt could be
anihilated by other elements (C, Si, Mn, Al) than
modifying elements (Mg, Ca, Ba, RE) because of
their higher concentration in the iron melt which
means higher activity. The sulphur added in the iron
melt has mainly one alternative that is the reactions
with Mn from the melt thus it has a great disponibility
to react with Mg, Ca, RE etc leading to their
anihilation and as result, decreasing the graphite
compactness and increasing the thickness of graphite
degenerated superficial layer.
The best results (a lower thickness of
degenerated superficial layer and a higher graphite
nodularity) were obtained by oxygen addition (Fig. 3,
4, Table 2).
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Fig. 1. Technical schedule of the experimental program
a)
b)
Fig. 2. The analysis procedure to evaluate the surface layer thickness (a) and the structure
parameters in the surface layer (b)
Table 1. Chemical composition of obtained irons
Chemical composition, [wt. %]*
CE**
C
Si
Mn
P
S
Mg
Ce
La
I
3.89 1.92 0.185
0.0438
0.0211
0.0014
0.0022
<0.00010
4.48
II
3.61 2.61 0.179
0.0447
0.02
0.0213
0.004
0.0022
4.43
III
3.74 2.47 0.199
0.0436
0.0208
0.033
0.0059
0.003
4.49
*Others: Cr: 0.045-0.0554, Mo: 0.0024-0.049, Ni: 0.0578-0.0678, Al: 0.074-0.0153, Cu: 0.0426-0.0483, Ti:
0.0082-0.0102, Pb: 0.00087-0.0013, Sn: 0.0033-0.0048, As: 0.004-0.0047, Ca > 0.006, Te: 0.0014-0.0024.
**CE = C + 0.3 (Si + P) - 0.03.Mn + 0.4S
Iron
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Mg-treated CaBaFeSi 0.026% S
iron
inoculated iron addition
0.013% O
addition
0.053% S
addition
0.026% O
addition
100 100
100
0 .3 0 1
0.4 8 3
20
100
1 .2 4 8
40
100
0 .2 9 1
0 .5 2 4
N o d u la r ity , %
60
100
4 .97 6
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80
Mg res = 0.0014% Mg res = 0.0213% Mg res = 0.033%

100
0 .9 9 6
Mg res = 0.033%
0 .7 78
0 .7 81
Mg res = 0.0213%
3 .3 6 5
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la y e r th ic k n e s s , %
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Residual Mg, %
Mg-treated CaBaFeSi 0.026% S 0.013% O 0.053% S 0.026% O

iron
inoculated addition
addition addition
addition
iron
Fig. 4. Influence of residual Mg content and the

S/O addition on the surface layer thickness
Fig. 3. Graphite nodularity in superficial layer

under S/O and residual Mg content influence
Mg-treated iron
CaBaFeSi inoculated iron
0.026% S addition
Mg-treated iron
0.026% S addition
0.013% O addition
0.053% S addition
0.026% O addition
0.013% O addition
0.053% S addition
0.026% O addition
0.6
0.5
0.4
0.3
0.2
0.1
0
S p h e r ic ity
C ir c u la r it y
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.005
0.01
Residual Mg, %
0.015
0.02
0.025
0.03
0.035
Residual Mg, %
b
0.026% S addition
0.053% S addition
0.026% O addition
A s p e c t R a tio
0.013% O addition
E lo n g a t io n
Mg-treated iron
Mg-treated iron
0.026% S addition
0.013% O addition
0.053% S addition
0.026% O addition
0.005
0.01
0.015
0.02
0.025
0.03
0.035
Residual Mg, %
0.005
0.01
0.015
0.02
0.025
0.03
0.035
Residual Mg, %
Fig. 5. Graphite shape factors in superficial layer under S/O and residual Mg content influence: acircularity, b- sphericity, c- enlongation, d- aspect ratio
Table 2. Thickness layer evolution under S/O addition and residual Mg content influence
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4. Summary
(1) Sulphur and oxygen have a different
behaviour if thei are added in Mg-trated iron.
(2) Sulphur has a clear degenerative effect,
determining decrease both of nodularity and shape
factors and increase the thickness of degenerated
graphite layer.
(3) Oxygen has no a visible degenerative effect
despite of its excedent addition by comparing with
necessary for Mg anihilation. This may be explained
by its reaction with C, Si, Mn prezent in a higher
concentration in the iron melt than the added active
elements such as Mg, Ca, RE etc. despite of higher
affinity towards oxigen of the last
Acknowledgement
The work has been funded by the Sectoral
Operational
Programme
Human
Resources
Development 2007-2013 of the Romanian Ministry of
Labour, Family and Social Protection through the
Financial Agreement POSDRU/107/1.5/S/76903.
References
[1]. D. E. Anca, M. Chisamera, Graphite morphology in Mgtreated iron - Sulphur and oxygen effect, Metalurgia International,
2013, Vol. XVIII, No. 5, pp. 37-42.
[2]. G. M. Goodrich, R. W. Lobenhofer, Effect of Cooling Rate

on Ductile Iron Mechanical Properties, AFS Transaction, 2002,
110, pp. 1003-1032.
[3]. S. Boonmee, D. M. Stefanescu, Casting Skin of Compacted
Graphite Iron Part II: Influence on Tensile Mechanical Properties,
AFS Transaction, 2010, 118, pp. 217-222.
[4]. D. M. Stefanescu, S. Wills, J. Masson, F. Duncan,
Quantification of Casting Skin in Ductile and Compacted Graphite
Iron and Its Effect on Tensile Properties, International Journal of
Metalcasting, 2008, pp. 7-26.
[5]. S. Boonmee, M. K. Moran, D. M. Stefanescu, On the Effect
of the Casting Skin on the Fatigue Properties on CG Iron, AFS
Transaction, 2011, 119, pp. 421-430.
[6]. S. Boonmee, D. M. Stefanescu, The Effect of Nodularity and
Surface Condition on the Fatigue Properties of CG Iron, AFS
Transaction, 2011, 119, pp. 205-2016.
[7]. M. Kuwamoto, T. Iwamoto, T. Saeki, The Effect of Skin on
Fatigue Resistence of Cast Iron, The Japan Society of Mechanical
Engineers, 1951, Vol. 17, No. 61, pp. 139-142.
[8]. C. Labrecque, M. Gagne, P. Cabanne, P. Francois, C.
Beret, F. Hoffman, Comparative Study of Fatigue Endurance
Limit for 4 and 6 mm Thin Wall Ductile Iron Castings,
International Journal of Metalcasting, 2008, pp. 7-17.
[9]. S. Boonmee, B. Gyesi, D. M. Stefanescu, Casting Skin of
Compacted Graphite Iron Part I: Evaluation and Mechanism for
Formation, AFS Transaction, 2010, 118, p. 10-067.
[10]. I. Riposan, M. Chisamera, S. Stan, T. Skaland, Surface
Graphite Degeneration in Ductile Iron Castings for Resin Molds,
Tsinghua Science and Technology, 2008, 13, pp. 157-163.
[11]. R. C. Aufderheide, R. E. Showman, M. A. Hysell,
Controlling the Skin Effect on Thin- Wall Ductile Iron Castings,
AFS Transaction, 2005, vol. 113, pp. 567-579.
[12]. N. Ivan, M. Chisamera, I. Riposan, Influence of Magnesium
Content and Coating Type on Graphite Degeneration in Surface
Layer of Iron Castings in Resin Sand P-Toluol Sulphonic Acid
(PTSA) Moulds, ISIJ International, 2012, Vol 52, No. 10, pp 18481855.
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MODEL TO EVALUATE OCCURRENCE OF INSTABILITY

AT STEEL-SLAG INTERFACE DURING STEEL
DESULPHURIZATION PROCESS
Petre Stelian NITA
Dunarea de JosUniversity of Galati
email: pnita@ugal.ro
ABSTRACT
The paper is dealing with the evaluation of the possibility of occurrence of
interfacial instability during desulphurization process in the system Low Carbon
Aluminium Killed steels- (CaO-Al2O3)slag, at low and moderate initial sulphur
contents, using an adapted model of interfacial oscillatory instability in the form of
compression-dilatational waves. The criterial relationship established in the
adapted to conditions model is satisfied for the physico-chemical parameters of the
mentioned metallurgical system and confirm the possibility that interfacial
oscillatory instability in the form of compression-dilatational waves could occur.
The adapted relations to compute critical values of Marangoni dimensionless
number and of frequency give the possibility to evaluate if this instability could be
possible in technical real conditions, but only when, is done a correct scaling of the
characteristic length, according to particular conditions in this system. The
corresponding values of sulphur content inhomogeneity will show if, in technically
restricted conditions, values of Marangoni number exceeds its critical values
making practically possible developing of this type of interfacial instability.
KEYWORDS: interfacial oscillatory instability, steel-slag
desulphurization process, critical Marangoni number, instability criterion
1. Introduction
The interest to contribute the clarifying aspects
of instability at steel-slag interface, especially during
some refining processes should be sustained by more
consistent activities in modeling and experimental
research. From far it is obvious that this subject is a
delicate one. Therefore it is quasi-neglected from
various reasons almost in the same measure by
technologists and physicists. Despite of these
attitudes the subject merits to be investigated due to
its observed or presumed contributions in obtaining
advanced refined steels belonging to the class of the
new generation of advanced steels. In this respect the
analysis of occurrence and influencing of the
interfacial turbulence is of a prime rank importance,
regarding in the same measure both its favorable and
deleterious effects. An important aspect is that of the
emulsification of steel and slag. Such process was
observed when transfer of sulphur from iron into slag
occurs even in initial quasi-stationary controlled
conditions of contact between iron and slag [1]. As it
was shown in other systems [2], spontaneous
system,
emulsification at interface steel-slag requires not only

the interfacial turbulence, which is a necessary but
not a sufficient condition, but also a low interfacial
tension along with cellular rotational velocity. In this
respect until now enough clear and argued points of
view concerning the contribution of capillarity
aspects in slag to such processes, consisting in
promotion of turbulence and emulsification, are not
reported. Instability could occur in the form of
stationary instability or oscillatory instability and in
the last case a particular form is that with
compression-dilatational waves along the interface.
2. Adaptation of the model of interfacial

oscillatory instability with compressiondilatational waves to steel-slag system and
desulphurization process
This general model belongs to a group of
reputed authors Birikh, Briskman, Velarde, Legros
[3]. It is dealing generally with the interfacial
instability in the form of dissipative compressiondilatational waves, in a system of two immiscible
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liquids. These waves are in the form of longitudinal

surface oscillations.
The model is adapted by authors to the mass
transfer and further, in the present paper it is adapted
to the case of interface steel-slag, fully respecting the
sense and rigor of initial notations [3]. The model fits
to the system Low Carbon Aluminium Killed steels(CaO-Al2O3) slag, at low and moderate initial sulphur
contents, usual in steel ([S]< 0.020%mass) and
sulphur contents in slag far from saturation
((S)sat<1.5-2%mass, according to ratio %CaO/%
Al2O3). This means that coverage ratio of sulphur at
interface, evaluated on the side of steel, is enough low
and therefore Langmuir isotherm is valid. Also the
sulphur will not precipitate in slag as CaS affecting
the viscosity of slag.
A surface active solute S (sulphur), adsorbed at
interface according to Langmuir isotherm and
distributed in each phase with a given bulk gradient
(1, 2) is transferred from the lower liquid phase (1steel) to the upper liquid phase (2-slag). In this
respect it must be said that the bulk gradient must be
seen as resulting from the gradient of chemical
potential between interface and bulk. The system is
considered initially at rest, but this could be extended
to relative velocity zero at interface, this being
located on the vertical coordinate z at height level z=0
in a rectangular system of axes (x, y, z). In the lateral
directions (x,y-coordinates) there are not effects of
solid side walls that means a real system, which is
physically limited, could be practically infinite in x
and y directions, in relation with a characteristic
dimension or length if this is enough small. In these
conditions the model can be used in the case of real
technical systems steel-slag.
Each phase is well definite by the following
physico-chemical properties, -dynamic (share)
viscosity, -kinematic viscosity, -density, and mass
transport properties by D- mass diffusion coefficient.
These properties are used as state and in the form of
ratios:
Where:
is the interfacial tension steel-slag;
/[S] is the concentration coefficient of the
interfacial tension, usually taken as constant in linear
analysis in order to make valid the Bousinesque
approximation;
d is a characteristic length; after the authors
this may be capillary length but need not to be
so[3].
The subject characteristic length or dimension,
more or less arbitrary established, many times even
neglected as state or simply eliminated by
mathematical shunts, merits an extended treatment
since a physico-chemical action is analyzed. This
action due to the Marangoni effect must be enough
strong, persistent and continual and more than this, it
must exceed with an appreciable order of magnitude
the other competing actions in order to consider that
the observable effects are really due to the
solutocapillary Marangoni effect. In conclusion the
characteristic length or dimension it is not at all an
arbitrary one and more, neither it can be neglected.
If Ma values is positive and has a moderate and
adequate value to conditions, Marangoni convection
could occur in the established conditions mainly in
the considered sense of transfer of the surface active
solute.
In these conditions the expected evolution of
such disturbance of solutal origin( two dimension
case x-horizontal coordinate, z- vertical coordinate) is
governed by the equations of continuity, NavierStokes and mass diffusion (Fick low) which are valid
on each side of the interface and also at the interface
itself.
In the dimensionless form the system of
equations is the following:
div v1 =div v2= 0
v1 p1 2 v1
v
2
+
= 2 + p 2 v 2 = 0 (2)
t
t
=2/1 ; =2/1 ; = 2/1 ; D=D2/D1

Considering [S]- bulk concentration of sulphur
in steel (1) and (S)- bulk concentration of sulphur in
slag(2), the partition ratio of sulphur at the analyzed
moment is LS=[S]/(S), which is the inverse of the
usual sulphur partition ratio used in steel refining
practice. This does not have to worry because in the
end it will be present in relationships as (LS)-1.
The major parameter to evaluate occurrence of
instability is the solutal Marangoni dimensionless
number and it is expressed in the form which relieves
the elasticity behavior of the interface:
Ma=(/[S])1 d2/1D1
(1)
[ S ]
(S )
1 2
w1 Sc1 [ S ] =
w2
t
t
Sc21D 2 ( S ) =0
(3)
Where :
vi (i=1,2) = (ui ,wi) with u and w represents
horizontal and vertical velocity components of the
disturbance velocity field;
pi (i=1,2) pressure at interface in the two
liquids;
Sci= i / Di represents the Schmidt
dimensionless number in the liquid phases (i=1, 2); it
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is the ratio between the moment dissipation () and

the mass diffusion (D).
Ideally it would be to use the dimensionless
number Sc with its value at interface but is is difficult
to evaluate the value of the two factors in the ratio
giving Sc.
Equations (1) (3) describing the evolution of
solutal disturbance for longitudinal waves are valid if
the surface deformation and the surface accumulation
of surfactant can be neglected, being very small and
for the following boundary conditions, written at
interface (z=0):
w1 = w2 =0
w1 w2
=
=0
z
z
Ma 2
2 w2 2 w1
a [S]
+
=0
z 2
t 2
Sc1
( S ) (( S ) [ S ])
=
Sc1
t
z
[S] = LS (S)
Where:
a is the wave number of Fourier normal mode;
is the Langmuir adsorption number [4]
representing the slope of the Langmuir adsorption
law, in number of moles/meter.
The neglecting of the surface deformation is
taken here as state but it needs an extended analysis
due to the fact that this is possible only in the case of
a characteristic length carefully scaled, according to
actions competing with Marangoni effect which must
be the stronger among the others.
The linearity of the problem imposes to seek
solutions using Fourier normal modes, which gives a
basic equation for oscillatory disturbance in the form
of the simplest harmonic oscillator. It is an equation
for longitudinal interfacial oscillations whose
damping coefficient can reach the value zero at a
certain value of the solutal Marangoni number. Using
the complex elasticity modulus of Lucassen[5],
because it is related to solutal Marangoni number, the
critical value of Marangoni dimensionless number is
obtained imposing the value damping coefficient to
zero:
(4)
(5)
(6)
(7)
(8)
)(
D 1 / 2 + 1 / 2 1 / 2 1 1 + LS D 1 / 2 Sc1
Mac=

1
Sc11 / 2 1 2
And the dispersion relation:
)(
D1 / 2 + 1 / 2 1 / 2 1
c = ac
1/ 2
Sc1 1 2
where 1 and 2 are simply common groups of

parameters facilitating the computations, without any
signification:
1/ 2
1=

(11)
2 = D1/21
(12)
The condition of value zero for damping
coefficient leads to the following direct and indirect
conditions to have oscillatory behavior at interface
steel-slag:
(13)
Mac 1<0
Or the equivalent form:
(14)
sign(Mac) = sign(1)
and other derived consequences in the form of the
following relations:
(9)
(10)
According to the signification of notations of

authors, indexes f and t in the relation (16) show how
the sulphur is transported f from the volume of
steel to the interface and further in slag, t from
interface to the volume of slag. This condition is a
preliminary one and is converted to the sulphur
transfer from steel to slag in the following form:
D[ S ]
D( S )
>
1
2
(17)
Due to the fact that and a must have only

positive values in order to have a physical sense, it
results from the dispersion relation (10) that, in order
to have oscillations, it is necessary that condition
from rel.(17) to be accomplished also the following
condition:
sign (Mac) =sign (1)
(15)
1
2
>
(16)
Reunion of the conditional relations gives

criterial relation for instability in the form of
Df
Dt
f
t
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longitudinal surface oscillations and dissipative

compression dilatational waves:
D[ S ]
D( S )
>
1
2
<1
(19)
inhomogeneity it must be analyzed how much could

be the maximal magnitude of the possible
inhomogeneity and finally it will be possible to
compute the maximal values of the Marangoni
dimensionless number.
3. Results of evaluation
4. Conclusions
A fast evaluation is made in the case of the

interface between a LCAK steels and the slag with
chemical composition (60%)CaO-(40%)Al2O3. The
parameters of both two liquids, interesting in relations
established above are shown in the Table 1.
An analysis of possibility to occur instability at

interface steel-slag in the particular system LCAK
steels-(60%)CaO-(40%)Al2O3 slag, where it could
take place flowing processes due to solutal effects
related to the interfacial tension, i.e. Marangoni
effect. The presented model analyzed and adapted to
the condition belonging to a group of reputed authors
(Birikh, Briskman, Velarde, Legros) [3] analyzes
occurrence of interfacial oscillatory instability in the
form of compression-dilatational waves. This model
is presented and commented and simultaneously it is
adapted to the particular system LCAK steels(60%)CaO-(40%)Al2O3 slag. Following the same
steps as those done by the authors the final criterial
relationship is presented and also adapted relations to
compute critical values of Marangoni dimensionless
number and the critical frequency of compressiondilatational waves. Based on the final criterial
relationship, using physico-chemical data referring to
the particular system LCAK steels-(60%)CaO(40%)Al2O3 slag, computations show that at the
interface of this system at 1873.15K occurrence of
interfacial oscillatory instability in the form of
compression-dilatational
waves
is
possible.
Computations of the critical values of Marangoni
dimensionless number, the associated critical value of
frequency and further and of other parameters, like
miminal value of chemical inhomogeneity
corresponding to the critical value of Marangoni
dimensionless number, must be performed carefully
according to the necessity that Marangoni effect to be
enough strong in comparison with other competing
physical and physico-chemical actions.
Table 1. Physicochemical quantities and

parameters of LCAK steels and (60%)CaO(40%)Al2O3 slag, at the temperature 1873,15K
Quantity,
symbol,
units
Density, , kgm3
phases, values, references

(1)steel
(2) slag
7000[6]
2685 [7]
=1/2=2.6071
-Dynamic
viscosity, ,
Pas;
-Kinematic
viscosity, , m2/s
Diffusion
coefficient
of sulphur DS,
m2s-1
Solubility of
sulphur, %mass
0.007 [6]
110-6
0.1184 [7]
4.4110-5
= 1 2 = 5.9122
=1/2=2.267610-2
4,410-9 [6]
2.4810-10
[8]
D = D1 D2 = 17.742
high
2.092 [9]
Using data from table 1, the conditions

according to the rels (16), (17) and their reunion
rel.(19) numerically are satisfied, as it follows:
17.742 > 2.267610-2 < 1
This means that the answer is affirmative, i.e.
the transfer of sulphur from steel to slag could occure
instability in the form of interfacial oscillatory
instability in the form of compression-dilatational
waves.
Further it would be necessary to compute the
values of the critical Marangoni number Mac but this
needs an extended analysis of the conditions. Once
these values computed it will be possible to compute
the magnitude of the minimal inhomogeneity of the
sulphur content, at interface on the steel side, which
can excite this mechanism of instability in order to
check if it is physically possible to exist such one,
from the point of view of this mechanism of
instability. Starting from the value of this chemical
References
[1]. Deng J., Oeters F., Steel Res., 61 (1990), 438.
[2]. Rudin J., Wasan D. T., Chem Eng. Sci, 48 (12) 1993, 22252238.
[3]. Birick R., Briskman V., Velarde M., Legros J.-C., Liquid
Interfacial Systems (Oscillations and Instability), Surfctant Science
Series, pp. 38-43, Marcel Dekker, Inc. New York, Basel (2003).
[4]. Davis J. T., Rideal E. K., Interfacial Phenomena, pp. 183184, Academic Press New York and London, (1963).
[5]. Lucassen J., Trans Faraday Soc, 64 (1968), Part 1, 22212229, Part 2, 2230-2235.
[6]. Kawai Y., Shiraishi Y., Handbook of Physico-Chemical
Properties at High Temperatures, ISIJ, Tokyo (1988).
[7]. ***, Slag Atlas, 2nd Editions, Verlag Stahleisen, D-Dusseldorf,
(1995).
[8]. Jonsson L., Du Sichen, Jonsson P., ISIJ int. 38, (1998), 260.
[9]. zturk B., Turkdogan E. T., Met. Sci., 15, (1984), 260.
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CORROSION RESISTANCE OF THE COMPOSITES Cu-Mo

OBTAINED BY ELECTROCHEMICAL METHOD
Lucica ORAC, Stela CONSTANTINESCU
Dunarea de Jos University of Galati, Romania
email: lucia_orac@yahoo.com
ABSTRACT
The paper describes reviews referring to the obtaining of composite coatings
in the copper matrix by electrochemical co-deposition of molybdenum.
The molybdenum particles having particle sizes of 3 m, respective 7m have
been used as complementary phase. The optimal conditions for codeposition were
determined, the structure and chemical composition of obtained coatings were
presented and the coating characteristics were tested. Electrochemical tests have
showed that the corrosion resistance of the composites copper- molybdenum is
higher than pure copper.
KEYWORDS: electrochemical deposition, structure, coating
1. Introduction
CuMo composites are attractive not only for
electronic packaging, but also for sliding electrical
contacts, motor brushes, and resistances, welding
electrodes, because of their hardness and electrical
conductivity. The CuMo composite coatings are
promising good materials for the electronic power
modules applications due to their properties and this
explain the recent researches in this field [1].
There were reported the obtaining of CuMo
composite coatings using different methods: vacuum
plasma sprayed, plasma vapour deposition sintering,
gelationcoreduction and combining mixture with
plating. The composites obtained have superior
physical and mechanical properties [2].
The possibilities of developing a good electrocodeposition process are sufficiently attractive for
need to have inexpensive and simple method for Cu
Mo composite coatings with electronic applications.
The method does not involve any special
equipment and conditions.
However, the study on electro-codeposition
parameters for these materials, which is becoming
important with the increased power electronic
modules production, has not yet been reported to our
knowledge. As a result, it permits to manufacture
refractory metal composites and ceramics coatings on
various substrates with large surface area. Another
advantage of the electrodeposition technique is that it
can easily fabricate components with different
materials compositions [3].
A study of the electrodeposition parameters and

dispersed phase concentration (Mo 37 m) in the
obtaining of CuMo composite coatings from
sulphate electrolyte is described in this work.
2. Results and experimental researches

The CuMo composite coatings on pure copper
(99.99%) substrate having the dimension of
80200.2 mm were obtained with a PotentiostatatGalvanostat in controlled temperature equipment
(202 C). The average diameters of Mo
microparticles (99.95%) used as dispersed phase were
3 m and respectively 7 m (Merck, Darmstadt,
Germany). A sulphate electrolyte free of additives
with the following composition: CuSO45H2O:
200g/L; H2SO4: 80 g/L having pH of 1.0 was used.
Since the composite materials Cu-Mo are
entirely new, the electrochemical deposition
technology was established. As with copper
electrodeposition certain parameters were kept:
orientation of electrodes, distance between electrodes
2cm. Two different concentrations of the Mo
microparticles were added in electrolyte. The CuMo
composite coatings were prepared by varying the
current density applied (1.5, 2, 3 Adm2), deposition
time and magnetical rotation speed (500 rpm) of the
electrolyte
suspension.
The
microstructure
morphology on cross-sections of the coatings was
analysed through optical and scanning electron
microscopy SEM and the elements distribution by
energy dispersive spectroscopy - EDS (figures 1, 2).
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Analyzing the cross-section microstructures it is

observed the uniform distribution of the molybdenum
layer [4, 5].
The concentration of particles in the composite layer

increases with increasing current density up to a
certain value (Imax) and then decreases.
Processing option: All elements analysed

(Normalised)
All results in
weight%
Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Cu
2.25
1.83
3.01
100
69.5
100
6.18
18.85
2.58
Mo
30.5
91.67
79.32
94.41
Total
100
100
100
100
100
100
Fig. 1. EDX analysis in crosssection and spot for Cu-Mo composite coatings obtained at
2 A / dm 2 , 180 min, 500 rpm, 40g/L particles in electrolyte solution, particle size 3m
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Processing option: All elements analysed

(Normalised)
All results in
weight%
Spectrum
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Cu
Mo
2.35
2.1
100
93.45
100
11.76
31.19
6.55
85.89
66.7
Total
100
100
100
100
100
Fig. 2. EDX analysis in cross section and spot for Cu-Mo composite coatings obtained at 2 A / dm 2 ,
180 min, 500 rpm, 40g/L particles in electrolyte solution, particle size 7 m
a)
b)
Fig. 3. Variariation of the percentage content of Mo particles in the composite deposit as a function
of current at a concentration of 20g / L, 40g / L, 60g / L Mo in the electrolyte solution,500rpm,
180min: a) Mo size 3m, b) Mo size 7m
Figure 3 illustrates the relationship of
interdependence between the concentration of Mo 3
m, 7 m particles in the composite layer and current
density for different amounts of particles contained in
the electrolyte [6].
The percentage of inclusion increases with
increasing current density to a concentration of 20
g/L, and the concentrations of 40, 60 g/L particles in
the electrolyte solution increases with increasing
inclusion rate of current density and reaches a
maximum at imax = 2 A/dm2 then decreases.
The highest degree of inclusion has been
determined for Cu-Mo composite coating obtained at
2 A/dm2, 180 min, 500 rpm, 40 g/L, and the minimum
degree of inclusion of molybdenum particle, size of 3
m (size 7 m) in copper matrix was obtained at 1.5
A/dm2, 30 min, 500 rpm, 20 g/L [7]. It is noted an

increase in the inclusion of molybdenum, particle size
of 3 micrometres and 7m, in the copper matrix with
increased concentration in the electrolyte up to 40 g/L
and for a concentration of 60 g/L, a decrease of
particle inclusion.
The presence of particles in the deposited layers
will change both their structure and properties. Layer
thickness values are given in table 1.
As regards roughness of the coatings obtained
by adding molybdenum particles in the electrolyte
solution there are quite large variations in the level of
roughness for composite coatings obtained under
different conditions.
These values are lower compared to the
roughness values determined for pure copper.
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Table 1. Thickness of Cu - Mo layer

Current density, i
2
[ A / dm ]
Thickness
[m], 180[min]
Conc. Fd. in electrolyte

[g/L]
1.5
Cu - Mo/ 3 m
Cu - Mo/7m
30
29
29.5
35
50
37
45
30
52
30
32
35
30
23
24
30
50
28
42
40
52
30
45
35
0
20
40
60
0
20
40
60
0
20
40
60
The average absolute roughness range from 2.9

to 1.6 m for Cu-Mo composite with particle size 3
m and for Cu-Mo composite with particle size 7 m
average absolute roughness range from 2.7 to 2 m
(Table 2). The presence of molybdenum particles
have catalytic role in the copper reduction reaction.

The immediate effect of this phenomenon is the
modification of the structure deposited by decreasing
the size of crystals which implicitly leads to lower
surface roughness [8, 9].
Table 2. Values of roughness for the blank sample and Cu-Mo composite
Current density, i
2
[ A / dm ]
Conc. Fd. in
electrolyte
[%]
Cu-Mo/3 m
Cu-Mo /7m
180
180
180
180
180
180
0
40
0
40
0
40
3.1
2.9
2.9
2.24
2.3
1.6
3.1
2.7
2.9
2.56
2.3
2
1.5
2
3
In order to determine corrosion resistance by

galvanostatic method following calculations are done:
- By means of the experimental data the Tafel
polarisation curves immersed in 3%NaCl are
obtained:
lgIcor = f(cor).
- By graphic interpolation of the two straight
Tafel line which intersect at a point, it is determined
the corrosion current , I cor on the ordonate axis Knowing the value of I cor it is calculated: - value of
current density:
icor =
I cor
S sample
Roughness
[m]
Electrodeposition
time
[min]
[A / m ]
2
where Ssample = sample area [m2 ];

- value of corrosion rate:
v cor = i cor
ACu 24
[g/m2day]
Z Cu 26,6
ACu- atom mass of Cu, Z number of changed

electrones.
- penetration index: p = vcor 0,365/Cu
[mm/year], where Cu [g/cm3].
By projecting the intersection point of the two
Tafel steps on the abscissa , the corrosion potential
value, Ecor is obtained [10].
Figure 4 illustrates the Taefel curves for Cu-Mo
composites with 3 m particle size obtained at current
density of 2 A/dm2, exposure time: 180min.
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1000
10
10
Eprobamartor
Eplatina
-2000 -1500 -1000 -500
1000
1000
100
100
Icor[mA]
100
Icor[mA]
100
Icor[mA]
Icor[mA]
1000
10
10
EMo20g/L
Eplatina
500 1000 1500 2000
-2000 -1500 -1000 -500
Ecor[mV]
500 1000 1500 2000
-2000 -1500 -1000 -500
Ecor[mV]
a)
E60g/LMo
Eplatina
E40g/LMo
Eplatina
b)
500 1000 1500 2000
-2000 -1500 -1000 -500
500
Ecor[mV]
Ecor[mV]
c)
d)
1000 1500 2000
Fig. 4. Taefel curves for Cu-Mo composites with particle size of 3 m ,current density of i =
2 A / dm 2 , 500 rpm, for maintaining 180 min: a) blank sample b) Cu-20 g/L Mo, C) Cu-40 g/L Mo,
d) Cu-60 g/L Mo
From Figure 4 we see that the corrosion current
density of the blank is greater than that of the
composite samples leading to the conclusion of an
increasing resistance to corrosion of composite
samples, the visual appearance of the samples being
clean, without oxide stains. The values of the current

density, corrosion rate and penetration indices when
testing for corrosion by the galvanostatic method are
given in Table 3.
Table 3. Behavior of Cu-Mo composites with particle size of 3 m obtained by the electrochemical
method when testing for corrosion by the galvanostatic method.
Corrosion
Current
jcor
rate
density
[ A / m2 ]
blank
Cu- 20g/L Mo
Cu- 40g/L Mo
Cu- 60g/L Mo
[ g / m 2 h]
20.3
16.7
15.5
17.9
10
Eprobamartor
Eplatina
Resistance
group
0.0069
0.0052
0.0048
0.0055
highly resistant
highly resistant
highly resistant
highly resistant
Figure 5 presents Taefel curves for Cu-Mo

composites with particle size 7 m obtained at current
density of 2 A/dm2, 500 rpm, for molybdenum
concentrations in the electrolyte: a) blank b) 20 g/L,
c) 40 g/L, d) 60 g/L, while keeping for 180 min.
1000
1000
1000
100
100
100
Icor[mA]
Icor[mA]
Icor[mA]
100
Penetration index
p
[mm/an]
0.007
0.0053
0.0049
0.0057
From table 3 it can be noticed that average

values of penetration index for composites Cu-Mo of
particle size of 3 m obtained by electrochemical
method are lower compared to the blank sample.
1000
v cor
Icor[mA]
Sample code
10
10
ECu-20g/LMo
Eplatina
-2000 -1500 -1000 -500 0 500 1000 1500 2000
-180-1
060-1
040-1
020-1
000-0800-600-400-20002004006008001000
1200
1400
1600
1800
2000
-180-1
060-1
040-1
020-1
000-0800-600-400-20002004006008001000
1200
1400
1600
1800
2000
Ecor[mV]
Ecor[mV]
Ecor[mV]
a)
ECu-40g/LMo
Eplatina
10
EMo40g/L
Eplatina
b)
c)
-2000 -1500 -1000 -500
500 1000 1500 2000
Ecor[mV]
d)
Fig. 5. Taefel curves for Cu-Mo composites with particle size of 7 m current density of i =2 A / dm 2 ,
exposure time 180min: a) blank b) Cu-20g /L Mo, C) Cu-40g/L Mo, d) Cu-60 g /L Mo
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From figure 5 it is observed that the corrosion

current density of the blank sample is greater than the
composite samples leading to the conclusion that
resistance to corrosion of the composite samples
increases, the visual appearance of the surfaces being

clean without oxide stains.
The values of the current density, corrosion rates
and penetration indices when testing for corrosion by
galvanostatic method are given in Table 4.
Table 4. Behavior of Cu-Mo composites with particle size of 7 m obtained by electrochemical

method, when testing for corrosion by the galvanostatic method
Corrosion
Current
Sample code
blank
Cu- 20g/L Mo
Cu- 40g/L Mo
Cu- 60g/L Mo
density
jcor
rate
v cor
[A / m2 ]
[ g / m 2 h]
20,3
15,6
14
16,2
0,007
0,0049
0,0044
0,0051
From the data presented we conclude that CuMo composite coatings with particle size of 7 m
have a higher corrosion resistance than those of size
of 3 m.
4. Conclusion
- By electron microscopy in cross section and
the EDX spot analysis it was observedthe inclusion of
the dispersed phase and homogeneous distribution of
the additional phase (Mo 3 m and 7 m,
respectively) in the copper matrix, when the
electrochemical method is applied.
- The degree of inclusion of molybdenum
particle size of 3 m and 7 m in the copper matrix
increases with increasing their concentration in the
electrolyte up to 40 g/L.
- The presence of molybdenum particles have
catalytic role in the copper reduction reaction.
- Cu-Mo composite coatings with particle size of
7 m have a higher corrosion resistance than those of
size of 3 m.
Penetration
index p
[mm/an]
Resistance
group
0,0069
0,0048
0,0043
0,0049
highly resistant
highly resistant
highly resistant
highly resistant
References
[1]. V. G. Grechanyuk, Electrical Contacts and Electrodes, Inst.
of Materials Science, I. N. Frantevicia NAN Ukraina, Kiev (2004),
p. 38.
[2]. S. Chemg-Yuh, L. Kuang-Hsiang, P. Cheng-Tang, P. W.
Peng, Thin Solid Films 520 (2012) 5936.
[3]. J. W. Jacobs, J. M. G. Rikken, Elctroless Deposition of
Metals and Alloys, M. Paunovic and I. Ohno, eds., Proceedings,
vol. 12, Electrochemical Society, Penington, NJ, 1988, p. 98.
[4]. N. Y. A. Shammas, Microelectron, Reliab. 43 (2003) 519.
[5]. R. Hocine, A. Boudghene Stambouli, A. Saidane,
Microelectron, Eng. 65 (2003) 293.
[6]. W. H. Safranek, The Properties of Electrodeposited Metals
and Alloys, 2nd ed., American Electroplaters and Surface Finishers
Soc, Orlando, FI., 1986.
[7]. O. Mitoseriu, S. Constantinescu, L. Orac, Electrochemical
deposition method to obtain composites coatings with metal matrix,
Conferinta internationala TEHNOMUS, Universitatea Stefan cel
mare Suceava, 2009, ISSN- 1224 029X, p. 479- 484.
[8]. D. E. Jech, J. L. Sepulveda, Proceed. of the 1997 IMAPS
Conf., Philadelphia, PA (1997), p. 72.
[9]. G. L. Romero, J. L. Martinez, Proceed. of the ISHM
Conference, Boston, MA (1994), p. 421.
[10]. A. Vashkialis, I. Iachiaysekene, Electrochemistry (Academy
of Science USSR), 17, p. 1816, 1981.
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RESEARCHES REGARDING THE EFFECT OF STEAM OXIDATION

ON MICROSTRUCTURE AND WEAR BEHAVIOR OF SINTERED
ALLOYS
Mihaela MARIN, Florentina POTECAU, Elena DRUGESCU,
Octavian POTECAU
email: mihaela.marin@ugal.ro
ABSTRACT
A surface treatment as steam oxidation can improve the corrosion resistance,
hardness and wear resistance of sintered steels. In this research, the sintered alloys
samples were subjected to steam treated at 550C for 45 minutes. The
microstructure of the surface layer was investigated by optical and scanning
microscopy and EDS. The wear behavior of samples was evaluated. The results
reveal that the samples subject to steam treatment can improve wear resistance of
sintered alloys.
KEYWORDS: powder metallurgy, sintering, surface treatment, wear
resistance
1. Introduction
Table 1. The chemical composition

of analyzed powders
The parts obtained by powder metallurgy are

presenting complex shapes and are close to final
form, with a precise surface. Compared to classical
metallurgy, additional processes (such as machining,
forging, etc.) are minimized in powder metallurgy.
The consolidation of parts by heat treatment,
called sintering - is a complex process based on
difussion. Steam treatment is a surface treatments
applied to sintered components to improve density by
sealing the interconnected pores. This treatment can
improve the mechanical properties of sintered alloys.
The oxide layer formed on the sintered iron
components is thciker than on the conventional
wrought ferrous parts steam treated. The water vapor
in the steam will react with the iron in the part to
form iron oxide, mainly magnetite (Fe3O4) [18].
The objective of this paper is to study the
influence of steam treatment on mechanical properties
of sintered alloys and their wear resistance.
The specimens prepared from atomized iron
powder and from pre-alloyed iron base powders were
analyzed in this paper.
The chemical composition of the powder
samples, pure iron and iron-based prealloyed powder
with Cu, Ni and Mo is presented in Table 1.
Powder
type
P1
Cu
Mo
Ni
0.10
0.01
0.05
<0.01
P2
1.50
0.50
1.75
<0.01
The powders were mixed with 1% zinc stearate.

The samples were compressed in a universal
mechanical testing machine to a pressure of 700 MPa,
the dimensions of disc specimens are 8 6 mm.
The samples were used to evaluate mechanical
properties such as Vickers microhardness and
abrasive wear.
The green samples were sintered in a laboratory
furnace at a temperature of approximately 1.150 C
and the sintering time was 120 min.
After cooling to room temperature, the samples
were steam-treated. Steam treatment was carried out
in a furnace with steam atmosphere at 550 C for 45
min.
The steam-treated specimens were air-cooled to
room temperature. The microstrucre of the sintered
and steam treated samples were observed by optical
microscopy.
The sitnered and steam treated specimens were
tested for abrasion wear test. The applied load was
855 g and the distance traversed in each case was
limited to 150 cycles corresponding to 76.5 m.
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The samples were subjected to circular motion.

The abrasion wear process included: in the first stept
fixing the abrassive paper on the wheel and, the
second step was sample loading on the machine.
The samples were weighed using a precision
balance with a sensitivity of 104 before and after
each test, so it was possible to evaluate the wear
mechanism of the material.
After the tribological tests, the worn surfaces
were examined by optical microscope, in order to
identify the characteristic wear mechanisms.

3.1. Microstructure
The optical micrographs representative of
typical microstructures for sitnered and steam treated
speciemns are reported in Figs. 1 a) d). Because
steam treatment is not a treatment that can produce
structural changes, all samples have the structure
consists of ferrite and pores filled with iron oxides. In
Fig. 2 is presented the EDS images of the steam
treated specimens, the enrich areas of iron oxide were
observed.
a)
b)
c)
d)
Fig. 1. Microstructure of the sintered steel: a)P1, b)P2 and steam treated: c)P1, d)P2,
etching 2% Nital.
Also, the microhardness tests were performed by
measuring
Vickers
microhardness.
The
microhardness was the average of three indentations
on the top and another on the bottom surfaces of the
samples. The aplied load was 100 g. Figure 3 shows a
comparison between the values of microhardness of
the steam treated samples studied.
The sample P2 shows higher values compare to

P1 (the reference) because of the formation of
homogeneous phase, due to the largest diffusion in
solid solution by the elements used in the preparation
of samples, respectively Cu, Ni and Mo.
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a)
Fig.2. EDS images of steam treated samples: a) P1, b) P2.

M ic ro h a rd n e s s [ u H V 1 0 0 ]
300
The depth and width of wear grooves of steam

treated samples P1 are greater compared to steam
treated amples with higher microhardness P2.
The wear rate was measured as the weight loss,
the sample P1 provided the greatest weight loss.
Figure 4 depicts a comparison between the weight
loss of sintered samples and steam treated tested to
abrasive wear.
Sintered
Steam-treated
250
200
150
100
0.6
0.5
P1
Sintered
Steam-treated
M a s s lo s s [g ]
50
P2
0.4
Sample type
0.3
Fig. 3. Vickers microhardness values of the

sintered and steam treated samples
0.2
0.1
3.2. Tribological tests
0
The worn surfaces of the sintered and steam
treated samples after abrasion tests were examined in
optical microscopes, the typical aspects of abraded
surfaces are represented in Fig. 5. The abrasion tests
were conducted under constant load.
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P1
P2
Sample type
Fig. 4. Weight loss of the sintered and steam

treated samples

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a)
b)
c)
d)
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Fig. 5. Photomacrographs of worn surfaces for sintered: a) P1, b)P2,

and steam treated samples: c) P1, d) P2.
4. Conclusions
References
- Based on the measurements of microhardness,

the sample P2 shows higher values compare to P1.
- A primary role on the resistance to abrasive
wear is played by the composition, the best behavior
was observed for the samples alloyed with Ni and Mo
(P2).
- The steam treated sample P1 presents a depth
and width of wear grooves greater, thus there is a
possibility of less resistance offered.
- The weight loss is less for the steam treated
samples P2.
- The steam treated samples presents best values
of microhardness and wear resistance compared to
sintered state.
[1]. P. Franklin, B. L. Davies, The effects of steam oxidation on

porosity in sintered iron, Powder Metallurgy, Volume 20, p. 11
16, 2001.
[2]. J. D. B. De Mello, I. M. Hutchings, Effect of processing
parameters on the surface durability of steam-oxidized sintered
iron, Wear, Volume 250, (1-12), p. 435-448, 2001.
[3]. K. Razavizadeh, B. L. Davies, The effects of steam treatment
on the wear resistance of sintered iron and Fe-Cu alloys, Wear,
Volume 69, 3, p 355-367, 1981.
[4]. G. Straffelini, D. Trabucco, A. Molinari, Oxidative wear of
heat-treated steels, Wear, Volume 250, 1-12, p. 485-491, 2001.
[5]. K. Razavizadeh, B. L. Davies, Combined Effects of Steam
Treatment and Age Hardening on Mechanical Properties of
Sintered Fe-Cu Alloys, Powder Metallurgy, Volume 25, p. 1116,
1982.
[6]. A. Molinari, G. Straffelini, Surface Durability of Steam
Treated Sintered Iron Alloys, Wear, Volume 181-183, p 334338,
1995.
[7]. A. Molinari, G. Straffelini, Tribological Steam Treated
Ferrous Parts, Int. J. Powder Metallurgy, Volume 33, p. 5562,
1997.
[8]. W. M. da Silva, R. Binder, J. D. B. de Mello, Abrasive wear
of steam-treated sintered iron, Wear, Volume 258, Issues 1-4, p.
166-177, 2005.
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INFLUENCE OF SILICON ON THE PHASE QUANTITIES RESULTED

ON THE GREY CAST IRON SOLIDIFICATION
Elena PANCIU, Denisa Elena ANCA, Mihai CHISAMERA
POLITEHNICA University of Bucharest, 060042, Romania
emails: elenapanciu@yahoo.com, denisa_elena_anca@yahoo.com,
m.chisamera@hotmail.com
ABSTRACT
The main purpose of this study is to determine by calculus the influence of
Silicon by comparing with Carbon on the primary quantities phases resulted on
grey iron solidification. It takes in mind the great influence of the primary phases
(dendritic austenite, eutectic austenite/ graphite conglomerate, primary graphite)
on the cast iron properties. On the other hand, anuseful algorithm for ease
calculation of primary phase quantities with direct application both on Fe-C and
Fe-C-X (X = Si, Mn P, S...) equilibrium diagrams is addressed both for didactic and
professional applications.
The paper presents as tables and graphs the results of theoretical calculus
which covers large regions both of Si and C variations (C=1.76...6.67;
Si=0.0...6.0%) related to grey iron solidification.
KEYWORDS: Cast Iron, binarysystem Fe-C(stable), Fe-C-X system (stable),
PRIMARYphase quantities, mathematical-calculations
1. Introduction
Over time it has established itself as the field of
research in metallurgy to require a series of
mathematical calculations, graphs and interpretations.
For this are a range of steps to ease the calculations of
theoretical and experimental. Something similar for
the computational modeling of cast iron was started
by the brilliancy of scientist, W. Oldfield, who, in
1966, developed a computer model that could
calculate the cooling curves. Oldfields seminal
article included many innovation among which
computational modeling of cast iron analitycal heat
transport + transformation kinetics.
Also in 1987 C.S. Kanetkar describe the method
which consists of solving the heat transfer equation of
conduction for temperature (T), as a function of time
(t) and position within the casting (x), by numerical
methods used at every step,which in turn can be
calculated with the lever rule from the phase diagram
[1].
This article attempts to summarize the major
contribution to the calculation of phase quantities on
the gray cast iron solidification using the age of
computational modeling, using macro commands that

Excel is a tool that is used when your actions must be
repeated on certain cells or even of different
spreadsheets. In principle, these commands allow you
to record your actions and then repeat.
Macros have the built -in feature of Excel 2010
that enables user to record different tasks and Apply
Them Some over on Another portion of the time. It
works on the back-end, recording each and every
mouse click, keystrokes That you do while
performing the task.The component macro allows you
to execute pivot tables, graphing tools, and a macro
programming language called Visual Basic for
Applications [7].

3.1. Binary System Fe-C (Stable)
The transformation of phase at solidification in
the stable binary system Fe-C runs with the primary
austenitic phase separation, on hypoeutectic
compositions while graphitic phase is separated on
hypereutectic iron compositions the quantities of
phases depending on the position of the iron given the
eutectic composition (Fig. 1) [4, 5].
Phase quantities are calculated using the inverse
levers rule [2, 3] as relations in Table 1. show.
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Fig. 1. Application mode of the reverse levers ruleat the grey cast iron solidification hipoeutectic (a)
and hipereutectic (b) in the binary system Fe-C C E = 2 , 0 3 % ; C C = 4 , 2 6 % . [6]
Table 1. Terms for the calculation of phase quantities on the grey cast iron solidification
No.
Crt.
1
2
3
The quantity of phase
The hipoeutectic iron
The primary austenite ( A ' ) or the

primary graphite ( G ' )
The remaining eutectic liquid
( LEut , L Eut )
A =
CC C X
100
CC CE
LEut =
C X CE
100
CC CE
A '+L Eut = 100
Review 1
L 'Eut =
100 C X
100
100 CC
G ' + L 'Eut = 100
eutectic ( qEut , q Eut ) composed from austenite ( AEut ) and eutectic graphite ( GEut )
qEut = LEut
The quantity of eutectic
The austenite from eutectic ( AEut )
AEut =
The graphite from eutectic ( G Eut )
G Eut =
Review 2
Theaustenite from eutectic cast iron

with carbon C X or C ' X
CX
C 'X
)
( AEut
, AEut
Thegraphite from eutectic cast iron

with carbon C X or C X
CX
C 'X
)
( GEut
, GEut
Review 3 (The carbon balance)
q'Eut = L'Eut
100 CC
100
100 CE
AEut =
100 CC
100
100 C E
CC C E
100
100 C E
G Eut =
CC CE
100
100 CE
A Eut + GEut = 100%

AEut
qEut
100
100 CC CX CE
=
100
100 CE CC C E
CX
=
AEut
GEut
qEut
100
C C C C
= C E X E 100
100 CE CC CE
CX
GEut
=
CX CE
100
100 CE
AEut
qEut
100
100 CC 100 C X
=
100
100 CE 100 CC
C 'X
AEut
=
GEut
qEut
100
C C 100 C X
100
= C E
100 CE 100 CC
C 'X
GEut
=
CA +CACX +CGCX =CX
CG + C C ' + C C ' = C X
C
CA ' = E A '
100
CG =G '
Eut
11
C X CC
100
100 CC
G =
After complete solidification concentration eutectic liquid ( LEut , L Eut ) was transformed into
10
The hipereutectic iron
C AC X =
Eut
Eut
CE
CX
AEut
100
C GC EXu t = G ECuXt
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AEutX
C '
AEut X
GEutX
CE C 'X
AEut
100
C 'X
C GCEut' X = G Eut

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The notations significance from figure 1 and

from table1:
A ' - The amount of primary austenite formed in
between T lichidus - T solidus, in %;
G ' - The amount of primary graphite formed in
between T lichidus - T solidus, in %;
L E u t , L ' E u t - Remaining amount of eutectic liquid
when the eutectic temperature is reached (solidus) in
hipoeutectic irons respectively hipereutectic, in %;
CC - The eutectic carbon contents, in %;
CE - The carbon content of austenite at the eutectic

temperature, in %;
C X and C ' X - The carbon content of cast iron hypo
respectively hipereutectic, in %;
qEut and q'Eut - The amounts of eutectic resulting from
C 'X
CX
and GEut
-The quantities of eutectic graphite
G Eut
from irons with the content C X
respectively, C ' X (hipereutectic), in %;
C A ' -The carbon content of primary austenite at the

eutectic temperature ( C A' = CE ), in %;
C ACEutX and C ACEut'X - Theeutectic austenite carbon contents

in both cases equal to C E , in %;
C -The corresponding amount of primary carbon
G '
graphite ( CG ' = G ' ), in %;
CGCX
Eut
carbon Cc, in %;
A EC u t and A ECu t' -Theamounts of eutectic austenite
X
from irons with carbon content C X (hipoeutectic),

respectively, C ' X (hipereutectic), in %;
and C
C '
GEut X
-The
amount
of
carbon
corresponding to the eutectic graphite

quantities of graphite eutectic results), in %.
the eutect liquid solidification to the irons

hipoeutectic respectively hipereutectic in %;
AEut -The amount of austenite in cast iron with
carbon eutectic Cc, in %;
GEut -The amount of eutectic graphite cast iron with
(hipoeutectic),
(equal
3.2. The System Fe-C-X (stable)

The presence of some X elements (X = Si, Mn,
P, S, ...) in the alloys composition of Fe-C (industrial
alloys) causes significant changes in the equilibrium
diagram (fig. 3.2) [4, 5]. which must be taken into
account while calculating the resulting phase
transformations during solidification or solid state
structure.
a)
b)
Fig. 2. Changes in Fe- C equilibrium diagram determined by the presence of silicon:

a) The hipoeutectic iron;b) The hipereutectic iron (stable system)
The influence of other elements than C, where
cast iron is characterized by the following relations:
[6].
-The eutectic Carbon ( CC ):
n
CC = 4, 26 + mi xi , in %
i =1
(1)
In which: mi - Influence coefficient of the element i;

Ex: mSi = 0,31 ; m P = 0, 33 ; mS = 0, 40 ;
m Mn =+0,027
xi - The contentproportion of the element i in iron
-The maximum carbon content of austenite at the
eutectic temperature ( C E )
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C
CE = 2, 03 + m1i xi , in %
(2)
i =1
In which: m1i - Influence coefficient of the element i;

Ex : mSi = 0,11 ,
m P = 0, 35 ,
m S = 0, 08 ,
m M n = + 0, 0 06
xi - The contentproportion of the element i in iron.

-The carbon equivalent iron ( CE ):
n
CE = C
m x , in %.
t
i =1
(3)
In which: Ct is the total carbon content of iron

(carbon chemical), in %.
xi - The percentage content of the element i in iron;mi the influence coefficients of the element i [see ex.
from the relation (1)].

-Eutectic temperature in the stable system ( Tst ):
methodology is identical to that presented in Table

3.1 for the binary Fe-C system [2].
3.3. Aplications
Tst =1152 + 7,5 Si 30 P 2 Cr, C;
(4)
-Eutectic temperature in the metastable system ( Tmst ):
Tmst = 1145 10 Si 30 P + 30 Cr, C
In the relations (4) and (5) Si, P, Cr are

percentage amounts from iron [6]. To calculate the
phase quantities at the primary transformation
(solidification) for the industrial gray irons it is
necessary first to establish their position in the Fe-C
diagram considering the influence of other elements
[5].
For this purpose we must calculate the carbon
values in eutectic points (C) and its solubility
austenite (E), resulting in points C', respectively, E'
(Fig. 3.2). Following carbon values in these points
became CC ' and C values that are used in the
E '
calculation relations from Table 3.1 instead of the
values CC and, CE . Otherwise, the calculation
(5)
Application will be made for the following

cases:
1)
The hypoeutectic iron with C X =3,2%; and
hypereutectic iron with C X'
systemFe-C, stabile.
Table 2 The results of calculus for the proposed applications
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=4,8%, in binary
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The hypoeutectic industrial cast iron with
CX = 3,2%, Si =1,8% and hypereutectic industrial cast

iron with C' X = 3,8%, Si = 2,5% .
The phase quantities variation with
3)
%C,for Si = ct
4)
The phase quantities variation with %Si,
for C = ct
In paragraphs 3) and 4) will be draw the

corresponding
graphs(for
hypoeutectic
and
hypereutectic irons respectively).
The results of calculus for the propsed
applications are presented in Table 2.
The results of calculations were plotted in
graphs as figs. 37 show while the specific influence
of C and Si respectively is summarized in Table 3.
Table 3 Specific influence of C and Si on primary phases quantities
*A primary austenite quantity, %; Eut eutectic quantity, %; G primary graphite quantity, %
a)
b)
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c)
d)
e)
Fig. 3 Influence of C and Si on primary phases quantities resulted on cast iron solidification
(stable system): a) )Binary Fe-C system (carbon variation);(b e)Ternary Fe-C-Si systems
(C or Si variation): b) Si variation on constant C=3.2%; c) C variation on constant Si=1.8
%; d) Si variation on constant C=3.8 %; e) C variation on constant Si=2.5 %
Some comments could be made on the obtaine
results:
* Both C and Si have similar effects on the variation
mode of primary phase quantities but with different
power of influence both on hypo and hypereutectic
irons.
3.3.1. Hypoeutectic irons
Carbon or Silicon increasing in the

hypoeutectic irons determines the decreasing of
primary austenite (A) quantities and coresponding
incresing of eutectic quantity (qeut); A + qeut = 100
%; [5].
Carbon increasing on constant silicon gives a

high power of primary phases quantity variation
depending of silicon values; thus, by silicon
increasing from 0 up to 2.5 %the primary austenite
quantity increases from 44.8 % /% C to 59.5 %/% C
(the eutectic quantity has an invers variation with the

same power of influence);
Silicon increasing on constant carbon gives a

much lower rate of primary phases quantities
variation but without visible dependence on carbon
values; thus, by carbon increasing from 3.2 up to 3.8
%the rate of primary pkase quantity variation changes
from 13.6 to 13.7 %/% Si;
If the carbon and silicon influence power is

compared on hypoeutectic composition irons, the
carbon influence power is four times the silicon one.
3.3.2. Hypereutectic irons
Carbon or silicon increasing on the

hypereutectic irons determines increasing of primary
graphite quantity and coresponding eutectic quantity
decreasing (G + qeut = 100 %) [5].; carbon
increasing on constant silicon gives a slow increase of
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primary graphite quantity and coresponding decrease

of eutectic quantity independently of silicon values;
thus, for silicon variation from 0 up to 2.5 %the rate
of primary phase quantityvariation is constant equal
with 1.04 %/% C;
Silicon increasing on constant carbon gives a

three times lower rate of primary phase quantity
variation by comparing with carbon;
The carbon influence is favoured by silicon

increasing on hypoeutectic irons while it is no
affected by silicon on hypereutectic irons;
The remarcs concerning C/Si influence on

the primary phase quantities variation have a very
strong connection with their effects on the physicalmechanical properties of cast irons if the role both of
matrix and graphite in this context is taken into
account.
4. Conclusions
A syntetic macros was emphasized to easy
calculation of carbon/silicon influence on the primary
phases separation both on Fe-C and Fe-C-Si alloys
solidification(stable system).
Based on the obtained results some iteresting
remarks can be poited out as follows:
Carbon and silicon have similar effects on
primary phases separation but with different
influence power; On the hypoeutectic irons the
carbon influence power is four times the silicon
one while on hypereutecic ironsthe carbon
influence power is three times the silicon one;
The carbon influence is favoured by silicon
increasing on hypoeutectic irons while it is no
affected by silicon on hypereutectic irons;
C/Si effects on the primary phases quantities

have a direct connection with the physicalmechanical properties of cast irons if the role
both of matrix and graphite in this context is
taken into account.
The calculus model for C/Si effects on the

primary phases quantities separated on cast iron
solidification could be an useful instrument both for
didactic and profesional applications to a more easy
utilization of the equilibrium Fe-C-X diagrams.
References
[1]. Doru M. Stefanescu, C.S. Kanetkar - Modelling and
Microstructural Evolution of Cast Iron And Aluminium Silicon
Alloys, the 54th INTERNATIONAL FONDERY CONGRESS,
New Delhi, India, November 22-26, 1987.
[2]. Aloman, Angel - Sistemul de aliaje Fe-C. Structura,
proprietile i diagrama de echilibru fazic(The Fe-C alloys. The
structure, properties and phase equilibrium diagram), Printech,
Bucureti, 1999.
[3]. D.Taloi, Drago Bratu, Constantin Florian, E. Berceanu, Optimizarea proceselor metalurgice (Metallurgical Process
Optimization), Editura Didactic i Pedagogic, Bucureti, 1983.
[4]. M. Stefanescu - Modeling of cast iron solidification-The
defining moments, The Minerals, Metals and Materials Society and
ASM International 2007 symposium , Vol. 38A, July 2007, pp
1433-1440.
[5]. Zhou Jiyang - Colour Metallography of Cast Iron, Dalian
University of Technology, China, symposium, Vol.6.no.1,
february 2009.
[6].L. Sofroni, I. Riposan, V.Brabie, M. Chisamera - Turnarea
Fontei( Casting of |Iron), Editura Didactic i Pedagogic,
Bucureti, 1985.
[7]. *** - Excel Macros(VBA) Tutorial: http://www.excelvba.com/excel-vba-contents.htm.
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TITANIUM BASED ALLOYS CHEMICAL SURFACE

FUNCTIONALIZATION
Ionu TIRBU, Petric VIZUREANU, Ramona CIMPOEU
Technical University Gh. Asachi Iai
email: ramonahanu@yahoo.com
ABSTRACT
Titanium based alloys are wildly used in biomedical field as implant elements.
Few chemical engraving methods including anodizing were used to prepare a Tibased alloy wire surface for further thin metallic or non metallic films deposition or
to be used as they are in implantation. Chemical, by EDAX, and microstructure, by
SEM, analyses were made to establish few surface characteristics after the surface
modification process.
KEYWORDS: anodization, functionalization, Ti based alloy
1. Introduction
Based on the number of published papers on Tibased alloy surface, especially recently, one might
conclude that this issue indeed deserves serious
attention. Various techniques and protocols have been
used for surface treatments; among them mechanical
and electro-chemical treatments, chemical etching,
heat treatments, conventional and plasma ion
immersion implantation, laser and electron-beam
irradiation, design of bioactive surfaces, and a proper
technique can easily be lost in that jungle of
publications. Some of the procedures that were
developed originally for pure Ti and their application
to Ti alloy not only may not bring any improvement
but, rather, can cause surface damage because of
inevitable other elements involvement.
Surface modification and coating of a Ti based
alloy named Nitinol (an acronym for NiTi Naval
Ordnance Laboratory), a system of almost equiatomic
alloys with shape memory and superelastic properties,
is a subject of numerous recent studies directed at
improving the materials corrosion resistance as well
as its biocompatibility through elimination of Ni from
the surface. This chemical element is known to be
allergenic and toxic, though essential for the human
body. Although it has been shown that the amount of
Ni recovered in biological studies in vitro may be
either very low from the beginning or drop to
undetectable levels after a brief exposure to biological
environments [1, 2], the nickel case keeps
reappearing. Thus, the recent results obtained on
commercial ready to be used orthodontic wires
showed that the other elements release varied in a
wide range from 0.2 to 7l g/cm2 [3]. Moreover, it has
been reported that the Ni release can actually

significantly increase with time [47], maintaining a
high level up to 8 weeks and even for a few months
[6, 7], indicating the need for better understanding of
the material/surface interface.
The electro-chemistry of TiNi is poorly
explored. Until recently, there have been no studies
on electro-polishing and anodizing of this material.
This situation is gradually improving with the
publications of papers on electro-polishing processes
in various electrolytes [8], and anodizing in various
solutions and voltage regimes [9]. The effect of
chemical etching (passivation) in HF+HNO3 aqueous
solutions on Nitinol surface chemistry has also been
studied [10].
In this study few chemical surface modification
methods are analyzed to improve the adhesion on
Nitinol with further superficial thin layers that can be
deposited on them.
2. Experimental details
A TiNi echiatomic alloy wire [11] was prepared
using different engraving solutions for surface
modification operation. The material a shape memory
alloy has 50.5 % Ni and 49.5% Ti mass percentages
and an oxide layer on the wire surface. The material
was attack with different solutions like 34% H2SO4
+12% HCl, 48% H2SO4 +18% HCl and anodization
processes. Alloy surface before and after chemical
treatments was investigated using SEM equipment
based on a SE detector and 30 kV power supply
tension of the gun lamp. Using an EDAX equipment
chemical analysis were performed on 2.5 mm2 surface
following especially the Ni and Ti percentage balance
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and evolution and also the other elements from the

surface like oxygen, fluorine, sodium or carbon based
on the aqueous solutions chemical composition.
3. Experimental results
Various techniques and protocols have been
used for surface treatments and among them
mechanical and electrochemical treatments, chemical
etching, heat treatments, conventional and plasma ion
immersion implantation, laser and electron-beam
irradiation, design of bioactive surfaces, and a proper
technique can easily be lost in that big mass of
publications. Some of the procedures that were
developed originally for pure Ti and their application
to NiTi not only may not bring any improvement but,
rather, can cause surface damage because of
inevitable Ni involvement.
The surface state of shape memory alloy NiTi is
presented in figure 1 at a 50 m scale. Can be observe
a smooth surface of the material obtained from the
element manufacturing that had a preparation
necessity for better adhesion of the superficial layers
ready for deposition or of the biological elements
content for a direct usage in implantology.
after the chemical process applied. Both nickel and

titanium elements decrease comparing with the initial
composition most of these percentages lost are based
on oxides form like TiO and the appearance of a
chloride element on the material surface. Increasing
the solution concentration to 48% H2SO4 +18 % HCl
and maintaining a similar exposure time the results
are presented in figure 3 as microstructures and table
2 as chemical composition variation.
a)
b)
Fig. 2. SEM microscopy of NiTi alloy surface

after 34% H2SO4+12% HCl solution treated at
a) 300x and b) 1000x image amplification
Fig. 1. Scanning electrons microscopy of Tibased alloy surface
In a first stage, the material was treated with a
34% H2SO4 +12% HCl solution for 60 minutes at
room temperature and the effects are presented in
figure 2 in two characteristic microscopies at 300x
and 1000x amplification power. The results present
an affected surface on entire area with many holes in
materials, made especially from lose of titan and
nickel oxides, no larger than 2-5 m.
The electrolytic etching explored in this case
induced highly porous NiTi surfaces that might lead
to enhanced Ni release. In table 1 is presented the
chemical composition of the shape memory surface
Tabel 1. Chemical composition of the NiTi alloy

surface after the etching process with 34%
H2SO4+12% HCl solution
Element
AN
Nickel
Titanium
Oxygen
Chloride
28
22
6
11
Sum:
[wt.
%]
45.1
39.5
5.9
2.4
93
[norm
wt.%]
48.47
42.49
6.36
2.66
100
[norm
at.%]
35.1
37.6
22.4
4.9
100
Error in
%
1.1
1.1
0.9
0.2
From figure 3 b) which is a detail from a) can be

observe a degraded surface obtained in this case with
loss of material, especially on percentages of titanium
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based on surface corrosion and especially on

appearance of sulfur and chloride chemical elements
even in reduce percentages. The formation of TiO
layer on the surface is a positive thing at nitinol
simple utilization but can became as a negative aspect
at the growing of new superficial layers on his
surface.
formation of Ti and Ni oxides [12], the preferential

oxidation of Ti on Nitinol surface always occurs. As a
result, bare Nitinol surfaces are built from Ti oxides
with Ni concentrations from 2 to 7 at. %, depending
on the electrolytes and regimes employed. Chemical
etching and electropolishing of NiTi can be used for
surface structuring as well.

surface after the etching process with 48%
H2SO4+18 % HCl solution
Element
b)

after 48% H2SO4+18% HCl solution treated at
The area affected, figure 3 b), is homogeneous
and fully attacked by chemical solution the sulfur
element find on the surface becoming dangerous in
any application to obtain thin layers.
Analyzing the surface statement these two attack
methods are not considered suitable because of the
surface prepared damaged and loss of materials and
structural modifications of the surface. Electropolishing and chemical etchings of Nitinol are known
to be efficient for the elimination of defective surface
layers and surface oxidizing. Owing to a gain in total
energy caused by the differences in the enthalpy of
[wt.%]
[norm.
wt.%]
[norm.
at.%]
Error in %
Nickel
28
49.25
48.37
34.4
1.25
Titanium
22
38.52
37.83
32.9
1.08
Oxygen
11.15
10.95
24.0
3.49
Sulfur
2.07
2.03
7.0
0.42
11
0.81
0.79
1.4
0.11
Sum:
101
100
100
Chloride
a)
AN
Anodizing is an electrolytic passivation process

used to increase the thickness of the natural oxide
layer on the surface of metal parts. The process is
called "anodizing" because the part to be treated
forms the anode electrode of an electrical circuit.
Anodizing increases corrosion resistance and wears
resistance, and provides better adhesion for paint
primers and glues than bare metal. Anodic films can
also be used for a number of cosmetic effects, either
with thick porous coatings that can absorb dyes or
with thin transparent coatings that add interference
effects to reflected light. Anodizing is also used to
prevent galling of threaded components and to make
dielectric films for electrolytic capacitors. Anodic
films are most commonly applied to protect the alloys
although processes also exist for titanium, zinc,
magnesium, niobium, and tantalum. This process is
not a useful treatment for iron or carbon steel because
these metals exfoliate when oxidized; i.e., the iron
oxide (also known as rust) forms by pits and flakes,
these flakes both fall off as well as trap oxygenbearing moisture, constantly exposing the underlying
metal to corrosion.
Anodization changes the microscopic texture of
the surface and changes the crystal structure of the
metal near the surface. Thick coatings are normally
porous, so a sealing process is often needed to
achieve corrosion resistance. The anodization
parameters are 55 C solution temperature, a current
of 0.8 mA in a 30 minutes period time.
In figure 4 SEM microscopies, realized at 1000
and 7500 image amplification times, of Nitinol
surface after the first anodizing process are presented
as general aspect in figure 4 a) and detailed in figure
4 b). As can be see the surface doesnt suffer big
modifications comparing with the surface presented
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in figure 1, keeping a nice aspect with small holes on

the surface.
Table 3. Chemical composition of the NiTi alloy

surface after the etching process by ANO1
conditions
Element
AN
[wt.%]
[norm.
wt.%]
[norm.
at.%]
Error in %
Nickel
28
46.0
46.12
32.91
1.17
Titanium
22
40.0
40.07
35.05
1.13
Oxygen
12.5
12.57
27.7
3.89
Carbon
1.2
1.23
4.30
0.29
Sum:
99.8
100
100
Micro structural results are similar with the

previously results with a smooth surface and small
holes remarkable only at high magnification images
with dimensions under micron scale.
a)
a)
b)

after ANO1 conditions treated at a) 1000x and
b) 7500x image amplification
In table 3 the EDAX analyze results, like mass
or atomic percentages, are presented having a
relatively high Oxygen percentage most based on
titanium oxide form on the surface and a reduce
carbon percentage. All results were taken from K
series with reduce errors in analyze. The experimental
results doesnt present an improve of the surface by
growing thin films point of view and present bad
results for this material after anodizing method, in
this experiment conditions, to be used like this
without other improvements based on the still
reduced percentage of titanium oxide and high
percentage of nickel for the alloy surface.
Using second anodizing conditions, 55 C bath
temperature, 0.8 mA activation current and 45
minutes period time, the surface is presented through
scanning electrons microscopies in figure 5 as general
view in 5 a) and detail in 5 b).
b)

after ANO2 conditions treated at
Chemical results are unsatisfactory as well for
the material surface usage in direct contact with the
human body [13].
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Keeping a high nickel percentage at the surface

the material is not improved and the surface is to
reduce engraved so applying in this conditions the
anodizing is not favorable for the nitinol material.
A reduce of the percentage of oxygen, six times
smaller than the previous experiment, represent a
small percentage of TiO form on the surface layer
that is seen by a researcher as a good alternative for
thin films deposition [14]. These results are
considered very important in chemical improvement
of the nitinol surface opening new research
opportunities like embedding the TiO thin layer but
also to open a path for anodizing process usage in
surface preparation The research on the surface of
nitinol material preparation by chemical methods
continued in a further article using other attack
solutions also observing the microstructural surface
aspect and chemical behavior in the same time with
observing the variation of TiO thin layer.

surface after the etching process by ANO2
conditions
Nickel
28
48.56
[norm.
wt.%]
51.51
Titanium
22
43.85
46.52
48.29
1.23
Oxygen
1.84
1.95
8.08
0.40
Sum:
94.6
100
100
Element
AN
[wt.%]
[norm.
at.%]
43.61
Error in %
1.24
4. Conclusions
Ti-based materials are widely used in the
medical field, many applications being in direct
contact with the human body.
Trying to improve the surface properties of these
materials for depositions of superficial thin layers is
considered a solution among the increase and evolves
of TiO thin layer. Different engraving solution was
used, part in this study and other in a further work, to
improve the surface of material for adhesion with thin
deposited layers the results being based on
micrographic analyze (macro and micro areas
analyzed) and chemical composition observation at

the surface as well. Anodizing methods involving
attack solutions were analyzed with good results in
increasing the TiO superficial layer but with no
decrease of nickel percentage at the surface.
References
[1]. Wever D., Velderhuizen A., De Vries J., Busscher H., Uges
D., Van Horn J., Electrochemical and surface characterization of
NiTi alloy, Biomaterials 1998, 19, p. 7619.
[2]. Cui Z., Man H., Yang X., The corrosion and nickel release
behavior of laser surface-melted NiTi shape memory alloys in
Hanks solution, Surf Coat Technol 2005, 192, p. 34753.
[3]. Arndt M., Bruck A., Scully T., Jager A., Borauel C., Nickel
ion release from orthodontic NiTi wires under simulation of
realistic in-situ conditions, J Mater Sci 2005, 40, p. 365967.
[4]. Sui J., Cai W., Effect of diamond-like carbon (DLC) on the
properties of the NiTi alloys, Diamond Relat Mater 2006, 15, p.
17206.
[5]. Kobayashi S., Ohgoe Y., Ozeki K., Sato K., Sumiya T.,
Hirakuri K., Diamond-like carbon coatings on orthodontic
archwires, Diamond Relat Mater 2005, 14, p. 10947.
[6]. Bogdanski D., Untersuchungen zur biocompatibilitat and
biofunctionalita t von implantatmaterialien am beispiel von nickel
titan formgeda chtnislegierungen, Dissertation, RuhrUniversita Bochum: Germany, 2005.
[7]. Clarke B., Carroll W., Rochev Y., Hynes M., Bradley D.,
Plumley D., Influence of Nitinol wire surface treatment on oxide
thickness and composition and its subsequent effect on corrosion
resistance and nickel ion release, J Biomed Mater Res 2006, 79A,
p. 6170.
[8]. Pohl M., Heing C., Frenzel J., Electrolytic processing of
NiTi shape memory alloys, Mater Sci Eng, 2004, A378, p. 1919.
[9]. Shi P., Cheng F., Man H., Improvement in corrosion
resistance of NiTi by anodization in acetic acid, Mater Lett, 2007,
61, p. 23858.
[10]. Shabalovskaya S., Anderegg J., Laabs F., Thiel P.,
Rondelli G., Surface conditions of Nitinol wires, tubing, and ascast alloys: the effect of chemical etching, aging in boiling water,
and heat treatment, J Biomed Mater Res, 2003, 65B, p. 193203.
[11]. http://www.saesgetters.com/default.a spx ?idPage=839.
[12]. Wagman D., Evans V., Parker V., Schumm R., Halow I.,
Bailey S., Churney K., J Phys Chem Ref Data, 1982, Suppl. 2:11.
[13]. Chuanjun Huang, Yibin Xie, Limin Zhou, Haitao Huang,
Enhanced surface roughness and corrosion resistance of NiTi alloy
by anodization in diluted HF solution, Smart Mater.
[14]. S. A. Shabalovskaya, Physicochemical and biological
aspects of Nitinol as a biomaterial, International Materials Review,
vol. 46, pp. 1 - 18, 2001.
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METHODS OF RECOVERY AT THE RENEWABLE ENERGY

SOURCES FROM BLAST FURNACES
Irina VLCIU1, Maria NICOLAE2, Avram NICOLAE2
1
Ecological University of Bucharest, 2Polytechnic University of Bucharest

emails: irina.vilciu@gmail.com, nicolae_maria@yahoo.com
ABSTRACT
Due to the global energy crisis, we are interested in energy recovery from the
metallurgical industry, but especially from siderurgy, because it is one of the major
fuel and energy consumers. The current major objective is to reduce the specific
energy consumption, primarily by increasing the use of heat.
KEYWORDS: regeneration, recovery, energy resources
Introduction
One of the aggregates where this problem arises
is the blast furnace, where the amount of heat
provided by coke burning is rather large, as we can
see below:
In the last 50 years, it was a significant reduction

in the energy consumption required to produce pigiron, and the consumption of reducing agents has
halved at the blast furnaces in the European countries.
In the same time, the productivity increased several
times. In the last 20 years, it was a significant
reduction in the coke consumption, being replaced
through addition of cheaper reducing agents. This
process can not continue indefinitely, because the
blast furnace process requires, for physical reasons, a
certain amount of coke. Currently, the minimum coke
requirement is of the order of 270 to 300 kg/t pigiron, and the other reducing agents are up to over 500
kg/t pig-iron. The purpose of this paper is to present
the characterization in terms of energy of the fuels
used for making pig-iron, and their potential cheaper
substitutes.
example, pig-iron on the segment blast furnace),

we deal with sequential energy consumption (Ces). If
we analyze the entire cycle of the integrated steel
plant which delivers externally its final product (for
example, flat products), then we refer to integral
energy consumption (Cei) and has the size of a total or
overall consumption. Both consumption categories
are presented as specific energy consumptions (per
mass unit or product volume).
Two situations can occur:
- the design phase, when the consumptions are
determined by calculation;
- the operational phase, when the consumptions are
recorded () by measurements and calculations.
The most common is the second phase, which
also confirms and homologates. As a general
calculation relation, it is recommended the equation:
where: Ces [J/t steel] is the sequential energy

consumption recorded by measurement directly to
certain sequences;
Ms [kg;
] is the specific consumption of
energy source recorded at a particular sequence;
1. Sequential and integral specific

energy consumptions
is the calorific power of that
The energy consumption represents the

quantities of energy (equivalent in the same
measurement unit) used to manufacture a certain
product. If it is an intermediate product made on a
certain segment of the manufacturing cycle (for
energy source.
At a modern integrated steel plant of flat
products (integration on the flow blast furnace converter - rolling mill), the integral specific
consumption is Cei = 19.3 GJ/t (value that has already
become famous).
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2. Expanding the fuel and energy sources

2.1. Inferior fuels
At blast furnaces, inferior fuels are considered
the coals (e.g. lignite) and the poor quality fuel oil,
but there are ways of introducing such energy sources
in the metallurgical circuit. In case of solid fuels, we
can apply two main methods: combustion in powder
form and gasification.
The combustion of powdery solid fuels in jet
flame can be introduced and even extended to various
types of furnaces, with the following economical and
technological considerations:
- the costs incurred by grinding are largely mitigated
by the fact that, currently, in the metallurgical sectors
result, due to manipulation, relatively large amounts
of coal dust and coke dust which, after a size sorting
operation, can be directed to combustion;
- the use of jet flame is technologically justified at
some furnaces in which oxide reduction processes
occur;
- the negative impact of the flame containing ash and
sulphur gases on the iron melts can be alleviated by
the modern means of refining offered by the
secondary metallurgy;
- significant amounts of coal dust can be used for
carburizing the unlit flames emanating from the
gaseous fuels.
Another possibility of using the coals is their
gasification, which results in a fuel gas called
producer gas which is directed towards the
combustion furnaces.
In figure 1, it is shown the functional diagram of
the gas generator. The process consists in passing an
oxidizing agent through an incandescent coal layer in
a plant called gas generator or gasifier.
The reduction zone:

C + (CO2 + N2 + H2 + CH4)
(CO + H2 + CH4) + N2 + CO2
The oxidation zone:
C + (O2) (air)
CO2 + N2 + (H2 +CH4)
C + H2O (steam)
Depending on the blown oxidising agent, there
are more industrial versions:
- air gas, found at air blowing; it has a low calorific
power, due to the high proportion of N2 (transferred
from air);
- water gas, resulting from the use of steam; the
process has the disadvantage that the carbon reaction
with water is endothermic;
- mixed gas, which in most cases is actually producer
gas, obtained from blowing a mixture of air and
steam;
- steam-oxygen gas, made by blowing the mixture of
steam and oxygen, or steam and oxygen enriched air.
The poor quality fuel oil also becomes a fuel
used without technological disadvantages or related
to environmental protection, by:
- gasification, process whose outcome is obtaining a
gaseous fuel, free of compounds that contain sulphur;
- carburizing the unlit flames of the gaseous fuels.
2.2. Combustible by-products

Following the processes that take place in the
blast furnace, there are resulting gaseous by-products
which, thanks to their composition (they contain
significant quantities of H2, CO, CH4), they represent
very cheap artificial fuels. After their capture and
treatment, these products are directed to the
combustion furnaces. Such fuel used on a larger scale
is the blast furnace gas product captured at the top
of the blast furnace, which contains: CO = 28% and
CH4 = 1%; Hi = approx. 4 MJ/ .
It is obvious that the blast furnace gas can be
used only within the confines of the metallurgical
units which have blast furnaces.
2.3. Substitutes for expensive

and deficient fuels
Fig. 1. Working principle diagram of the

gas generator
At the blast furnaces from our country, the coke

and fuel oil are expensive, and the natural gas has
become an expensive fuel, too. In order to reduce the
consumption of such materials, the scope of the
research is to find ways to replace part or all of them,
by covering the following routes:
- partial replacement of coke in blast furnaces by
blowing jets of pulverized coal;
- partial replacement of coke by blowing poor quality
fuel oil;
- replacement of natural gas with artificial gaseous
fuels or mixtures thereof.
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3. Recirculation of process gases

At the German blast furnaces (currently the best
in the world), the industrially achieved average value
is only 7% higher than the "utopian" ideal. These
blast furnaces are therefore operated with an
efficiency = 93%.
One of the major ways recommended to the iron
makers to achieve such yields is changing the
composition of the gas phase in the combustion zone
(the combustion air is called in some papers wind).
Firstly, it is about the technologies based on

blowing large amounts of oxygen instead of hot air,
or as additive in the blown hot air.
Secondly, it is about the modification of the
gaseous phase blown in the blast furnace by
technological recirculation of the process gases (blast
furnace gas components, which are not released
outside the unit contour, but they are re-blown in the
combustion zone). In figure 2, it is presented the
sketch of a pilot plant showing the operation of the
blast furnace with process gas recirculation.
Fig. 2. Sketch of the blast furnace operation with process gas recirculation
1 treatment plant for the blast furnace gas; 2 installation for blowing the blast furnace gas;
3 blowing auxiliary reducing material; 4 reactor for obtaining high temperature reducing gas.
The blast furnace has two levels of tuyres:
- At the lower level (regular), it is blown a synthetic
"wind", cold, poor in nitrogen, whose main
components are the oxygen and carbon monoxide
(Synthetic Cold Blast SCB-Technology);
- At the higher level, located in the shoulders or in the
bottom of the shaft, there are the tuyres, through
which it is blown gaseous CO preheated to 900 C.
The CO heating is achieved by partial
combustion in a special reactor, placed before the
tuyres of the upper level. There is no need to use
Cowper stoves.
After the removal of CO2, a gaseous residue
results by absorption, having almost the same
calorific power as the gases from the classic blast
furnaces. This will be an externally available gas.
By outsourcing the waste gas, we avoid nitrogen
enrichment of the blast furnace gas.
Under
the
conditions
examined,
the
concentration of nitrogen in the synthetic "wind" will
be less than 5% (volumetrically).
The carbon dioxide absorption from the process
gas is currently industrially achievable. The plants for
carbon dioxide absorption operate with activated
carbon, silica gel or molybdenum, by absorbing water
vapours.
They have the advantage to do not require other
chemicals. For treating large volumetric flows,
special absorption installations are used in siderurgy
for a long time.
For blast furnace operation with cold "wind", it
was chosen, for treating the blast furnace gases
through absorption with pressure variation (Pressure
Saving Absorption PSA), a PSA installation made
by the company Linde AG.
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The obtained gas, with more than 82% CO and

10% H2 is a valuable reducing gas. By introducing it
in the blast furnace, we achieve the purpose to reuse
the reducing potential of the blast furnace gas.
The remaining gas leaving the PSA has a
calorific power similar to the conventional blast
furnace gas. It can be used for other purposes, as gas
outsourced, outside the blast furnace. The gas blown
through the nozzles located at the higher level should
be brought at temperatures of 900 - 1000 C, by direct
or indirect heating.
For indirect heating, there is available the
regenerative technology, well-known from Cowper
stoves, but which is very expensive. Therefore, it is
advisable to use the common technology in the
gasification technique - the partial oxidation. Here, a
part of CO and H2 is burnt with oxygen, and the
reaction heat is used for heating (self-heating).
The SCB technology described is characterized
by the following features:
The enthalpy carrier, introduced directly into the
blast furnace, which is the nitrogen from the gasified
air, is replaced by a low-nitrogen gas, consisting of
CO and H2, with small impurities of N2, CO2 and
H2O; this one bears enthalpy and, in the same time, is
a reducing agent. This reducing agent is obtained
from the gases exhausted in the course of the blast
furnace processes. Its reuse in these processes is a
highly effective form of recycling and reduces the
demand of reductants to be brought in from outside.
In the furnace will be an unusually high
reducing potential. In the example mentioned above,
the partial pressure of CO becomes more than double,
and in the same time the partial pressure of N2
decreases to less than 1/10. As a result, it is expected
a higher efficiency of the reduction process.
The enthalpy and reducing gases intake, divided
into two levels, relieves the lower part of the blast
furnace; in this way, the amount of gases that pass
through the bottom will be limited to minimum.
Since the bottom of the blast furnace causes the
most specific pressure loss, thus will be created the
required conditions to increase the productivity.
The technological particularities mentioned

above create possibilities of sudden drop of coke
consumption and CO emissions.
Since 2000, in Austria began experiments on
blowing reducing gas which is, in fact, a bi-gas
formed by mixing the converter gas with coke gas
).
(about
4. Conclusions
In the siderurgy sector, especially at blast
furnaces, the problem of renewable energy recovery
has a particular importance in reducing the
consumption of coke and power (which becomes
more and more expensive).
At blast furnaces, the coke can be largely
replaced by inferior fuels, as coal (e.g. lignite) and
poor quality fuel oil, by applying new methods, as:
combustion in powder form and gasification.
These fuels are used only within the confines of
the metallurgical units which have blast furnaces.
The plants for carbon dioxide absorption operate
with activated carbon, silica gel or molybdenum, by
absorbing water vapours. They have the advantage to
do not require other chemicals.
The technological particularities of the SCB
technology lead to possibilities of sudden drop of
coke consumption and CO emissions.
References
[1]. Nicolae A., Predescu C., Nicolae M., .a.
Operaionalizarea conceptului DD n siderurgie, Editura
Printech, Bucureti, 2006;
[2]. M. Nicolae, C. Dobrescu, I. Vlciu, N. B. Milea Caracterizarea resurselor energetice regenerabile de la
instalaiile termotehnologice metalurgice, Analele Universitii
din Oradea, Fascicola de Energetic, Nr. 13, Editura Universitii
din Oradea, 2007;
[3]. Nicolae, A., Predescu, C. Bazele teoretice ale agregatelor
termotehnologice din industria materialelor metalice. Bucureti,
Editura Printech, 2001.
[4]. Nicolae, M. Dezvoltare durabil n siderurgie prin
valorificarea resurselor secundare. Bucureti, Editura Printech,
2004.
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STUDIES ON THE MODIFICATION OF PROPERTIES BY HEAT

TREATMENTS OF STEEL RUL2
Drago-Cristian ACHIEI, Petric VIZUREANU,
Viorel GRANCEA
Gheorghe Asachi Techical University from Iai
emails: dragos_adc@tuiasi.ro, peviz2002@yahoo.com, viorelgrancea@yahoo.com
ABSTRACT
This paper presents experimental tests made on samples of type RUL2 steel
sample subjected to heat treatments annealing, hardening martensitic and low
recovery. Improving the physical and mechanical characteristics of bearing steels
used in construction machinery is a prerequisite to ensure the best reliability
bearing.
KEYWORDS: bearing steel, heat treatment, hardness, microstructures
1. Introduction
The bearings are formed, in the general case, the
two rings or washers, a number of rolling elements
and a cage [1].
Rings, outdoor and indoor meet in radial
bearings, while washers, jet and housing meet the
thrust bearings.
Both the rings and the washers are processed
into the interior of the bearing raceways.
housing. The cage is to maintain the fixed distance

between the rolling elements.
There are special bearings which need not be
one or more components. Thus, there is no bearing
ring or rings with two, in this case, the rails are made
directly on the shaft or/and to the chassis. Also there
are bearings that can deprive cage [2].
Bearing constructive diversity requires choosing
appropriate criteria for classification: the rolling, the
main load direction, how to answer inclination,
number of rows of the rolling element, form cage
design and material, specific design elements.
Depending on the destination, the bearings can
be: general purpose bearings and special bearings [4].
General purpose bearings are bearings used in
most machines and are made usually in normal
precision class. Special bearings include: bearings for
equipment and instruments, high-precision bearings,
large bearings, ball bearings for linear motion
bearings, self-lubricating, low precision bearings.
2. Bearing materials
Fig. 1. Ball bearing
Rolling elements (balls or rollers) are in direct
contact with the two rings by means of rolling.
By means of rings or washers are directly
connects the bearing assembly is mounted, the inner
ring is mounted on the shaft, and the outside the
housing [3].
The spindle bearings thrust washer is mounted
on the shaft and housing washer is mounted in the
Severe regime of requests and the particularly

complex phenomena of damage were not possible to
establish a direct link between standard mechanical
properties and quality of the steel used to manufacture
bearings [6].
To assess the quality of steel bearings should be
considered following mechanical and physical
properties:
- durability of contact at the request of fatigue;
- hardness at ambient temperature and at high
temperature;
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- coefficient of expansion;
- tenacity;
- resistance to corrosion;
For normal use and application conditions, the
only crucial first two properties, the other becomes
important only in special applications [7].
Steels used for making rings and rolling bodies
are in most cases with high carbon content, however,
by using some cement steels [8]. Regardless of the
type of steel, the minimum acceptable hardness of 58
HRC.
The composition is specified in Table 1.
Table 1
Chemical composition [%]
Fe
Si
Mn
Cr
rest
0.97
0.60
1.10
1.53
The sample analyzed is part of bearing steels

(RUL 2).
4.2. Changing the properties of hardness by

heat treatment
3. Characterization and use of bearing

steels
Durability and safe operation of the bearings is
ensured by high resistance to breakage and fatigue
and high dimensional stability of steel Bearing:
RUL1; RUL2; 13CrNi15; 20MoCr05; 90VMoCr180
and 55SiMo5.
The most important feature is the hardness of
the bearing steel after the final heat treatment, which
depends on the austenitising temperature for the
quenching and the tempering temperature.
Bearing capacity and durability are significantly
reduced with increasing temperature recovery or use
[6]. The recovery temperature is lower, the two
properties are higher and the amount of residual
austenite is greater than it affects the dimensional
stability and resistance to fatigue by pitting.
For this reason, the bearings, it is preferred
cryogenic treatment of (-70 C) immediately after
quenching in oil, in order to reduce the amount of
residual austenite, followed by a recovery to low
temperature in order to tension easing. Status of
delivery bearing steel is rolled, rolled annealed,
annealed - peeled, annealed - pulled, peeled - smooth
shot - annealed, calibrated and polished in the form of
bars, wire or other products. Rings and rolling bodies
are made of special chrome steel bearings, in-rolled
or cold drawn bars [8].
After appropriate heat treatment, the hardness of
the bearing components should be within the
following limits:
- Ring: HRC = 61 ... 64 kgf/mm2;
- For ball and roller: HRC = 62 ... 65 kgf/mm2.
Breaking breach must be steel, bronze, brass,
silky-looking porcelain. The material can be steel
cage, bronze, brass, duralumin, textolite or other
synthetic materials.
The heat treatments applied to experimental

samples were performed on the electric furnace, with
hearth fixed, type UTTIS.
Samples used in experimental tests from rolled
bar.
To be machined, steel bearing is subjected to a
heat treatment RUL2 primary normalization,
observing the following parameters:
- heating 890 C.
- maintainig 120 minutes.
- low cooling with furnace.
Heat treatment parameters to improve are:
quenching
- heating 860C with speed 10 C/minute.
- maintaining 60 minutes.
- oil cooling.
recovery
- heating 180 C with speed 10 C/minute.
- menaining 60 minutes.
- low cooling in air.
4.3. Hardness measurements

Changes RUL2 steel properties by heat
treatment annealing, hardening martensitic and low
recovery can be highlighted by hardness
measurements performed on Universal Hardness
Testers Wilson Wolpert 751N.
Hardness scale used was Rocwell using a
conical diamond penetrator and a touch of 150 kgf
weight.
Experimental values of hardness are presented
in table 2.
Table 2
#
Heat treatment
Normalizing
4. Experiments
4.1. Chemical composition determination
Martensitic
quenching
Analysis of the chemical composition of the

samples was performed on a spectrometer Foundry
Masters - 01J0013 model.
Low
recovery
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Value
18.9
20.3
21.6
62.3
61.9
62.4
61.5
61.8
60.8
Average
20.26
HRC
62.2
HRC
61.3
HRC
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4.4. Microstructures analysis

Previously analyzed samples were prepared by
cleaning, sanding and polishing.
Cleaning was performed using a bench grinder,
equipped with a brush, aiming decarburized layer
removal.
Polishing
was
done
gradually
metallographic paper with different grits. Polishing
was done on a felt soaked with a solution of
aluminum oxide 1 m. To reveal microstructural
constituents, samples were challenged with reactive
nital 4%.
b)
Fig. 3. RUL2 steel, nital 4% attack: a) 200X,

b) 100X magnification
a. Sample microstructure by heat treatment of

normalizing annealing
c. Microstructures samples after low recovery

heat treatment
a)
a)
b)
Fig. 2. RUL2 steel, nital 4% attack: a) 200X,

b) 100X magnification
b)
b. Microstructures samples after martensitic

hardening heat treatment
Fig. 4. RUL2 steel, nital 4% attack: a) 200X, b)

100X magnification
5. Conclusions
a)
Rolled steels RUL2 state has a fine grain

structure sipping, where rolling end temperature was
low and if cooling after rolling was fast.
If rolling over at high temperatures and cooling
was slow, the structure consists of pearlite with
blades more or less thick and a network of cementite.
This structure would adversely affect further
processing that is why we recommend removing
annealing.
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After quenching the steel structure RUL2 oil

hardened fine needle martensite and carbides found
evenly dispersed.
Improving the physical and mechanical
characteristics of the steel bearings used in machine
building is and remains a very complex issue with the
multitude of alloy steels that can be used in their
construction.
Addressing aging phenomena occurring in
bearings is a necessary but not sufficient to choose
the class of alloy steel which will ensure the best
reliability.
Loss of material due to the aging process will
lead to changing the size and geometric shape of the
contact surface of the bearing and consequently to
decrease the yield of the bearing.
References
[1]. Gafiteanu Mihai, s.a., Rulmenti proiectare si tehnologie,
vol. I, Editura Tehnica, Bucuresti, 1985.
[2]. Jinescu V. V., Utilaj tehnologic pentru industrii de proces,
volumul 2, Ed. Tehnic, Bucureti, 1984.
[3]. Alexandru I., s.a., Alegerea si utilizarea materialelor
metalice, Editura Didactic si Pedagogic, Bucureti, 1995.
[4]. Buzdugan Gh., s.a., Rezistena materialelor, ediia a IX-a,
Editura Tehnic, Bucureti, 1970.
[5]. Buzdugan Gh., s.a., Calculul de rezisten la solicitri
variabile, ediia a II-a, Editura Tehnic, Bucureti, 1963.
[6]. N. Cimpoeu, S. Sergiu, M. Meyer, I. Ioni, R. Cimpoeu
Hanu, Effect of stress on damping capacity of a shape memory
alloy CuZnAl, Journal of Optoelectronics and Advanced Materials,
12, (2010), p. 386-391.
[7]. Balta Stefan, Sotto Arcadio, Luis Patricia et al., A new
outlook on membrane enhancement with nanoparticles: The
alternative of ZnO, Journal of Membrane Science, Volume 389
Pages 155-161, Published FEB 1 2012.
[8]. Ionela Poenia Brloag, Traian Buzatu, Ecaterina Matei,
Physical methods for processing electronic and electrical
equipment waste (weee) for nonferrous metals recovery, U.P.B.
Sci. Bull., Series B, Vol. 73, Iss. 4, 2011, ISSN 1454-2331.
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THERMOMECHANICAL PROCESS OPTIMIZATION TREATMENT

USING AN ALUMINUM ALLOY GRADIENT METHOD
Marian NEACU, Doru HANGANU
emails: uscaeni@yahoo.com, doru_hanganu@yahoo.com
ABSTRACT
This paper presents a method of optimizing a thermo-mechanical treatment
process, applied to an aluminum alloy of high strength.
Applying thermo-mechanical treatment optimization of the gradient method is
based on a system of equations, which is the mathematical model of thermomechanical treatment process, the equations which describe the dependence of
mechanical properties depending on the process parameters.
Gradient method is an iterative method that through many iterations
whereabouts enables property sets simultaneously complying with restrictions.
KEYWORDS: mathematical modeling, optimization, gradient method,
thermomechanical treatment
1. Introduction
Optimization of the technological process is
based on a mathematical model that should describe
as accurately as that process, the mathematical model
is the main element in the management process.
It follows immense importance to obtain a
mathematical model that describes how closely that
process, ie between the mathematical model and
describe the process you must be a more precision
[3].
The optimal solution is obtained by determining
the values of the independent variables so as to obtain
the nearest mechanical property imposed by function
- objective function (optimized).
Taking into account the characteristics of the
steel industry, namely:
consuming raw materials, fuel and

energy;
high complexity of processes;
Ability generally high production of

machinery (furnaces, steelworks, rolling mills), there
obviously need to implement management methods,
the processes themselves, in order to achieve
economies of raw materials, fuel and energy [1-3].
Choice of function - objective is the main step in
solving an optimization problem. The effectiveness is
assessed by several indicators, so it is necessary to
choose the most representative indicator and final
verification of how the optimal solution corresponds
to the other indicators.
In search of a solution is chosen initial vector x0

and x1 algorithm determines a vector which leads to a
better value of the objective function, the process is
repeated to obtain a series of vectors x0, x1, ..., xk, ...,
each enhancing the value objective function
compared to the previous. This sequence converges to
x*, the solution of the problem. In linear
programming problems solution is obtained after a
finite number of steps
In nonlinear programming problems string never
touches the solution, but converges to it. Basically,
the algorithm stops when a point close enough to the
obtained solution.
Model equations expressing correlations
between process variables and deducted either by
theoretical analysis is based on experimental
observations (empirical) [2].
Model restrictions consist of functions of type
equality and/or inequality, which determine the areas
allowed the optimized variables (the input to the
process) can take values.
The performance (objective optimization
criterion) expresses the dependence between the main
independent variables and the main performance
followed in conducting the process.
The performance is expressed by the relation:
Y = Y(X1, X2, ... Xn)
(1)
The performance is unique and objective criteria

optimization and process management [4].
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Typically,
the
function
of
economic
performance is a clear criterion (for example, the
manufacturing price of a product, the maximum
profit, and so on), but can also be a non-economic
criteria, but has the economic (as used in the
extractive metallurgy, in product obtained undergoes
further processing) as: aggregate productivity
(tons/hour, tons/unit volume, etc.), specific
consumption (raw materials/product unit; energy/unit
of product, etc.) yields metal (metal removal yields
the assimilation of alloying elements, impurities
removal efficiency), etc. [3]. Methods of optimization
are of very general application. On the one hand,
most natural and economic phenomena are
compromises between conflicting cases, and as such
many of the problems of engineering, economics,
mathematics, statistics, medicine, and especially
decision-making processes can be formulated as
optimization problems. On the other hand, most of
the numerical methods can be reformulated as

optimization problems.
The objective function when optimizing
thermomechanical processing parameters of the alloy
studied is the energy:
"Q = f (t, , )"
where Q is the amount of energy consumed in the
thermo-mechanical treatment;
T - temperature at which the process;
- time thermomechanical treatment;
- the degree of deformation.
2. Mode of action
For optimization using mathematical models
derived from mathematical modeling to achieve for
each property of the researchers, AL5,7ZnMgCu
alloy.
Mathematical equations are:
Y1 (t , , ) = 611,51 1,195 t + 7,609 + 2,64 0,029 t
(2)
Y2 (t , , ) = 522,371 0,8375 t + 8.25 + 5,25 0,0328 t 0,0212 t (3)

Y3 (t , , ) = 8,65 + 0,018 t 0,05 0,1
(4)
Y4 (t , , ) = 189,535 0,525 t + 1,562 + 0,875
(5)
where: Y1 is the mechanical strength in [MPa];

Y2 - yield strength in [MPa];
Y3 - elongation in [%];
Y4 - Brinell hardness in [HB].
The problem to be solved by optimization is
obtained for all the mechanical properties, the values
imposed by EN_485-2-2007 minimum energy
consumption.
Solving the problem must take into account the
following restrictions:
Rm 540 MPa
Rp0,2 470 MPa
A5 7 %
HB 161
120 C t 200 C
4 ore 20 ore
30% 10%
(6)
(7)
(8)
(9)
(10)
(11)
(12)
Gradient method is an iterative method that

through many iterations whereabouts enables
property sets simultaneously complying with
restrictions.
We calculated the partial derivatives of the
function Y1 (t, , ), (Y1 is the main feature that
requires manual for the maximum value under the
circumstances):
Y1
= 1,195 0,029
t
Y 1
= 7,609 0,029 t
Y1
= 2,64
(13)
(14)
(15)
Thus, the gradient vector for Y1 which is the

tensile strength is:
grad Y1 = (-1,195-0,029; 7,609-0,029t; 2,64) (16)
The starting point is chosen point coordinates: t1
= 120 C, 1 = 20 hours 1 = 30%, at which point it
starts to calculate the direction of minimum gradient.
By replacing the values of t1, 1 gradient in the
expression of Y1 follows:
grad Y1(1) = (-1,079; - 4,129; 2,64).
The next step, verify the conditions of restriction
to the initial point, shows that satisfied not only
strength properties and plasticity:
Rm(1) = 629.90 MPa;
Rc(1) = 582.631 MPa;
HB(1) = 184.025;
A5(1) = 6.81%.
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- To find the optimal point or points shall be

determined as follows:
- This is the step change h = - 0.4;
- Step manner to achieve the transformation to
the initial point is described by a vector of the form:
xi(N+1) = xi,N + h
Yi , N
x i , N
, i = 1,2,...k
(17)
- Calculate the relationship, xi(N+1) = xi,N +
Yi , N
x i , N
, i = 1,2,...k the coordinates of the point 2,
where xi is the thermomechanical treatment variables

(t, , ): t2 = 120,71 C; 2 = 18,348 hours; 2 = 28,94
%;
- Calculate Rm, RP0, 2, A5 and HB using
mathematical models and replacing the: t, , , with:
t2, 2, 2 is obtained
Rm(2) = 619.056 MPa

Rc(2) = 572.081 MPa
A5(2) = 7.011 %
HB(2) = 180.148
Iteration 2 check restrictions.
- Is replaced in equation (16) T, , calculated
in equation (17) and obtain: degree Y1 (2) = (1727,
4108, 2.64) is necessary to calculate the variables t3,
3 3 the next iteration.
Further we proceed similarly, using the same
algorithm, a number of 40 iterations for finding those
values that satisfy the conditions imposed restrictions.
3. The results
Of the 40 iterations, the values that the
conditions imposed are listed in Table 1.
Table 1. Calculation results for the gradient method iterations leading to acceptable values for
mechanical properties
No. Iteration
accepted
2
3
4
5
6
7
t
[C]
120.71
121.40
122.07
122.73
123.36
123.97
[ore]
18.35
16.71
15.07
13.44
11.82
10.21
[%]
28.94
27.88
26.83
25.78
24.72
23.66
Rm
[Mpa]
619.05
608.35
597.78
587.34
577.01
566.81
Rp0,2
[Mpa]
572.08
561.67
551.41
541.28
531.28
521.41
A5
[%]
7.01
7.21
7.41
7.61
7.81
8.00
HB
180.15
176.29
172.46
168.65
164.87
161.10
Fig. 1. Graphical representation of the values of the mechanical properties obtained by calculating
the gradient method to the 40 iterations (marked are those that meet the restrictions)
In Figure 1. are the mechanical properties of the
alloy studied obinuute by calculation, using the
gradient method for 40 iterations.
In that the iterations of the calculation, 2, 3, 4, 5,
6, 7, both the values obtained for the mechanical
properties and parameters studied t, , fall within the
thermo-mechanical treatment of restricted conditions
(equations: 6 12).
4. Calculation of thermal energy Q [kWh]

To find out which of the six types of
thermomechanical treatment is the best option in
terms of economic calculation is performed thermal
energy Q [kWh].
Calculation of energy in the form of heat
(thermal energy) calculation of the mean of the total
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energy consumed in the furnace, heat treatment is

carried out for the mill final artificial aging used,
according to the equation below.
(18)
Qtotal = Qtotal cuptor + Qlam
Qtotal oven - the amount of heat necessary to
achieve and maintain temperature treatment
throughout the performing heat treatment;
Qlam - the amount of energy consumed for
rolling samples.
Energy consumption for final heat treatment
resulting from the performance of the furnace heat
balance of treatment.
It expresses the amount of heat energy
consumption necessary to achieve and maintain
temperature treatment throughout the performing heat
treatment according to the relationship:
Qtotal cuptor = QA + QB
(19)
QA - the amount of heat (energy) consumption

during heating acuptorului;
QB - The quantity of heat (energy) consumed by
maintaining the temperature during heat treatment;
A - the heating of the furnace from room

temperature to the annealing temperature;
B - the keeping temperature inside the oven to
heat tratamernt;
nc - the oven heating time [hours];
meninere - while keeping the furnace at a
temperature of treatment [hours];
ta - ambient temperature [C];
tt - temperature of the heat treatment [C].
4.1. Energy consumption calculation for

laminating SAMPLE Qlam [kWh]
(20)
Qlam = U tlam I, [kWh]
Qlam - energy consumed cold flow;
U - motor supply voltage mill;
U = 380 V;
tlam - during the rolling of the specimen;
I - intensity of electricity used in lamination.
In Table 3 are listed the values of current
intensity for different degrees of plastic deformation
corresponding to situations arising from the
calculation of gradient method on the laboratory mill
faculty.
t, [C]
Table 3. The current values for various degrees

cold plastic deformation
tt
,[%] 24
I, [A] 17.8
ta
A
nc
B
mentain
25
18
26
18.2
27
18.4
28
18.6
29
18.8
Based on the presented algorithm was calculated

for the 6 energy thermomechanical treatment
regimens, determined after application of the gradient
method the mathematical model equations.
The results obtained after these calculations are
presented in Table 4
, [hours]
Fig. 2. Heat treatment chart
Table 4. The results of calculation of heat consumption for thermomechanical treatment options
that meet the requirements of restrictions
Qac pies A
[kWh]
0.009985
2.577351
0.050396
3.07477
0.2297
5.9422
0.010054
2.596428
0.050768
2.82349
0.2293
5.71004
0.010122
2.614941
0.05113
2.56548
0.2289
5.47057
0.010185
2.632366
0.051642
2.306352
0.2284
5.22895
0.010251
2.650361
0.051994
2.043663
0.228
4.98427
0.010313
2.66754
0.052412
1.776192
0.2247
4.73116
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QB, [kWh]
Qpierd zidarie B
[kWh]
Qlaminare,
[kWh]
Qtotal,
[kWh]
QA, [kWh]
Qac zidarie A Qpierd zidarie A
[kWh]
[kWh]
No.
iteration
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5. Conclusions
The data in Table 4 shows that the optimum
values ensuring that the concomitant mechanical
properties required at the lowest level of energy
consumption is given by iteration 7 with the
following technological parameters:
artificial aging temperature T = 124 C;
aging time = 10.21 hours;
the degree of plastic deformation = 24%.
Mechanical property values obtained for these
parameters are:
strength Rm = 567 MPa;
yield strength Rp0, 2 = 521 MPa;
elongation at break A5 = 8%;
Brinell hardness HB = 161.
Alternatively the method for calculating the

gradient of optimizing the thermomechanical process
provides fewer opportunities for combining the
factors (T, , ) as artificial aging temperature range
resulting from 120 C to 124 C.
References
[1]. Ciuc I., Dumitriu S., Modelarea i Optimizarea Proceselor
Metalurgice de Deformare Plastic i Tratamente Termice, Editura
Didactic i Pedagogic, Bucureti, 1998.
[2]. Taloi D. .a., Optimizarea proceselor metalurgice, Editura
Didactic i Pedagogic, Bucureti, 1983.
[3]. Taloi D., Optimizarea proceselor tehnologice aplicaii n
metalurgie, Editura Academiei, Bucureti, 1987.
[4]. erban R., Dumitrescu T., Metode de optimizare, Editura
Matrix Rom, Bucureti, 1998.
[5]. Neacsu M. I., Teza de doctorat, Galati 2012.
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RESEARCH ON THE PRODUCTION OF SINTERED POWDER 410

Simona BOICIUC, Petric ALEXANDRU
Dunrea de Jos University of Galati

email: simonaboiciuc@yahoo.com
ABSTRACT
The 410 stainless steel powders are typically used in applications requiring
good corrosion resistance, cavitation, erosion wear resistance. The paper presents
some experimental research on the production of sintered 410 stainless steel
powders and their characterization in terms of microstructure and wear resistance.
KEYWORDS: powder metallurgy, 410 stainless steel, abrasive wear
1. Introduction
2. Experimental conditions
The technological process of manufacturing

sintered parts includes the following phases:
obtain powdered materials;
make homogenous the powder or powder
mixture
having
the
desired
chemical
composition;
obtained by pressing or other means the tablets
of metal powders;
presintering and sintering of powder tablets at
high temperatures in a protective atmosphere;
secondary operations: calibrating the sintered
parts, machining or other finishing processes of
the sintered parts, oil or esily fusible alloys
impregnation of the sintered parts;
reception and control of the sintered products.
Special attention has been paid in recent years to
obtain products of high corrosion-resistant steels with
ferritic or austenitic structure.
The 410 stainless steel are very good mechanical
properties, fair corrosion resistance and soft magnetic
properties.
The 410 stainless steel offers good corrosion
resistance to atmospheric corrosion, water and some
chemicals because it forms a tightly adherent oxide
film which protects the surface from attack. Type 410
resists oxidation up to 816 C but for continuous
service the temperature should not exceed 649 C. A
wide range of properties may be obtained by
hardening and tempering this stainless steel.
The 410 stainless steel powders are designed for
medical and surgical instruments, parts guide, gears,
and automatic ABS sensing devices.
This paper presents some experimental research
on the production of sintered powder 410 stainless
steel products and their characterization in terms of
microstructure and wear resistance.
To obtain a sintered parts a powder of 410

stainless steel with the following chemical
composition was used: 0.15%C; 13.5%Cr; 0.8%Si;
0.2%Mn; 0.14%Ni; 0.015%S; 0.035%P; rest Fe.
Fig. 1. shows the aspect of 410 stainless steel
powder.
25 m
Fig. 1. Aspect of 410 stainless steel powder

Looking at Figure 1 it can be seen that 410
stainless steel powder has an irregular shape specific
to water atomisation.
Microhardness determined on the polished
section of the particles under a load of 50 g was
HV0.05 = 2309 MPa.
The pressing process used was cold pressing,
with universal machine for mechanical tests.
The 410 powder compaction pressures used were
540, 628, 726, 863 MPa.
Compact samples are cylindrical with
dimensions of approximately 8 x 6 mm.
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Powder tablet sintering was carried out in an

electric oven. Sintering temperature was 1150 C and
the exposure time to this temperature was 60 minutes.
Samples were placed in a ceramic cylinder, where
graphite was added. Graphite has an important role in
the cooling stage to prevent air intake in the cylinder,
thus providing protection to the atmosphere. After
sintering, all samples were cooled slowly.
The main purpose of sintering is to reduce
porosity. Sintering process is often accompanied by
changes in material, some of them desirable, others
not: changes occur in the mechanical strength,
hardness; particle size and shape are affected, there is
variation in pore shape and size, the chemical
composition and crystalline structure may change too
due to the appearance of the chemical reaction
processes in solid phase.
Microscopic analysis of sintered samples was
performed by a Neophot 2 microscope with computer
data acquisition. HV 0.1 microhardness determined
on sintered powder tablets was conducted on a PMT3 microhardness meter of 100g load.
410 stainless steel sintered samples were
subjected to wear test on a rotary disk with sand
paper. The method consists in successive pressing,
under identical conditions, two samples of size 8 x 6
mm, onto a rotating disk covered with 120 grit sand
paper. A radial displacement mechanism of the
specimen with 0.5 mm / rev provide spiral running on
the rotating disc surface. A device for applying a load
of 6.229 N provides perpendicular pressing of the
specimen on the sandpaper to 0.123 N/mm2 pressure.
At a disk speed of 25 rev / min, a lenght of 11,6 m
was run.

Microscopic analysis of the pressed tablets
performed by Neophot 2 microscope reveals the
presence of pores and their shape (Fig. 2).
6 m
6 m
628 MPa
540 MPa
6 m
6 m
863 MPa
726 MPa
Fig. 2. Microstructure of 410 stainless steel at different pressures
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In Fig. 2 it can be seen that porosity decreases

increasing pressure. Microscopic analysis
performed on sintered samples by the microscope

Neophot 2 is illustrated in fig. 3.
6 m
6 m
628 MPa
540 MPa
6 m
6 m
726 MPa
863 MPa
Fig. 3. Microstructure of 410 stainless steel samples, attack-free

Looking at Fig. 3 it can be seen that porosity
decreases with increasing pressure. Microstructure of
sintered samples under electrolyte attack with 50%

HNO3 solution is presented in Fig. 4.
6 m
6 m
540 MPa
628 MPa
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6 m
726 MPa
863 MPa
Fig. 4. Microstructure of sintered 410 stainless steel, electrolyte attack, solution 50% HNO3
From Fig. 4 it can be seen that samples
microstructure consists of ferrite and carbides.
Formation of carbides is due to sintering environment
used (graphite).
The HV 0.1 microhardness determined on
samples of sintered powder was HV 0.1 = 6222 MPa,
Fig. 5.
Fig. 5. Determining microhardness of 410

stainless steel samples
The 410 stainless steel sintered samples were

subjected to wear test on rotary disk with sand paper.
The results, as average of three determinations,
are presented in Table 1.
Analyzing Table 1 and Fig. 6 one can say that
410 stainless steel powder is recommended to be
pressed at pressures lower of about 540 MPa to
ensure superior resistance to wear. Pressing at higher
pressure leads to a higher compaction which results in
lower wear resistance.
Sample porosity was determined by the linear
segments method. Porosity variation vs formation
pressure is presented in Fig. 7. It can be seen that with
increased pressure porosity is reduced both in the
middle of the samples and at their edge.
Pressing low pressure causes a greater porosity
which probably improves carburizing of the samples.
This leads to increased wear resistance.
Wear variation vs average porosity is presented
in Fig. 8. It can be seen that with decreasing porosity
the wear resistance decreases.
Wear/length run, [g/m]
0.0008
0.000715517
0.0007
0.000603448
0.000586207
0.0006
0.0005
0.0004
0.00037931
0.0003
0.0002
0.0001
0
540
628
726
863
Pressure of compaction [MPa]
Fig. 6. Abrasive wear behavior of sintered powder products
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6.00
4.80
Porosity [%]
5.00
4.30
3.50
4.00
3.40
2.80
3.20
3.00
edge
2.80
2.40
center
2.00
1.00
0.00
540
628
726
863
Pressure of compaction [MPa]
Fig. 7. Porosity variation with formation pressure

0.00075
0.000715517
0.0007
Wear/length run [g/m]
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0.00065
0.000603448
0.000586207
0.0006
0.00055
0.0005
0.00045
0.0004
0.00037931
0.00035
0.0003
4.15
3.75
3.10
2.60
Average porosity [%]
Fig. 8. Wear variation vs average porosity
Fig. 9. 3D image of the sample surface pressed with 540 MP subjected to abrasive wear
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Fig. 10. 3D image of the sample surface pressed with 628 MPa subjected to abrasive wear
In fig.9 12, 3D images are presented made
with an Image J software, of the 410 powder sample
areas obtained from the abrasive wear test.
Analyzing the previous images one can see good

wear behavior of the samples pressed at lower
pressures.
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4. Conclusions
References
The production of 410 austenitic stainless steel

powders revealed the following:
[1]. H. N. Ch'ng, J. Pan, Modelling microstructural evolution of

porous polycrystalline materials and a numerical study of
anisotropic sintering, J. Comput. Phys. 204, 430461, 2005;
Journal of Computational Physics, Volume 204, Issue 2, 20, 2005.
[2]. D. Bernard , D. Gendron , J. M. Heintz, S. Bordere , J.
Etourneau, First direct 3D visualisation of microstructural
evolutions during sintering through X-ray computed
microtomography, Acta Materialia 53, 2005.
[3]. Y. V. Levinsky, The Behavior of Closed Pores at the Final
Stage of Sintering, ISSN 1067-8212, Russian Journal of NonFerrous Metals, 2009, Vol. 50, No. 3, pp. 298316. Allerton
Press, Inc., 2009.
[4]. Deleanu L., Ciortan S., Evaluating Tribological Damages by
3D profilometry, EHD Lubrication and Traction, May 6-8, 2010
VAREHD 15, 2010, Suceava, Romania, http://www.varehd.usv.ro/,
ISSN 1844-8917, pp. 163-169, 2010.
[5]. E. Drugescu, O. Potecau, F. Potecau, M. Marin, V.
Mereuta, L. Deleanu, Mechanical properties, abrasive wear
behavior and surface quality evaluation of new sintered iron
alloys, Rotrib, Universitatea Tehnic Gh. Asachi, Iai, Tomul
LVII (LXI), Fasc. 1, 2011.
[6]. Deleanu L., Cantaragiu A., Ciortan S., Surface Quality
evaluated by 3D Functional Parameters, Proceedings of 10th
Intern. Conf. Research and Development in Mechanical Industry,
RaDMI 2010, 16-19 September, Donji Milanovac, Serbia, pp. 311318, 2010.
[7]. Palfalvi, Metalurgia Pulberilor, Editura Tehnic, Bucureti,
1988.
[8]. T. Surdeanu, M. Perne, Piese sinterizate din pulberi
metalice, Editura Tehnic, Bucureti, 1984.
[9]. Marshall D, Austenitic Stainless Steels. Microstructure and
mechanical properties, 1984;
[10]. ASM Specialty Handbook, Stainless Steels 2004.
* the powder used in the experimental research

has an irregular shape specific to water atomisation,
being suitable for conventional compaction in mold
and sintering at a theoretically higher density;
microhardness of the particles was HV0.05 = 2309
MPa.
* the pressures used for 410 powder compaction
were 540, 628, 726, 863 MPa;
* it was found that increased pressure leads to
reduction in tablets porosity ;
* sintering of powder tablets at 1150 C, for one
hour has reduced their porosity;
* samples microstructure consists of ferrite and
carbides; this is due to carburizing occurred during
sintering;
* HV0.1 microhardness determined on sintered
powder tablets was HV0.1 = 6222 MPa, higher than
the initial state powder;
* as regards the abrasive disk wear resistance it
was found that 410 stainless steel powder is
recommended to be pressed at pressures lower than
about 540 MPa to ensure superior resistance to wear.
* pressing at high pressure leads to a higher
compaction resulting in decreased wear resistance.
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A SHORT OVERVIEW OF HIGH ENTROPY ALLOYS

Gheorghe BULUC, Iulia FLOREA, Ioan CARCEA
Gheorghe Asachi Technical University of Iai, Faculty of Materials
email: gheo_u@yahoo.com
ABSTRACT
A high-entropy alloy (HEA) has been defined by use to have at least five
principal elements, each of which has an atomic concentration between 5% and
35%. In the exploration on this new alloy field, we find that HEAs are quite simple
to analyze and control, and they might be processed as traditional alloys. There
exist many opportunities to create alloys, better than traditional ones in a wide
range of applications. In this paper, I present generalizations about high entropy
alloys.
KEYWORDS: High-entropy Alloys(HEAs), properties, multi-principalelement alloy, preparation
1. Introduction
High entropy alloys (HEAs), containing five to
thirteen metallic elements, with a concentration in the
range of 5 to 35 % for each element, exhibit very
interesting properties (mechanical, tribological,
formability, magnetism) [1]. Up to the 1970s, almost
all traditional alloys has been developed and provided
a wide spectrum of properties and performance. There
have been about 30 commonly used traditional alloy
systems, including steel, aluminium, copeer, etc, as
depicted, for example, in the ASM Metals
Handbooks.
However, they were unsatisfactory in many
aspects of application [1]. Therefore, many efforts
have been exerted to develop new metals in the last
four decades.
In alloys with high entropy will be no element
mole fraction greater than 30% so there will be no
metal matrix in alloy composition. Studies of high
entropy alloys have shown that they have a almost
amorphous structure demonstrated by X-ray
diffraction and differential scanning calorimetric
analysis. HEA has a high atomic disorder with
mechanical properties comparable to the glass
therefore are brittle. [2] .The research performed
showed that this alloy exhibits high hardness and
corrosion resistance and good thermal stability as
well. [3, 4] High entropy alloys could have many
applications for example: tools, molds, dies,
mechanical parts and furnance parts foundries and
marine application for piping and pump components
which requires an excellent corrosion resistance, hard
and antisticking coating for molds and tools and so on
[1]. Their high mixing entropy promotes the

formation of simple solid solutions with amorphous
or nanocrystallized structure. Bulk pieces of these
alloys are known to be stable at relatively high
temperature (until 800 C) [1]. In general,
commercial alloy systems are based on one principal
element and the total quantum of solute atoms is not
large in many cases. In contrast, high entropy alloys
are equiatomic multicomponent alloys. These alloys
form simple solid solutions due to the large
configurational entropy [2]. If these multimetallic
cocktails are made in nanocrystalline state, they are
expected to have high strength coupled with
reasonable formability. Nanocrystalline high entropy
alloys can be made easily by high energy ball milling.
High entropy alloys are a fairly new area of research
that explores that potential of nontraditional alloy
systems. Typical alloys are made up of a base metal,
which makes up the majority of the composition,
combined with small amounts of alloying elements
[2]. High entropy alloys on the other hand, are
comprised of five or more principle elements with
between 5% and 35% of each by atomic
concentration. These alloys have a tendency to form
simple structures, like fcc and bcc, instead of
intermetallic compounds.This is because the high
entropy of mixing reduces the free energy of the
system and stabilizes these simple structures. The
large majority of the currently-used high-performance
complex metallic alloys were developed in the 1970's.
These alloys were typically composed of one or
two principal elements, minor elements being added
in order to modify their properties [2, 3]. As elements
we can use the main metals: beryllium (Be),
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magnesium (Mg), aluminum (Al), scandium (Sc),

titanium (Ti), vanadium (V), chromium (Cr),
manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni),
copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr),
niobium (Nb), molybdenum (Mo), rutheniu (Ru),
rhodium (Rh), palladium (Pd), silver (Ag), hafnium
(Hf), tantalum (Ta), tungsten (W), platinum (Pt), gold
(Au), lanthanum (La), cerium (Ce) and so on. Of
course in addition to these items we can add minor
elements, named like this because their molar
fraction in the alloy is lower than 3.5%. In a high
entropy alloy, the elements can be metallic or
nonmetallic and can be selected from the following
elements: lithium, sodium, scandium, titanium,
vanadium, chromium, manganese, iron, cobalt,
nickel, copper, zinc, gallium, germanium, strontium,
yttrium, zirconium, niobium, molybdenum, rutheniu,
rhodium, palladium, silver, cadmium, indium,
platinum, gold,bismuth, lanthanum metal. Nonmetallic elements may be for insatnce, carbon, boron,
silicon, phosphorus, sulfur, hydrogen, oxygen,
nitrogen and so on.
Since 80's the study of new alloys containing
more elements showed that the increase of element
number improves properties. If thirteen elements are
arbitrary selected, then, 7099 alloys are theoretically
able to be synthesized, and more, if some elements
such as Si, C or B are added in low concentration.For
example, AlCoCrCuFeNi, AlCo0.5CrCuFe1.5Ni1.2
or AlCo0.5CrCuFe0,5Ni0.12B0.1C0.15 [1] have been
studied. An interesting property of such films is their
hydrophobic character which makes an alternative
candidate for anti-adherent application and, for
example, for replacement of Teflon [3].
2. Preparation of high entropy alloys

Dried method. This method include many forms,
which are all carried out in the no-liquid system.
Casting method. Casting method is the first and
most commonly used method. The method is that
metal powder of a certain proportion is placed in the
vacuum arc furnace [2] or other metal melting furnace
to several smelt. The sample is continuous casted
after homogenization of the alloy composition.
Smelting method with the atmospheric
protecting slag. Song Chunhui, et al. [5] designed a
series of alloy whose elements gradually increased
such as AlMg, AlMgZn, AlMgZnSn, AlMgZnSnPb,
AlMgZnSnPbCu,
AlMgZnSnPbCuMn
and
AlMgZnSnPbCuMnNi.
Metal powder, weighted at an equimolar ratio,
was placed into crucible sintered with mixed oxidealumina and graphite and smelted in the highfrequency induction furnace. While smelting, the
appropriate amount of magnesium alloy covering
agent was added to prevent oxidation and
combustion, and the quartz rod stirred to promote

homogenization, then, casting with copper mold.
Mechanical alloying.
S. Varalakshmi [7] added Al, Fe, Ti, Cr, Zn, Cu
powders with purity higher than 99.5% in equiatomic
ratio into high energy planetary ball mill (Fritsch
Pulverisette P5) carried out up to 20 h in at 300 rpm
with a ball to powder weight ratio of 10:1.Tungsten
carbide vials and balls were used as a milling media
and toluene was used as a process controlling agent.
The powder samples were taken at regular intervals of
5h of milling.
Magnetron sputtering. Zhang LD, et al[8]
prepared the crystal AlCrTaTiNi high entropy alloy
thin films on Si(100) substrate with a multi-target RF
magnetron sputtering technique under different
sputtering power (40 ~ 100W) in pure argon
atmosphere. The purity of Target Ta, Ti, Al, Cr is
higher than 99.95%, and purity of Ni sheet is 99.95%.
Right-angled fan-shaped Ni piece are respectively
placed on the target Ta, Cr, Ti. The matrix are
ultrasonic cleaned by alcohol, acetone, then dried and
sputter 15 min in the vacuum chamber. The base
pressure was 1.2 10-4Pa.Specific processes of thin
film deposition is that AlCrTaTiNi high entropy alloy
thin films are deposited on Si substrate by magnetron
sputtering, The parameter is that Ar flow 20 mL/min,
sputtered working pressure of 0.3 Pa, the power of
sputtering 40W, 60W, were deposited thickness for
180 nm, 280 nm AlCrTaTiNi film, 80W deposition
thickness at 280 nm, 550 nm AlCrTaTiNi high
entropy alloy thin films a 100W deposited film
thickness of about 280 nm AlCrTaTiNi film
Microwave-assisted combustion synthesis.
Wang Teng [9] took the oxides such as Fe2O3, CuO,
Ni2O3, Co2O3, Al high purity powder as raw material
to synthesis the block FeCoNiCuAl high entropy
alloy by the method of the microwave-assisted
combustion, aluminum thermal reaction mechanism.
Wet method. Wet method preparation is carried
out in the liquid, and this research area less than other
methods.
Electrochemical deposition method. Yao
Chenzhong [10] utilized electrochemical deposition
method
successfully
to
prepared
BiFeCoNiMn,TmFeCoNiMn,BiTmFeCoNiMn,
RE(Ce, Nd,Ho)FeCoNiMn in the three-electrode
electrolysis cell of the organic system in the oil bath.
Many research were studied on the relationship
between the alloy composition, organizational
structure and performance.
Antioxidant property. For oxidation behavior of
alloy, Jiang Jichao [11] used non-self-consumption of
vacuum arc melting furnace under condition of argon
protection
to
prepare
AlCuTiFeNiCr
and
AlCuTiFeNiCrSi alloy whose oxidation behavior was
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studied in-depth at 850 in the air. Research show

that AlCuTiFeNiCrSi alloy is prominent antioxidation property.
The SEM showed there arelotus-like oxide
belonging to branches crystal system, and which
organization play a key role in preventing the metal
elements to continue react with oxygen atoms.
Constituent phases effect. For phase research,
Ren Ming-xing [12] prepared CrFeCoNiCu high
entropy alloy. Phase diagram analysis showed that the
alloy material occur twice phase change at about 1400
and 1100 , and ultimately formatted the FCC
solid solution phase with dendrite area containing Cr,
Fe, Co.
Other research.Guo Na-na et al. [13] prepared
the 5-8 element alloy AlFeCuCoCr, AlFeCuNiCrV,
AlFeCuCoNiC rTi and AlFeCuCoNiCrTiV to study
the impact of the main element number on the
organizational structure and performance of highentropy alloys.
Result show that the ingredients subcooled
gradually replace the temperature subcooled with the
number of alloy main alloys increased in during
solidification. Alloy organization presents the trend of
transition from dendrites to equiaxed crystal. the
hardness of the alloy increases with the main element
number. Alloy composition is segregation.
3. Conclusions
High entropy alloys have great interest to
researchers in analyzing their structure and properties.
Studies show that these can be used in a wide range
of applications.
References
[1]. Jien-Wei Yeh, Yu-Liang Chen, Su-Jien, High entropy alloys
A new area of explotation, Materials Science Forum Vol. 560 pp
1-9, 2007.
[2]. Yeh J. W., Chen S. K., Lin S. J., Gan J. Y., Chin T. S.,
Shun T. T., et al., Nanostructured high entropy alloys with
multiple principal elements: novel alloy design concepts and
outcomes, Adv Eng Mater, 6, 299, 2004.
[3]. Iulia Muscalu, Oana Bltescu, Raluca Maria Florea,
Vasile Soare, Romeu Chelariu, Ioan Carcea, High entropy
alloys, Journal of optoelectronics and advanced materials, Vol. 15,
No. 7- 8, July August, pp. 761 767, 2013.
[4]. J. W. Yeh, S. K. Chen, S. J. Lin, J. Y. Gan, T. S. Chin, T. T.
Shun, C. H. Tsai, S. Y Chang, Adv. Eng.Mater.Vol. 6, 2004.
[5]. Ranganathan S., Alloyed pleasures:multimetallic cocktails,
Current Science, no. 85, p. 1404-1406, 2003.
[6]. Zhang Li-sheng, Ma Guo-liang, Fu Li-chao, Tian Jing-yi
Recent Progress in High-entropy Alloys, Advanced Materials
Research Vols. 631-632, 2013.
[7]. S. Varalakshmi, M. Kamaraj, B. S. Murty, Synthesis and
characterization of nanocrystalline AlFeTiCrZnCu high entropy
solid solution by mechanical alloying, Journal of Alloys and
Compounds, 460, 253257, 2008.
[8]. Zhang Li-dong, Liu Chun-hai, Sun Hua-dong, et al.,
Crystalline structure of AlCrTaTiNi high entropy alloys, Journal of
Functional Materials, no. 3, 394-397, 2012.
[9]. Wang Teng, Kong Jian, Chao Bingxuan, Microstructure and
mechanical properties of FeCoNiCuAl high-entropy alloy prepared
by microwave-assisted.
[10]. Yao Chenzhong, Preparation of rare earth high entropy
alloy with electro-chemical means and research of Pb alloy
nanomaterial, Guang Zhou: Zhong Shan University, 2009.
[11]. Jiang Jichao, Luo Xiuyan, Research on oxidation behavior
of AlCuTiFeNiCr and AlCuTiFeNiCrSi High entropy alloy, Silicon
Valley. 24, 46, 125, 201.
[12]. Ren Ming-xing, Li Bang-shen, Phase Analysis of
CrFeCoNiCu High Entropy Alloy, Journal of Materials
Engineering. 1 9-12, 24, 2012.
[13]. Guo Na-na, Sun Hong-fei, Gao Peng, et al., Effect of the
Number of Principal Elements on Microstructure and Performance
of High-entropy with Multi-principal Elements, New Technology
& New Process, no. 6, 87-91.
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CORROSION ANALYSIS OF A STAINLESS STEEL

FUEL PIPE
Ion PALAMARCIUC, Dan Gelu GALUC,
Drago Cristian ACHIEI
Gheorghe Asachi Technical University of Iai, Faculty of Materials Science and Engineering
email: nexiro@yahoo.com
ABSTRACT
The susceptibility of an austenitic stainless steel pipe exposed to aggressive
environment has been investigated by spectroscopy, optical and scanning electron
microscopy (SEM) surface characterization methods, in order to detect and
examine the corrosion of the microstructure. This paper reports the possible causes
of the observed corrosion effects of an austenitic stainless steel fuel pipe, used for
transportation of kerosene-type jet fuel.
KEYWORDS: corrosion in petroleum products, austenitic stainless steel, fuel
pipelines
1. Introduction
Corrosion is a common phenomenon related to
pipelines and has concern over economics, human
safety and conservation of metal resources.
Transportation of the petroleum products leads to
formation of corrosive products, that increases with
the time, thereby affecting the surface more
vigorously [1].
The severity of conditions under which
corrosion-resistant steel pipes serve, such as large
temperature gradient, high flow rates, as well as
conditions where the metal is subject to the
simultaneous action of an aggressive medium and
mechanical loadings has resulted in the fact that local
corrosion of the steel is one of the most frequent
forms of corrosion failures. Intergranular corrosion,
knife-line corrosion, pitting, etc. are classified as local
corrosion. According to Japanese and American
researchers, 65-70% of commercial equipment
operating in contact with active corrosive media fail
due to local corrosion.
It is known that austenitic stainless steels
possess high corrosion resistance. They have virtually
no inclination to corrosion cracking and offer good
resistance to pitting corrosion. But nonmetallic
inclusions, both sulfides and oxysulfides, are
preferential centers of pit formation in stainless steels
[2].
Most kerosene fuels contain relatively large
amounts of sulphur and sulphur products. The
presence of free sulphur and hydrogen sulfide are key
factors in causing fuel to be corrosive.
The attack mechanism is complex and can be

caused by absorption of atomic hydrogen in steel.
Internal corrosion depends on pressure, temperature,
pH value of the fluid, fuel quality, sulphur and water
content. In addition, fuel contamination may take
many forms, including solid particles, water, ice and
bacterial growth.
Improper management of the fuel system has
caused more aircraft accidents than failures of any
other single system [3].
2. Research methods and material

The specimens used in experimental analysis
were cut from a stainless steel fuel pipe that has been
used in the fuel system of an aircraft turbofan engine
for jet fuel transportation.
The analysed pipe is made from J92603 austenitic
stainless steel with the following chemical
composition:
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Table 1. Chemical composition of the J92603

austenitic stainless steel
Element
C
Mn
P
S
Si
Ni
Cr
Mo
Min.
0.2000
8.0000
18.0000
-
Max.
0.4000
2.0000
0.0400
0.0400
2.0000
12.0000
23.0000
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For chemical composition analysis by optical

emission spectroscopy, the specimens have been
prepared by flattening. Then other specimens have
been cut transversely from the pipe, prepared and
mounted for scanning electron microscopy and
optical microscopy analysis.
The obtained results were used to create a graph

with the chemical composition variation (Fig. 2).
2.1. Chemical composition analysis

The chemical composition on the internal and
external wall surface has been determined using an
optical emission spectrometer. The results presented
in Table 2 are for the important elements. The
chemical analysis confirms that the pipe sample is
made of stainless steel as per J92603 standard
specification.
Table 2. Chemical composition on the internal

and external wall surface of the pipe
Element
Fe
C
Si
Mn
S
Cr
Mo
Ni
Ti
V
W
Internal
(%)
68.8
0.227
0.346
1.33
0.0742
16.9
0.0993
11.7
0.676
0.0585
0.205
External
(%)
67.0
0.353
0.477
1.23
0.0673
17.5
0.146
12.0
0.590
0.0434
0.163
Fig. 2. Chemical composition variation in 12

points (%)
2.2. Microstructural analysis

The microstructure analysis (by SEM) showed
that the internal wall has been damaged (Fig. 3).
The results presented in Table 2 required

explanations regarding the differences between
internal, external and theoretical composition.
Scanning electron microscopy was used to see
if/how the chemical composition of the elements
fluctuates between the walls of the pipe. The
chemical composition was analysed in a line of 12
points, from the internal to the external wall, as
shown in Fig. 1.
Fig. 3. SEM micrographs showing the damage

of the internal wall surface
Fig. 1. The line of 12 points to analyse
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The examination of the specimens by optical

microscopy confirmed that the pipe has been
damaged by internal corrosion (Fig. 4), as the
external surface did not present any damage.
sulphur in nickel and nickel steels is therefore

pronounced due to the influence of nickel in
increasing the solubility of sulphur in steel. Nickel
offers, therefore, very little resistance to sulphur
atmospheres and failure chiefly takes place through
intercristalline embrittlement. Even contamination of
nickel with sulphur results in intense pitting [4].
This form of corrosion is associated with
chemical segregation effects (impurities have a
tendency to be enriched at grain boundaries) and
specific phases precipitate on the grain boundaries.
Such precipitation produce zones of reduced
corrosion resistance in the immediate vicinity,
making the grain boundary zone anodic relative to the
remainder of the surface (Fig. 5) [5].
Fig. 4a. Optical microscopy picture showing the

crack propagation from the internal wall
Fig. 5. Intergranular corrosion.
Fig. 4b. Optical microscopy picture showing the

crack damage on the internal wall
3. Corrosion mechanisms and factors

discussion
The mechanism of attack of metal components
exposed to sulphurous media, proceeds basically with
the penetration of sulphur into the metal surface and
grain boundaries on the principle of counter current
diffusion and chemical interaction. Whereas sulphur
atoms tend to diffuse inwards, the metal atoms try to
migrate to the surface through the scale.
Sulphur and its compounds react strongly with
nickel forming nickel sulphide with which nickel
forms a eutectic series of alloys. The penetration of
This also explains the chemical composition

variation: increased content of sulphur on the internal
surface (due to sulphur diffusion in steel) and
decreased content of chromium on the same surface.
In actual practice the mechanism is not however so
simple but is highly complicated due to
heterogeneous conditions. The process is therefore
dependent upon a number of factors in common with
all diffusion phenomena, but the most important are
that of temperature, oxygen, alloying elements, water
vapour and mechanical stresses [4].
Another problem is the microbial growth. Jet
fuel is sterile when it is first produced because of the
high refinery processing temperatures. However, it
quickly becomes contaminated with microorganisms
that are always present in air and water [6] and leads
to microbial corrosion.
MIC (microbiologically influenced corrosion) is
caused by microbes whose actions initiate the
corrosion cycle. Internal corrosion can occur in liquid
pipelines by bacteria forming an acidic biofilm that
traps electrolytes and acids [7, 8].
The water contamination is produced primarily
by condensate that is formed as the aircraft descends
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from cruise altitudes after a long, cold soak. The

growth of fungus is particularly encouraged at
temperatures between 25 and 35 degrees Centigrade
in undissolved water at interfaces with the fuel. The
growth process is not entirely understood but it has
been found that the growth mechanism is selfpropagating in that it actually feeds on the fuel and
that, as the material builds up, further water is trapped
to encourage other types of fungal growth [3, 9].
4. Conclusion
It is known that the austenitic stainless steels
have good corrosion resistance, so an initial
macroscopic analysis of the fuel pipe could not give
any information regarding possible damage.
Nevertheless, the results of the microstructure
analysis proved that intergranular corrosion is very
important and hazardous.
The presence of nickel in austenitic stainless
steels is very important, on the other side it increases
the solubility of sulphur in steel and leads to internal
intergranular corrosion.
In addition, the formation of water in aircraft
fuel systems is a process that is hard to control,
resulting in contamination of the fuel and the fuel

pipes.
Obviously
understanding
the
corrosion
mechanisms is very important, mainly when it
concerns human safety and not only in the aircraft
industry.
References
[1]. A. Jayaramanand, R. Saxena, Corrosion Paper No. 221,
NACE International Conference and Exposition, 1996.
[2]. Ya. M. Kolotyrkin, E. A. Ul'yanin, Refining austenitic
stainless steels, Translated from Metallovedenie i Termicheskaya
Obrabotka Metallov (Introduction to metals and thermal treatment),
No. 5, pp. 2-9, May, 1981.
[3]. Roy Langton et al., Aircraft fuel systems, Wiltshire, UK,
2009.
[4]. K. W. Krishnan, P. K. Gupte, Failures of metals in sulphur
and sulphur bearing media, Jamshedpur India.
[5]. Pierre Roberge, Handbook of Corrosion Engineering, NY,
1999.
[6]. Greg Hemighaus et al., Aviation Fuels Technical Review
(FTR-3), Chevron Corporation, 2006.
[7]. Michael Baker Jr., Pipeline Corrosion, Final Report,
November 2008.
[8]. Nalli. K, Corrosion and its Mitigation in the Oil & Gas
Industry, PetroMin Pipeliner magazine, Jan-Mar 2010.
[9]. B. J. Little, J. S. Lee, Microbiologically Influenced Corrosion,
Wiley, Hoboken, NJ, 2007.
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ASPECTS REGARDING THE INFLUENCE OF TRIBOLOGYCAL

FACTORS ON THE SUPERFICIAL LAYERS OF STEELS TREATED
WITH PLASMA NITRIDING APPLIED AFTER THERMO-MAGNETIC
REGIMES
Carmen-Penelopi PAPADATU
Department of Material Science, Dunarea de Jos University of Galati,
111, Domneasca St., Romania
email: cpapadatu@ugal.ro
ABSTRACT
It were considered some 38MoCrAl09 (SAE 4038) steel grade samples. This
material was subjected to the plasma nitriding treatments regimes. The structural
aspects of the superficial layers of the steel are studied after the wear tests by
friction, using an Amsler type machine, taking two sliding degrees at different
contact pressures and testing time.
The tests were done to detect the influence of the tribological factors
(operating parameters) on the superficial layers and to detect the sustainability of
this material.
KEYWORDS: plasma nitriding
tribological parameters, wear process
process,
thermo-magnetic
treatment,
1. Introduction
For the first instance, it were applied a magnetic
field (alternative current or direct/ continuous current)
during the basic treatments, modifying the cooler
conditions of the heat treatments initial applied. In
this case, it were obtained properties modified caused
by external factors applied.
Plasma nitriding modify the strain limit, and the
fatigue strength of the metals being treated. For
instance, mechanical properties of austenitic stainless
steel like wear process can be significantly reduced
and the hardness of tool steels can be double on the
surface [1, 2, 3, 5, 14].
The superficial layer is defined according to the
type of interaction between the external action and
materials.
In figure 1 was presented one of the first model
of the superficial layer [2, 4, 5, 15].
Introducing a surface treatment as nitriding
process with plasma (ionic) nitriding, the wear
resistance increases and the resistance of corrosion
increase too.
The diffusion process and the interaction of the
nitrogen and carbon with the basic material lead to
structural constituents whose nature determines a
major hardness of the nitrided layer.
Fig. 1. One model for the superficial layer

The chemical combination area consists of two
phases:
- the phase is a solid solution based on the
chemical compound of Fe3N, rich in nitrogen (8.2 %
to 11.2% of N) having a hexagonal compact (HC),
crystal lattice and it is highly resistant to wear, [1, 4,
5] and corrosion;
- the phase a solid solution based on the
Fe4N compound, presents a centred-face cube
(C.F.C.) crystal lattice, has a lower nitrogen solubility
(5.7 to 6.1% N), showing very high values of
hardness and tenacity.
The diffusion area is composed of the following
elements:
- the phase (the nitrided ferite) is a
nitrogen connate solid solution in Fe crystallizing
in centre volume cube (C.V.C.) lattice, showing a
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maximum solubility of 0.11% at a temperature of

590oC;
- the phase (the nitrided austenite) a
nitrogen connate solid solution in Fe (C.F.C.),
having a maximum nitrogen solubility of 2.8%at a

temperature of 650 oC (see Figure 2) [4, 6, 15].
Fig. 2. Fe-N diagram of equilibrum

The transformation of - martensite with
nitrogen (a suprasatured solution of nitrogen in Fe),
showing a very high values of hardness, takes place
from the nitriding temperature, in case of a rapid
cooling of austenite with nitrogen ().
The hardness and the depth of nitrided layer, are
determined both by the chemical composition of the
chosen material and by the technological parameters
of the thermo-chemical treatment [4].
The friction and wear processes are complex,
being of physical, chemical, mechanical or
metallurgical nature [2, 3].
These processes appear during dynamic or static
contact between surfaces of two solid bodies where
may be or not be in a gaseous atmosphere, liquid or
solid lubricant.
The depth of the superficial layer varies between
some atomic layers, in case of wear and chemical
processes, and can attain up to (50100) m in case
of dry friction.
In this paper were represented some structural
aspects of the superficial layer of the steel and the
influence of external factors (the magnetic field)
applied during heat treatments regimes.
2. Experimental researches
For experiments it were used 38MoCrAl09 steel
grade samples. The material was subjected to the
plasma nitriding treatment regime, after thermomagnetic treatment regimes. The classic treatment,
without magnetic field applied, was considered too.
The structural and diffractometric aspects of the
superficial layers of the steel are studied after the
wear tests by friction. It was used an Amsler type
machine, taking two sliding degrees at different
contact pressures and testing time (see Figure 3).
The tests were done to detect the evolution of
the superficial layer through different tests. It was
established the influence of the tribological factors
(operating parameters) on the superficial layers.
Table 1, presents the 38MoCrAl09 steel grade
composition. The steel analyzed reach a max score
4.5 from inclusions and a fine grain (score 8-9).
Table 2 presents the standard mechanical
characteristics of the steel 38MoCrAl09 (SAE 4038)
[2, 4], corresponding to The Society of Automotive
Engineers (SAE) and The American Iron and Steel
Institute (AISI).
Table 1. Chemical composition of the materials [6, 8]

Steel grade
38MoCrAl09
C(%)
0.38
Mn(%)
0.50
Si(%)
0.25
P(%)
0.026
S(%)
0.020
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Cr(%)
1.38
Cu(%)
0.058
Mo(%)
0.17
Al(%)
1.18

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Table 2. Mechanical characteristics of the steel [6, 8]

Steel grade
Rp0,2
Rm
A5
[daN/mm2]
38MoCrAl09
AISI(SAE)
4038
85
KCU300/2
100
15
KCU300/5
[daJ/cm2]
[%]
The treatments applied were the following:

a) t1 = martensitic hardening process at 920 C
and high recovery at 620 C classic treatment
(Magnetic field intensity is H =0 A/m).
b) t3 = quenching (hardening) (920 C) and high
tempering (620 C) applied to steel 38MoCrAl09,
cooling being performed in alternative current (a.c.)
magnetic field (H = 1300 A/m);
c) t4 = quenching (920 C) and high tempering
(620 C), cooling being performed in d.c. (direct
continuous) magnetic field (H = 1300 A/m);
The samples of the steel suffered a Martensitic
hardening process at 920 C and high recovery at 620
C (classic improvement treatment which was noted
with t1) followed by nitriding process at 530 C. It
was noted T12=T1= t1 + ionic nitriding (plasma
nitriding) at 530 C.
T13 = T3 = t3 + ionic nitriding (plasma
T14 = T4 = t4 + ionic nitriding (plasma
The treated samples were used for wear tests on
Amsler machine (see Figure 3) and the
diffractometric analysis were performed by means of
a Dron 3. It were determined the durability of the
rollers and the surface structure evolution for
different parameters of testing regimes.
The other factors which influence the wearing
process are: the contact geometry of the friction
couple (roller on roller, roller on ring etc.), the
technological parameters (surface quality, heat
treatments etc.) and the exploitation conditions (the
thermal solicitation, for example).
Wear tests were carried out on an Amsler
machine (see figure 4), using several couples of
rollers (see figure 3), each couple corresponding to
different sliding degrees , defined as:
=[ (1-2 ) / 1 ] 100 [%]
50
HB
(State of
annealing)
[daN/mm2]
229
n2=162 rpm; =18% is obtained for a pair of tested

rollers having d1=44 mm, n1=180 rpm and d2=40 mm,
n2=162 rpm; the level of the stress is corresponding to
a specific load of 150 daN (as normal load is Q=1.500
N) and the contact between roller is b=10 mm [2, 4,
8].
Magnetostriction may cause local plastic
deformations, thus determining a cold hardening of
the residual austenite. Furthermore, this implies
higher material hardness and for many applications
good endurance characteristics (see figure 5).
Introducing a thermo-chemical treatment as
nitriding process with plasma (ionic nitriding),
increase the wear resistance and increase the
resistance of corrosion, too.
Fig. 3. Couples of rollers corresponding to

different sliding degrees [6, 8]
(1)
where v1 and v2 are the peripheral velocities of the

rollers in contact, each one having their specific
peripheral velocity due to a particular combination of
angular speeds (n1, n2) and diameter sizes (d1, d2).
Index 1 or 2 are added for the roller 1 or 2,
respectively, both of the same tested friction couple.
For instance, =10% is obtained for a pair of tested
rollers having d1=40 mm, n1=180 rpm and d2=40 mm,
Fig. 4. Wear tests were carried out on an Amsler

machine [6, 8]
In figure 5, was presented the evolution of the
hardness number function by the magnetic field
regimes applied.
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Cod R
411
H [A/m]
H=1300
H=240
Plasma nitrided layers had a different evolution

during wear process.
In table 3 are presented: characteristics,
symbols, mathematical relations used during the
study of superficial layers tribological evolution
corresponding to wear process (damp wear case).
Using an Amsler machine, it were obtained the
following results:
341
H=0
298
100
200
300
400
500
HB
Fig. 5. The influence of the magnetic field regimes

on the hardness value, for code R samples
(38MoCrAl09)[6]
Table 3. Characteristics, symbols, mathematical relations used during the study of superficial layers
tribological evolution [13, 16]
Characteristics
Symbol
u.m.
Relations
The diameters of the rollers
d1, d2
Mm
The width of the rollers

(dimension of the contact)
Mm
Longitudinal Elasticity Module

(the equivalent size)
MPa
(N/mm2)
E= 2E1E2 / (E1 + E2)
Speed of the rollers
n1, n2
Rot./min.
Specific glide
=2 (1 k d2 / d1) / (1 + k d2/d1) 100%
Task loading (the force applied)
Qi
N (daN)
The radius of curvature

equivalent
= d1d2 / 2(d1+d2)
Hertsiana maximum pressure
pm
Pm = 0,418 (QE / b)-2
Testing time
Moment of friction
Mf
N mm
Will be measured
Coefficient of friction
= 2Mf / d1Q
Length of friction
Lf
mm
Lf = d1n1t /60
The used layer depth
Uh
mm
Will be measured
The wear strenght (intensity of

the wear)
Iu
Iu =Uh / Lf
See table 4
Wear class
Table 4. Wear classes [6, 8, 13]

The
class
number
II
II
IV
VI
VII
VIII
IX
Iu
10-1310-12
10-1210-11
10-1110-10
10-1010-9
10-910-8
10-810-7
10-710-6
10-6105
10-510-4
10-4-10-3
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Table 5. The partial results for wear tests

Materi
al Code
Roller
Code
Treatme
nt
regimes
code
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
R
122
122
122
122
222
222
222
222
422
422
422
422
322
322
322
322
CA1
CA1
CA1
CA1
CA2
CA2
CA2
CA2
CA0
CA0
CA0
CA0
CA
CA
CA
CA
T1
T1
T1
T1
T1
T1
T1
T1
T1
T1
T1
T1
T1
T1
T1
T1
T3
T3
T3
T3
T3
T3
T3
T3
T4
T4
T4
T4
T4
T4
T4
T4
Sliding
degrees
(%)
Qi
[daN]
10
10
10
10
10
10
10
10
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
75
75
75
150
150
150
190
190
190
150
150
150
150
150
150
190
190
190
190
190
190
150
150
150
The initial
diameter of
the
conducting
roller
40
40
40
40
40
40
40
40
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
44
The used
layer
depth
x10-1
[mm]
0,09
0,14
0,18
0,13
0,065
0,100
0,105
0,100
Duration
of the
wear
process
[h]
0
1
2
3
0
1
2
3
0
1
2
3
0
1
2
3
0
1
2
3
0
1
2
3
0
1
2
3
0
1
2
3
t
[h]
0
1
1
1
0
1
1
1
0
1
1
1
0
1
1
1
0
1
1
1
0
1
1
1
0
1
1
1
0
1
1
1
0.2
0.14
0.15
0.12
0.1
Uh [mm]
Uh [mm]
0.08
0.1
0.06
0.05
0.04
0.02
0
T1'
T3'
T4'
Treatment regimes
T1'
T3'
T4'
Treatment
Fig. 6. The influence of thermo-magnetic

treatment regimes applied before of the plasma
nitriding on the used layer depth evolution (Uh),
during wear tests, for task loading Q=150 daN
( = 20%)
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treatment regimes applied before of the
plasma nitriding on the used layer depth
evolution (Uh), during wear tests, for task
loading Q=190 daN ( = 20%)

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In figure 6 was represented the used layer depth

(Uh) evolution for task loading Q = 150 daN, during
three treatment regimes. It were considered constantly
all the treatments parameters, inclusive the wear tests
parameters: task loading (the applied force, Q), the
coefficient of friction, () and sliding degrees
(=20%).The variational factor is the magnetic field
intensity, H) applied during thermal treatment
regimes, before of the plasma nitriding. In figure 7
was represented the used layer depth (Uh) evolution
0.14
0.12
0.1
0.08
Mass loss [g]
0.06
0.04
0.02
0
for task loading Q = 190 daN, during three treatment

regimes. It were considered constantly all the
treatments parameters, inclusive the wear tests
parameters: task loading (the applied force, Q), the
coefficient of friction, () and sliding degrees
(=20%).
The variational factor is the magnetic field
intensity, H) applied during thermal treatment
regimes, before of the plasma nitriding, as in the first
case (see figure 6).
0.2
0.15
Mass loss [g]
0.1
0.05
T1'
T3'(ca)
T4'(cc)
T1'
Treatment

nitriding on the mass loss evolution , during
wear tests, for task loading Q=150 daN ( =
20%) (conducting roller)
T4'

plasma nitriding on the mass loss evolution,
during wear tests, for task loading Q=190
daN ( = 20%) (conducting roller)
0.14
0.2
0.12
0.15
Diameterloss
0.1
[mm]
0.05
0.1
Diameter loss 0.08
[mm]
0.06
0.04
0.02
0
T3'
Treatment
0
T1'
T3'(ca)
T4'(cc)
Treatment
T1'
T3'
T4'
Treatment

nitriding on the diameter loss evolution, during
wear tests, for task loading Q=150 daN ( =
20%)

plasma nitriding on the diameter loss
evolution, during wear tests, for task loading
Q=150 daN ( = 20%)
4. Metalographic aspects
Metalographic aspects of the superficial layer
unconventional treated for 38MoCrAl09 (Code R)
steel grade samples are presented in figures 1113.
As a results of processing and metallographic

analyses of the samples, it were obtained the pictures
represented in Figs.12-14:
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Fig. 12. Superficial layer

before wear tests , T1
treatment regime (x100).
Nital attack 2%

before wear tests, T3
treatment regime (x100) (a.c.
magnetic field applied). Nital
attack

before wear tests, T4
treatment regime (x100) (d.c.
magnetic field applied). Nital
attack
5. Conclusions
References
It was realised a comparison between classic

treatment and un-conventional (thermo-magnetic)
treatment.
In the case of alternative or continuous magnetic
field applied to the steels (T13, T14), it was observed
a higher initial quantity of martensite and carbonitrurs, comparing with the classic treatment. During
the wear process, the martensite quantity increase and
the carburs quantity decrease very rapidly. The
internal tensions (II) increase easily according with
the duration of wear tests.
The positive influence of the volume thermomagnetic treatment on the surface layer treated
thermo-chemically resulted in a higher hardness [4].
Increase the wear resistance and decrease the depth of
the used layer [5, 7] by approx. 50%.
It has been shown that, when apply an
alternative current (a.c.) magnetic field treatment (for
example, H=1300 A/m), the thickness of the thermochemical treated layer increases up to 25% as
compared
to
the
conventional
(classic)
thermal/thermo-chemical treatment (H=0 A/m).
It was observed that for the classic treatment
applied to 38MoCrAl09 steel grade, the martensite
quantity and the nitrides are maintained constants
after the friction-wear process. In the case of
alternative (a.c.) or continuous-direct (d.c.) magnetic
field applied to the steels (Tca, Tcc), it was observed
a higher initial quantity of martensite and nitrides
[14].
A good influence of the thermo-magnetic
treatment on the surface layer resulted in a higher
hardness [4, 11] and a good wear resistance, too.
[1]. Berkowitz, A. E., s.a., Magnetism and Metallurgy, Academic

Press, New York and London, 1969.
[2]. Gheorghies C., Papadatu C. P., Stefanescu I., Study on the
model of behaviour of some non-conventional treated steels, during
friction process, CENTIMFE, Marinha Grande, Portugal, 2004.
[3]. Gheorghies C., Controlul structurii fine a metalelor cu
radiatii X, Editura Tehnica, Bucuresti, Romania, pp. 30-45, 1990.
[4]. Bozorth R. M., Feromagnetism, New York, Van Nastrand,
Co.Inc., 1951.
[5]. Cedighian S., Materiale magnetice, Editura Tehnica,
Bucuresti, 1974.
[6]. Papadatu C. P., Cercetri privind ameliorarea proprietilor
i creterea fiabilitii unor oeluri folosite n construcia utilajelor
metalurgice, Ph.D. Thesis, Galai, 2005.
[7]. Popescu N., s.a., Tratamente termice neconvenionale, Editura
Tehnice, Bucureti, 1990, pp. 105-117.
[8]. Papadatu C. P., Posibilitati de imbunatatire a calitatii unor
oteluri utilizate in industria metalurgica, Editura Fundatiei
Universitare Dunarea de Jos, 2007, ISBN 978-973-627-371-1,
Galati.
[9]. Stefanescu I., Contribuii la studiul influenei tratamentelor
termomagnetice asupra unor caracteristici mecanice ale oelurilor
de rulmeni RUL1, Suceava, 1981.
[10]. Vonsovschi S.V., Teoria modern a magnetismului, Editura
Tehnica, Bucureti, 1956.
[11]. Papadatu C. P., Stefanescu I., Experimental study on the
behaviour of some non-conventional treated steels during friction
process (I), Tanger, spol.s.r.o., Ostrava, 2005.
[12]. Papadatu C. P., The possibility to increase the durability of
the steels overlapping a magnetic field on the convention al heat
treatment before thermo-chemical treatment, Annals of Dunarea
de Jos University of Galati, Fascicle II, Year III, (XXXIV), 2011,
pp. 175-182.
[13]. Stefanescu I., Incercari tribologice. Teste de uzura, Indrumar
de laborator, Galati, Universitatea Dunarea de Jos, 2004.
[14]. Papadatu C. P., Vasilescu E., Some Aspects Regarding the
Influence of the Tribologycal Factors on the Superficial Layers of
Treated Steels with Plasma Nitriding, The Annals of DUNAREA
DE JOS University of Galati, Fascicle IX, METALLURGY AND
MATERIALS SCIENCE, No. 4, 2012, ISSN 1453-083X, pag. 8894.
[15]. Levcovici S, s.a., Ingineria suprafetelor, Note de curs, 2004.
[16]. Crudu I., Palaghian L., Gheorghies C., Structural
modifications in the superficial layer of metallic material in wear
and fatigue process, Japan International Tribology Conference,
Nagoya, 2004.
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HIGH ENTROPY ALLOYS OBTAINED

BY INDUCTION MELT METHOD
Iulia FLOREA, Gheorghe BULUC, Ioan CARCEA
Gheorghe Asachi Technical University of Iai, Faculty of Materials Science and Engineering
email: iuliamuscalu@yahoo.com
ABSTRACT
In 1995, Yeh suggested the formation of an alloy made up of at least five
metallic elements which have large mixing entropy solutions with many elements
forming solide alloys. Research into the use of these alloys is made because the
increasing of content alloying elements above certain limits led to in the most cases
to the increase over the allowable limits of hardness and brittleness. The idea to
used the alloying elements in large number can lead to improved mechanical
properties and maintaining fragility. High entropy alloys are alloys which have
approximately equal concentrations, formed by a group of 5 to 11 elements
majority in composition, mole fraction of each major metallic element in the alloy is
between 5% and 30%.
High entropy alloys shows properties superior to conventional alloys. These
high entropy alloys allows us to be used in as many applications such as tools,
forms, dies, machine parts and oven parts that require resistance, thermal stability
and resistance, wear and oxidation temperature application up to 800 C.
KEYWORDS: high entropy alloys, alloy design, resistance and good thermal
stabilit, high-entropy effect
1. Introduction
Looking at the traditional alloys is observed
that almost all of these are based on a single base
metal and rare element have more than three main
elements. For example, we may say that in a steel the
main component is iron, in the case of superalloys we
meet basic elements like Ni, Co, Fe, metal matrix
composites are based on Si, Mg, Cu or Al. It was
noted that these alloys exhibit a high fragility and also
difficulty in processing. This led to the emergence of
a new alloy composed of at least five elements of
metal, the entropy of mixing elements forming large
solutions with it [1]. A new approach for alloy
designhigh entropy alloys'' was started in Tsing Hua
University of Taiwan since 1995 by Yeh et al. We
could define high entropy alloys as having
approximately equal concentrations, made up of a
group of 5 to 11 major elements in the composition,
mole fraction of each major metallic element in the
alloy is between 5% and 30%. As elements we can
use the main metals: magnesium (Mg), aluminum
(Al), titanium (Ti), vanadium (V), chromium (Cr),
manganese (Mn), iron (Fe) , cobalt (Co), nickel (Ni),
copper (Cu), zinc (Zn), molybdenum (Mo), tantalum
(Ta), tungsten (W), platinum (Pt), gold (Au),
lanthanum (La), cerium (Ce) and so on. Of course in

addition to these items we can add minor elements,
named like this because their molar fraction in the
alloy is lower than 3.5%. In a high entropy alloy, the
elements can be metallic or nonmetallic and can be
selected from the following elements: lithium,
sodium, scandium, titanium, vanadium, chromium,
manganese, iron, cobalt, nickel, copper, zinc,
molybdenum, silver. Non-metallic elements may be
for insatnce, carbon, boron, silicon, phosphorus,
sulfur, hydrogen, oxygen, nitrogen and so on [1, 2].
They have concluded that high entropy alloys
could be made, processed and analyzed like
conventional alloys. Moreover they exhibit several
interesting features as previously reported:
Tend to formed simple solution phases, such
as FCC and BCC phases, with nanostructures or even
amorphous structures;
Range form 100 to 1100 in hardness;
Have microstructures with good thermal
stability;
Can have high-temperature precipitation
hardening between 500 and 1000 C;
Can have a positive temperature coefficient
of strength and hence maintain a high strength level at
elevated temperatures [1];
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Can possess excellent corrosion resistance,

wear resistance and oxidation resistance [1].
High entropy alloys could have many
applications for example: tools, molds, dies,
mechanical parts and furnance parts foundries and
marine application for piping and pump components
which requires an excellent corrosion resistance, hard
and antisticking coating for molds and tools and so on
[1].
In his "High-Entropy Alloys - A New Era of
Exploitation" Yeh the alloys divided the alloys into 3
broad categories such as: low-entropy alloys are
traditional alloys, high-entropy alloys are the alloys
with at least five major elements and medium-entropy
alloys are the alloys with 2-4 major elements. The
high entropy effect of promoting the occurrence of
the disordered solution phase is essentially found in
the high-entropy alloy field and should be less
prevalent in the medium-entropy alloys. The
stabilization of the simple solid solution phase is very
significant in terms of the microstructure and
properties which can be obtained in these materials
[2, 3]. The 3 categories of alloys can be seen in the
figure below.
characteristics. The micro-structure simplify and tend

to nano- and amorphous for the effect of high
entropy. High hardness, high intensity, good
temperature resistance and corrosion resistance are its
main performance characteristics[4, 6].
Antioxidant property. For oxidation behavior of
alloy, Jiang Jichao used non-self-consumption of
vacuum arc melting furnace under condition of argon
protection
to
prepare
AlCuTiFeNiCr
and
AlCuTiFeNiCrSi alloy whose oxidation behavior was
studied in-depth at 850 C in the air. Research show
that AlCuTiFeNiCrSi alloy is prominent antioxidation property[4, 5].
Hot forging property. Liu Ze [7] added any two
elements among Ni, Co, Al to prepare three highentropy alloys based on the four elements Cr, Fe, Mn,
Cu and just did hot forging performance test.
NiCoCrFeMnCu alloy shows good deformation
properties and crack propagation resistance
performance, but the reasons was not analyzed.
Constituent phases effect. For phase research,
Ren Ming-xing [8] prepared CrFeCoNiCu high
entropy alloy. Phase diagram analysis showed that the
alloy material occur twice phase change at about 1400
C and 1100 C, and ultimately formated the FCC
solid solution phase with dendrite area containing Cr,
Fe, Co, and Ni, and with interdendritic area
containing the amorphous phase and Cu, Ni [4].
3. Experimental procedures
Fig. 1. The 3 major categories of alloys by Yeh

[1]
It has been noted that this type of alloy instead
of forming multiple intermetallic phases it forms a
single phase solid solution with a cubic crystal
structure, and this is especially noticeable in high
temperatures. This tendency is explained by the high
entropy of the second principle of thermodynamics.
The second principle of thermodynamics specifies the
conditions in which heat energy turns into mechanical
energy. This has a qualitatively character which
points out the direction in which it is produced with
no bearing on the quantities of changed energy [3].
2. The impact of the component elements

on the performance
For main elements of collective leadership high
entropy
alloys
performance
high-entropy
To obtain a high entropy alloy we used an

induction furnace. Induction heating is a process
which is used to bond, harden or soften metals or
other conductive materials. For many modern
manufacturing processes, induction heating offers an
attractive combination of speed, consistency and
control.
The basic principles of induction heating have
been understood and applied to manufacturing since
the 1920s. During World War II, the technology
developed rapidly to meet urgent wartime
requirements for a fast, reliable process to harden
metal engine parts. More recently, the focus on lean
manufacturing techniques and emphasis on improved
quality control have led to a rediscovery of induction
technology, along with the development of precisely
controlled, all solid state induction power supplies
[9].
Advantage. The advantage of the induction
furnace is a clean, energy-efficient and wellcontrollable melting process compared to most other
means of metal melting. Most modern foundries use
this type of furnace and now also more iron foundries
are replacing cupolas with induction furnaces to melt
cast iron, as the former emit lots of dust and other
pollutants. Induction furnace capacities range from
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less than one kilogram to one hundred tonnes

capacity and are used to melt iron and steel, copper,
aluminium and precious metals. Since no arc or
combustion is used, the temperature of the material is
no higher than required to melt it; this can prevent
loss of valuable alloying elements.
Disadvantages. The one major drawback to
induction furnace usage in a foundry is the lack of
refining capacity; charge materials must be clean of
oxidation products and of a known composition and
some alloying elements may be lost due to oxidation
(and must be re-added to the melt).
Crucible induction furnaces are used to make
high-quality steels, cast iron, non-ferrous metals and
alloys such as aluminum, copper, nickel, etc. [10, 11].
In terms of supply voltage frequency, crucible
furnaces include:
Industrial frequency (50 Hz);
Medium frequency (100 ... 10,000 Hz);
High frequency (50 ... 400 kHz).
Fig. 3. Longitudinal section of a induction

furnace [9]
We used a frequency induction furnace for
8000h (Fig. 4).
Current capacity furnaces industrial frequency

has values between 0.8 to 50 t, the power reaches 20
to 25 MW, the specific consumption of electricity is
520 to 700 kWh / t [10, 11].
Principal building blocks of crucible furnaces
are:
- crucible;
- inductor;
- magnetically shielded;
-short network - comprised of flexible cables
and power supply rails;
- reversal mechanism [10, 11].
Items shown in figure (2).
Fig. 2. Schematics induction heating furnace

crucible: 1 inducer, 2 - the molten metal, 3 refractory crucible, 4 - cylinder asbestos, 5 screens ferromagnetic [10, 11]
Fig. 4. Induction heating furnace of medium

frequency 8000 Hz [10]
By this method we managed to obtain
AlFeCrMnNi. Quantities used for the attainment of
this alloy are: Fe 36 %, Cr 22.19%, Mn 23.67%, Ni
13.76%, Al 3.52%. Temperature of the alloy was
between 1530-1580 C [10].
Another material that we managed to obtain
using this method is MnMgAlZnCu. Chemical
analysis was obtained using EDAX. In the analysis it
can be seen the concentrations of the formed alloy.
These values are reported in Table 1. Figure 5 shows
a variation of chemical elements in the alloy
MnMgAlZnCu without oxigen and carbon. We can
see that the initial quantities used for the attainment
of this alloy was like the alloy mentioned before.
After casting we can see that the quantities are Mn
19.92%, Mg 11.03 %, Al 10.25%, Zn 20.3%, Cu
38.48%. The final quantity was 99.98%.
Figure 6 shows a variation of chemical elements
in the alloy MnMgAlZnCu with oxigen and carbon.
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Fig. 6. Variation of chemical elements in the

alloy MnMgAlZnCu with O2 and C2
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Fig. 5. Variation of chemical elements in the

alloy MnMgAlZnCu
Table 1. Chemical composition of the alloy MnMgAlZnCu

Element
Copper
Zinc
Manganese
Magnesium
Aluminium
Oxygen
Carbon
Element
29
30
25
12
13
8
6
Element
K-series
K-series
K-series
K-series
K-series
K-series
K-series
Element
45841
20877
38574
4756
6287
1619
1664
Sum:
4. Conclusions
The micro-structure simplify and tend to nanoand amorphous for the effect of high entropy. High
hardness, high intensity, good temperature resistance
and corrosion resistance are its main performance
characteristics.
Crucible induction furnaces are used to make
high-quality steels, cast iron, non-ferrous metals and
alloys such as aluminum, copper, nickel, etc.
Induction furnace capacities range from less
than one kilogram to one hundred tonnes capacity and
are used to melt iron and steel, copper, aluminium
and precious metals.
The materials obtained using this method are
AlFeCrMnNi, MnMgAlZnCu.
References
[1]. Jien-Wei Yeh, Yu-Liang Chen, Su-Jien Lin and Swe-Kai
Chen, High-Entropy Alloys A New Era of Exploitation, Materials
Science Forum Vol. 560 (2007) pp 1-9.
[2]. Iulia Florea, Raluca Maria Florea, Oana Baltatescu, Vasile
Soare, Costel Roman, IoanCarcea, Research on physicochemical
properties of high entropy alloys, Proceedings of the 15th
Element
30,87208
16,3744
15,99033
8,896933
8,231418
5,188013
3,783122
89,3363
Element
34,55715
18,32894
17,89903
9,958923
9,213968
5,807284
4,234698
100
Element
20,78244
10,71206
12,45098
15,65898
13,05049
13,87127
13,4738
100
Element
0,79705
0,442745
0,444004
0,579763
0,466808
1,127306
0,774232
International Conference, Modern Technologies, Quality and

Innovation, ISSN 2069-6736, Volume I, 2013, ModTech
Publishing House.
[3]. Iulia Florea, Raluca Maria Florea, Costel Roman,
IoanCarcea, Research on high entropy alloys, Tehnomus, New
Technologies and Products in Machine Manufacturing
Technologies, ISSN -1224-029X, No. 20-2013, pp. 250-253.
[4]. Zhang Li-Sheng, et al., Recent Progress in High-entropy
Alloys, Advanced Materials Research Vols. 631-632, pp. 227-232,
(2013).
[5]. Jiang Jichao, Luo Xiuyan, Research on oxidation behavior of
AlCuTiFeNiCr and AlCuTiFeNiCrSi High entropy alloy, Silicon
Valley 24 2011, 46, pp. 125.
[6]. Hsu C. Y., Yeh J. W., Chen S. K., et al., Wear resistance and
high-temperature compression strength of Fcc CuCoNiCrAl0.5Fe
alloy with boron addition, Metallurgical and Materials
Transactions A-5, pp. 1465-1469, (2004).
[7]. Liu Ze, Wang Yao, Zhang Jian-fei, Study of hot forging
properties of high entropy alloy, Da Zhong Ke Ji, pp. 65-66,
(2012).
[8]. Ren Ming-xing, Li Bang-shen, Phase Analysis of
CrFeCoNiCu High Entropy Alloy, Journal of Materials
Engineering 1- 9, pp. 12-24, (2012).
[9]. http://www.gh-ia.com/induction_heating.html.
[10]. Iulia Muscalu, Oana Bltescu, Raluca Maria Florea,
VasileSoare, RomeuChelariu, IoanCarcea, High entropy alloys,
Journal of optoelectronics and advanced materials, Vol. 15, No. 78, July August 2013, pp. 761 - 767.
[11]. M. Dumitrache, Metallic materials science - Laboratory
Guidelines, 2011.
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STUDIES ON LAYER-MATERIAL INTERFACE AT DEPOSITION BY

IMPULSE ELECTRICAL DISCHARGE METHOD
Manuela-Cristina PERJU, Carmen NEJNERU, Petric VIZUREANU,
Mihai AXINTE, Drago-Cristian ACHIEI
Gheorghe Asachi Technical University from Iai, Romnia, Faculty of Material Science and Engineering
email: cryss_ela@yahoo.com
ABSTRACT
Purpose of this paper is to analyze the layer bonding between the pulsed
electrical discharge method deposited layer and the substrate base material (OLC
15 steel) when in the laminated condition. Deposited layer adherence will be
studied following the layer cracking pattern for the tensile test specimens.
Depending on the technological properties for the base material, the deposited
material will create an interface area with different sizes and physico-technological
properties.
KEYWORDS: test tensile, OLC 15 steel, deposition, interface, layer
1. Introduction
The machine building industry is one of the
major consumers of material, in particular metal
material.
Competition in this field, the technical process
and imposed requirements, asks for good knowledge
of material properties, development of new materials,
treatments and processing technologies to ensure
operational requirements at minimum cost. Steels
used for machine parts in relative motion and contact
with other parts must ensure high toughness
characteristics for core while the surface area must
provide good resistance to wear. Such characteristics
can be obtained by heat treatment, Thermo-chemical
surface treatments or coatings using a variety of
methods.
One of these deposition methods is pulsed
electrical discharge method, which is a method in the
actual research, method being used at coating by
deposition on the systems components working in
heavy abrasive wear in wet and dry conditions, in
order to obtain surface layers with high tribological
qualities.
Obtaining thin films with special properties
(wear resistance, corrosion resistance and impact
resistance) requires a correct choice of filler material
in strict correlation with the physical and mechanical
properties of the support material, [1, 5, 10].
The elements that characterize thef thin films
quality deposition are: layers uniformity, layer
adhesion on the substrate, thin layers composition and
their depth.
The layer adherence coated by pulsed electric

discharge electrode depends on the nature of the
electrode as well as the nature of the substrate
material (chemical composition, grain size austenitic
grade, mechanical properties (elongation, c, r,
KCU, Rm), physico-chemical properties, also the steel
treatment (strain hardened, annealed, normalized,
quenched and tempered) [9].
2. Characterization of steel OLC 15

For the experiment was used OLC 15,
(EN10083/2+A1-2002) laminated bar. This is a high
quality carbon steel with low carbon content, also
called case-hardening steel, whose chemical
composition is shown in Table 1, determined by
spectrometer Foundry Master.
Table 1. Chemical composition OLC 15 [%]

Fe
Mn
Si
Cr
Ni
99.1
0.16
0.3
0.1
0.02
0.01
0.06
0.04
Oth
ers
Bala
nce
Fig. 1. Steel sample OLC 15 for tensile testing

Specimens were made, whose dimensions can
be seen in Figure 1. The specimens have tensile
testing standard shape for metal sheets.
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Microstructure pictures were made with the

optical microscope for both, the control sample and
heat-treated samples, using the magnification of
200X.
comparable properties of the anchor layer with the

support material and coating surface with required
properties.
4. Laminated samples tensile test

Tensile tests were performed on rectangular
laminated control samples (OLC 15 steel rolling) on
drive tester Instron 3382.
Tensile tests were performed both until breaking
the specimen and until the bottleneck.
For the control test samples two types of tests
were made:
- a tensile test (complete with broken specimen)
- a stress tensile test completed with elongation
of the specimen the middle section to highlight the
load behavior for the coating layer (mode of cracking,
possibly deposited layer flow mode), also for studies
on the load behavior for the alloying micro region on
the coating-support layers.
4.1. Tensile test with breaking

Fig. 2. OLC15 steel microstructure, laminated,
obtained with the optic microscope 200X,
nital 2% etching
For microstructure analysis the samples were
subjected to subsequent grinding and polishing
preparations, and nital 2% etched. For the sample
preparation FORCIPOL 2V grinding and polishing
machine was used, and to analyze the microstructure
was used the inverted metallographic optical
microscope - Zeiss.
It is observed from the analysis under the optical
microscope, a specific laminated structure with
partially oriented ferrito-pearlitic grain, (structure
obtained after recrystallization heat treatment after
plastic deformation).
In the case of OLC 15 steel annealed, on tensile

stress test, finalized with breaking, the measured
parameters on the characteristic curve - are
presented in table 2.
Table 2. The values for the breaking tensile test

Characteristi
c curve -
for the steel
OLC 15
Tensile
strength
r (MPa)
411.08319
Maximu
m force
(N)
Breaking
displace
ment
r (%)
42.11
20,575.1
Yield
strenght
c (MPa)
220.48
Elasticity
modullus
E (MPa)
9,676.84
Yield strain
c (%)
2.33485
3. Specimens coating by pulsed electric

discharge method
We achieved thin layer coatings by pulsed
electric discharge method, [6, 7], in order to modify
the surface properties for the base material, steel
OLC15, both for the laminated sample, also the heat
treated samples. Titanium and tungsten was the metal
filler that we have been used as electrodes, [2, 4, 8,
11]. The coating is carried out using the system
Elitron 22A, [3, 12], with the optimum parameters
(A5) and regime (r4).
Taking into account that the main objective is to
improve the wear behavior by deposition of hard
layers, it appears to be necessary, in order to achieve
the objective of multilayer surfaces generation:
Fig. 3. Breaking specimen tensile test
4.2. Macroscopic analysis of laminated

specimens after tensile test
Macro photos of breaking were studied and were
observe striations and longitudinal cracks in the
direction of drawing, which shows great adhesion of
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the coating to the substrate, acting as micro-alloyed

area.
b)
Fig. 5. SEM microstructures: a) 50 m;

b) 50 m
Fig. 4. Images for breaking area on the tensile

subjected semples
The drawing force was high enough, so if the
adherence between the coating layer and support was
reduced the submitted layer would be exfoliated.
4.3. SEM analysis of the fracture tensile

test specimens
Due to the different characteristics of plasticity,

different modulus and hardness, in figures 5 b) are
shown surface cracks, ignited in the areas with
deposited layer (unevenness, overlapping material
area).
The coating has a relatively constant thickness
23-30 m (fig. 6).
The sample presents a ductile fracture type due

to predominantly ferritic steel structure OLC 15.
Ignition of cracks is inherently related by the
pores in the coating due to the incorporation of
dissolved gas in the melt bath material from microalloyed electrode (fig. 5a).
Fig. 6. Coating thickness
4.4. Tensile test without breaking
a)
OLC 15 sample part was subjected to

incomplete tensile test, stopped in plastic domain by
monitoring the time of force application.
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highlighted in figure 8 at different magnification

orders.
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Table 3. Tensile test values for the specimen

to the bottleneck
Characteris
tic curve for the
steel OLC
15
Maxim
um
force
(N)
Breaking
displacem
ent
r (%)
Elasticity
modullus
E (MPa)
20,489.
5
42.97
9,231.34
Tensile strength
r (MPa)
409.66769
Yield
strenght
c (MPa)
266.01
Yield strain
c (%)
2.80218
In the case of loading the parts coated with thin

layers by electrical pulse discharge method it presents
more interest the state of tension comparing to the
displacement. Status substrate changes curve
characteristic (-), meaning, by default, the yield
strength, tensile strength, ultimate strength, elasticity
modulus.
Fig. 7. Bottlenecking tensile test

The deposited layer presents the yield strength,
and elasticity modulus characteristic to the electrode
elements and do not coincide with those of the base
material, which means that the layer and the substrate
does not fall within plastic domain at the same time
and ultimate strength varies.
Generally, the coatings are achieved in order to
improve the wear and/or corrosion resistance, which
makes that the coating layer to be tougher than the
support, with poor elastic characteristics, and the
cracks are, ignites faster in the coating layer than the
support.
4.5. SEM analysis of the tensile test

specimens without breaking
The sample subjected to drawing force till the
plastic domain was SEM analyzed.
It is observed that the coating layer is cracking
uniformly and the microtaps are perpendicular to the
direction of drawing.
The coating layer does not exfoliates and does
not detach, due to strong anchoring in the substrate,
Fig. 8. Microstructures obtained on SEM;

100 m.
This is due to the presence of micro-alloyed
zone between the coating and the substrate, relatively
soft area with good compatibility, and coherence with
ferrito-pearlitic base matrix. W and Ti carbide forms
a hard and relatively compact crust on the sample
surface. Following SEM analysis for traction sample
on edges of the sample, is observed that the
microtaps, separates the layer islands with good
continuity without notice pieces of detached or
exfoliated layer. The deposition layer is formed by
apparently drops, the propagating cracks are generally
spreaded near the coating drops. Microconcentrators
that lead to the generation of cracks are generally
located in areas with pores of the coating.
5. Conclusions
1. Electrode deposition of W and Ti carbide on a
support of OLC 15 steel presents very good
compactness, relatively uniform layer deposition with
a thickness of about 25-30 m.
2. On tensile test for the annealed steel the layer
coating cracks on perpendicular directions to the
direction of flow for the visco-plastic material on the
maximum loading.
3. Cracks are evenly distributed without
exfoliation and layer separation, which is due to
coherence between coating and substrate material
obtained from microalloy process of the core and the
obtained coating.
4. Due to the difference between the coating and
the substrate properties, the first one being tougher
than the second one, the microtaps are visible in SEM
micrographs on the surface of the coatings and not on
the substrate (E, c, r are different for the base
material from the coating).
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5. Due to the difference between film and

substrate properties, the first being tough the
microtaps are visible in SEM micrographs that are on
coating and not on the substrate, (E, c, r are
different if the base material and the deposited
material).
References
[1]. Adrian A., Strugaru S. I., Alierea i depunerea superficial
prin scnteie electric-Influena tratamentelor termice asupra
caracteristicilor straturilor, Editura Tehnopress, Iai, 2008.
[2]. Cheng Luo, Shijie Dong, Xiang Xiong, Microstructure and
Properties of TiC Coating by Vibrating Electrospark Deposition,
Key Engineering Materials 373-374, 2008, pp. 180-183.
[3]. Dan-Gelu Gluc, Carmen Nejneru, Manuela-Cristina
Perju, Drago-Cristian Achiei, Tehnologii de tratare a
suprafeelor metalice. Straturi subiri obinute prin depunere.
Indrumar de laborator, Editura Tehnopress, Iai, 2012.
[4]. Liu Dongyan, Gao Wei, Li Zhengwei, Zhang Haifeng, Hu
Zhuangqi, Electro-spark deposition of Fe-based amorphous alloy
coatings, Materials Letters 61, 2007, pp. 165167.
[5]. Manuela-Cristina Perju, Dan-Gelu Gluc, Carmen

Nejneru, Maricel Agop, Straturi subiri: descrcri n impuls,
Editura Ars Longa, Iai, 2010, ISBN 978-973-148-049-7.
[6]. Reynolds, J. L., Holdren, R. L., Brown L. E., Electro-spark
deposition, Advanced Materials and Process, 161 (3), p. 35-37,
2003.
[7]. S. Frangini, A. Masci, A study on the effect of a dynamic
contact force control for improving electrospark coating
properties, Surface & Coatings Technology 204, 2010, p. 2613
2623.
[8]. Tang, S. K., Nguyen, T. C., Zhou, Y., Materials Transfer in
Electro-Spark Deposition of TiCp/Ni Metal-Matrix Composite
Coating on Cu Substrate, Welding Research, vol. 89, p.172-180,
2010.
[9]. Valeria Suciu, Marcel-Valeriu Suciu, Studiul materialelor,
Editura Fair Partners, Bucureti, 2007, ISBN 978-973-1877-01-3.
[10]. Vermean G., Vermean E., Jichisan-Matiesan D., Cretu
A., Negrea G., Vermean H., Vlad M., Introducere n ingineria
suprafeelor, Editura Dacia, ISBN 973-35-0922-1, 1999.
[11]. Wang Ruijun, Qian Yiyu, Liu Jun, Interface behavior study
of WC92Co8 coating produced by electrospark deposition,
Applied Surface Science 240, 2005. pp. 4247.
[12]. ***, Instalaie Elitron 22, Academia de tiine, Republica
Moldova, Chiinu, 1992.
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ENGINEERING BIOCOMPATIBLE IMPLANT SURFACE

Mirabela Georgiana MINCIUN, Petric VIZUREANU,
Alina Adriana MINEA, Drago Cristian ACHIEI
Faculty of Materials Science and Engineering, Gheorghe Asachi Tehnical University from Iai,
Blvd. D. Mangeron 41, Iasi, 700050, Romnia
email: dragos_adc@tuiasi.ro
ABSTRACT
The current paper reviews significant issues surrounding how we assess the
biological safety of materials, with a historical summary and critical look at the
biocompatibility literature. Biomaterials are commonly characterized as materials
used to construct artificial organs, rehabilitation devices, or implants to replace
natural body tissues. More specific, biomaterials are materials that are used in
close or direct contact with the body to augment or replace faulty materials.
implants,
KEYWORDS:
biocompatibility, properties
cobaltchromium
1. Introduction
Biocompatibility has been defined as the
ability of a material to perform with an appropriate
host response in a specific application.
This means that the material or any leachable
products from it do not cause cell death, chronic
inflammation or other impairment of cellular or tissue
functions, [5].
The biocompatibility of surfaces plays a crucial
role as the surface is directly exposed to the living
organism. Therefore it is necessary to tailor exposed
surfaces in view of their chemical, physical,
biological and morphological features [9].
In best case the physical and chemical properties
of the chosen implant material should be in accord
with the replaced tissue.
To reach a maximum in implant success it is
necessary to combine the synergistic effects of
various biomedical material systems.
Cobaltchromiummolybdenum (CoCrMo)
alloys have been widely used for removable partial
denture frameworks because of their excellent
strength, corrosion resistance, and castability [17].
They have the advantage over nickel containing
alloys of not creating any allergic reactions.
Relative to gold alloys, it is a much cheaper
alloy, hence more democratic, and has enhanced
mechanical properties such as Young's modulus and
higher hardness [17].
Base metal alloys have higher melting ranges
(14001500 C) than gold alloys (8001050 C),
which requires more expensive melting equipments.
alloys,
microstructure,
Base metal alloys are also generally considered

technique-sensitive because processing variables such
as temperature of the molten alloy, mold temperature,
and the sprue size and arrangement can affect the
properties of the finished casting as much as
composition does [18].
2. Materials used for implants

The choice of adequate materials for
applications in the living organism is description by
their application.
In case of implants that are dedicated for the
replacement of bone tissue, key targets are
themechanical properties that can take high loads
[15].
For the success of an implant material
introduced to the living organism, besides the need of
biocompatibility of the material itself, also criteria
such as sterilizability, required physical and chemical
strength, or very simplified the ability to process the
material have to be provided.
Material
specifications
for
biomedical
applications [13].
It has to be considered that biocompatibility for
implants are not only defined by the intrinsic
properties of the material but also by the
manufacturing process as well as by possible posttreatments such as sterilization.
Mechanical
properties,
wear
resistance,
corrosion resistance and biocompatibility may be
influenced by the microstructure which depends on
the thermal treatment applied to the material [7].
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of this alloy would improve its solution treatment
behavior [12].
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Table 1.
Property
Physical
characteristics
Biocompatibility
Manufacturability
Sterilizability
Desirables
Elasticity, durability,
strength
Non-toxic, noninflammatory, nonallergic, nonpyrogenic,
noncarcinogenic, blood
compatible.
Extrudable, moldable,
machinable.
Not destroyed by typical
sterilizing techniques
like autoclaving,
radiation,
ethylene oxide, dry heat.
An ideal material used in dental, must be the

least harmful for the dental pulp and soft tissues do
not contain toxic substances spreadable into general
circulation, do not contain elements of allergic
potential and do not reveal carcinogenic effect
immediately or with time [10]. In order to improve
the physic-chemical and mechanical properties of
these CoCrMo alloys, thermal treatments are carried
out on the base materials [6].
Metals commonly used for implants [2].
Table 2.
Metal
Cobalt
chromium alloys
Titanium alloys
Stainless steel
Silvertincopper
alloys
Gold or platinum
Application
Dental prosthesis,
orthopedic fixation plates,
artificial heart valves,
vascular stents, artificial
joint components.
Dental implants, artificial
heart valves, artificial
joint components,
vascular stents, orthopedic
screws
Dental prostheses,
vascular stents, orthopedic
fixation plates.
Dental amalgams
Dental fillings
These treatments produce an important

modification of the microstructure of the alloy,
provides high amount of defects, such as lack of
homogeneity or porosity and may change the
biocompatibility of the alloys through the
modification of the electrochemical properties.
Daniell and Clemow examined the influence of
time and temperature upon the solution treatment on
the metallurgical behaviour of CoCrMo alloy and
they proposed that a reduction in the carbon content
Fig. 1. CoCr alloy microstructure, 200:1 [4]

Therefore, although the influence of changes in
the microstructure on CoCrMo alloy, consequence of
the thermal treatments, has been studied by numerous
authors, no clear consensuses of the effect of
microstructure on the corrosion mechanisms of
CoCrMo alloys were found [14].
According to Davidson and Georgette the
corrosion behaviour of CoCr alloys is dependent on
the microstructure. Similarly, Cawley et al. analysed
mechanical properties and hardness of a CoCrMo
alloy thermally treated and they found a correlation
between wear-rate and carbide volume fraction but
they do not observed any influence on themechanical
properties. A more stable, uniform oxide layer would
be expected with a more homogenous matrix than
with a highly dendritic structure. On the contrary
[11], Robertson and Dobbs showed that heat
treatment improved the mechanical properties of the
alloy without loss of corrosion resistance.
Jacobs et al. stated that changes in the
microstructure resulting from incipient melting of
carbides during the porous coating sintering process
may cause an increase in corrosion potential for
porous-coated alloys as compared to conventional
alloys. Preferential or localized corrosion of the
porous coating can lead to cracking and increase the
susceptibility for failure [1].
Placko et al. also studied the effects of
microstructure on the corrosion behaviour of CoCr
porous coatings and they observed a progressive
dissolution of the matrix with preferential attack of
the grain boundaries and regions adjacent to carbides
due to sensitization [8].
Yan et al. [16] found that load and articulations
could increase the corrosion rate and the metal ion
release processes.
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Electrochemical methods can affect the protein

adsorptions process, resulting in the transition of wear
and corrosion mechanisms [3].
Recently, it has also been determined that
CoCrMo hip bearing surfaces undergo chemical
reactions and microstructural changes with the joint
environment during articulation that produce a
mechanically mixed zone of nanocyrstalline metal
and organic constituents, referred to as a biotribolayer
[12].
3. Conclusions
The demand for metallic materials in medical
devices is large. They are essential for orthopaedic
implants, artificial joints, external fixators, bone
fixators since they can substitute for the function of
hard tissues in orthopaedics. Especially, rigidity,
electrical conductivity, toughness and elasticity are
main properties for metallic materials used in medical
devices.
The materials most commonly used to make
implants are alloys of Co-Cr-Mo. Inspite of their
undeniable advantages that biomaterials posses in
medicine their use still remains limited by their
biocompatibility degree and possibly negative
interactions at the biomaterial-host tissue interface.
For the correct manufacturing of the surface of
orthopaedic implants of CoCrMo alloys it is
necessary the application of thermal treatments at
high temperatures, the suitable application of the
different treatments on orthopaedic implants and
superficial coverings facilitates and increases
osteointegration in the implant.
References
[1]. D. F. Williams, D. F. Williams, Biocomp-atibility of Clinical
Implant Materials, vol. I, CRC Press, Boca Raton, FL, 1981.
[2]. P. Crook, L. J. Korb, Metals Handbook-Corrosion, vol. 13,
9th ed., ASM International, Ohio, 1987.
[3]. M. Niinomi, Recent metallic materials for biomedical
applications. Metallurgical and materials transactions A 33, (3),
2002, p. 477-486.
[4]. M. G. Minciun, P. Vizureanu, D. C. Achiei, M. C. Perju,
A. V. Sandu, Co-Cr-Mo alloys used in medical application ,
Buletinul Institutului Politehnic din Iai, tomul LVIII(LXII), fasc. 4,
secia tiina i Ingineria Materialelor, 2012 acceptata spre
publicare.
[5]. H. Y. Lin, J. D. Bumgardner, Biomaterials, 25, 2004, 1233.
[6]. M. G. Shettlemore, K. J. Bundy, Biomaterials, 22, 2001,
2215.
[7]. K. S. Katti, Colloids and Surfaces B: Biointerfaces, 39, 2004,
133.
[8]. M. G. Minciuna, P. Vizureanu, Cobalt alloys research used
in medical applications, Metalurgia International, Special Issue 6,
2013, p. 123-126.
[9]. J. J. Jacobs, R. M. Latanision, R. M. Rose, S. J. Veeck,
Journal of Orthopaedic, Research 8, 1990, 874.
[10]. A. Nanu, Tehnologia materialelor, Editura Didactic i
Pedagogic, 1977.
[11]. J. Cawley, J. E. P. Metcalf, A. H. Jones, T. J. Band, D. S.
Skupien, Wear, 255, 2003, 999.
[12]. S. Hiromoto, E. Onodera, A. Chiba, K. Asami, T. Hanawa,
Biomaterials, 26, 2005, 4912.
[13]. F. S. Georgette, J. A. Davidson, Journal of Biomedical
Materials Research, 20, 1986, 1229.
[14]. D. L. Wise, Humana Press, Totowa, NJ, 2000.
[15]. J. B. Park, J. D. Bronzino, Biomaterials: principles and
applications, 2003, CRC Press, Boca Raton.
[16]. Y. Yan, A. Neville, D. Dowson, Biotribocorrosion an
appraisal of the time dependence of wear and corrosion
interactions, I. the role of corrosion, Journal of Physics D: Applied
Physics 39, 2006, 3200.
[17]. H. W. Roberts, D. W. Berzins, B. K. Moore, D. G.
Charlton, Int. J. Prosthodont, 18, 2009, p. 188 194.
[18]. R. G. Craig, J. M., Powers, in: Restorative dental materials,
11th ed., Mosby, 2002, pp. 480492.
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PROBLEMS OF RECYCLING PROCESS FOR

USED ALUMINUM BEVERAGE CANS
Anisoara CIOCAN, Simion BALINT, Vasile BASLIU

email: aciocan@ugal.ro
ABSTRACT
The present study investigates the efficiency of metallurgic recycling process
for a typical scrap, the used aluminium beverage cans. These are 100% recyclable
into new beverage cans. The recycling process reduces waste, saves energy and
conserves the natural resources. Despite aluminum can has achieved high levels of
recycling, scraps like used aluminum beverage cans showed low levels of efficiency
in metallurgical recovery process. The researches were realized to improve the
aluminum scrap fusion process and to reduce the residues generated in production
of aluminum alloys. The cans were melted in an electric crucible furnace. Some
salts were used in experiments as fluxes to reduce the aluminum losses by oxidation
and to improve the separation of melted metal from dross.
KEYWORDS: recycling, aluminium, beverage cans, crucible furnace
1. Introduction
In the early twentieth century, aluminum has
started to be used to the achievement of packaging, at
once with the production of the thin sheets (foils)
through the mechanical methods the use of
aluminium thin sheets has expanded rapidly. These
were used instead of other materials at achievement
of packaging for drinks and food. The characteristics
of aluminum (perfect impermeability to water, gas,
flavours and fats; does not absorb liquids and grease;
has a high thermal resistance; is opaque to light; is
not affected only by strong acidic or basic solutions;
possess a high capacity for reflection of rays and
good shine; not age, is not toxic and does not favour
bacterial growth) make him one of the main materials
used in the manufacture of packaging for food
products [1]. Aluminum beverage cans offer comfort
and quality. They began to be manufactured around
the years 1950 and aerosol containers in 1955. The
composite materials with aluminum laminate layer
were introduced in the 1960s. Over the years, the
economic benefits, favourable properties and
improving of technology led to the rapid development
of strong industries from containers manufacturing
for different areas: food packaging; sheets; tubes;
boxes for pharmaceutical and cosmetic products;
bottles; boxes; doses for chemicals.
The progress in the sheet rolling processes of
aluminum alloys have reduced the sheets thickness
and accordingly the continuous decreasing of
aluminum amount used to produce the same

packaging quantity.
In 1980, an aluminium beverage can of 330ml
weighed 230 grams, while today, it weighs less than
140 grams. Other technical performances in the
packaging industry were reflected in the achievement
relief printing, printing and colouring of aluminium
sheets and foils.
The different aluminum alloys are used for
manufacturing the packaging used in diverse
applications. So the beverage cans are made of two
aluminum alloys: 3004 ASTM with ~ 1% Mn and ~
1% Mg for the main body; 5182ASTM with ~ 4.5%
Mg and ~ 0.35% Mn for lids [2, 3].
2. Recycling systems performances of the

aluminium beverage cans
At the end of life of its useful functions, the used
aluminium beverage cans are collected, shipped and
recycled back in new aluminium products. Due to
their characteristics, aluminium is infinitely
recyclable. The used beverage cans is 100%
recyclable into new beverage cans. The recycling of
aluminium beverage cans reduces waste, saves
energy, conserves natural resources, decreases the
quantity of landfilled wastes and not least provides
considerable revenue [4]. Recycling performances of
this typical scrap in Europe differ from country to
country according to various collection systems
applied (Figure 1) [5].
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Fig. 1. Recycling rates of the aluminium beverage cans within the various collection systems
in Europe (2008) [6]
For used aluminium beverage cans the recycling
rate per country in Europe varies and depends on its
packaging recovery/recycling management system.
These may be collected by schemes organised by
municipality, by individuals or groups interested in
generating revenue. In the early 90, only 30% of all
beverage cans were recycled. The overall recycling
rate only for aluminium beverage cans in EU27 in
2009 was 64.3% and rose to ~67% in 2010 (Figure 2)
[6, 7]. The countries that have efficient infrastructures
for collection and sorting (organized systems that

collect aluminium beverage cans together with other
metal packaging and then can easily sort out the
aluminium fraction for remelting by the aluminium
recycling industry) report higher values than 90: 91%
for Belgium (+Luxembourg) and Switzerland; 93%
for Norway; 95% for Finland; 96% Germany. In
comparison the Romanian industry reports a very low
value of recycling efficiency: 20% was reported for
2010 [8].
Fig. 2. Evolution of recycling process for aluminium beverage cans in Europe,

period 1991-2010 (EU27 + EFTA & Turkey) [8]
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The recycling process is firstly influenced by

efficiency of collection and sorting systems for used
aluminium beverage cans. Secondly, despite
aluminum can have achieved high levels of recycling,
these scraps are difficult to be recycled because the
low thickness of can bodies and lids. This leads to
low recycling yield for metallurgic process and
decreased efficiency in recovery.
The used aluminium beverage cans should be

recovered separately because they can most
effectively be reused to manufacture the same
products. In Europe, the first unit specialized in the
recycling of used aluminum cans was put into
operation by Alcan Recycling in the UK in
Warrington-Cheshire, in 1991 (Figure 3) [9].
Fig. 3. Aluminium cans recycling plant-Warrington UK

The present study investigates the efficiency of
metallurgic recycling process for aluminium beverage
cans. The researches were realized to improve the
aluminum scrap fusion process and reduction of the
rate of generation of residues.
3. Production of secondary aluminium by

melting of used aluminium beverage cans
The closed loop recycling system of aluminium
scraps has as final stages the metallurgical processes
(melting and casting) for obtaining secondary
aluminium or aluminium alloys. The metallurgical
efficiency of recycling process is influenced by
several factors. The recycling of aluminium cans is a
four-stage continuous process: shredding, decoating,
melting and casting. The recycling of used beverage
cans has as the key element the pre-treatment for
removal of organic coatings. The organic
concentration in the scraps is around 4% [10]. At
melting of scraps the impurities present on their
surface (coating, inks, and solvents) generate
important pollutant emissions. Also the oxidation
processes are intensifying and more dross results.
Simultaneously, some elements from coatings
(primarily titanium from paints) contaminate the

molten metal. Thus, at melting of contaminated
scraps decrease the metal yield. Also, the small
thickness of aluminium sheets from which are
manufactured body and lids of aluminium cans has
directly influence on process efficiency.
To improve the melting process the scraps must
be treated prior to their charging in the furnace.
Firstly, the used beverage cans are shredded to
remove trapped water and other contaminants. Then
shredded scrap passes into a decoating unit. The
thermal pre-treatment for removing of organic
coatings is most often applied, resulting the
vaporization and oxidation of the coatings. The clean
aluminium scraps can be melted in different types of
furnaces using protection salts during the fusion
process. In some cases alloying additives are also
added in the bath in accordance to the final
specifications of the alloys produced.
4. Experimental
In experiment for melting of used aluminum
beverage cans was occurring in an electric tilting
crucible furnace (Figure 4).
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Fig. 4. Laboratory crucible furnace used to melt the used aluminum beverage cans
Prior to introduction into the crucible for
melting aluminum cans were shredded, the pieces
obtained pressed and dried. In experiment the
coatings dont were removed from surface scraps.
Thus involve the utilization at melting of more
quantities of protection salts. Even so, the use of
some scraps has generated large and visible amounts
of gaseous emissions during melting process (Figure
5).
Fig. 5. Gases emitted at melting of uncleaned

scraps
Cryolite, sodium chloride, sodium hydroxide
(caustic soda) and the flux sodium borate/sodium
chloride mixture are recommended in the practices of
secondary aluminium production [11].
In experiments sodium chloride was chosen as

covering flux. It must be preheated in range of 10 200 oC prior to introduction into the crucible of
laboratory furnace. For melting of aluminium, a metal
with higher oxidability, under the form of scraps with
high reaction surface with oxygen is recommended to
use the greater quantities of the saline flux: in
amounts of 30 40 % in weight, in relation to the
total load (compared to the amount of molten
aluminum) as against 5 10 % for normally process.
By other hand some recommend that half from this
flux to be loaded together with the scraps and the rest
to be dispersed over bath in formation [10, 12].
Other melts the flux in the first place, after this
the furnace is loaded with the scrap to be melted. In
experiment, sodium chloride was prior melted and
superheated to 825 oC in the furnace.
In addition the cryolite (Na3AlF6) was added as
protective flux of the aluminum bath: in amounts of 3
% in weight (2 3 % is recommended), in relation to
the total load (compared to the amount of molten
aluminum).
The recovery yield of aluminum scraps
calculated for all experiments was 88.3%.
The average chemical composition of alloys
obtained from melted aluminum scraps determined
with a X-ray fluorescence metal analyzer is given in
Table 1.
Table 1. Chemical composition of the secondary aluminum obtained from scraps

Elements
Concentration, %
Si
0.53
Mg
0.33
Fe
0.67
Mn
0.62
The bath resulted from scraps can be used to

obtain secondary aluminium alloys. After slagging of
the melted aluminum the alloying elements or
ferroalloys can be added to the bath to obtain desired
secondary aluminum alloys.
Cu
0.18
Zn
0.04
Ti
0.00
Al
rest
In experiments FeSi and FeMn (after their

preheating) were added in the aluminum bath to
increase the silicon and the manganese contents. The
average chemical composition of obtained alloys is
Table 2. Chemical composition of the secondary aluminum alloy

Elements
Concentration, %
Si
1.62
Mg
0.33
Fe
1.05
Mn
1.43
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Cu
0.07
Zn
0.02
Ti
0.00
Al
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5. Conclusions
The recovery of aluminum from used beverage
cans is possible and efficient in laboratory furnace.
The recovery yield of aluminum scraps calculated for
all experiments was less than 90 %.
The absence of pre-treatment for cleaning of
paints that covered the body of used aluminium
beverage cans can explain the less efficient of the
recycling process. Is recommended the application of
adequate treatments prior to their melting in a
furnace. Simultaneous these prevent the releasing of
gaseous pollutant emission from furnace. The fluxes
used were in accordance with the recommendation
from literature and industrial practice.
The increasing of amount and their correct
utilization can prevent the oxidation process and
reduce the losses.
References
[1]. *** Aluminium in packaging, http://www.alueurope.eu/wpcontent/uploads/2011/10/Aluminium-in-packaging-brochure.pdf.
[2]. *** Life Cycle Impact Assessment of Aluminum Beverage
Cans,
May
21,
2010,
Final
Report,
http://www.aluminum.org/Content/ContentFolders/LCA/LCA_RE
PORT.pdf.
[3]. K. A. Al Saffar, L. M. Hasan Bdeir, Recycling of Aluminum
Beverage Cans, Journal of Engineering and Development, Vol. 12,
No. 3, September (2008).
[4]. *** http://www.aluminum.org].
[5]. *** http://www.alueurope.eu/wpcontent/uploads/2012/04/Alu-Pack-Recycling-Progress-DepositsMarch2011_updated1.pdf.
[6]. M. G. Labberton, Progress on Aluminium Packaging
Recycling in Europe focus on beverage cans: deposit systems
versus
other
collection
schemes,
2011,
http://www.alueurope.eu/wp-content/uploads/2012/04/Alu-PackRecycling-Progress-Deposits-March2011_updated1.pdf.
[7]. *** http://www.alueurope.eu/aluminium-beverage-canrecycling-rate-hits-64-in-europe/.
[8]. *** Alu_bevcans_recycling, European aluminum association,
press_release_Brussels,
2012,
http://www.alueurope.eu/wpcontent/uploads/2011/08/Press-Release-Alu-bevcans-recycling2010, final_16July2012.pdf.
[9].
***
http://www.docstoc.com/docs/20096725/UsedAluminium-Can-Recycling-Plant-Warrington.
[10]. A. R. Valentim, I. Luiz de Oliveira, J. L. Kovaleski,
Recovery Of Aluminum Foil In The Induction Furnace, XVI
International Conference On Industrial Engineering And
Operations Management, Challenges and Maturity of Production
Engineering: competitiveness of enterprises, working conditions,
environment, So Carlos, Brazil, 12 - 15 October, 2010.
[11]. A. Ciocan, Valorificarea deeurilor metalice, GUP 2012.
[12]. M. A. Rabah, Preparation of aluminiummagnesium alloys
and some valuable salts from used beverage cans, Waste
Management 23 (2003), pp.173182.
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USE THE ECO-FRIENDLY PROPULSION WITH COMPRESSED AIR

IN THE PLACE OF THOSE WITH FOSSIL FUELS
Stefan DRAGOMIR, Marian BORDEI

email: sdragomir@ugal.ro
ABSTRACT
Gases emitted from traffic contribute, both to an increase in atmosphere
acidity, as well as and troposphere ozone formation.
These gases have direct and indirect effects on all the components of the
medium (vegetation, fauna, soil, water). These heavy metals in the exhaust gases
affect the quality of the soil and water, the health status of flora and fauna. The
parking areas of motor vehicles with engines fever occurs ground pollution with
different waste oils derived from some shortcomings in motor vehicles, as well as
with different substances.
In this context in work it is proposed to use propulsion with compressed air.
Solution originality lies in the fact that compressed air will operate a type of
engine which functional classic with gas. Amendments have been made to the fuel
system of the engine classic for the supply of compressed air. Amendments have
cost very little.
KEYWORDS: eco-friendly propulsion, compressed air engine
1. Introduction
For the purpose of reducing emissions in the
transport field, were organized throughout the country
numerous activities.
For reduction of emissions due to transport, it is
used vehicles fitted with engines EURO III and
EURO IV with convector catalytic reactors meeting.
In municipalities is carried out large
modernization programs car park through the use of
buses witch are supply with LPG fuel gasIn many town in Romania, in the field of local
public transport, progress were developed individual
projects on "environmentally friendly alternative for a
sustainable development of cities Europe" and
measures concerning influencing transport demand
for sustainable development". Like example the
project SMILE II, consists in the creation of spaces
sidewalks, improving the infrastructure existing
sidewalks,
parks
modernization,
promoting
alternative fuels, attracting citizens in a process
superstructures and co-decision-making, consultation
and information. The results of this project are:
increase in number of passengers and more efficient
public transport, the translation of part of the
application for mobility, more and more increased in
the past few years, to the service of public transit, the
increase of the quality services for the public
transport company, reducing the level of pollutant

emissions and noise, improving the monitoring and
management traffic, extent of areas with low
emissions and the establishment of a sidewalks,
develop plans for custom mobility and promoting the
integration of alternative transport arrangements,
modernization of road infrastructure and sidewalks,
improving information and acceptance of protection
measures dedicated environment and quality of life
can be lifted, the rise in consumption[1].
Midas project has aimed at consultative
meetings organization for the collection of data and
information, which have been taken into account
awareness impact of human activities on the
environment and encouraging mentality change
relating to the means of existing mobility, for the
purpose of determining various systems integration,
energy-saving and environment-friendly, for the
reduction of pollution due to traffic, energy
consumption and traffic congestion.
2. Theoretical ruling on operation of the

eco-friendly engine with compressed air
Successive phases of a cycle of the engine with
compressed air are shown in figure 1. The structure of
this curves figures have by plotting absolute pressure
P in the room turn on the compressor and the abscissa
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the volume V of this camera, volume of which is

constantly changing during operation. When the
piston is set out in item 1 the chamber is filled with
air at atmospheric pressure Po point 1 corresponds to

the piston position when the volume is at a maximum
active camera.
Fig. 1. Compressed air engine cycles [2]
3. Original solution, on power-up of a

classic engine, with compressed air
The movement of the piston from point 1 to
point 2 - since the two valves, intake relief and R are
closed- air from the volume V is compressed up to
the pressure Pr.
In point 2 the exhaust valve R opens and
compressed air is expelled by the engine at the
pressure. Moving takes place up to the point (3),
lowest point, top, this corresponds to the minimum
volume Vo.
From this moment the piston movement was
reversed, and the relief valve R is hereby terminated.
In point 4 of the suction valve open and air
entering the cylinder until the piston returns in point
1. From this moment cycle begins again.
The relief valve shall provide air pressure
engine. Compressed air pressure must be higher to
compensate for any loss of pressure to the pressure
relief valve [3].
As regards the inlet valve, the flow through it is
possible only if pressure in the chamber is less than
atmospheric pressure Po.
Original solution of this type of engine classic

implies the existence following components
necessary for the operation in good conditions of the
system, namely: -solenoid valve; -electromagnetic
relay; -dehydrator with compressed air; - pressure
gauge.
Engine used to experimenter develop a power of
4.2 hp at 4800 rpm /min. Cylinder capacity of the
engine is 150 dm3.
Prototype system may be used, and in the frame
moving a boat, the source of compressed air in this
case being some oxygen tubes that must have a
capacityof 150 litri, a pressure of max 8 Barr air and
which to an average consumption of about 0.2
Barr/sec, a tube will consume in about two hours.
In order to ensure its survival craft autonomy for
a period of four hours will be used four tubes of
oxygen.
The tubes can also help you with the better
flotation of survival craft.
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Fig. 2. Drive System Schematic of an engine classic with compressed air:1-propeller; 2-piston;
3-conrod; 4-crankshaft; 5-button crank handle; 6-system driven; 7-solenoid valve; 8-electromagnetic
relay 9-pressure gauge; 10-cylinder with compressed air; 11-classic engine
3.1. Operation
Compressed air from gas cylinders which
constitute the supply tank is released by opening
canister valves.
Compressed air with pressure of between 4 and
8 Barr will enter the solenoid valve, which acts and of
pressure regulator (similar acceleration from a car),
after which rejoicing solenoid valve, penetrate the

engine cylinder pushing him.
The propeller takes over the rotating movement,
obtained from the shaft. Propeller Shaft receives the
rotating movement of the engine operated by
compressed air. For a range of functioning of about 2
hours are necessary 4 tubes with compressed air at
pressure of 8 Barr.
Fig. 3. Drawing a craft that works with compressed air: 1-propeller; 2-engine; 3-compressed air
pipe; 4 - The compressed air canister.
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Minimum pressure at minimum speed = 60 rot /

min(at flywheel shaft).
Maximum pressure at maximum speed = 150 rot
/ min(at flywheel shaft).
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At the engine flywheel shaft is obtain a torque

(Mac) and a speed of rotation (nac). [4].
The shaft is put in touch with the propeller via a
linkage by bolts.
The Insufflations pressure will be greater with
both the rotational speed and torque will be higher,
tapping is required for functioning of the equipment
[5].
3.3. Motor shaft Power

Motor shaft power (Pm) is determine with:
Pm = kd Mac nac / 9550
kd Coefficient of overload pressure = 1.2
Mac = Fb e cos
Eccentricity is e = 0.06 m.
The angle of rotation of crank handle = 30
cos = 0.86.
Random of the engine = 80 %
Pm = 1.2 Mac nac / 9550
Pm = 1.8 kw
3.2. Engine torque calculus

Engine torque calculus at crank shaft:
Mac = Fp e cos ( N m )
e = 0.06
Fp measured force
= 30
cos = 0.86
Mac = 88.73 Nm
Speed of the crank eccentric button:
The conrod speed vb(m/min) is
vb = e
vb = ( nac e) / 30
4. Measurements and record the

parameters for the prototype achieved
They have measured and recorded following
parameters for type carried out, namely: pressure,
torque and the rotational speed as follows (table no
1):
Engine flywheel shaft speed of rotation nac = 30

Vb / e.
Table 1
Parameters
t1=0 s
t2=10s
t3=20s
t4=30s
t5=40s
t6=50s
t7=60s
Pressure
(solenoid valve)
(bar)
4.1
4.4
4.6
4.9
5.2
5.8
6.4
The rotation
speed of crank
shaft (rot/min)
60
82
96
110
125
136
152
The torque on
the shaft axle of
the engine (Nm)
88
73
61
48
35
23
14
Although energy efficiency of vehicles has been

and is increasing, this is compensated by the increase
in average length of a journey, an increase in the
numerical fleets, as well as other variables, such as
driving style, hold-ups traffic etc. ,which translates
into an increase of the intensity of greenhouse gas
emissions, as shown in the Figure no. 4.
Figure shows that the diesel is the most
commonly used to supply vehicles with engines
fever, there follows the fuelled by petrol and gas.
The European Union's sustainable development

strategy, in respect of transport, is to ensure that
transport systems that meet current needs economic,
social and environmental, minimizing at the same
time undesirable effects on the economy, society and
the environment".
With regard to CO2 emissions from light
commercial vehicles, their mean value, corresponding
new car fleet, must attain target of 120 g/km for the
years 2011 to 2014, and 115 g/km in 2015.
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(Vehicles/year)
2010
2011
2012
2013 (year)
Fig. 4. The supply of classic engines with: gas (gray color), petrol (black color) and diesel oil
(white color)
5. Conclusions
For minimising the environmental damage
caused by road transport may be taken into account of
the community strategy to reduce CO2 emissions
from passenger cars.
The next step is to improve the efficiency of fuel
consumption remain unchanged, in the sense that the
objective European community of 120 g CO2/km is to
be achieved through the implementation combined
application of the three pillars of existing strategy,
namely -"no change in policy"-voluntary agreements
from the associations of producers of cars to reach
140 g CO2/km by 2008/2009, informing consumers
through labelling vehicles and tax measures to
promote efficiency fuel consumption by;
The objective European community in respect of
emission related average new car fleet is 120 g
CO2/km by 2012 and achieve only through
improvements to the manufacturing technology cars.
Another objective of the European Community
refers to the limitation of CO2 emissions to 120 g/km,
for fleet of new cars. This objective will be achieved
through an integrated approach, involving producers
of cars, producers of tires, the competent authorities
of the member states, etc.
In this context, priorities in the medium term,
laid down by the governing program 2009 to 2012, as
well as other documents of public policies and
institutional commitments (sectored strategies,
national
development
plans,
programs
of
development) are, in particular, to:
- modernization and development of transport
infrastructure;
- development and modernization means and
facilities of transport with a view to improving
quality of service, traffic safety, security, quality of
the environment and to ensure interoperability of the
system of transport;
- strengthening social and territorial cohesion at

national and regional level by ensuring links between
cities and increasing the degree of accessibility of the
population to public transport, including in areas with
low density of population and/or cores dispersed;
- the increase of competitiveness in the transport
sector, the liberalization of the internal transport
market;
- to improve transport behaviour in the
relationship with their environment, the reduction in
global impacts of transport (climate change) and
reducing ambient quality in the natural environment
and urban areas.
To alleviate the negative effects of air pollution
on the health of the general population and the
environment, in urban, as a result of exhaust
emissions from passenger cars, with pollution level
very high;
- compliance with the limit values emissions
permitted at European level for ambient air;
- prevention of the formation of waste, as a
result of abandonment worn cars and targets provided
for the communitarian acquits of the medium on the
recovery and recycling of waste from used vehicles.
References
[1]. Dorin Al., Dobrescu T., Actionarea Pneumatic a Robotilor,
Editura Bren, Bucuresti 2012.
[2]. Lazea Gh., Echipamente de automatizare pneumatice si
hidraulice indumator de laborator, Editura Lito IPCN, Cluj
Napoca, 2002;
[3]. Ionescu Fl., Catrina D., Dorin Al., Mecanica fluidelor i
actionari hidraulice si pneumatice, Editura didactica si pedagogica,
Bucuresti, 1994.
[4]. Ionescu C., Automatizari, Editura Didactica si Pedagogica,
Bucuresti 2002.
[5]. Radcenco Vs., Alexandrescu N., lonescu M., Ionescu M.,
Calculul si proiectarea elementelor si schemelor pneumatice de
automatizare, Editura Tehnica, Bucuresti, 2005.
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CHARACTERIZATION OF DUSTS AND SLURRIES FROM IRON AND

STEEL INDUSTRY IN TERMS OF CHEMICAL COMPOSITION,
MORPHOLOGY AND PHYSICAL PROPERTIES
Vasilica-Viorica (CORCOOI) TONI 1, Maria VLAD1,

Gelu MOVILEANU2
Faculty of Materials Engineering and the Environment, University Dunrea de Jos Galai, Romania
Environment Engineering and Biotechnology, Faculty of Valahia University, Trgoviste, Romnia
email: vioricatonitza@yahoo.com
ABSTRACT
From making steels and cast irons resulting dust is entrained gases. Offgases, captured at the top of the making installation are subjected to early
treatment operations which are generally performed in wet or dry systems. Slurry
consisting of fine dust fractions is subject to removal operations of water with
vacuum filters or centrifugal systems and recovery of slurry with coarse fractions is
done in the classroom with the squeegee.
This paper presents a synthesis of existing information in the literature
regarding the characterization of dusts and slurries from siderurgycal industry in
terms of physical-chemical properties. Documentary study results will underpin the
development of experimental research for obtaining of reusable materials that can
be used in various industries due to the enrichment of the chemical composition,
mineralogical composition and physico-mechanical properties.
KEYWORDS: dusts, slurry, siderurgy, properties, waste
1. Introduction
The Romanian iron industry is facing a serious
crisis regarding the recycling of waste which results
from iron and steel smelting. The wastes consisting of
iron, manganese, carbon, etc. and oxides from
different elements can be called by-products because
through various methods of advancements to
chemical compounds, they can be used within the
same generated flow sheet and also in other branches
of industry. The high price of raw material and their
depletion lead to finding effective solutions that can
direct them to a closed flow of production: generator
by-product technology raw materials
consumer.
Generator
Subproduse
Consumator
Materie
prim
Tehnologie
performant
Fig. 1. The closed circuit (Generator) of iron

and steel waste
Many steel processing plants from the entire

world have taken recycling measures leading to
operational and economical performances [1, 2]. In
our country the recycling of these chemical wastes
pose big problems due to the lack of modern
technologies that could transform them in base
materials for the industry, due to the absence of
storage space which is stipulated in the active
legislation regarding environmental protection,
because of the high transportation expenditure of the
decanting pits and their depletion, etc. The direct use
of the metallic dust and lime residue resulted from the
process of cast-iron and steel production is not
possible because of certain component elements such
as zinc, lead, oxides from certain elements, humidity,
granulation [3], which can damage the function of the
blast furnace and the quality of steel. The high price
of raw materials imported by the market participants
from the iron and steel industry and the productivity
impairment lead to finding new ways of exploitation
and refinement of the existing iron and steel industry
waste from Romania, either through direct gathering
from the generating line or through decanting pits and
waste dumps collection.
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2. Materials and processes

The industry of steel and cast-iron demands the
following waste processing: clinkering, briquetting
and pelleting. The aim of research and laboratory
tests is to find effective methods of enriching
chemical composition and their transformation in
materials that can be used in various branches of
industry. The blast-furnace slurry is a mixture of dust
collected from: dust bags coming from the dust
exhaust facility inside the cast bay were the cast-iron
slag gets ejected and the cast-iron gets transported in
the Torpedo buckets, from the electric filter servicing
the bunker scaffolds, from the exhaust port of the
furnace where the burnt gas gets collected, from the
electric filters coming from the coal blast, from the
slag granulation and also from the purge recovery
system which is fitted with a cyclone collector and a
dust bag.
The mixed dust then gets transported to the
blast-furnace supply base but not before taking
samples and analyzing probes from each sector. The
chemical composition determines the quality of the
by-product through the concentration of metallic
components, non-metallic components, sterile
elements and residue, and it also determines the
properties and the structure of steel and cast-iron. [1].
The determination of the chemical composition is
very important in finding the valuable and unwanted
elements from the process of collection,
transportation and waste storage. [4].
The dust and the lime residue have a blackish
color due to the high content of carbon and the
darkness of the smoke.
When wet they have a certain brightness that
fades away when humidity drops. Determining the
humidity from the dust and lime residues can be made
by interpreting Table 1 and is graphically represented
in Figure 5 along with furnacing loss and the existing
carbon count in them. In a dry state, these wastes
have a dark-brown color which indicates the presence
of iron oxides.
The long term storage of these wastes result in
their solidification in big boulders thus making them
easier to carry to the destination in the humidity is
between 20-30%. The furnace and the metallic dust
are not easily transportable while being in dry state
they are toxic to the storage area. The grain size
fraction of dust and lime residues is numerically
represented in Table 2 and graphically in Figure 6.
The dust and lime residue have basic pH
determined by HANNA 9125 apparatus (Figure 2)
and it varies from 12-12.5, while the ones from a steel
melting plant vary from 10.7-10.9.
The dust and lime residue from steel melting
plant have a bigger grain size fraction than the ones
from a furnace (Table 2 and Figure 6), having a
visible glow which indicate the presence of high

amounts of iron oxides.
The mineral composition of sludge [5] is mainly
made out of an agglomerated cake consisting of iron
glace, magnetic iron-ore, ferrite calcium core and
ferrite glass core scattered closely, rock-crystal,
silicates and carbonates and also limps of coke
(Figures 3 and 4). The calcium oxide (CaO) from the
sludge can be found in the form of calcium hydroxide
Ca(OH)2 which can act as an efficient binding agent.
[6].
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Fig. 2. PH-meter HANNA 9125
Fig. 3. X-ray spectrometry [14]
Fig. 4. The distribution of elements

in the sample [14]
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Table 1. The numerical values of moisture, loss calcination and C

for dust and blast furnace sludge, dust and slurry steel works, in %
Determinations, in %
Loss calcination
%
Sort
Humidity
%
Steel works dust

Steel works
slurry
Blast furnace
dust
Blast furnace
slurry
1.5
0.20
0.07
39.92
18.50
6.07
11.8
39.6
39.76
21.1
31.01
24.46
Carbon
%
Fig. 5. Graphical representation of the values for moisture, loss calcination and carbon dust and
blast furnace slurry, dust and slurry of the steel works
Table 2. Granulometry of materials
granules
dimension
[mm]
> 10
>8
> 6.3
>5
>4
> 3.15
>2
> 1.25
> 1.00
> 0.50
> 0.125
> 0.10
Granulometry, in %
blast
blast
steel
furnace
furnace
plant
dust
slurry
slurry
[%]
[%]
[%]
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.44
0.23
0.02
0.59
0.02
0.04
0.84
0.03
0.06
0.36
0.01
0.07
12.55
0.10
0.05
4.70
0.23
0.05
2.31
0.90
1.91
5.14
16.82
56.27
20.83
71.10
20.29
0.24
5.35
- 112 -
steel
plant
dust
[%]
43.91
14.16
0.20
0.75
0.93
1.09
1.85
1.99
1.37
4.25
12.26
0.51
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Fig. 6. Graphical representation of particle size fractions for dust and blast furnace slurry, dust and
slurry from steel works, in %
3. Experimental measuring
The characterization of waste requires the
knowledge of physical, chemical, mechanical and
technological properties, its workability and also its
morphological structure.
Professional literature abounds in information
concerning the chemical properties of waste. The
mechanical properties of waste refer to their behavior
when being manipulated.
Fig. 7. Pressed samples method

1. blast furnace dust; 2. blast furnace slurry; 3.
steel works dust; 4. steel works slurry
The technological properties relate to the
workability and exploitation methods employed in
different domains of industry.
In the present paper, in order to accurately
determine the concentration of elements from the
samples taken (furnace and steel melting plant dust
and cast iron) I used quantitative analysis means
based on physical principles and chemical reactions.
The ppm level of component elements from the

samples taken could be analyzed through X-ray
spectroscopy with wavelength dispersion (WDXRF).
In the case of WDXRF each element gets analyzed
starting from Be to U, and the samples can even be
powdery or liquid.
The cast spectrum is scattered in discrete wave
lengths (for example a crystal) that get detected by a
direct scintillation spectrometer or gas.
The experimental part
For the dust and cast-iron samples taken I chose
two preparation methods:
- pressing;
- melting.
In the case of the pressed samples there are two
side effects that influence the precision of the
analysis: the size of the fraction and its mineral
structure. The sample got grinded until they reached a
granulation under 100 m, then a binding agent was
added until it became a homogenious compound.
The next step was to stamp it down for 40
seconds in a pressing machine with a force of 45TF.
The result was 40mm in diameter and 4mm in
tickness button with a plate and even surface (Figure
7).
The concentration determination through
fluorescence was realized using an analytic program
using the ARL 9800 XP spectometer (Figure 8) to the
following elements: phosphorus pentoxide (P2O5),
silicon dioxide (SiO2), Iron (Fe), Aluminium Oxide
(Al2O3), Vnadium Oxide (V2O5), Titanium Oxide
(TiO2), Chromium Oxide (Cr2O3), Calcium Oxide
(CaO), Magnesium Oxide (MgO), Mangan Oxide
(MnO). The time spent on processing and analysing
the samples at the spectometer was aprox. 20
minutes.
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Fig. 8. Spectrometer ARL 9800 XP

In the case of the samples processed through
melting the granulation got increased to under 100
m and then got mixed with a certain quantity of
additives (Figure 10). The homogeneous compound
got placed into a platinum skillet on a lair of flux. The
skillet then got heated at a temperature that secured
oxidation of the metallic particles from the samples,
after that it reached a temperature which helped the
flux melt thus combining with the oxides from the
samples. The blending got molded on a plane surface
where the solidification process took place (Figure
10) thus attaining the bottle shaped sample (Figure 9).
An ARL 9800 XP spectometer was also used for
50 seconds and the results acquired can be found in
Table 3, 4, 5, 6 and represented in figures 12, 13, 14,
15.
Fig. 10. Process of obtaining samples by melting

method
Fig. 9. Melting samples method

1. blast furnance dust; 2. steel works dust;
3.steel works slurry
Fig.11. Typical fusion procedure at a

temperature of 900-1000 oC while agitating
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Table 3. Composition of furnace dust

Sort
Blast
furnance
dust
Method
used
Pressing
Meltind
Source
Separator
G.A.
Fe
20.70
Mn
0.23
SiO2
7.30
CaO
5.32
Component and elements, in %

MgO Al2O3
P
S
K2O
1.20
1.40 0.044 1.000 0.420
Na2O
0.056
TiO2
0.114
ZnO
0.200
Cr2O3
54.10
Fe2O3
22.79
21.00
0.22
6.98
4.94
1.16
0.047
0.102
0.178
54.10
23.15

Al2O3
P
S
K2O Na2O
1.39 0.066 1.340 0.297 0.190
TiO2
0.106
ZnO
1.950
Cr2O3
40.50
Fe2O3
29.292
0.097
1.790
40.50
31.085
1.56
0.041
2.258
0.370
Table 4. Composition of furnace slurry

Sort
Blast
furnance
slurry
Method
used
Source
Pressing
Separator
Fe
26.60
Mn
0.34
SiO2
7.16
CaO
8.29
MgO
0.88
Melting
Separator
28.20
0.36
6.56
8.04
0.73
Elementecomponente,in%Sursa
45
Elementecomponente,in%Fe
40
Elementecomponente,in%Mn
35
Elementecomponente,in%SiO2
30
Elementecomponente,in%CaO
Elementecomponente,in%MgO
25
Elementecomponente,in%Al2O3
20
Elementecomponente,in%P
15
Elementecomponente,in%S
10
Elementecomponente,in%K2O
Elementecomponente,in%Na2O
1.47
Presare
Topire
Praf oelrie
2.269
0.207
0.120
45.00
40.00
35.00
30.00
25.00
20.00
15.00
10.00
5.00
0.00
Elementecomponente,in%TiO2
0.059
Elementecomponente,in%ZnO
Elementecomponente,in%FeO
Separator
Separator
Presare
Topire
Slamdefurnal
Elementecomponente,in%Fe2O3
Elementecomponente,in%Cr2O3
Fig. 12. Graphical representation of the components of blast furnace dust Fig. 13. Graphical representation of the components of blast furnace slurry
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Table 5. Composition of steel works dust

Sort
Steel
works
dust
Method
used
Pressing
Melting
Sursa
OLD1
Fe
39.80
Mn
11.90
SiO2
3.11
CaO
12.85

MgO Al2O3
P
S
K2O
1.62
0.89 0.089 0.460 1.050
Na2O
0.074
TiO2
0.041
ZnO
1.410
FeO
19.10
Fe2O3
44
40.50
1.18
3.16
12.90
1.69
0.06
0.04
1.48
19.10
44.78
0.94
0.09
1.07
Table 6. Composition of steel works slurry

Sort
Steel
works
slurry
Method
used
Pressing
Fe
48.50
Mn
0.69
SiO2
3.04
CaO
24.20
MgO
0.29
Melting
49.90
0.72
3.18
24.80
0.30

Al2O3
P
S
K2O Na2O
0.28 0.065 0.022 0.288 0.025
0.29
0.07
0.27
0.02
TiO2
0.032
ZnO
0.043
FeO
49.46
Fe2O3
53.62
0.03
0.04
50.89
55.17
Elementecomponente,in%Sursa
45
40
35
30
25
20
15
10
0
Presare
Topire
Praf oelrie
Elementecomponente,in%FeO
Fig. 14. Graphical representation of the steel works dus components
Fig. 15. Graphical representation of the steel works slurry components
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197 6

N0. 1 2011, ISSN 1453 083X
References
4. Conclusions
The results from the experiment have shown that
the two methods can be used depending on the
requirements specified in the production process.
When a large quantity of samples need to be
analyzed in a fairly short amount of time it is
advisable to use the pressing method, but if a precise
analysis is required and the costs and time are not an
issue then it is advisable to use the melting method.
These materials can replace a part of the basic
synthesizing.
[1]. Ciocan A., Valorisation of waste generated in small and dust

metallurgy, Grup Editorial Naional, 2003, Bucuresti.
[2]. Ciocan A., Metallurgical Valorisation of waste, Processes and
technologies, 2008, Galai University Press.
[3]. Vlciu I., PhD Thesis Research on new technologies for
recovery and recycling of metallurgical industry waste, University
Polytechnic din Bucureti.
[4]. B. Das, S. Prakash, P. S. R. Reddz, S. K. Biswall, B. K.
Mohapatra, V. N. Misra, Effective Utilization of Blast Furnace
Flue Dust of Integrated Steel Plants, The European Journal of
Mineral Processing and Environmental Protection, 2002.
[5]. Migral S. R. L., Research and proposals for the use of blast
furnace sludge deposited on concrete pad UCC-2, 2007, Bucureti.
[6]. Dakun V. I., Esezobor D. E., Rostovsky V. I., Reclamation of
Dumped Sludge in Steel Industry, Journal of the Republic
Environmental Control and Rational Utilization of Natural
Resources, Donetsk.
[7]. http://www.claisse.com
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AIR POLLUTANT EMISSIONS FROM THE BASIC OXYGEN

FURNACES SECTOR OF INTEGRATED STEEL PLANT AND THE
ABATEMENT MEASURES AVAILABLE
Beatrice TUDOR, Anioara CIOCAN, Catalin ZAHARIA

ABSTRACT
The most significant environmental problem in the BOF steelmaking sectors
refers to the impact on air factor of existing processes and activities. The emissions
of pollutants resulted can be sources of risk with global implications, regional or
local. The typical pollutants resulted are heavy metal particles, CO2, CO, SO2,
NOx, VOC. Them are added other emissions, quantitatively less important but more
toxic, chloride and organochlorines, polychlorodibenzo-p-dioxins and
polychlorodibenzo-furans, fluorides, etc. Air pollutants, from diffuse sources or
continuous, can be transported over long distances, may spread in air, can reach
the ground through precipitation or sedimentation, affecting and other environment
factors. Thus they are involved in: climate change, photochemical pollution, acid
rain, environment and human toxicity. This paper concerns the identification of
main air pollutant emissions from the basic oxygen furnaces sector of integrated
steel plant, their origin and the measures available applied for their diminishing.
KEYWORDS: basic oxygen furnaces, air pollutant emissions, sources,
abatement measures
1. Introduction
The knowledge of the atmospheric pollutants
(origin and concentration) emitted by an industrial
process is essential to assess their impact on
environment and people and to applied the best
measures to them eliminate or reduce.
Romania is listed as a country with a relevant
production of crude steel in the EU27. In accordance
with data from 2006 presented in [1, 2] the Romanian
had an integrated steel plant with 5 basic oxygen
furnace installations (type LD) in operation and 4374
kt/yr reported steel production (101 is total number of
basic oxygen converters and 123283 kt/yr the BOF
steel production of integrated steelworks in the EU27).
The main environmental issues for oxygen
steelmaking are pollutant emissions to air. These are
released from various sources diffuse sources or
continuous.
The air pollutants are transported on long
distances and are dispersed in the air or reach on the
sol through precipitation or sedimentation. So the air
pollutant emissions affect other environment factors.
As result, they are involved in: climate changes (CO2,
CO, NOx, N2O, COV, CH4), photochemical pollution

(COV, NOx), acid rains (SO2, NOx), ozone layer
destruction (COV, HCF, CFC, HCFC), human and
environment toxicity (some VOC as PAH, PBa,
PCDD/PCDF etc. and some heavy metals as As, Pb,
Cu, Zn, Ni, Cr, Cd, etc.).
The main emissions from BOF sector are
particulate matter, CO2, CO, SO2, NOx, and COV.
Also quantitatively less important, but more toxic are
emissions of chlorides, dioxins and furans.
Potential sources of risk with direct effect on the
human factor are the diffuse emissions that affect air
quality in the workplace.
The controlled emissions have an indirect
influence on the human factor by changing the
conditions of life.
This paper concerns the identification of main
air pollutant emissions and their sources from each
sector from BOF steelmaking process.
These are correlated with BAT (Best Available
Techniques) for environmental protection in the
production and refining of steel using the basic
oxygen
process,
including
upstream
ladle
desulphurisation, downstream ladle metallurgy and
slag processing.
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2. Sources of pollutants emissions in BOF

steel production plant
The production of steel by the BOF process is a
discontinuous process which involves the following
steps [2]:
- transfer from the BF and discharge;
- pre-treatment of hot metal (desulphurisation,
deslagging);
- transfer, weighing and reladling;
- oxidation in the BOF (decarburisation and
oxidation of impurities);
- secondary metallurgical treatment;

- casting (continuous or/and ingot).
BOF steelmaking process contains many sources
of environmental pollution. These can be identified in
all technological steps of flow sheet of BOF steel
production: transfer, storage and pre-treatment of hot
metal (desulphurisation); BOF steelmaking (charging,
melting, refining, tapping, and slag handling);
secondary metallurgical treatment; continuous
casting.
The individual stages and their associated
emissions are summarised in Figure 1 [2, 3].
Fig. 1. Stages of oxygen steelmaking with respective individual emission sources

The most significant emissions from BOF
steelmaking are released during the oxygen blow
period. During oxygen blowing, converter gas is
released from the converter. This gas contains large
amounts of dust. These gases emissions and
particulate matter are classified as primary emissions
and are collected in a hood above the mouth of the
basic oxygen furnace (BOF). The predominant
compounds from primary emissions are emitted
mainly as result of oxidation processes
(decarburisation,
oxidation
of
accompanying
elements and impurities). These are carbon oxides
(CO2, CO), iron oxides (including FeO and Fe2O3),
and other metal oxides. Relatively small amounts of
sulphur oxides (SO2) and nitrogen oxides (NOx) are
present in the gaseous emission. Also, some
undesirable impurities from metallic feed are
removed by oxidation processes and released as
oxides in the off-gas (another part of these are
transferred into liquid slag). Heavy metals (Al, As,
Cd, Cr, Cu, Fe, Hg, Mg, Mn, Pb, Zn), very small
amounts of PCDD/Fs, PAH, and hydrogen fluoride
are usually present. Other operations generate

secondary off-gases and particulate emissions.
Secondary off-gases are emitted from hot metal
transfer, scrap charging, handling of additives and
slag, tapping of steel and slag. BOF charging releases
particulate emissions. Charging emissions vary with
the quality and quantity of scrap metal charged to the
oxygen converter and with the pour rate. Those
emitted from tapping operations include iron oxides,
sulphur oxides, and other metallic oxides. Hot metal
transfer emissions are mostly iron oxides.
Steelmaking process in the converter is usually
followed by post-treatments. This period is named
secondary metallurgy and comprises a number of
diverse metallurgical operations: mixing and
homogenising; adjustment of chemical compositions;
temperature adjustment in time for the downstream
casting process; deoxidation; removal of undesirable
gases such as hydrogen and nitrogen; improvement of
the oxides purity by separating non-metallic
inclusions. These processes release minor emissions
as primary and secondary off-gases.
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A part of the emissions generated from BOF

steelmaking are controlled (captured and routed to
wastewater treatment plants) and other part is
dispersed into the air with negative effects on the
environmental factors.
The pre-treatment of hot metal (BF iron)
involves desulphurisation by utilisation of specific
agents (calcium carbide, caustic soda, soda ash, lime
and magnesium impregnated materials). The process
emits particulate matter (about 10 g/Nm3 or 1000 g/t
steel). This is controlled by collection in local hoods
and treated in cleaning gas systems (filter bag or
ESP). The measures applied provide the decreasing of
these emissions at ~1 7 g/t steel.
3. Air pollutant emissions at basic oxygen

steelmaking
- CO and CO2 emissions. Carbon from the hot
metal and scrap is oxidized with oxygen blowed in
furnace and generates CO2 or CO. The converter gas
produced during oxygen blowing (converter gas)
contains large amounts of carbon monoxide formed
during start and end of blowing when the combustion
is suppressed. Specific emission value for CO to air
from a basic oxygen furnace with suppressed
combustion varies in range of 7.0 16 kg carbon
monoxide per tonne liquid steel. Typically BOF gas
contains 55 80 vol-% CO and 10 18 vol-% CO2
[4, 5].
Minor emissions of CO2 and CO occur during
other operations as the using of CH4 flame for
preheating (ferroalloys and aluminium; moulds for
sampling of the molten metal; intermediate ladles;
slag ladles), moulds for steel casting as ingots etc.
Also during these processes no representative NOx,
COV emissions are released in air.
- Nitrogen oxides (NOx).In the oxygen converter
are conditions for thermal NOx formation by
oxidation of nitrogen from impurities contained in
oxygen, but quantities are extremely limited. The
emission level of nitrogen oxides (NOx) to air from a
basic oxygen furnace with suppressed combustion is
ranged between 5.0 and 20 g/t liquid steel [4, 5]. High
values are specific when full combustion is
employed, the presence of nitrogen in the ambient air
into the ventilation system can increase NOx by 20 g/t
of liquid steel.
- Sulphur oxides (SO2). SO2 emissions from
BOF steelmaking sectors are generally small
compared to emissions from primary sectors of the
integrated steel plant (production sector of coke,
sinter, pig iron). Relatively small amounts of sulphur
oxides (SO2) are emitted during oxygen blowing.
Specific emission values to air from a basic oxygen
furnace with suppressed combustion are in the range
of 0.4 - 5.5 g/t liquid steel [4, 5].
- Organic compounds are mainly generated by

scrap impurities. Very small amounts of PCDD/Fs
(<0.001 0.06 g I-TEQ/t liquid steel) and PAH
(0.08 - 0.16 mg/t liquid steel) are emitted during
oxygen blowing [4, 5]. Their content is determined by
the presence of organic compounds (from paints,
plastics, lubricants etc.) in contaminated scrap.
- Particulate matter. The oxygen steelmaking
process generates considerable quantities of
particulate matter. The hot metal transfer, scrap
charging, oxygen blowing, tapping, and slag handling
are the operations that generate fugitive emissions.
The most significant particulate emissions from the
basic oxygen furnace process occur during the
oxygen blow period. Minor emissions of particulates
arise from secondary metallurgical treatment. The
predominant compounds emitted during oxygen
blowing are iron oxides (FeO and Fe2O3). The heavy
metals and fluorides are also usually present.
Particulate matter is emitted both during charging of
scrap and hot metal and during tapping from the
BOF. The emission factor for dust at charging stage
varies with the quality and quantity of scrap metal.
Also dust emissions from tapping operations depend
from grade of scrap used. These include iron oxides
and other metallic oxides. Mostly iron oxides are
present in the emissions from hot metal transfer.
- Heavy metal emissions. Most of the hazardous
air pollutants generated in the BOF are heavy metals,
including cadmium, chromium, lead, manganese, and
nickel. The heavy metals are associated with airborne
particles generated from oxygen converters. The
source of As, Cd, Cr, Cu, Fe, Pb, Zn are remelted
scraps. Zn emissions originated from the recycled
scrap, materials that are usually galvanized, are
relevant. The source of other elements is the alloyed
scrap or ferroalloys used as addition materials. At
high temperature the metals are transferred from
metallic input to the gas phase and collected in dusts.
The emission of the heavy metals depends on
composition and quality of the scrap and alloying
materials needed in relation with grade of steel [6].
A part of the emissions are controlled (captured
and routed to treatment equipments), and another part
is dispersed into the air of workplaces worsening the
environmental conditions.
Before
equipments
modernization
and
implementation of special measures the level of
emissions is higher. Also the measured emissions
differ in the areas of a BOF steelmaking sector from
the Romanian integrated steel plant. The air
emissions have decreased over time as result of the
measures that were required to apply. So for areas of
oxygen converter, steel and slag tapping the CO
varies in range of 20.7-37%; SO2 varies in range of
2.1-2.3%; the dust in range of 37.9-110mg/Nm3. For
storage
and
pre-treatment
of
hot
metal
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(desulphurization) the levels of emissions are 21.1 48% CO, 6.6 - 13.4% SO2; the airborne dust is 21.9
200 mg/Nm3. The dust emitted from ferroalloys and
scrap handling was at level 14.5 - 22.4 mg/Nm3. In
the casting area the emissions measured were: 52.2180 mg/Nm3 dust, 21.2 - 23.6% CO and 1.8 - 2.2%
SO2. From sector of ladles preparing the dust
emission varies in range of 59.4 115 mg/Nm3. The
value of measured CO in sector of secondary
treatment of steel (with RH installations) is variable
from 6.3 to 9.1%. The dust emission in this sector
was minor, 8 mg/Nm3. The emissions in different
areas of continuous casting sector were variable:
30.5mg/Nm3 dust and 12.2 - 101.1% CO for casting
area these are and 11.1 - 16.6mg/Nm3 and 21.3 - 56%
CO for extraction and cutting of slabs. In sector of
preparing scrap the dust emission is placed in range
of 11.2 - 15.8 mg/Nm3 and the CO content in range of
14.1 - 28.3%. The values measured for other
emissions were not exist [7].
The emissions released into environmental
factors (in this case into air) are conditioned by the
performance of abatement measures available.
Fugitive emissions from the BOF during oxygen
blowing are minimized by capture with a primary
hood placed directly over the open mouth of the
oxygen converters. Charging and tapping emissions
are controlled by a variety of evacuation systems and
operating practices. The primary emissions are
usually controlled by a wet scrubbing system or an
electrostatic precipitator. The fugitive emissions from
hot metal transfer, scrap charging, oxygen blowing,
tapping, and slag handling are usually collected by
local hooding and cleaned in fabric filters.
In accordance with the requirements on
environment protection the Romanian integrated
steelmaking plant have developed an integrated
programme to monitoring and control all pollutant
emissions. The process-integrated techniques and
end-of-pipe measures were applied. The emissions
from oxygen steelmaking sectors are controlled and
captured by holes placed in point source of emissions
(for each subprocess in the BOF steelmaking plant).
The best solutions of air control techniques were

chosen. The gas captured is treated in primary and
secondary cleaning equipments. As example a
secondary dedusting installation (modern venture
type scrubbers) were recently placed [5].
4. Conclusions
As result of stringent regulations Romanian steel
integrated plant elaborated a modern program to
control and monitoring the pollutant emissions for
reduction theirs environmental impact. For eliminate
and limitation the level of air emissions was
necessary the correct evaluation of the atmospheric
pollutants and identification of theirs sources. Also
was important the knowledge and selection of the
best available techniques (BAT) for environmental
protection in the BOF steel production plants. As
result of correct solutions selected and implemented
to control of air emissions the environmental
pollution was substantial reduced.
References
[1]. *** Stahl, Statistisches Jahrbuch der Stahlindustrie 20092010, Stahleisen-Verlag, 2008.
[2]. R. Rainer, M. A. Aguado-Monsonet, S. Roudier, L. Delgado
Sanch, JRC REFERENCE REPORT, Best Available Techniques
(BAT) Reference Document for Iron and Steel Production, 2013,
www.http://eippcb.jrc.ec.europa.eu/reference/BREF/IS_Adopted_0
3_2012.pdf.
[3]. *** Eurofer. Eurofer comments on tables and figures of
Chapter
8.
BOF
and
continuous
casting,
2007,
http://ec.europa.eu/enterprise/sectors/metalsminerals/files/final_report_steel_en.pdf.
[4]. *** Integrated Pollution Prevention and Control (IPPC), Best
Available Techniques Reference Document on the Production of
Iron and Steel, December 2001.
[5]. C. Zaharia, Emisii poluante sectorul de elaborare a oelului n
convertizorul cu oxygen proiect GPPEP, Universitatea Dunrea de
Jos din Galai, 2013.
[6]. *** Best available techniques for controlling emissions of
heavy metals and their compounds from the source categories
listed in Annex II, Working group of strategies and review, 49th
Session, 12-16 September 2011, Geneva.
[7]. *** ICEM SA Bucuresti, Studiu de evaluare a riscului la
ISPAT-SIDEX Galai.
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INVESTIGATING OFFSHORE WIND FARMS CONNETIONS

Cristina Madalina DRAGAN, Mircea Viorel DRAGAN

email: vdragan@ugal.ro
ABSTRACT
Offshore wind energy is one of the key components in helping the EU to fulfill
the agreement to achieve the 20% of renewable energy from the total energy by
2020. Currently limitations are encountered in connecting the large scale offshore
wind energy. Also the current onshore transmission networks cannot be able to
integrate the energy that can be available in most of the large scale offshore
projects. To correct these deficiencies a redesign of the grid infrastructure, system
management, grid regulation and grid codes are needed. The large scale offshore
wind farms have to be treated as conventional power plants, thus the necessity for
both national and cross border network upgrades is increasing. That is why a key
factor which plays an important role in achieving all of this is selecting the proper
connection type between the farm and the grid.
KEYWORDS: AC/DC connection, power, efficiency, wind farm
1. Introduction
An important issue regarding the grid
connection of large wind power is the necessity of
connecting remote offshore wind farms to the high
voltage or extra high voltage backbones of the
electrical system. This aspect will determine an
increase in the total length of the cable connecting the
offshore site beyond the shore limit. On this subject,
future offshore wind farms may benefit of
technological developments such as Flexible AC
Transmission (FACTS) or High Voltage Direct
Current (HVDC) systems each with its own areas of
application. FACTS devices are a good option in the
case of offshore wind farms located within about 100
km to a connection point to the transmission system
while HVDC can prove economical for higher
distances [1-3].
One of the challenges is to find a suitable type
of connection for offshore wind farms, having
different power ratings and different distances from
the onshore connection point.
This selection should be done by taking into
consideration power efficiency and economical
aspects.
Two alternatives are available for connecting an
offshore power plant to the main grid:
HVAC transmission;
HVDC transmission.
Until now for the already build WFs, like Horns

Rev I, Nysted, Middelgrunden, in Denmark, the only
connection used was the AC connection. The reasons
for choosing this type are [4]: lower station costs, no
power converters needed a simple layout for the
offshore park.
2. Connection types
2.1. Connection
A typically offshore WF layout is depicted in
Figure 1.
By choosing the AC transmission for the
offshore WF several disadvantages are encountered,
like [5]:
the need of reactive power compensators,
such as SVCs or STATCOMs;
AC cable cost becomes higher as the
distance grows;
long AC cables produce large amounts of
capacitive reactive power;
the decrease of the transmission capability of
AC system decreases together with distance because
of the dielectric losses and the reactive power that is
produced along the cable.
The optimization of the AC system is made by
taking into consideration two parameters, the
transmission voltage level and the number of cables
used in the system [4].
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Fig. 1. Offshore WF layout for AC transmission
2.2. DC Connection
As the future offshore WFs planned to be build
are further away from the shore side and become
higher and higher in size, an important question will
rise: What type of transmission system is more
suitable for the WF with high voltage levels and
larger distances to the onshore connection point?
The solution could be the HVDC transmission.
The benefits of using HVDC transmission

instead of AC transmission are [5]:
less power losses for long distances;
lower cost for cables above certain distances;
it can connect asynchronous AC networks;
offshore WFs can operate at variable speeds;
decoupling of the connected AC networks
(i.e. it allows asynchronous operation of the offshore
WF AC network and the main grid).
Fig. 2. Offshore WF layout for HVDC transmission

The main structure of an offshore wind farm
connected using HVDC transmission is summarized
as presented in Figure 2.
The link to the grid is made through a power
converter which guarantees the reactive power control
and a smooth grid connection [6].
Depending on the power semiconductors used in
the converter topology, the HVDC transmission can
be classified as follows:
thyristor based line-commutated converters
(classical HVDC);
VSC based HVDC technology.
The classical HVDC converter is based on
thyristor valves which perform the conversion from
AC/DC and DC/AC. This system can be used for the
transmission of significant powers at large distances
having low losses (voltage level up to 800kV [7]).
When it comes to offshore wind farms the

classical HVDC may not be the best solution because
it requires large converter station for both, the
onshore and the offshore side (see Table 1). It is
needed also an auxiliary service at the offshore
converter station for the operation of the linecommutated converters when there are power failures
[7]. For the thyristors based system it is essential to
have an AC voltage source in order to commutate and
only when they received it they can transfer power
between two AC networks. This also makes them not
an adequate solution for offshore WF because the
offshore grid needs power before they start to operate.
Besides, no independent control of the active and
reactive power is provided [8].
The second option is the VSC-based HVDC
which is a relatively new technology based on the use
of high switching frequency transistors like IGBTs.
The IGBTs are power semiconductors with self-
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commutated turn-on and turn-o_ capability, allowing

the generation of reactive power to supply the wind
turbines [8]. One of the benefit of using this
technology is that it provides voltage and power
control. When dealing with isolated and fluctuating
power plants, such as offshore WF, the voltage
control and reactive power plays an important role in
the stability of the system. That is why VSC-HVDC
can be the proper solution in connecting a large
offshore WF to the shore point.
One disadvantage of HVDC option, compared to
AC connection, is that it can increase significantly the
costs of the wind farms, mainly because of the power
converters used in the systems. However the benefits
can justify the costs. The HVDC-VSC technology is
used by several manufacturers, two of them can be
mentioned: Siemens which developed HVDC Plus
(12 pulses) and ABB which HVDC Light (6 pulses).
From the available VSC-HVDC options, HVDC
Light technology was the first to be involved in an

offshore WF project [9].
2.2.1. HVDC Light

HVDC Light it is ABB's trade mark. This
technology is based on voltage source converters
(VSC) and it was designed as a power transmission
system for underground and submarine cables.
Reasons that make HVDC Light a feasible solution
for offshore wind farms are that the converters
stations are design in compact module, suitable for
offshore and also the possibility of connecting this
farms to the AC network without any distance
limitations.
The cables are light weight and oil-free which
neutral electromagnetic fields which make them
environmental friendly [10]. This technology ensures
stable voltage and frequency by controlling rapidly
and independently the active and reactive power.
Fig. 3. Circuit diagram of HVDC Light

The HVDC Light concept is based on a 6-pulse
bipolar VSC with ratings up to 330 MW/150 kV DC
for one bipolar unit as presented in Figure 3 [11]. The
IGBTs can switch at high frequency around 2 kHz.
This fast commutation reduces the harmonics in the
system, thus the number of filters will be reduced
compared to the 'classic' HVDC converters.
Each converter can operate as rectifier or
inverter at variable frequency and to absorb or deliver
reactive power to the AC grid. Four quadrant
operations is possible for each power converter thus,
a bidirectional active power flow is possible [7].
The first commercial project that involved the
installation of an HVDC Light system was in Gotland
in 1999. The purpose was to connect a wind farm
with remote load center to the grid, via a 70 km
underground cable. With this project the ABB
technology proved to be reliable in terms of [12]:
stable voltage and reactive power;

less stresses on both WTs and the connected
grid;
low voltage ride-through-capability in case
of grid faults;
flicker problems eliminated and transient
phenomena disappeared;
power flow control to optimize the overall

performance and losses in the adjacent AC grid;
compact, environmentally adapted converter
station design;
low operation and maintenance costs.
Germany is the country which began the first
HVDC Light project for connecting an offshore wind
park. Since September 2007 E.ON Netz is building
the largest offshore wind park in the world (400 MW)
and the largest distance from the mainland (128 km).
The wind park Borkum 2 is expected to be finished in
2009 and it will be the first connection to the grid
using DC [9].
2.2.2. HVAC vs. HVDC

When it comes to decide which is the best
transmission system option, two parameters which
have a great impact on transmission efficiency and
costs are considered. These are the transmitted power
and the distance. Figure 4 reveals what is the suitable
connection type for electrical systems.
It can be seen in Figure 4 that the HVAC is the
best solution for small power systems and short
distances. One of the reasons is the increased price for
installations and cables when it comes to transmit
high levels of power on long distances. As the power
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and distances increase the HVDC connection should

be considered. The VSC-HVDC technology is
preferable to transmit medium amount of power on
long distances, but when it comes to transmit on large
distances a significant amount of power, the solution
is classic HVDC [7].
reinforcement that may be significant in the AC case

compared to VSC-HVDC solution.
Fig. 5. HVAC & HVDC transmission system

costs
Fig. 4. Transmission type depending on power
and distance
Figure 5 highlights what are the costs involved
in building an AC or DC system. As it can be seen
DC transmission is a cost effective technology when
significant amounts of power must be transmitted on
long distances. The decision should be made by
considering other factors such as the expenses of grid
Also the costs for power flow equipment in the

AC system are greater than in the VSC-HVDC
solution. One advantage more for the VSC-HVDC
system is that it offers the possibility to go further on
land with an underground cable at a very moderate
cost [12].
A comparison between classic HVDC and
HVDC Light can be seen in Table 1.
Table 1. HVDC Light vs. Classic HVDC
3. Conclusions
As the distance to the shore connection point
increases, the AC transmission efficiency decreases at
a higher rate than with HVDC. That is why an answer
to this problem could be to usage of HVDC
transmission for large offshore parks with large
distances between the farm and the grid connection
point because there will be less transmission losses
thus efficiency will increase.
References
[1]. Peter Sandeberg, Lars Stendius, Large scale Offshore Wind
Power Energy evacuation by HVDC Light, EWEC. Brussels 2008.
Belgium.
[2]. ABB Group website, HVDC Light Technology, [cited

October
5].
Available
from:
http://www.abb.com/cawp/gad02181/d7779a6f38fcbdc0c1256f9d0
046d2b0.aspx.
[3]. Dawei Xiang, Li Ran, Jim R. Bumby, Peter J. Tavner,
Shunchang Yang, Coordinated control of an HVDC Link and
Doubly Fed Induction Generators in a Large Offshore Wind Farm.
[4]. K. Eriksson, D. Wensky, System Approach on Designing an
Offshore Windpower Grid Connection, ABB Utilities. [cited 10
March
2009].
Available
from
library.bb.com/global/scot/scot221.nsf/veritydisplay/34ec041beda6
6334c1256fda004c8cc0/$File/03MC0132%20Rev.%2000.PDF.
[5]. Lazaros P. Lazaridis, Economic Comparison of HVAC and
HVDC Solutions for Large Offshore Wind Farms under Special
Consideration of Reliability, Royal Institute of Technology.
Department of Electrical Engineering. Stockholm 2005.
[6]. Fernando D. Bianchi, Hernan De Battista, Ricardo J.
Mantz, Wind Turbine Control System, Springer-Velgad London
Limited 2007. ISBN 1-84628-492-9.
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[7]. Ervin Spahi and Gerd Balzer, Offshore Wind Farms - VSCbased HVDC Connectionm, Power Tech, 2005 IEEE Russia. ISBN:
978-5-93208-034-4.
[8]. Stephan Meier, Novel Voltage Source Converter based
HVDC Transmission System for Offshore Wind Farms, Royal
Institute of Technology. Department of Electrical Engineering
Electrical Machines and Power Electronics. Stockholm 2005. ISBN
91-7178-206-0.
[9]. Lars Stendius, Nord E.ON 1 - 400MW HVDC Light Offshore
Wind Project, ABB Grid Systems. Berlin December 2007.
[10]. ABB, It's time to Connect, Technical description of HVDC
Light technology. ABB - Grid Systems -HVDC. SE-771 80
Ludvika, Sweden.
[11]. Anca D. Hansen, Florin Iov, Poul Srensen, Nicolaous

Cutululis, Clemens Jauch, Frede Blaabjerg, Dynamic wind
turbine models in power system simulation tool DIgSILENT, Ris
National Laboratory. Technical University of Denmark. Roskilde,
Denmark 2007. ISBN 978-87-550-3553-9.
[12]. Bo Normark, Erik Koldby Nielsen, Advanced power
electronics for cable connection of offshore wind, Paper to be
presented at Copenhagen Offshore Wind 2005. [cited 12 March
2009]. Available from:www.abb.com.
[13]. Adelina Agap, Cristina Madalina Dragan, Multiterminal
DC Connection for Offshore Wind Farm, Master thesis, Institute of
Energy Technology, Aalborg University. Aalborg 2009.
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STUDIES OF ENVIRONMENTAL RISK

FOR TOTAL SUSPENDED
Stela CONSTANTINESCU
email: stela.constantinescu@email.ro
ABSTRACT
This paper presents some results in a study of environmental risk for
particulate matter inside the SC Arcelor Mittal steel plant Steel Galati and border
area. Environmental risk assessment for particulate matter (PM10) was based on
immission calculation results of the Arcelor Mittal Steel Galati SA and was
conducted both in the Steel Galati, and border area.
KEYWORDS: environmental risk, total suspended particulates (TSP), border
area
1. Introduction
This paper presents some results of a study
where environmental risk for particulate matter inside
the SC Arcelor Mittal Steel Galati and border area.
Dispersion model used for particulate matter is
Industrial Source Complex 3 - ISC3 - AERMOD
View, developed by Lakes Environmental Software,
Canada, and several studies used to develop the
dispersion of air pollutants and environmental risk for
Galati Steel platform [1]. Modern industrial
civilization in the opinion of many international
bodies is characterized as "risk society". Abstract
concept of 'risk' has become a dominant structural
principle, surpassing importance in some cases
traditional type concepts of social, political or
economic [2]. Mittal Steel Galati uses, manipulates,
stores or generates the quantities of raw materials,
energy, gas, wastewater and wasted. In aggregate
steel raw materials are processed at high temperatures
and pressures using large amounts of energy (in the
form of fuel and electricity). This activity has a high
environmental impact due to significant amounts of
gaseous pollutants, wastewater and waste they
generate. Thus in certain operating situations
(abnormal or even normal situations favorable
environmental conditions), this activity may be a
source of risk to people, environment and property.
Methodology for assessing environmental risk
generated by the steel industry economic unit should
start the environmental assessment and risk
characterization [3, 4].
This required the development of a conceptual
model should include:
* source of risk characterization - description of

processes, facilities or operational causing or may
cause pollution;
* impact area boundary - determining the spatial
limits of development conceptual model;
* identify pollutants - pollutants or hazardous
substances determining what are or be released into
the environment;
* transport mechanisms - describe physical,
chemical or biological methods for transfer of
pollutants from source to point of exposure;
* exposure points - description of areas in which
an individual may come in contact with pollutants
considered;
* exposure mode - shows the manner in which
pollutants may come into contact with body;
* types of receptors (human or ecological) persons who are or may be affected emissions. For
ecological receptors, they can include individual
organisms, populations, communities or habitats and
ecosystems[5].
Environmental risk assessment for particulate
matter PM10 immission calculation was based on the
results of the activities of the SC Arcelor Mittal Steel
and was conducted both within the SC Arcelor Mittal
Steel and for the border area (including the city of
Galati and the border with Ukraine and Republic of
Moldova) [6, 7].
To obtain an image of the real immission
situations, dispersion particulate matter was made in
several variations depending on the pollutants (total
suspended particulates - TSP and particulate matter,
PM10 fraction, sources and receptors (Table 1).
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Table 1. Prognosis for the dispersion of particulate matter

Case study
Poluant
Point sources
Receiver
Total particulate matter.
baskets MSG
P1-Brila
Total particulate matter
baskets SMG
P2, P3-border
Particulate matter
(PM10)
Baskets MSG+ baskets

Electrocentrale Galai
P4 Movileni
P5 endreni
P6-P10 Galai
Particulate matter
(PM10)
Baskets MSG + baskets

Electrocentrale Galai
+other sources MSG
P4 Movileni
P5 endreni
P6-P10 Galai
2. The methodology used

In this paper we will present only the results
obtained in variant 2, and will be analyzed the impact
on the area of the border with Ukraine and Republic
of Moldova. Map area considered receptors are
present in version 2 of Table 1 are shown in Figure 1.
area sources;
line source;
open cavities;
variable flow multiple sources of emissions.
The model used ISC3 requires hourly
meteorological data records to define the conditions
of transport, diffusion, deposition and cant pollutant
plume. The estimated concentration value or deposit
for each source and receptor combination for each
hour of meteorological data input and calculates
averages specified term. Meteorological data used in
the dispersion Galati particulate matter were
purchased in 2012 from the National Meteorology
Administration- NMA [10].
The annual variation of frequency of the wind
on the ground shows the highest values for NW
direction, followed by SW direction. In Figure 2 is
presented in the winds rose Galati in 2012. Annual
average wind speed on the ground in 2012 was 2.85
m / s, reached maximum values at 10 m/s.
Fig. 1. Map Galati area, including receptors in

the border area
Dispersion model used for particulate matter is
Industrial Source Complex 3 - ISC3 - AERMOD
View, developed by Lakes Environmental Software ,
Canada, and used for evaluation and legislative
regulations in both the U.S.A and in the EU. Model
complex industrial sources (ISC3) allows modeling of
emissions from a range of sources that could be
presented in an industrial activity. On the basis of the
Gaussian plume model equation stand pollutant
plume movement in stable conditions on a rectilinear
direction , the equation used to some changes in point
source emissions modeling , simple, from the baskets
[8, 9].
Emission sources are categorized into the
following basic types:
point sources;
source volume;
Fig. 2. Galatz wind zone in 2012.

For Modeler atmospheric dispersion of
particulate matter were found 60 point sources [11].
The parameters considered were:
source coordinates (XY );
mass flow (g/s);
height cos (m);
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the exit gas temperature (K);

the exit gas velocity (m/s);
diameter of the chimney (m);
Network type receptors uneven cartesian
Number of recipients: 400
Coverage of network receivers 950 Km2
Receptors select: northern limit of Galati and the
border with Ukraine and Republic of Moldova [12,
13]. The averaging period: 24 hours and annually;
Location of the sources, the network considered
and selected receptors are shown in Figure 3.
3. Analysis of results
For immission of total suspended particulates
(TSP), daily maximum concentration values reach a
value of 177.43 mg/m3, measured by the coordinates
(12000, 13000), located inside the plant.
Fig. 4. Map izoconcentratie curves for TSP

(daily maximum values) - the border
Map imissions TSP izoconcentratie curves,
maximum daily values are presented in figure 4.
P2 and P3 receptor, daily maximum TSP
concentration values are presented in table 2.
Fig. 3. Location of the sources, the network

considered and selected receptors
Table 2. Particulate matter- border area

Receiver
Daily maximum concentration,

g/m3
P2
23,50
P3
52,20
Daily concentration limit value PM10,

g/m3
2011
2012
60,34
50
60,34
Note that the TSP to P2 immission limit values

are for both 2011 and 2012, the more than PM10
immission representing a fraction of the TSP.
Where to par P3 is found that the TSP is
immission limit values for 2011 but not for 2012 [14].
For this receptor were detailed analysis was
performed for all calendar days of 2012.
Thus in Figure 5 shows the variation of
concentration of total suspended particulates (TSP).
There are days when the concentration was zero.
Note the exceeding of the limit values for both
2011 and 2012, 2 Days (15/10/2011, 24/12/2012
respectively ) , days when weather conditions favored
the development of these values in the border area
[15].
50
Fig. 5. Changes in concentrations of TSP in the

border area (10000, 1000), in 2012
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Concentrations of TSP distribution function of

frequency (Figure 6) shows that over 90% of the
calculated values are less than 30 g/m3.
Map izoconcentratie imissions TSP curves
(Figure 7), for the fourth value relative to the
maximum daily, 4 receptors each point of the
network, showing no overtaking in any point of the
analysis.
Fig. 7. Map izoconcentratie curves for TSP

(fourth daily maximum value)
For immission of total suspended TSP, annual
concentrations for 2012 amount to 22.01 g/m3, the
point of coordinates (12000, 13500), located inside
Steel Works Galati [16]. Map izoconcentratie
imissions TSP curves, maximum daily values is
shown in Figure 8.
P1 and P2 receptors, TSP are annual
concentration values presented in Table 3.
Fig. 6. Distribution of TSP concentrations

depending on the frequency of occurrence for
the receiver (10000, 1000), 2012
Table 3. Annual concentration total suspended particulates

Daily concentration limit value PM10,
g/m3
2011
2012
Receiver
Daily maximum
concentration,TSP, g/m3
P2
7,4
50
30
P3
6,2
50
30
area, are subject to both 2011 and 2012, much more

as a fraction of TSP PM10.
4. Conclusions
Fig. 8. Izoconcentration map for TSP

(annual concentrations)
Note that the immission of TSP (annual
concentrations) in points considered in the border
As a general conclusion, it is found that there

are very rare overruns in the border area of daily
immission concentrations of TSP (activities due of
MSG), and only when weather conditions are
favorable.
For particulate matter PM10 (fraction of TSP)
immission due to other sources besides standing in
the border area (transport, soil dust, industrial
sources, etc.).
The contribution of the sources of particulate
matter in MSG (and evaluated by dispersion made in
version 2) may result in exceedances of the limit for
24 hours (1 to 2 days per year).
These observations are consistent with
determinations that show daily exceedances PM.
Also in a few days in 2012.
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References
[1]. M. Balanescu, I. Melinte, A. Nicholas, Environmental risk
assessment in metallurgy, ed. Printech, Bucharest, 200.
[2]. M. Balanescu, A. Nicholas, Mathematical models for
environmental risk assessment in the steel industry, International
Conference on Advanced Materials and Technologies, ROMAT,
2004, Bucharest, p. 657-666.
[3]. T. Tibor, A guide to the New Environmental management
Stadards, ISO 14000, 1996.
[4]. D. Sagre, The Competitive, Advantage of Environmental
management, Dolray Beach. St. Lucie Press, 1996.
[5]. Gh. Lzroiu, Dispersion of particulate pollutants, AGIR
Publishing, Bucharest 2006.
[6]. A. Hammer, Selling petty and powdery waste, National
Publishing House, Bucharest, 2004.
[7]. V. Voicu, Air technical iron, Technical Publishing House,
Bucharest 1988.
[8]. S. Constantinescu, L. Orac, The impact of technological
activities conducted at UAF Mittal on the environment,
TEHNOMUS 2013, Suceava, p. 197-202.
[9]. A. A. Poinescu, C. Z. Rizescu, I. F. Popa, A. D. Botea, S.

Teodorescu, Monitoring environmental pollution with heavy
metals from settable and suspended powders resulted from electric
arc furnaces - case study, Proceeding EE'10 Proceedings of the 5th
IASME/WSEAS International Conference on Energy &
Environment, 2010, p. 292-295.
[10]. I. Colda, A. Damian, Dedusting installations and equipment,
Ed. Conspress, Bucharest, 2005.
[11]. Gh. Baran., N. Baran, New solutions for dedusting
installations, Ed. Energy, Bucharest, 1990.
[12]. N. S. Balakrishnan, G. H. Cheng, M. N. Patel, Emerging
technologies for air pollution control, 1979.
[13]. A. C. Hoffmann, L. E. Stein, Gas cyclones and air tubes:
principles, design and operation, Ed. SPVB, Berlin, 2007.
[14]. N. Avram, s.a., Environmental management in metallic
materials industry, Ed. Fair parteners, Bucharest, 2001.
[15]. V. Rojanschi, Environmental Policies and Strategies Ed.
Teora, Bucharest, 2002.
[16]. Northern Environmental, Guide for Small to Medium Sized
Companies, 2000.
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IMPACT OF WASTE DUMP FROM THE INTEGRATED STEEL MILL

PLANT ON ENVIRONMENTAL FACTORS
Anisoara CIOCAN, Tamara RADU

ABSTRACT
European legislation transposed into national regulations has required a new
approach to solve the problems of waste dump from integrated steel mill plant
Galati. This was based on the opportunity to recover the valuable materials, on the
necessity to conserve the natural resources and to find effective solutions to
mitigate their environmental impact. The waste dump management should cover all
activities of collection, transport, treatment, recovery and disposal of waste,
including monitoring of these operations and monitoring of landfills after dump
closure. In this paper is presented the characteristics of the dump from integrated
steel mill plant Galati, its environmental impact and the measures applied to
protect and monitorized the environmental factors at its exploitation.
KEYWORDS: integrated metallurgical plant, wastes dump, environmental
impact
1. Introduction
A long time at start of the work in the integrated
steel mill plant Galati, from the year 1968, all wastes
have uncontrolled been dumped in cone-shaped heaps
that formed a huge dump (on the second place at the
national level). It is placed near of way to Tecuci at 5
km from the town of Galati, on right side, about 3 km
of road (Figure 1).
dump start at elevation +10.00 m, today having a

height of about 50 m, which is not the same
throughout the area, there are sections (fronts) where
the dump starts to be exploited (Figure 2).
Fig.2. View of waste dump
Fig. 1. Image from satellite of lanfill with

location of the waste dump (google earth)
Over the years it has expanded, this goes to
affect an area of approximately 110.8 ha by the
accumulation of ~57 million tons of industrial waste
(approximately 31,462,106 cubic meters, about
68,902,014 tons, considering an average density of
material dumped about 2.19 t/m). Location of the
The land is totally covered with industrial waste:

slag from making sectors of iron, steel and nonferrous
alloys; dusts and sludge; debris and refractory waste;
moulding sand waste from foundry. These are
dispersed throughout the area. There were built eight
fronts for storage and rail or car access.
The dump operation has caused the changes in
the landscape, social impact and visual discomfort.
Also, it has the potential to pollute air, soil and water
environments and landscapes through dust
generation, leachate production etc. To limit the
amount of waste dumped and its environmental
impact, since 1999, ArcelorMittal Galati ceased the
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stockpiling of the steel slag. It was valorized on free

market. A similar decision was taken in regards of
blast furnace slag. From 2007 it no longer get to
landfill, is treated and sold. At present, technological
waste is no longer stored in this waste dump. For this
purpose is an especially designated areas on a platter
landscaped in the west of plant. Consequently,
ArcelorMittal was forced to apply an appropriate
policy environment for a proper management and
finally to close the dumps with rehabilitation of the
area.
Arcelor Mittal Galati has established a global
environmental programme focused in the first stage
on the recovery of waste. The final target is to
greening the space occupied by waste and bringing it
to its original state. Solid waste management has
become a challenge for the efficient and cost effective
to ArcelorMittal Galati. The environmental problems
regarding the exploitation activities was analysed and
an adequate environmental policy regarding the waste
management was applied. In this paper is presented
the characteristics of the dump and the materials
dumped, their environmental impact and the measures
applied to protect and monitorized the environmental
factors.
2. Characterization of landfilled waste

In the waste dump from ArcelorMittal Galati are
different solid waste materials. The solid waste
generated in the sectors of integrated steel mill plant
has been broadly classified into categories: waste
generated from process units; solid waste generated
from pollution control equipment; waste from
maintenance and repair of technological equipments.
The waste dumped are in the form of: slag (blast
furnace slag, LD slag, EAF slag, cupola slag and
other foundry slag); dusts (lime dust, limestone dust,
dolomite lime dust); sludge from gas cleaning plant
(of blast furnace, steelmaking sector) and oil sludge
from cold rolling mill; scale (mill scale from hot strip
mill); debris (from blast furnaces, from steelmaking,
from lime and dolomite masonry fabrication, from
foundry); refractory bricks and lining waste from
furnaces and ladles; steril; moulding sand waste from
foundry of cast pieces and from foundry of iron
moulds.
The
key principles
of
environmental
management for this waste dump can be determined
by more accurate characterization of the deposited
material.
In order it is considering several parameters
such as chemical and physical characteristics of each
group of waste, the quantitative evaluation of of each
type of waste; capabilities of materials recovery, the
distances between source of producing waste and the

storage location etc.
Over the years in this dump (usually named
slag dump), were stored many types of waste that
have the physico-chemical characteristics given
below:
- Blast furnace slag with following average
chemical composition: 33 - 38% Si02, 10 - 12%
Al203, 41- 46% CaO, 3 - 5% MgO, 0.5 -1.4% MnO,
3.1- 3.6% CaS <1% FeO. Blast furnace slag is a solid
material, relatively homogeneous, and processed as
granular or expanded materials.
- LD slag with following average chemical
composition: 10 - 15% Si02, 40 - 50% CaO, 1
2.50% MgO, 1 - 3% P205, 3 7% MnO, 17 - 24%
Fetot. At slowly cooled to room temperature this slag
becomes a solid material, homogeneous, with hard
stone look, sometimes glassy.
- EAF slag with average chemical composition:
40 - 47% Si02, 15 -20% FeO, 20 - 30% MnO. This
waste is in the form of granules or crusts.
- Cupola furnace slag from ingot molds foundry
with following chemical composition: 40 - 50 %
SiO2, 6 - 14% Al2O3, 23 - 35% CaO, 0,4 6% MgO,
0.5 2% MnO, 4 - 20% FeO, 0.1 0.4% P2O5, 0.4
0.6% Na2O, 0.2 0.6% K2O.
- Debris from steelmaking that are silicoaluminous (40 - 50% Al2O3, 37 - 47% SiO2) and
dolomite refractory wastes (about 38% MgO, 58%
CaO);
- Debris from fabrication of lime and dolomite
masonry with 40 - 50% Al2O3, min 65% SiO2, max.
2.5% Fe2O3;
- Lime powder with ~ 82% CaO i 2.1 2.4%
MgO;
- Limestone powder that has ~97% CaCO3, max.
1.5% MgCO3 i max. 0.6% Al2O3;
- Wastes from limestone preparation that are
limestone powder with 59 - 58% CaO, 37.1 37.6%
MgO, 1.4 2.1% SiO2, 0.6 0.1% Fe, 0.9 1.1%
Al2O3 and wastes of dolomite masonry with min.
35% MgO, max. 1.9% SiO2, max. 1% Fe2O3, max.
0.6% Al2O3.
- Debris from ferrous/nonferrous foundry and
ingot molds foundry with max. 65% SiO2 , 2.5%
Fe2O3, respectiv 20 - 34% Al2O3 + TiO2.
- Metallic scrap.
The estimated share of landfilled materials is
following: approximately 47% BF slag; about 30%
steel slag; about 23% refractory wastes and the other
materials. It is estimated that approximately 6.5% of
the total amount of material deposited is the ferrous
and nonferous metallic wastes (5% can be directly
recovered and 1.5% recovered by electromagnetic
separation from slag after its crushing).
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- effects of other industrial activities from

steelworks;
- natural causes: air currents, flooding,
groundwater flow to and from the puddle Malina.
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3. Environmental factors affected by the

existence of the dump and its operating
activities
General aspects of potential pollution sources of
soil, water and atmosphere, can identify as:
- uncontrolled disposal of wastes off-site of
deposition;
- gaseous emissions and particulates from
storage operations of wastes;
- infiltration of wastewater from rainwater that
percolats waste dump or drains on its slopes
- effective storage of waste and unauthorized
activities conducted on and near the dump, movement
of vehicles and operation of machines, etc.;
3.1. Air pollution

The main sources of air pollutants are operating
activities of materials from dump and the operation of
equipments/vehicles used for this purpose
(bulldozers, excavators, dumpers, and loaders).
Pollutants emitted into the atmosphere from
equipments have not a significant impact on air
quality. They are assessed in accordance with their
operating time and fuel consumption (Figure 3).
a.
b.
Fig. 3. Image from exploitation works of dump: a excavation; b - loading

In windy periods, especially during tipping
waste dump slopes, particulate emissions occur. The
dispersion of suspended particles depends on
meteorological factors such as wind and atmospheric
temperature. The particulates are carried away and
setteld on surrounding areas of dump, many of them,
agriculturally cultivated. The the location of areas
polluted with dust settled and the level of pollution
are manly influenced by wind direction. Especially
the particles are carried away by the wind from the

north to the villages Sendreni and Movileni.
Sometimes the particles carried by wind are
directioned to Galati county.
Also, the dispersion of suspended particles
depends on technological factors of operations for
valuable materials recovering (Figure 4). Combustion
emissios and solid particles entrained by air flow
easily cross the area of dump.
Fig. 4. Particulates suspended by technological activity at materials procesing
3.2. Soil and subsoil pollution

The storage of the wastes over many years and
current mining exploitation lead to major changes of
landscape and configuration of soil morphology.
The extraction works require the dislocation and

transport of large quantities of materials inside of
dump. As result, new areas are in constant change
along of exploiting period (Figure 5).
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Fig. 5. Soil pollution in terms of morphology by

exploitation activities
The past dumping operations and actual
subsequent operations for closing and recovery of
iron containing materials are activities that affected
large areas of land. The water leakages on the slopes
lead to flooding of new areas (Figure 6). This water is
an important transfer vector of pollutants (heavy
metals are most significant) from wastes to soil,
subsoil and groundwater.
The dump and specific activity taking place on

its site does not generate wastewater. However as was
mentioned before, rainwater can percolate the
material piles, and by infiltrating the soil reaches as
groundwater to puddle Malina. Also, the water drains
on the slopes of the dump washing them and, finally
ending in puddle.
Also, the water inflitred on the height of dump
or drained on its slopes is an important transfer vector
of pollutants (heavy metals as chromium, lead, zinc,
and nickel and oil and grease are most significant) to
groundwater.
Dump stability is affected by the occurrence of
landslides and cave-ins (Figure 7) at water imbibition,
charging of upstream party, failure or exploitation at
the leg of dump.
The anthropogenic vibration generated by
equipments operation, explosions or earthquakes can
have a similar action.
Fig. 7. Landslides and cave-ins in the dump

Fig. 6. Soil polluted near the dump by meteoric
waters that drain the slopes of deposit
3.3. Water pollution

The infiltration of technological wastewater
downloaded in the clarifiers ponds Malina and from
rainwater that percolates the landfill is the main
source of groundwater pollution.
The granulometric structure and chemical
composition of material deposited make possible the
infiltration of rainwater to groundwater. The
movement of groundwater is dependent of water level
fluctuation in puddle Malina and of rainfall regime. In
the periods with low water levels of puddle or during
of abundant rainfall on the dump surface, the water
moves from dump to water of puddle Malina,
carrying and discharging the pollutants as suspended
solids, dust, lubricating oil, and other pollutants
depending on the composition of wastes landfilled. In
the periods of increasing of water level in puddle
Malina and without the abundant precipitation in the
dump area, the groundwater movement is reversed,
and the transport of pollutants from the puddle
Malina to the underground of dump content is
favored.
For entire wastes dump the stability increases as

long as excavation work is performed in rungs in
accordance with the respectarea of excavation angles.
It is important to note that at increasing of the
material height its stability decreases and also
increase the efforts in the field of foot rung.
When height and deposition angles increase the
landslide at the top (overload zone) can occur.
On side dump from connection canal between
northern and southern parts of puddle Malina is
observed the pollution of soil located near the dump
by rainwater that drain the slopes of dump (Figure 8).
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Fig. 8. Soil polluted near of the dump around

puddle Malina
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3.4. Impact on vegetation and fauna

The pollution generated by waste dump leads to
biopedologic changes. The soil fertility and
composition biocoenoses on the surrounding fields
are changed. The effects on vegetation and fauna will
persist on long term and after rehabilitation of the
area occupied today by wastes.
The emissions of pollutants that can affect
vegetation and fauna in this area are: the dust
(particulate matter) resulting from the transport and
storage of wastes; gas emissions from equipments
that processing and transports the materials in the
landfill.
The wastes dumped removed the natural
vegetation from at large areas, Figure 9.
Fig. 9. Destroyed vegetation in the dump and

surrounding areas
3.5. Impact on human settlements in the

vicinity of the dump
The dump is located in the west of the Galati
city, on plant platform, in its western part, at about 3
km from inhabited areas, at about 50 m of puddle
Malina and at about 2 km of the ways of
communication. It is neighboring to north, west and
south Balta Mlina and to east with the way to
commune endreni. The dump starts at elevation +
10.00 m (above sea level). It is located on a plateau
between the valleys Ctua and Mlina and the
farmland of villages Smrdan and Movileni. The
activity recovery of materials from landfill
settlements does not affect the neighboring human by
emissions of gaseous pollutants, particulate matter
and noise pollution. Over the years, when the landfill
was used, the industrial waste accounted a health risk
because of their toxic substances contained in these
such as heavy metals (lead, cadmium).
4. Measures for the protection and

monitoring of the environment
To minimize environmental impact, the
integrated metallurgical plant was obliged to comply
with all environmental laws and regulations and
develop appropriate environmental strategies.
The programs include measures of ecological

recovery that could be grouped into legislative and
technological.
The management and closing activities of dump
with recovery of metallic scrap impose certain
measures for reducing of environmental impact.
These include: operating measures for maximum
restriction of its limits; measures for dump
stabilization, made both during its operation and after
the release of waste from dump; monitoring measures
(issues related to precipitation, temperature of
leachate collected, water collected from the areas
covered with wastes, surface waters in the vicinity of
the landfill, gaseous emissions, groundwater,
compaction of body dump); technical and operational
measures to cessation of activity in mining areas;
remedial action for rehabilitation of damaged natural
resources; specific measures for dump framing in the
zonal landscape structured into operational phases of
exploitation and post-closure; solutions for total
desilting of the channel Mlina-South Mlina and
restoration of specific natural ecosystem; designing a
system for leaking and dump gasketing and
presentation possibilities of monitoring their;
implementation and compliance of monitoring
procedures afyer dump post-closure.
Regarding mining operations to recover the
metallic scrap by dumped wastes processing
(crushing, separation, transport etc.), the adopted
program
includes
specific
measures
for
environmental protection.
To reduce air pollution during operation will
take the following measures as filters at processing
equipments to reduce the dust emissions, spraying
with water on transport roads during summer etc.
For vibrations reducing and monitoring of their
effects on the dump will taken specific measures.
As regards the reducing environmental pollution
of water, to ensure the stability and the safety of the
dump and activity from dump are recommended to
make the embankments for contour and subdivision
in the ponds Malina North and South. It requires
special attention to water management on the surface
of the dump, especially in excavated depression areas.
So is eliminated the ponding that is a contributing
factor for water infiltrations in the dump body. Also it
is recommended the compacting and leveling the area
from foot waste dump, over the whole surface,
avoiding the creation of vibration during excavation.
The measures are taken to avoid the landslide due the
small slope angles.
The evaluation of soil characteristics for the
wastes dump area showed that due to mining and
dumping activities of material after metallic scrap
extraction, soil has.
The dump surfaces require ecological
reconstruction works to improving the soil quality for
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their integration into the natural area (arrangement of

terraces, addition of soil, seeding of vegetation etc.).
References
[1]. T. Dinu, Impactul de mediu al depozitului - halda de zgur i
posibilitatea de ecologizare a acestuia, Lucrare de disertaie,
Universitatea Dunrea de Jos din Galai, 2013.
[2]. Cl. Popescu, Industria Romniei n secolul XX. Analiz
geografic, Ed. Oscar Print, Bucureti, 2000
[3]. Cl. Popescu, Zonele miniere defavorizate din Romnia.
Abordare geografic, Ed. ASE Bucureti, 2003.
[4]. *** Legea nr. 350 din 6 iulie 2001 privind amenajarea
teritoriului i urbanismul, Monitorul Oficial nr. 373 din 10 iulie,
Bucureti.
[5]. *** Legea nr. 351 din 14 mai 2001 privind aprobarea planului
de amenajare a teritoriului national.
[6]. *** Raportul Comisiei pentru Administraie Public,
Amenajarea teritoriului i Echilibru ecologic al Parlamentului
Romniei, Bucureti, 2000.
[7]. *** Sectorul privat al intreprindelor mici i mijlocii. Raport
anual, ANDR, 2000.
[8]. *** Carta verde. Politica de Dezvoltare Regional n
Romnia, Bucureti, 1997.
[9]. C. Horaicu, Monitorizarea integrat a mediului, Ed. Tipo
Moldova, Iai, 2009.
[10]. V. Munteanu, Calitatea mediului, Ed. Fundaiei Universitare
Dunrea de Jos Galai.
[11]. D. A. Humelnicu, M. Puanu, Arcelor Mittal's Industrial
Waste Management, Lucrrile seminarului geografic Dimitrie
Cantemir NR. 32, 2011.
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LOW ENERGY CONSUMPTION OF AN MODERN

ECOLOGICAL HABITAT
Stefan DRAGOMIR, Maria VLAD

email: sdragomir@ugal.ro
ABSTRACT
There is a trend toward a rapid development of houses passive and in other
European countries due to the fact that these homes are of a particularly healthy
and eco-friendly.
European Union has developed a few directives, among them "The energy
performance Directive" that each member country of the European Union should
adhere.
In these directives are provided obligations for better thermal isolation of
buildings old and new, used of environment-friendly technologies and construction
of passive houses, in the place of classic building.
The Government of Romania [1] had to comply with European trend and
legislation so that he is granted subsidies for renewable energies. For heating and
cooling this houses used renewable sources. These renewable sources are solar
cells, photovoltaic, wind system. Outward eco House is well insulated because use
windows with three sheets of window and sun protection, ensuring a healthy
environment for life, without thermal differences in the same room.
KEYWORDS: renewable energies, passive house, intelligent system for waste
management
1. Introduction
A passive house is a human habitat without
conventional heating system (heating with methane
gas or electrical energy or wood), that do not
eliminate noxious in the atmosphere.
A standardized passive house has an external
enveloped very well thermal isolated. The windows
are made from laminated wood. In fact a lot of layers
of wood is laminated together and the result is a very
thermal resistant material.
For heating this type of house has an integrated
ventilation system, which eliminates vitiated air from
the building and he passes through a heat exchanger.
This heat exchanger retrieves a part of the thermal
power by transferring it to the incoming fresh air
outside of home. This type of houses is built now in
Germany, Austria, Switzerland and Sweden. At the
modern passive house the systems that are used for
preheat fresh air outward.
This air being brought in the building via the

piping buried in the ground by using the heat that is
take into the ground.
Modern passive house represents a new way of
approach to the construction of houses on the
skeleton of wood. It is a modern house, which was
carried out on the structure of wood and the walls
from prefabricated modular materials.
Can be carried out in the variant -efficient heat
shield - (a heat coefficient for the walls of 0.18
W/m2K) or for the passive house (a heat coefficient
for the walls of 0.12 W/m2K).
It can build the house in the limits of initially
budget and extension in time, according to needs and
in the light of financial opportunities.
On the first stage of the design shall be taken
into account the possibilities of future enlargement
and provide elements which allow for 'connecting' the
house parties, in a short period of time (1-2 weeks)
with a minimum of clutter.
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kWh/m3year
45
40
35
30
25
20
15
10
5
0
Country
Fig. 1. The consumption of energy for building hitting in C.E. country [1]
Fig. 2. Modern passive building on wood structure [1]

For each insulating layer heat flow can be
written with relationship:
2. Research on the heating system of

passive houses that uses renewable
sources of energy
q=
A passive house needs only a very good thermal

isolation and an efficient system of ventilation with
intercooler [3]:
Ti
Ri
1.1)
Where: Ri are the thermal resistance of n
layers.
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Equivalent thermal resistance of one

inhomogeneous construction element with several
layers perpendicular to direction of the flow heat
shield is:
R =
T
q
(1.2)
Or using relationship (1.2), we can write:
R =
T1 + T2 + +Tn
= R1 + R2 + + Rn
q
For a passive house we can use performing

(ecological) materials for thermal isolation
(enveloped) of building are sowing in table no. 1.
Table 1
Types of
material
U/M
CELLULOSE
PULP
BASALTIC
MATERIAL
MINERAL WOOL POLYSTYRENE
inorganic/synthetic organic/synthetic
organic/natural inorganic/synthetic
Quartz sand, soda,
Styrole (din
95 % Diabas, basalt i
90 % recycled
petroleum),
5 % liaison material, borax, sodium sulphate
Components
paper,10 % bore
phenolformaldehydharz, phenolformaldehydharz, benzyl, pentane,
salt
petroleum
petroleum
brome
Mechanical properties
Thickness
mm
20 400
20 200
20 240
10 400
Density
Kg/m
30 80
30 90
14 50
10 20
Pool
N/mm
0,0007 0,8
0,005
0,15 0,52
resistance
breaking
N/mm
0,00012 0,0075
0,005 0,015
0,09 0,22
strength
Thermal properties
Thermal
2
0,037
0,035 0,040
0,035 0,040
0,035 0,040
W/(m K)
conductibility
For most of the year this leads to the
maintenance of constant temperatures in the interior
of the house, without the need for other heating
system.
In the winters with extreme low temperatures (20 oC) there is a need for an active heating element
(radiator electrically with oil, etc. ) but one of power
very low, so that even in conditions of extreme
minimum temperatures in the house passive
temperature will be one comfortable.
Typically, the investment used to implement a
system of effective classic heating it will be used for a
better thermal isolation of windows and exterior walls
and for better ventilation of the house interior.
The heating system, ventilation and airconditioning are focused on the use of renewable
energy sources. In the first place, in order to cut down
energy consumption provides for use of a heat
exchanger placed in the soil. In winter it takes thermal
energy stored at the ground and using it for air preheating freshly inserted into the flat.
In the summer, the air was taken from the
atmosphere and inserted into the flat is in pre-cooled,
by passage through the same heat-exchanger in the
assembly.
To ensure that a building can be categorized by
Passive House Institute like a passive house, it is
made a research of demand for thermal energy for

heating. The passive house space, must necessity less
than 15 kWh/m2/year (this corresponds to combustion
of less than 1.5 l of petrol/m2/year) to be a passive
house.
In this way, energy demand for heating house
liabilities is about ten times smaller than in the case
of a conventional house.
Secondly, there should be provision for use of
solar energy for heating water bins. The fluid is
heated, in solar receptors located on the roof building
and is then directed to a storage reservoir. In this tank
is taken over heat required at the time of the wishes
hot water consumption.
Everything here can be taken over by heating
and for air heating announced by ventilation system,
in the case where it is necessary to this intervention.
Fresh air (which in winter can have for example
temperature of -10 C) is first drawn from the outside,
filtered and then introduced into underground
exchanger of the heat.
Soil temperature at a depth of 2 meters varies
between 7 and 10 C even in the cold weather season.
As a result, after exit from air exchanger may have
temperature of about 7 C.
In collector heat, in counter-current, over 80%
of vicious heat content of the air flow, which comes
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out of the building, it is transferred to the air flow. In

this way fresh air is heated to approximately 18 C.
A heater system [4] consists of a doubled burned
with a heat exchanger supplied with hot water. First
component comes into action only when there is
available hot water. After exit from fresh air heater
has desired temperature, usually at approximately 40
C. Air is then circulated through the pipes that pass
through the inside insulated chambers up to nozzles
of relief.
Due to transfer of heat by conducted transients
and radiation on this path the air penetrates the rooms
at a temperature between 20 and 22 C. Vitiated air is
extracted from the kitchen and the bathroom and
constitutes in collector, in fact, a heat source for the
air fresh.
Collector of the output of vitiated air at

temperature of about 7 C, and it is cooled to about 1
C in a small heat pump. Energy recovered here is
sent to the storage reservoir of the thermal power.
The other source of heat for this tank is made up
of the system to capture the solar energy. If neither of
these two sources is not able to supply energy needed,
the tank has to have a electric heater or using other
sources conventional of energy.
Another limit imposed on a passive houses
refers to overall energy consumption conventional
obtained, directly or indirectly, on fossil fuels (which
includes energy for heating the home, formulation hot
water, lighting, commissioning of the equipment
electrical, etc.) which does not exceed 122
kWh/m2/year. (figure no. 3).
Fig. 3. Solar energy heating system [2]

In the event of a draft a dwelling proves that
these two energy limits are not exceeded, German law
granted important economic facilities of owner.
Consumption of heat measured of the first passive
houses constructed in the country was less than 16
kWh/m2/year. A safe way to supplement the
electricity necessary to the household equipment

functioning is to use photovoltaic panels mounted on
the roof of the passive house.
Thermal load to a normal building is of the order
of 10 kW to 100 m2 habitable surface, which means
approximately 100 W/m2. Standard insulated heating
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systems used are the same in more than 80% of cases;

they shall consist of heaters with water or oil, pipes
and radiators.
Can be shown quite easily that the thermal load
of the building is less than 10 W/m2, the heat required
can be transmitted using only ventilation system. This
is the idea which is at an essential basis of the
"passive houses" to which heat losses are reduced so
much that it is no longer required a separate heating
system.
Depletion of reserves of conventional fuels, the
effects of pollution due to their use and the progress
in using renewable energies are a permanent incentive
to the creation of new energy technologies. This
allows to the limits of 122 kWh/m2/year to be
included new consumers energy industry (such as, for
example, the air conditioning systems used in the
course of season hot), which are usually more
difficult can be accessed via a 'houses' usual passive,
although it can be integrated also solar solutions for
cooling in addition to general compliance of the
building.
Domestic hot water preparation can be the
greatest consumer of energy in a passive house (about
80% of the total requirement of heat). Because this
operation requires only ensure that average
temperatures, can be easily accomplished through the
use of renewable energy such as solar energy.
Fig. 4. The wind system (with propeller) used for

electrical energy production [4]
Another source of renewable energy be taken
into account is that of the soil, it can serve and the air
pre-heating freshly what is entered into the flat.
A passive house standard exterior envelope
contains a very well insulated (usually at least 10 cm
of expanded polystyrene high-density of 30 kg/m3),
windows from laminated wood with three layers of
glass and a ventilation system integrated which
eliminate vitiated air from the inside, It passes

through a heat exchanger which recovers a part of the
thermal power by transferring it to fresh air coming
from the outside into the house.
For a passive house, in addition, we can use a
wind system to produce electrical energy (figure no.
4).
The second element of a passive house is the
heating system that is replaced by a simple ventilation
system, but smart, whose costs do not raise much
above costs of a heating classic system.
So we get loss much less power when we
ventilated house (less than warm air to the outside)
and more comfort in the interior (less cold air
entering into your home).
Passive houses are reflected in construction of
houses, villas, boarding houses, holiday homes,
modern residential neighborhoods, offices, shops,
warehouses. Can be build in areas of earthquakes,
floods and hurricanes frequent with (0-10 %) above a
price of construction for conventional houses.
It is to be noted that if they increase step scoop
(and the angle of inclination), increase the power
provided by wind turbine.
There's some additional costs (thermal isolation
in addition, frames at the window, and triple window,
the ventilation system particular seal and the
implementation of the tire perfect dwelling), which in
fact are compensated for the savings obtained by
eliminating heating system.
Invoice cost of energy will be of 5 to 10 times
less than in a conventional house.
Another advantage undeniable of building a
passive house is the quality of materials, there is no
condensation and undesirable molds and, factors that
extend the life of the building with a tens of years
compared with a conventional home.
Speed of construction of the house is very high,
so that your investment is dampened much faster than
in a classical building, and the quantity of labor is
reduced significantlyIn conclusion, passive house is
defined by two basic elements: to envelop of the
building very well thermal isolation and the missing
of classic heating system.
A passive house needs only 10-15 kWh/m2 per
year, or the equivalent of a maximum of 1.5 m3 of
natural gas or 1.5 liters of fuel oil per 1 m2 for the
heating surface per year.
It shall be reduced with 10-20% the
workmanship of house execution, both to the
structure, as well as the finishes that are much easier
to be performed, as compared with construction of
conventional type.
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Power (Hp)
Wind speed (mph)
Fig. 5. Power curve to a wind turbine

Another important advantage is the high speed
of construction of the house. That is between 3-5
months (foundation, walls, a layer of plaster on the
outside, windows and exterior door, magnificent
residence, section of metal roof).
For construction is not necessary heavy
machinery and equipment of buildings.
3. Conclusions
A passive house is a dwelling which does not
eliminate noxious gases and which do not require a
auxiliary heating system (on gas or electric current).
Thermal energy is supplied by a ventilation
system that picks up the air from the outside of the
house and then this air is constitutes in collector, in
fact, a heat source for the air fresh condensed that
ensures the thermal comfort of the dwelling.
Passive houses are completely independent
energy that uses alternative energy systems,
unconventional and renewable energy sources (solar
panels, photovoltaic panels, wind energy, heating
pomp system, radiant panels).
This type of house offers habitable conditions
very comfortable and healthy, both in winter and
summer.
Those that suffer from various allergies (current,
dust, asthma, etc.) may without any problems to keep
the windows closed in spring or autumn, because
your home is permanently supplied with fresh filtered
air.
The system provides resistance to moisture and

rotting. Waters from flooding does not penetrate the
walls and the construction material used does not
absorb more than 3% moisture. Outer walls are 50%
more resistant to weathering than the walls of brick
classics. Condensation is eliminated inside of house
because the dew point is moved 100% outside
building. The system supports any type of interior and
exterior finishes. How to perform passive house
offers very good stability to hurricanes, storms and
strong winds and earthquakes. Passive House
architectural design allows for an unlimited. The
building costs shall be detected by the reduction with
85% of the costs of heating costs in the winter and
cooling costs in the summer. Due the protected
casting of concrete, passive houses can be constructed
in cold weather (about -5 oC). Longevity and
durability of construction is much higher than the
conventional systems.
References
[1]. Ministerul Mediului i Dezvoltrii Durabile (MMDR)
http://www.mmediu.ro.
[2]. Passivhaus Institut Darmstadt, Germania http://www.passiv.de.
[3]. M. Vlad, T. Radu, O. Mitoseru, F. Potecasu, Environment
Quality Improvement at Hot-dipGalva nisation and the Recycling
of ZincBy-products, Journal of Environmental Protection and
Ecology 12, No 3A, 14151423, (2011), ISSN 1311-5065.
[4]. Teodor Miroslav Muntean, Copyright2008 AustrocasaSr,
lhttp://www.austrocasa.roIai.
[5]. http://ec.europa.eu/europe2020, Europe 2020: a new economic
strategy.
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BIOMASS AS MAIN RENEWABLE SOURCE FOR BIOFUELS

Liliana ONEL
Saint Mary High School of Galati
email: ionelonel@yahoo.com
ABSTRACT
Organic substances produced by the metabolism of living organisms is the
biomass. This can be used as a resource for biofuels. Biodiesel is an alternative fuel
that can successfully replace natural oil, is an ideal choice, by being biodegradable
and non-toxic for the environment. Research aimed biodiesel from vegetable oils
such as the sunflower oil. A complex process can be carried out in three steps: first
using an acid, the second using a base, followed by washing, the final step.
Initialization is based on the fatty acid content of the used oil, but could equally be
that of some animal fats / vegetable waste, regardless of its content more or lower
of fatty acids.
KEYWORDS: biofuel; biomass; biodiesel, sunflower, trans-esterification
1. Introduction
Biomass represents the most abundant
renewable resource on the planet. It includes
absolutely every organic substance created by the
metabolic processes of living organisms.
Biomass as a source of alternative energy
currently amounts to 14 % of the global consumption
of primal energy [1].
At the present time, the energy sources are
represented by fossil fuels (oil, natural gas, coal),
radioactive compounds or other sources (the Sun,
hydroelectric, wind power, and tidal power) which
aids in the production of mechanical work and heat.
Among these, oil and natural gas are declared to be
the main energy sources of the planet. These natural
resources are irreversibly exhaustible [2]. The
estimations made on the level of current global
consumption and on the evaluation of the inventory
of fossil fuels, shows that these might be used for
another 44 years (the oil), another 62 years (the
natural gas) and another 280 years (for coal) .Fossil
fuel reserves are irregularly distributed around the
globe and the exploited quantity increases with each
passing year. Therefore we have to pay a considerable
amount of attention to biofuels created by biomass.
Biomass can be used as a resource for producing
befouls, and an increase of their use will modify the
level of the biomass used as a raw material and the
level of implicit transformation technologies [3].
On a medium and long term, the increase of the
biomass quantity can be guaranteed by plantation
(fast-growing trees and shrubberies) on degraded or
set aside plots of land, and also, by the integral

development of the existent resource, oleaginous
plants processed into biodiesel and the energetically
revaluation of the remains of the plant, glycerol and
waste collection [4].
Biofuel represents a liquid fuel source which is
completely recoverable which can be used as an
alternative to fuel made with oil. The usual sources of
triglycerides used for obtaining biodiesel fuel
represent vegetable oils and animal fats. The most
common vegetable raw material used are soybeans,
canola, sunflower, cotton seeds, colza seeds, castor
oil seeds, peanuts. In the present time, there are
promising studies about new sources of raw
materials, like kelp or mustard.
It is a yellowish translucent liquid, with a low
miscibility compared to water. It has a high boiling
point and a low steam pressure. The common
biodiesel fuel, methyl ester, has an ignition
temperature of 150 C, thus making it less flammable.
Its density is of 0.86 kg/cm3 and it is considered nontoxic if it hasnt been contaminated with its raw
materials [5].
2. Processes and technologies for biodiesel

obtaining
Biofuels are composed of alchohol, ethers,,
esters and other chemical substances obtained from
celulose biomass, such as various plants, residues
originating from lumber exploitation and farming,
and also a large part of industrial and municipal
residues. Used in the greater European area, biofuels
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can be found in three states: biodiesel, bioethanol,

and pure vegetable oils. Chemically-speaking,
biodiesel is a mix of mono-alchil esters of fat acids,
obtained usualy through transesterification of
triglycerids with an inferior alchohol.
Technically-speaking, biodiesel is a methil ester
of a fat acid. It is usually obtained through the
reaction of lipids (triglycerids) with a primary
alchohol (methanol) and a base (sodium hydroxide).
This process is called base catalysis.
Triglycerids + Methanol
base
Methil ester +
Glicerine
Oil
The latter reaction, known as transesterification,

leads to the formation of biodiesel and glicerin in a
volumetric raport of 10:1. If the prime ingredients
contain high values of free fat acids, the process of
acid cathalysis is recommended instead of the base
one. The most common method of obtaining biodiesel
is trans-esterification. The starting points are
vegetable or animal oils and methanol. The reaction
takes place in the presence of a catalyst, usually a
base, and the obtained product is a methyl ester of fat
acids in the oil. The trans-esterification reaction is
reversible and moderately exothermic.
The process schematics of a base transesterification flux is showed in figure 1.
Methanol
Biodiesel
The first stage of the process is the

discontinuated introduction of the alchohol, vegetable
oil, and the catalyst in an energetic-mixing reactor.
Usuall, the reactor is heated to under the boiling
temperature
of
the
alchohol
used
for
transesterification. As soon as the reaction is
complete, the products are separated. The biodiesel
layer foams up above the glycerin layer. In both
layers there we can still find impurities that need
multiple stages of purification. The level of purity
depends on the source of the raw material, because
refined oils have less impurities than residual fats and
oils. With biodiesel, they can be easily mixed with
water employing through multiple means, such as
mixing or spraying. When water is introduced to the
biodiesel, it sinks under the surface, below the latter,
because of its higher density and its inability to
disolve.
The study of the trans-esterification reactions
kinetic characteristics with sodium hydroxide as a
catalyst, the molar ratio oil/methanol of 1/6 and at
temperatures between 50 and 65 oC showed that the
reaction has a global kinetic order of 2 (order one
compared with each reactants) [6].
The reaction develops quickly in the first 10-13
minutes and then it evolves slower, reaching its
equilibrium after a couple of minutes, depending on
the used proportion of the catalyst and the
temperature. For example, to a molar ration of 1/6 oil/
methanol, a quantity of catalyst, respectively sodium
hydroxide representing 0.3 % of the reactors quantity
and a temperature of 60 oC , the necessary time for
reaching the maximum conversion is two hours.
When increase the temperature with 10 oC that
leads to increasing with about 2.5% of the reactions
Glycerine
speed. Experimental studies of the decantation of the

glycerol phase showed that in almost 30 minutes,
most of the glycerol resulted in the process separates
itself.
Depletion of the remaining methanol into
biodiesel fuel after the reaction (0.5-5%) takes only
one theoretical segregation equilibrium.
Water washing of the biodiesel for removing the
alkalinity and the glycerol traces is an operation that
can create big problems because of the formed
emulsions. Glycerol traces and alkalinity that the
biodiesel fuel contains can be removed by washing it
with demineralised water in 1-2 stages, depending on
the level of the impurities, to the volume ratio water:
biodiesel fuel of l/4l/3.
The experiments showed that centrifuging a
sample of raw biodiesel, alkalinity and the glycerol
content can decrease to values of 0.1% to 0.004% for
relative centrifugal forces of 7000-9000 [7].
Drying the biodiesel fuel requires a theoretical
segregation equilibrium and it can be done in vacuum
300-400 torr abs. and temperatures of 120-150 oC.
Raising the acidity of the oil leads to rising of
the glycerol phase quantity which, besides glycerol,
also contains soaps and solubilised biodiesel as a
micro emulsion. Researches showed the possibility of
purifying biodiesel fuel with absorbents. In this
operation the catalyst trades (NaOH), soaps, glycerol
etc are removed from the biodiesel fuel.
One-step purification through absorption is
efficient if absorbents that amount to about 5% of
biodiesel are used and if it has the maximum
alkalinity of 0.5 mg NaOH/g.
This can be achieved by working with fresh oil
extracted from adequately-kept seeds, the oil being
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stored under a nitrogen blanket. These procedures

ensure a low acidity of the oil, which makes it easier
to process. Also the amount of water in the raw
materials and the quantity of the catalyst has to be as

low as possible also ensuring that the reaction time is
kept under reasonable limits.
Fig. 1. The block diagram of basic trans-esterification

Research showed that raising the temperature
disadvantages the final conversion with its influence
on the equilibrium constant. At the same time, is has
been proved that raising the methanol/oil molar ratio
leads to speeding up of the conversion through its
influence on the equilibrium constant [8].
The proposed technology for obtaining biodiesel
fuel includes the following main stage:
- the trans-esterification reaction;
- recovery of the unreacted methanol;
- segregation of the glycerine phase;

- purifying the biodiesel fuel;
- drying and filtering the biodiesel fuel.
For the reaction an amount of 0.3% NaOH
catalyst is proposed, calculated with respect to the
weight of the total mass of the reactants, over the
necessary amount for neutralizing the acidity of the
oil.
Working at a temperature of 60 oC, the
necessary time for a complete reaction is two hours.
Fig. 2. Continuous biodiesel production process
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Feeding the fuel necessities of the busses with a

diesel- biodiesel mixture (5-20%) led to the following
conclusions: the fuel consumption is raised by about
3% because of the lower calorific power of the
biodiesel given by the oxygen content in the
molecule. Also, the opacity coefficient of the
discharged gas decreased with about 20%.
Peterson and his collaborators study present an
example of a continuous process of obtaining
biodiesel, fig. No. 2.
The advantages of using a continuous process,
compared to a discontinuous one, include a reduced
production time and cost, as well as obtaining a
significant quantity of biodiesel.
3. Experimental research
3.1. Preparing the biodiesel fuel starting
with sunflower oil
Fats represent one of the most important natural
sources of prime material for the obtaining of
biofuels, having the advantage of regenerating in the
natural cyclic process of plants and animals from
which they originate, figure No. 3. Fats are,
chemically-speaking, esters of glycerin with saturated
and unsaturated carboxylic acids, and in some cases
with hydroxi acids, having an even number of carbon
atoms.
Fig. 3. Basic technological scheme for biodiesel production

The recipe is a complex procedure taking place
over 3 stages: the first one using an acid, the second
one using a base and the third one based on washing
of the biodiesel. The initialization is made according
to the fat oil content from the used sunflower oil, but
in equal measure can it be the ones of
animal/vegetable residual fats, indifferent of their
content of fat acids.
First stage - using an acid as a catalyst:
- Oil/fats volume which are about to be
processed is measured in litres;
- Raw material is heated to 55 C, creating
conditions for all the solid fats to melt;
- Measuring and adding 0.1 litres of methanol
for each litre of fat/oil (10% volumetric dilution).
Methanol has been about 6 minutes, until a reaction
occurred because of the intervention of polarity
modifications (methanol is a polar compound,
glycerine is strongly apolar), and precipitations
appeared in the mixture.
The second stage -using a base as a catalyst:
- The mixture is heated again to 58 C, making
sure that every solid fat has been melted;
- Other half of the NaOH solution is added,

mixing continuously for about an hour, with a
constant, low speed;
- The mixture is left to decant about 10 hours;
- After the segregation of the glycerine, the
biodiesel fuel is obtained.
Washing the biodiesel- the final stage:
- pH of the fat acid of the methyl ester is
measured;
- The acid is poured in a vase mixing it with an
equal or halved quantity of water, to wash it;
- Water pH has to be much lower than 7 because
the value of the methyl-ester pH is higher than that.
Reducing the water pH can be done using acetic acid;
- Using compressed nitrogen to create bubbles in
the vase with the methyl-ester and water mixture. The
procedure lasts for about 6 hours.
The internal perturbation (similar into boiling)
will lead water towards the surface. When the water
will exhibit the tendency to fall back to the bottom, it
will attract all the impurities (soap) and the excess of
the fat methyl-ester (FAME), allowing the acetic acid
to neutralize the remaining layer. After about 14
hours of decanting, the water will gather to the
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bottom of the vase, turning white. The biodiesel is

now of much greater purity.
4. Conclusions
1. Biomass is the fourth largest energy source
worldwide, following coal, oil and natural gas.
2. Biomass offers significant advantages as a
raw material for combustion, due to the high volatility
and high reactivity of the fuel and the resulting ash.
However, it should be noted that, in comparison with
solid fossil fuels, biomass contains less carbon and
more oxygen and it has a low heating power.
3. The use of biomass as an alternative energy
source to obtain bio-fuels, including biodiesel,
remains a valuable option with good prospects in
practice despite the high production costs.
4. Biodiesel is a much more efficient fuel, with
lower CO2 emissions than petrol-based diesel.
5. Ordinary sources of triglycerids used to
obtain biodiesel are vegetable oils and animal fats.
6. The type and composition of fat acids in the
prime ingredients determine a series of properties of
the obtainable biodiesel. For example, of the prime
ingredients is mainly consisted of saturated fat acids,

the obtainable biodiesel will have a high octane mark.
7. Biodiesel represents a completely regenerable
liquid fuel source that can be used as an alternative to
petrol-based diesel.
References
[1]. Chum H. L., Overend R. P., Biomass and renewable fuels,
Fuel Processing Technology 71, 2001, 187195.
[2]. Demirbas A., Recent advances in biomass conversion
technologies, Energy Edu Sci Technol 2000; 6:1941.
[3]. Demirbas A., Sustainable cofiring of biomass with coal,
Energy Conversion and Management 2003; 44:146579.
[4]. Demirbas A., Combustion characteristics of different biomass
fuels, Progress in Energy and Combustion Science 30 (2004) 219
230.
[5]. Burnete, N., Research concerning the Diesel engine using
vegetal oil as fuel, In vol.: FISITA, World Automotive Congress,
Barcelona, Spain, 23-27 may, 2004, Paper Reference Number:
F2004V047.
[6]. Dizge N., Aydiner Imer C. D. Y., Bayramogly M.,
Tanriseven A., Bioresource, Technol., 100, 2009, 1983-1991.
[7]. Naik S. N., Vaibhav V. Goud, Prasant K. Rout, Ajay K.
Dalai, Production of first and second generation biofuels: A
comprehensive review. Renewable and Sustainable Energy
Reviews 2010; Volume 14 (2): 578-597.
[8]. Dragota D., Moisescu V., Biocarburanii n Romnia,
Ministerul Educaiei i Cercetrii, ISBN 9738702321.
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COOLING SYSTEM DESIGN BASED ON THERMAL STORAGE

FOR PUBLIC TRANSPORT BUS
Octavian POTECASU, Florin Bogdan MARIN

email: florin.marin@ugal.ro
ABSTRACT
Currently cooling systems for public transportation buses consist of air
conditioning system required to cool the air inside the bus. These cooling systems
not only are expensive, expensive to run, but also pose an environmental risk
pollution concerning air-conditioning refrigerant, bus diesel consumption, and
releases waste heat to the atmosphere. The use of air conditioning enhance street
air temperatures at a major scale, affecting temperature on the streets but also,
most important in bus stations. This paper presents a cooling system design based
on latent thermal storage. Using latest simulation Computational Fluid Dynamics
(CFD) simulation the authors designed a cooling system designed for short to
medium bus route.
KEYWORDS: thermal storage cooling; public transport, TES
1. Introduction
Nowadays cooling systems for public
transportation buses is using air conditioning system
(A/C) that uses mechanical work out of bus engine.
These cooling systems pose an environmental risk
pollution concerning air-conditioning refrigerant,
diesel consumption, and releases waste heat to the
atmosphere. The use of air conditioning enhance
street air temperatures at a major scale, affecting
temperature on the streets but also, most important in
bus stations. This paper presents a cooling system
design based on latent thermal storage. Using latest
simulation Computational Fluid Dynamics (CFD)
software simulation the authors designed a cooling
system designed for short to medium bus route. The
aim of the paper is to demonstrate storage cooling
system feasibility in case of high environment
temperature. The concept behind Thermal energy
storage (TES) is straightforward: the coolant (e.g.
water) is cooled by chillers in a stationary plant or
during off-peak hours on electric grid and stored in an
insulated tank. This stored thermal energy is then
moved in the specific thermal energy tank in the bus.
During the bus tour there is no energy consumption as
the cooling storage is cooling the passenger
compartment passively. Thermal energy storage
technologies are possible to contribute to avoid
releases waste heat to the atmosphere, preliminary at
a stationary plant with high-efficiency the coolant is
charging TES material into vehicle for bus passenger
compartment cooling. Electric vehicles are already in

the automobile market though not very popular. It is
expected for the next generation automobile, at least
used for short trips to be the next generation popular
vehicle. Also in the domain of public transportation
there is research for electric bus and Siemens
Company is already testing electric buses. The
electric vehicles lack thermal energy sources
passenger compartment. Using the energy from
batteries for cooling translates in questionable energy
efficiency for the vehicles.
TES is able to use external energy which is
stored thermally into thermal accumulators in
advance. Globally, there is a concern reflected also in
environment politics to mitigate heat in metropolitan
area. For instance Tokyo Metropolitan Government
came up with a Heat Island Control Measures Policy
carrying out a set of heat island control measures,
such as rooftop greening [1]. The term "Urban Heat
Island phenomenon" refers to the fact when a
temperature of a city part increases more inner city
than that in the suburbs. Several authors studied
thermal influence in urban areas [2-6].
Other issues emerge when using A/C in the bus
the A/C system cannot handle in extreme hot weather
conditions and usually is turned off by bus drivers.
Governments are imposing law concerning
engine idling as EPA Region 3 Anti-Idling
Regulations a set of several laws concerning idle
engine [12]. Also the high heat release in bus station
is another important fact.
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2. Problem statement
The authors want to determine whether a generic
design of cooling system design based on thermal
storage using nowadays bus compartment is able to
cool at a satisfactory level in a severe hot weather.
Also the authors aim to evaluate minimum mass
of coolant performance for short length of bus trip
and to asses if such a cooling system is feasible.
3. Simulation setup
solution and therefore considered one phase (liquid)

of the coolant;
7) The bus roof is heat generator with 60C
constant temperature as radiated by sun;
8) Average walls heat transfer rate is 20W/m2/K;
9) Every person is a heat generator of 100 W;
10) 2 thermal storage system on bus are placed
containing 450 kg of water;
11) Overdoor air curtain assure no mass of air is
transferred during stops at bus stations between
passenger compartment and outside.
The simulation scenario considered a cad CAD

model of a generic bus: Length 12 m, Width 2.4 m.
The CFD (Computational Fluid Dynamics) software
allows the authors to simulate the virtual tour in
certain conditions. The simulation considered the
following conditions:
1) 2 hours bus tour;
2) Variable speed up to 54 km/h;
3) Every randomly 3 10 minutes the bus stops
for randomly 30 - 120 seconds;
4) Passengers number randomly increased or
decreased with 1-10 persons at every bus stop;
5) Bus passenger compartment air is replaced
with 28 C cooled air at trip end;
Fig. 2. Simulation setup
Fig. 3. Overdoor air curtain
Fig. 1. Generic CAD Bus design considered

for simulation
6) Bus water coolant at -14 C is replaced at trip
end. We considered the water and anti-refrigerant
The CAD model of a bus is 1:1 scale to a bus

and use CFD software to simulate fluid dynamics.
In order to evaluate temperature distribution the
temperature variation was recorded at point1, as
depicted with red in Fig.4 and Fig.5, at the level of
bus chairs. Simulation considered 39 C environment
temperature. It is an extreme weather condition which
often occurs in temperate climate.
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With respect to thermal comfort, the Predicted

Mean Vote (PMV; Predicted Percentage of
Dissatisfied [PPD]) is a well-known performance
indicator (Fanger, 1970). This comfort indicator is
based on thermal discomfort as voted by a large
population. There are alternative comfort related
indicators over the last years.
The Netherlands for instance has a specific
regulation represented by guideline (ISSO 2004)
issued allows calculation of the running mean outdoor
temperature specifically with respect to the building
inside temperature. That means the comfort at 30 C
is far better than the temperature of 39 C. Moreover,
many authors [3] argue that the difference between
outside temperature and inside temperature of
buildings/cars is in a comfort zone if there is no
difference above 8 C.
Fig. 4. Temperature at level of point 1 after 20

minutes
Simulation results show a difference of about

9C during 2 hour simulation of the tour. As depicted
in Fig. 6 the temperature is at level of 30 to 31 during
the virtual tour of the bus in the above stated
conditions.
We identify several disadvantages of the system
simulated:
a) Relative high weight which translates in
higher consumption in case of road climb.
b) The latent thermal storage using thermal
storage accumulators might be unusable in case of
long trips travel time above 3 hr. for the water mass
discussed.
c) The cooling system cannot be controlled
compared with A/C system for a certain temperature.
A forced air ventilation system might provide certain
level of control but not in the manner A/C is able.
The system studied in this paper presents the
advantages:
a) The most important so far as we are
concerned is that no heat waste in atmosphere is
released.
b) No overheating of the engine is produced.
c) The system can be used in extreme colder
climate as heating system during cold period without
any modification.
d) The system use electricity as cooling energy
(which is possible clean energy if renewable source
are used to produce it).
e) The electricity source can be used avoiding
pick consumption - that is - the thermal fluid is
cooled during night during off-peak hours on electric
grid when electric consumption is low and
consequently protecting environment.
f) The in-bus system has basically no
maintenance.
4. Conclusions
Fig. 5. Temperature at level of point 1 after 100
minutes
We conclude the thermal storage cooling system

can be used for short bust trip with great environment
benefits. One of the most important is avoiding heat
release in urban environment and using electricity
grid during the night and avoiding pick consumption
period.
Further research is needed so far that concern
human comfort. In this respect, humidity and air
circulation inside passenger compartment must be
taken into account. Also better insulation of bus
passenger compartment is required.
References
Fig. 6. Temperature variation during 2 hours of

virtual tour simulation
[1]. Guidelines for Heat Island Control Measures Summary

Edition, July, 2005 Bureau of the Environment, Tokyo
Metropolitan Government.
[2]. Cheng, H. , R. Ooka, K. Harayama, S. Kato and X. Li,
Study on outdoor thermal environment of apartment block in S
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henzhen, China with coupled simulation of convection, radiation

and conduction, Energy and Building, 2004.
[4]. Oue, H., H. Tagashira, K. Otsuki and T. Maruyama, The
Characteristics of Heat Balance and Temperature Regime, in the
Paddy, Potato, Bare Fields and in the Asphalt Area, Trans. JSISRE,
97-104, 1993.
[5]. Fujino, T., C. S hibahara, T. Asaeda, N. Murase, A. Wake,
Characteristics of Heat and Moisture Transport of permeable
pavement, Proceeding of Hydrol. Eng., Vol.38, 235-240, 199.
[6]. Kondo, H. and F. Liu, A study on the urban thermal environ
ment obtained through one-dimen sional urban canopy model,
Journal of Japan Society of Atomospheric Environment, 33 (3),
pp.179- 192, 1998.
[7]. Herb W. R., Janke B.D., Mohseni O., Stefan H.G., 2009b.
Runoff temperature model for paved surfaces, Journal of
Hydrologic Engineering 14(10): 11461155. Incropera FP, DeWitt
DP. 2002.
[8]. Modeling thermal enrichment of streams due to solar heating
of local urban stormwater. In New Applications in Modeling
Urban Water Systems, Chapter 8, James W (eds), Pubished by

CHI: Guelph.
[9]. Janke B. D., Herb W. R., Mohseni O., Stefan H. G., 2006.
Quasi-2D model for runoff temperature from a paved surface,
Project Report 477. St. Anthony Falls Laboratory, University of
Minnesota: Minneapolis, MN, USA, Available online:
home.safl.umn.edu/bmackay/1pub/pr/pr477.pdf.
[10]. Janke B. D., Herb W. R., Mohseni O., Stefan H. G., 2009,
Simulation of heat export by rainfall/runoff from a paved surface,
Journal of Hydrology 365: 195212.
[11]. Jia Y., Ni G., Kawahara Y., Suetsugi T., 2001,
Development of WEP model and its application to an urban
watershed, Hydrological Processes 15: 21752194.
[12]. Office of Transportation and Air Qulaity, Compilation of
State, County, and Local Anti-Idling Regulations, United States
Envinronmental Protectian Agency, 2006.
[13]. Yukari Lino, Uriko Igarashi, Akihiro Yamaghishi, Study
on the improvement of envinronmental humidity in houses for
erderly, Envinronmental Ergonomic Published by Elsevier.
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ENVIRONMENTAL RISK MANAGEMENT IN A SIDERURGICAL

SLAG DUMP
Tamara Radu1, Maria VLAD1, Gelu MOVILEANU2
1
Material and Environment Engineering, Faculty of Dunarea de Jos University, Galati, Romania
Environment Engineering and Biotechnology, Faculty of Valahia University, Trgoviste, Romania
email: Tamara.Radu@ugal.ro
ABSTRACT
Environmental risk management shows both specific stages of any type of
management and specific actions, such as: hazard identification, risk assessment,
risk prioritization, response at the risk. This paper presents a case study achieved at
slag dump of the steel plant in Galati. Were identified and carried out chemically
analyzed of the waste types presented in the slag dump, the technology and
operating equipment as well as work organization. We established the
environmental pollution hazard, the likelihood of them and the consequences. The
risk was assessed both on each hazard and globally. According to management
criteria were identified unacceptable risks, the measures to be taken for elimination
or reduce them and monitoring mode.
Environmental risk management gives the organization the ability to organize
and lead the work so that environmental pollution will be minimal and under
continuous monitoring.
KEYWORDS: risk assessment; slag dump; pollution; management; waste
1. Introduction
Assessment of the environmental risk is a
complex action which in respect of a specific activity
quantifies the impact on environmental factors
resulted from producing an hazard. The danger can be
generated by an event, an action or absence of action.
Possible consequences ranging from the beneficial to
the catastrophic [1].
The environmental risk may concern:
- resources of water, air and soil;
- flora and fauna;
- health and economic well-being of the people;
- resources, energy and climate.
Environmental risk management shows both
specific stages of any management type, namely:
planning, organization, control and specific actions
such as: [2; 3]:
- identification of hazards;
- establishing the criteria of the risk assessment;
- risk assessment taking into account the
likelihood of the occurrence of a hazard and on the
severity of consequences in the production of hazard;
- prioritizing risks identified and compliance
with acceptable and unacceptable risks;
- the response to risk.
Each stage of risk management process have to
be documented. The documentation must contain data
on the assumptions, methods and sources of used

information, and as well as the results obtained.
Speciality literature presents various methods of
identification of hazards [1, 4, and 5] such as: Check
list, What if? Tee Fault Analysis, Analysis of Failure
Modes and Effects "(FMEA) Brainstorming, Hazard
Study and Operability (HAZOP), etc.
The progress of risk management requires both
commitment and decision- of the leadership at the top
and employee involvement, because they can identify
first an incident, a potential hazard or an opportunity
to improve.
Risk management gives any organization the
ability to better understand of the scrolling mode of
operations and the ability to respond more effectively
to changes of the internal and external circumstances.
Environmental risk management may lead to direct
benefits for any organization, by improving available
information [6].
So that, risk management environment may:
- minimize organization's exposure to risk;
- reduce expenses;
- increase the likelihood of continuation under
normal conditions of the activity and obtaining of
new notices and authorizations;
- improve image and organization's reputation.
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2. Case study
Case study has achieved at slag dump of the
steel plant in Galati city, Romania. It has a deposit of
non-hazardous waste, which has been set up in the
year 1968, and over the years it has developed and
ended up at the surface of approximately 110 hectares
and a quantity of technological waste about 57
million tonnes.
To limit the amount of the stored waste and
extending of landfill, Arcelor Mittal Galati has taken
measures to increase of the granular furnace slag
degree ( >90 %) and to process at a rate of 100 %.
Since 2009 in slag dump have not been deposited
waste being carried out only processing activities for
recovery.
An approximate proportion of the stored
materials in slag dump is following:
- the blast furnace slag about 47%;
- slag a steel mill about 30%;
- refractory waste and more 23 %.
Furnace slag, has on average following
chemical composition: 33-38% SiO2; 10-12% Al2O3;
41-46% CaO; 3-5% MgO; 0.5-1.4% MnO; 3.1-3.6%
CaS; 1.15- 1.50% S; 1% FeO.
Steel works slag has on average following
chemical composition: 10-15% SiO2; 40-50% CaO;
1-2.50% MgO; 1-3% P2O5; 3-7% MnO; 17-24% Fe.
Steel work rubble has following content: 4050% Al2O3; 37-47% SiO2 and refractory dolomitic:
38% MgO; 58% CaO.
Rubble in the manufacture of lime and dolomite
blocks, with the following chemical composition: 4050% Al2O3; min 65% SiO2 ; max. 2.5 % Fe2O3.
Quantity of resulted slag on obtaining flow of
the steel products depend to a large extent by
technological process performance and quality of raw
materials, ranging from 240-360 kg slag/tonne of cast
iron.
In slag composition there are pieces of metal
waste (approximately 6.5 % of the total quantity).
Usually are ferrous waste and scrap, the latter having
the highest share.
Operations processes of the slag dump are [7]:
- slag excavation, by means of mechanical
equipment;
- iron selection;
- loading and transportation of iron and slag
selected.
Taking into account by deposited materials,
technological flux applied and used equipment were
identified potential hazards and it has been
appreciated the gravity of the consequences and
probability of them manufacture, the risk and the risk
level.
The risk, for each identified hazard, is calculated

by taking into account the severity and probability
class, according the following formula:
R= SP
(1)
where:
R - risk size, S - severity classes, P - probability
classes.
In this paper it is proposed an environmental
risk assessment using five classes of severity [1] and
the consequences specified:
- 1st class: negligible consequences (for people insignificant effect; without emissions; to ecosystems
- some minor adverse effects on weed species or parts
of the ecosystem, short term and reversible);
- 2nd class: small consequences (for people first aid necessary; for emissions - emissions
immediately detained inside the target; to ecosystems:
- minor damage, rapid and reversible);
- 3rd class: medium consequences (for people need medical treatment; emissions inside the target,
retained with external support; to ecosystems: temporary and reversible damage);
- 4th class: high consequences (for people important effects; emissions - off-site emissions
without harm; to ecosystems - the death of animals,
large-scale damage, damage to local species and
extensive destruction of habitats);
- 5th class: serious consequences (for people
death; emissions: - off-site emissions of harmful
effects; to ecosystems - many animal death,
destruction of flora, air quality requires evacuation,
permanent and widespread contamination of soil).
In risk control, the severity is not easier to be
controlled than the danger probability. Therefore the
probability occupies an important place in the
response to risk. From the efficiency point of view, is
not possible to work with probabilities strictly
determined for each risk factor. It is therefore
appropriate for the probabilities to be established,
usually, by prediction and to be grouped in intervals.
For this reason, we use five intervals (classes), which
we can order as follows:
- 1st class: extremely rare: P < 10-12events/h;
- 2nd class: very rare: 10-12 < P < 10-8 events/h;
- 3rd class: rare: 10-8 < P < 10-6 events/h;
- 4th class: slightly frequent: 10-6 < P < 10-4
events/h;
- 5th class: frequent: 10-4 < P events/h.
According to the five classes of severity there
were established five risk levels, in ascending order:
- N1 - very small risk level, R=1-4;
- N2 - small risk level, R=5-9;
- N3 - moderate risk level, R=10-14;
- N4 - high risk level, R=15-19;
- N5 - extremely risk level, R=20-25.
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If we consider all possible combinations

between probability classes and severity classes, we
obtain a risk matrix with five lines (severity classes),

and five columns (probability classes), Table 1.
Table 1. Risk matrix

Probability classes:
Severity classes
small
medium
2
3
negligible
1
extremely rare
high
4
serious
5
very rare
10
rare
slightly frequent
3
4
6
8
9
12
12
16
15
20
frequent
10
15
20
25
In table 2 are presented hazards identified and

their analyse in terms of severity and probability and
risk assessment and the level of using the mentioned

method.
Table 2. The severity class, the probability class and the risk for hazards identified
Code
1.
2
3
4
5
6
8
9
10
Hazard
Severity
classes
Probability
classis
Risk
Risk
level
15
12
12
16
Gaseous emissions into the

atmosphere resulted in exploitation
process of slag dump.
Powders in suspension from the
exploitation process of the slag
dump.
Noise pollution due to equipments
which work on dump.
CO2 emissions from equipments
which work on dump.
Soil pollution by leaching of the
waste waters from the rain water.
Soil pollution in the vicinity of the
slag dump by the rain water
pouring down on dump hillsides.
Soil and underground pollution
through the exploitation work of
the dump slag from
morphologically point of view.
Destruction of vegetation and
fauna of the slag dump area and of
close areas.
Land slides and caved in field.
Pollution of groundwater by waste
water infiltration and rain water.
The global risk level (Rg) is calculated as a

weighted average of the risk size established for the
identified risk factors.
The formula for calculating the overall risk level
is as follow [8]:
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Ri
Rg =
i =1
n
i
i =1
(2)
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where:
Rg is the global risk level on the workplace;
Ri = risk size for the risk factor "i";
n is number of risk factors identified at the
workplace.
Global risk for analyzed slag dump is given by
following relation:
Rg = 104/10 = 10.40
In Figure 1 is shown the risk on each hazard,
therefore the partially risk.
18
16
14
risk
12
10
8
6
4
2
0
1
10
hazard code
Fig. 1. Risk value on each hazard

From figure 1 it can be seen that global risk is
exceeded by four hazards (code 2; 5; 6; 8). In any risk
assessment action, significance will be attributed to
considerable risks with a great impact on environment
and people. A ranking is made of risks scale, which
gives the possibility of establishing a priority of
prevention and protection, according to the risk factor
with the highest risk level.
Figure 2 shows the level of the risk for each
hazard analyzed. A high risk is for two hazards:
particulate matter in the air and the destruction of
vegetation and fauna by the slag dump space and the
adjoining too. These risks require urgent measures to
minimise them.
5
risk level
4
3
2
1
0
1
10
hazard code
Fig. 2. Risk level for each hazard analyzed
2.1. Measures for preventing and reducing

the risk level
Risk minimization is a complex process, which
does not involves only the maximum possible
reducing of the risk value, but also the identification
of the most effective methods and rational solutions
for treatment the risk (reduction, coverage-insurance,
transfer, acceptance). The answer to risk can be
accomplished in the following steps [9]:
- effects analysis of these options on the
probability and risk impact;
- availability analysis for risk and cost-benefit
ratio;
- design and implementation of response actions
at risk.
These steps of the risk management contribute
to bringing the risk level in approved tolerance limits.
Basically the attitude to risk is differentiated in
two categories: to tolerate risk or consider it
unacceptable.
The attitude of tolerance, which does not take
any measure of risk mitigation, but a regular
monitoring is carried out in order to see whether that
risk registers significant growth, or level of exposure
would be acceptable. Unacceptability attitude refers
to major or catastrophic risks. In these cases it
adopted solutions for reducing the probability of
producing and effective solutions to reduce the
consequences.
In the treatment of such risks, remain
permanently activated the security component of the
people and the environment. Attitude of
unacceptability can contribute a lot to the reduction of
environmental damages resulted from the production
of major and disastrous risks, which can not be
prevented [9, 10].
Options of risk management are:
- the treatment, which lays down implementing
measures (internal control forms corresponding to the
specific organization or improvement of existing one)
so that inherent risk to be reduced at minimum level
of exposure;
- the removing, when the activity which is
associated with the risk in question ceases for reasons
of efficiency;
- the transfer, which takes into account if it is
possible or risk taking by someone from outside.
After choosing of the reaction at risk, leadership
resizes the risk on based accepted level, considering
that a hazard will exist as long the activity exist to
which it is associated.
Table 3 shows the treatmen measures of
identified risks at siderurgical slag dump.
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Table 3. Measures to reduce, monitoring and control of identified risks

Risk factor
Risk level
Powders in suspension
from the exploitation
process of the slag
dump.
high risk
Destruction of
vegetation and fauna of
the slag dump area and
of close areas.
high risk
Soil pollution by
leaching of the waste
waters from the rain
water.
Soil pollution in the
vicinity of the slag
dump by the rain water
pouring down on dump
hillsides.
moderate
risk
Proposed measures
- useful of the best practices for the exploitation of slag
dumps;
-watering of the access ways several times a day by
means of tanks with water;
-covering the machine during the transport of materials
that generate dust.
- avoiding of soil degradation through oil and diesel
spills from shipping and processing equipment;
- prohibition cutting of the forests in bordering area in
order do not trigger surface erosion;
- creation at the dump base of one forest drapery.
- protection of the exhaust channel of rainwater
through the realization of contour dams and bulkhead
using sterile from dump;
- in the protection areas of the channel to be denied
access of heavy equipments and the storage of slag.;
- treating waste water before discharge in ponds;
-will be avoided and eliminated the formation of lakes
through good housekeeping surface water.
The measures referred to above are not

restrictive and will be filled in depending on the
needs and nature of the activities.
3. Conclusions
The materials deposited in slag dump,
technological flow applied to its operation and the
equipments used, can cause hazard with a specific
gravity of consequences and likelihood of occurrence.
After the analysis it was established a global risk at
10.4, applying a method where the maximum size of
the risk is 25.
Have identified four dangers which exceed the
global risk, two of which have reached the risk level 4
(high risk) of maximum 5.
All identified risks present possibilities of
minimising through the application of measures
modernization of the operational technologies and by
monitoring.
References
[1]. Ozun A., Anghel C., Evaluarea riscului tehnologic si
securitatea mediului, Ed. Accent 2007Cluj Napoca.
[2]. Moraru R., Bbu G., Cadrul general al managementului

riscului de mediu, Buletinul AGIR nr. 3/2006, iulie-septembrie, p.
103-107, 2006.
[3]. Bbu G., Moraru R., Environmental risk characterization
principles, Proceedings of the 6th Conference on Environment and
Mineral Processing, part. I, p. 17-21, VB-TU Ostrava, Cehia, 27 29.06.2002.
[4]. Kletz T., Hazop and Hazan Identifying and assesing process
industry hazards, Fourth Edition Institution of chemical Engineers,
1999.
[5]. Lees F. P., Loss Prevention in the process industries: hazard
identification, assessement and control, Second Edition, United
Kingdom 1996.
[6]. Beer T., Ziolkowski F., Environmental risk assessment: An
Australian perspective, Supervising Scientific report 102,
Supervising
Scientist,
Canberra,Australia,
1995,
(http://www.deh.gov.au/ssd/publications/ssr/102.html).
[7]. Tudorel Dinu, Lucrare de disertatie, UDJ, Galati 2013.
[8]. Tamara Radu, Maria Vlad, Marius Bodor, Enviromental
risk management at hot dip galvanizing, The Annals of Dunarea
de Jos University of Galati, Fascicle IX Metallurgy and Materials
Science, ISSN1453-083X, May 2011, special issue, pag. 263.
[9]. Moraru R., Bbu G., Environmental risk management in
mining An overall approach, Proceedings of the Third
International Symposium Mining and Environmental Protection,
p. 22-27, Belgrad-Vrdnik, Yugoslavia, 2001.
[10]. Lucica Balint, Tamara Radu, Simion Ioan Balint,
Environmental risk assessment on coke plant decommissioning,
The Annals of Dunarea de Jos University of Galati, Fascicle IX
Metallurgy and Materials Science, ISSN1453-083X, May 2011.
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3D FACE MODELING TECHNIQUE

FROM UNCALIBRATED IMAGES
Gheorghe FLOREA, Florin Bogdan MARIN

email: florin.marin@ugal.ro
ABSTRACT
3D face modeling from 2D images is needed for face recognition, animation,
art and entertainment. The authors determine a procedure to automatically build a
3d model using computer vision algorithm followed by 3d subtle refining in
Autodesk Maya of the model. The developed computer vision program is able to
automatically find the correspondence between uncalibrated images through
identification of eye, nose and mouth position. An initial 3D face model obtained
after developed computer vision application is refined to obtain a better 3d model
to correct depth information to achieve high assemblance to the real model.
KEYWORDS: 3d face modeling; computer vision,3d reconstruction; depth 3d
model, 3d reconstruction
1. Introduction
The aim of the paper is to propose a technique
that allows building a 3d model of human face using
low resolution images and using few images as input.
A sculptor is using one image or several images to
reconstruct 3d shape of a bust though the artist has
never been seen the person who is depicting.
Computer vision is a field which aims, besides
other applications, to build 3d model of an object out
of images. Computer vision community developed
semi-automatic
tools
using
single
image
reconstruction of objects [7, 8, 15].
Fig. 1. Tridimensional modeling of human using

calibrated images [14]
Whereas calibrated images provide enough
information for 3d reconstruction, by using markers
(as seen in Fig. 1 in case of humans) or by using

known camera relative position to object (Fig. 2) the
modeling using unregistered image is a challenge.
Fig. 2. Image sequence at predefined angles and

distances [15]
3D facial reconstruction is considered by many
scholar research groups. There were developed
several different solutions [1-4]. Every solution
design is taking into account specific application
challenges. For instance some authors aim to
construct 3d face model in real time using high
performance hardware, while other authors aim is to
get a refined model regardless of the computational
time. The video game is one domain that finds
computer vision 3d modeling of a very interest today.
Research in the area of video game aims to use
computer vision technology which is available today
(many source code library are freeware e.g. OpenCV)
as well as hardware needed (computer vision requires
considerable computational resources). The goal is to
develop applications once impossible to deploy on
game devices to produce immersion into 3d game
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environment. For instance the face of the player is

introduced as game character producing user avatar.
Furthermore, the actual position of the gamer in real
space is recognized and over-imposed in 3d virtual
space in the game. To replace character game face
with a 3D rendering of their own sometimes could be
challenging as the light condition in the room might
not be as ideal or insufficient or many view angle
pictures are not provided by the user.
So far that concern methods and techniques
proposed for 3d face many authors developed
illumination normalization methods [15, 16] which
are applied to obtain calibration in order to obtain 3d
model.
3D face modeling from 2D images is needed for
face recognition, animation, art and entertainment. In
this paper the authors want to obtain the 3d model to
be used for art or security application.
2. Problem statement
We consider in this research the 3d model using
low-resolution images and with few images as input.
The difficulty degree increases as the images are low
quality concerning details in the images (blurred
images) and also as the resolution of the input image
decreases. Our method, however, is semi-automatic,
requiring subtle refinement after the automatic 3d
modeling is performed.
A shown in Fig. 3 the 3d model is to be used for
art (cast representation of the upper part of the human
figure), for security software application (to build 3d
model of person to be compared with other models in
the data base for identification) or for game software.
3. Problem solution
Our technique implies one step which
automatically build a rough 3d model and a second
one, which implies manual modeling. The computer
vision algorithm needs a second step to achieve a
rough result if sufficient information are provided
to the computer vision algorithm developed, followed
by a manual refinement using popular 3d modeling
Autodesk Maya software. As our aim is to use only
automatic 3d modeling on this research, we are
working to further employ automatic methods to
replace manual steps.
Several challenges are meant to overcome.
Firstly, images are taken from different view that
means no pose of the camera information is provided.
Secondly images are taken at different illumination
with substantial difference and also in third place the
subject of the test is not fully described by the
pictures, as there are areas unseen in the images.
To recognize faces across a wide range of
illumination conditions and partial view is a big
challenge. Furthermore the problem is amplified as
certain face features need to be detected such as eye,
mouth or nose position.
Fig. 3. Problem statement of 3d face modeling using

uncalibrated images
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Fig. 4. Input images for software
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The authors determined a technique to

automatically build a 3d model using computer vision
algorithm followed by 3d manual modeling in
Autodesk Maya of the model. The developed
computer vision program is able to automatically find
the correspondence between uncalibrated images
through identification of eye, nose and mouth
position. An initial 3D face model obtained after
developed computer vision application is refined to
obtain a better 3d model to correct depth information
to achieve high assemblance to the real model (Fig.
5).
Model Intrinsic and Extrinsic parameters of
images taken from different view at different
illumination means to determine relative illumination
and normalize all image in respect to illumination.
In case of partial view of the face manually is
determined symmetry, if any info available and mesh
is re-built.
The detection of face components, eye, nose,
and mouth recognition is performed by using well
known Haar like feature detection. The algorithm was
trained with 300 different positive pictures taken from
different angles.
Fig. 5. The proposed technique steps

The morphable Model of 3D Faces is built by
interpolating similitude face feature (eye, nose)
coordinates by finding correspondence of 2 vectors:
F1 =(x1, y1 , z1 , ..xn , yn , zn )T
F2 =(X2, Y2 , Z2 , ..Xn , Yn , Zn )T
where:
x1,y1,z1 is the coordinate of first remarkable
point on first picture, X1, Y1,Z1 is the coordinate of
second picture of first remarkable point, so on. and
pixels at (xk, yk, zk) have colors (Rk, Gk , Bk) on a
given remarkable point on face.
Fig. 6. Remarkable points on face

Concerning hardware setup used, we have used
an accessible system on a standard desktop PC
containing cheap hardware and uses computer vision
open source software. Specifically, we are using an
AMD Athlon X2 3.2 Ghz processor, 4GB of RAM,
and a NVIDIA 9800 GTX+ GPU with 512 MB of
memory. We develop the program in Visual C 2010
along with OpenCv 2.4 well known computer vision
library. We tested with input of 3, 4 and different 5
images with resolution between 200X300 and
800X600 pixels.
We consider that the obtaining depth with
acceptable error is difficult to obtain using 2d images
of low resolution. Therefore, after automatically
obtain a rough 3d model we simply compare certain
face component ratio and modify the 3d rough model.
We measure on image ration between the distance of
mouth length to the distance eye to eye and we
modify the morphable model accordingly. We further
refine the model by iteratively repeating the following
process until an acceptable result is obtained.
In this sense we use several operations of
modifying the mesh over the 3d model.
We found the algorithm to perform well on face
3d modeling when low resolution image are provided
as input and pictures are taken in different
illumination conditions. However, the algorithm
could be further to identify other shape with feature to
be detected.
Remarkable points localization consists in
automatically detect facial landmarks in all pictures.
Landmarks remarkable points are presented in Fig. 6.
There are 2 points for each of mouth, eye, and nose
and 25 - 30 on face contour.
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Once we have the facial landmarks on different

face images the correspondence between the
uncalibrated face images can be determined through
landmark alignment.
As discussed above an interpolation based
algorithm is used to recover the 3D face shape
determining remarkable points on each of the picture.
Different from previous work in this area of interest
we employ a technique model to reconstruct the 3D
face shape in the condition of few images and low
resolution images.
Further the process of fitting the generic 3D face
to 2D face images implies using a generic 3d head
volume.
We determine the correspondence by localizing
predefined feature points on each picture.
The software builds 3d model with few images

(3-4 images) taken in different:
Illumination;
different angle;
no calibration;
different resolution;
partial view.
4. Conclusions
We conclude that the technique developed is
suitable for cases where few images and low quality
are provided such as art and security domains. In case
of game the computer vision algorithm might provide
an acceptable result. Further research is needed in
order to eliminate manual step for refining the model.
References
Fig. 7. Tridimensional model obtained with missing

surfaces in the refining step
To extract the face texture, we directly map
portions of the image to the 3d model and we retain
detailed and realistic features in face image. The
texture is smoothed and applied in 3d model.
We identify several disadvantages of the
algorithm:
a) computational resources are important. Time
needed to build a 3d model: 1-2 hours on an Intel
Xeon Processor E5504 2Ghz and 2-3 hours on
AMD Athlon X2 3.2 Ghz processor.
b) algorithm fails when reflections are present in
pictures or all pictures are low resolution (lower than
200X300 pixels).
c) needs manual symmetry modeling in case of
partial view.
Nevertheless, we identify several advantages of
the algorithm:
[1]. R. Cipolla, G. Fletcher, and P. Giblin, Surface geometry

from cusps of apparent contours, In ICCV, 1995. 2.
[2]. A. Criminisi, I. Reid, and A. Zisserman, Single view
metrology, IJCV, 40(2), Nov. 2000, 2.
[3]. F. Han and S.-C. Zhu, Bayesian reconstruction of 3D shapes
and scenes from a single image, In Workshop on HigherLevel
Knowledge in 3D Modeling and Motion Analysis, 2003. 2.
[4]. J. Atick, P. Griffin, and A. Redlich, Statistical approach to
shape from shading: Reconstruction of three-dimensional face
surfaces from single two-dimensional images, Neural Computation,
8(6):13211340, 1996. 2.
[5]. V. Blanz and T. Vetter, A morphable model for the synthesis
of 3D faces, In SIGGRAPH, 1999. 1, 2.
[6]. R. Dovgard and R. Basri, Statistical symmetric shape from
shading for 3D structure recovery of faces, In ECCV, 2004.
[7]. B. Oh, M. Chen, J. Dorsey, and F, Durand. Image-based
modeling and photo editing, In SIGGRAPH, 2001. 2.
[8]. L. Zhang, G. Dugas-Phocion, J.-S. Samson, and S. M. Seitz,
Single view modeling of free-form scenes, In CVPR, 2001.
[9]. H. Wang and S. Z. Li, Face recognition under varying
lighting conditions using self quotient image, In Proceedings of
Automatic Face and Gesture Recognition, pages 498505, 2004.
[10]. R. Gross and V. Brajovic, An image preprocessing
algorithm for illumination invariant face recognition, In
Proceedings of Audio and Video-Based Biometric Person
Authentication, pages 1018, 2003.
[11]. H. Han, S. Shan, L. Qing, X. Chen, and W. Gao, Lighting
aware preprocessing for face recognition across varying
illumination, In Proceedings of the 11th European Conference on
Computer Vision, pages 308321, 2010.
[12]. X. Tan and B. Triggs, Enhanced local texture feature sets
for face recognition under difficult lighting conditions, IEEE Trans.
Image Processing, 19(6):16351650, 2010.
[13]. Kutulakos, K., Seitz, S., A Theory of Shape by Space
Carving, In International Journal of Computer Vision, 38(3),
199{218, 2000).
[14]. Zhang, Z., A exible new technique for camera calibration, In
IEEE Transactionson Pattern Analysis and Machine Intelligence,
22(11), 1330-1334, (2000).
[15]. M Turk, A Pentland, Eigenface for recognition, Journal of
cognitive neurosciences 71-86, 1991.
[16]. R. Gross and V. Brajovic, An image preprocessing
algorithm for illumination invariant face recognition, In
Proceedings of Audio and Video-Based Biometric Person
Authentication, pages 1018, 2003.
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RESEARCH REGARDING THE SAFETY WORK IN THE

CONTINUOUS CASTING MACHINE
Beatrice TUDOR, Anisoara CIOCAN

email: btudor@ugal.ro
ABSTRACT
This paper presents the tasks and work environment in section TC-UOR, the
risk factors identified and assessed and suitable measures for reducing or
eliminating them, resulting in a safer environment for the development of
production activities job-specific and decreased risk of work accidents in this
sector.
KEYWORDS: casting machine, evaluation, risk level, job security
1.Work system components of evaluated

1.1. Workload
The task of the worker in the casting slabs
masines area, includes a number of distinct activities,
and for each of them wrote a specific documentation
what is described in the technical working
instructions provided by the section continuous
casting after as follows:
- Instruction and safety rules for mould worker
operating heating station dip tubes [1];
- Instruction and labor protection rules for ladle
worker [2];
- Instruction and labor protection rules for
operator from the pulling and straightening slabs [3];
oxygen flame cutting [4];
- Instruction and labor protection rules to the
desk worker suspended casting[5];
- Instruction and labor protection rules for the
lever foundry [6];
- Instruction and labor protection for operators
of the casting machine [7];
- Instruction and labor protection rules
installing dispensers [8];
operator of hot cutting machine[9];
- Instruction and labor protection rules for plant
worker from bubbling [10].
1.2. Work environment

The main characteristics of the work
environment are specified in analysis reports.
According to analysis bulletins are allowed
exceedances of the following pollutants: dust, CO,

noise, dust lime [11].
The work environment is characterized by:
- Low light levels at some points of the work
and very high in the viewing area of the molten steel;
- The presence of infrared;
- By draft.
2. Research on risk factors slabs

continuous casting machine
Risk factors identified in the work areas of
continuous casting machine slabs are divided into:
2.1- Risk factors identified in the use of means
of production.
2.2 - Risk Factors in the workplace.
2.3 - Risk Factors of the work task.
2.4 - Risk Factors of the performer.
2.5 Omissions.
2.1. Risk factors identified in the use of

means of production are:
The risk factors identified in the production
areas are:
2.1.1 Mechanical Risk Factors

Moving parts of machines - grip, drive the
cutting machine, caja drawing, port-tundish trolley,
tippers and burners for tundish.
Flow of fluids - liquid steel, slag.
Flick the automobiles and railways to move
through the plant premises.
Sliding bark tundish.
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Roll of parts, materials based cylindrical or

stored without stability.
Flick the cart port-tundish and hot cutting
machine.
Flip materials, parts - improperly stored or
accidentally hit the crane load.
Free fall tundishs, materials, spare parts etc. the
handling crane.
Leakage of liquid steel accidental ladle
perforation or transport tundishs.
Splashes of molten metal of the bubbling, ladle
opening, tiping ladle, release tundish with oxygen
barreled.
Diversion of materials or parts for their transport
cranes.
Balance of parts and materials transported by
cranes.
Recoil from using pneumatic hammer.
Jet, rash at the accidental cracking tracks energy
fluid or hydraulic systems.
Contact with surfaces or dangerous outlines rugs, fabrics or plastics reinforced.
2.1.2. Thermal risk factors

High temperature of objects or surfaces accidental touch surfaces with high temperature.
Surprise the flame to the heating tube
immersion, in cutting pipe with O2.
2.1.3. Electrical risk factors

Electrocution by direct - current paths
unprotected and damaged.
Electrocution by indirect contact - accidental
leakage current - corroded earthing systems.
Brightness - view incandescent material.

Radiation - in the vicinity of premises with
liquid steel, on the footbridge, near the ladle.
Natural disasters earthquakes.
Excessive dust - according to the attached ballot
determinations.
2.2.2. Chemical risk factors

Accumulation of toxic gases - as attached
analysis bulletins.
Flammable or explosive gases or vapors explosive mixture of oxygen, methane, etc.
2.3. Risk factors of work task

2.3.1. Content inappropriate
Waiver of ladels weighing 260 t with 250 tf
cranes.
2.3.2. Physical strain

Forced postures or vicious - cleaning the gutters
cooling chamber, ignition tubes for heating slabs,
molding machine control.
Dynamic effort - dust bag handling, materials,
etc.
2.3.3. Mental overload

Difficult decisions in short action.
Short cycle repetitive tasks - opening and
closing the casting plugs (for maintaining the steel
crystallizer).
2.4. Risk factors of contractor
2.1.4. Chemical Risk Factors

Working with flammable substances - hydraulic
oil.
Possibility of explosion of liquid steel at
accidental contact with dissociation water.
2.2. Risk factors identified in the work

environment of continuous casting
machine slabs are:
2.2.1. Physical risk factors
High temperature of the air (according to
analysis bulletins).
Low temperature of the air in specific points in
winter.
Airflow natural draft, premises enclosures.
High noise level - according to the attached
analysis bulletins determinations.
Low level lighting on some routes and some
points of intervention - no lighting lamps.
2.4.1. Wrongful
Execution of contingency operations work load
or other way than technical provisions work.
The wrong order in time to catch ladle crane
hook steel balance.
Closing
accidental
cooling
circuit
of
crystallizer, during casting explosion.
Wrong position on the table of ladle bubbling ,
or cooling slabs.
Setting wrong oxygen or gas flow.
Trouble with crane.
Closing the circuit for cooling during casting.
Travel and stationary hazardous areas - close to
the liquid steel pots under high load funds, on the
access roads.
Fall on same level - uneven surfaces, materials
stored on the access roads, etc.
Falls from heights: by stepping into the void, the
imbalance by sliding - to travel on walkways, stairs
access to interventions curved wire.
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3. Measurements and recordings of risk

factors specific slabs continuous casting
machine area
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2.5. Omissions
After research studies, targeting the risk factors

for workers in casting machine area, were measured
a total of 49 cases corresponding to specific activities
of hardware, each with an appropriate level of the
hazard site analyzed work Was constructed diagram
of Figure 1.
Partial levels of risk
Failure to start circuit cooling crystallizer explosion.

Failure personal protective equipment (E.I.P),
individual work equipment (E.I.L), and other means
of protection provided (which was granted by the
employer).
F1
F2
F3
F4
F5
F6
F7
F8
F9 F10 F11 F12 F13 F14 F15 F16 F17 F18 F19 F20 F21 F22 F23 F24 F25 F26 F27 F28 F29 F30 F31 F32 F33 F34 F35 F36 F37 F38 F39 F40 F41 F42 F43 F44 F45 F46 F47
Risk factors
Fig. 1. Risk Factors Chart continuous casting machine (partial levels of risk)
Explaining risk factors F1 to F49, are given below:
F1-moving parts of machines - grip, drive the cutting
machine, caja drawing, port-tundish trolley, tippers
and burners for tundish;
F2-fluid flow - liquid steel slag;
F3-flick the automobiles and railways to move
through the plant premises;
F4-sliding bark tundish;
F5-roll of parts, materials based cylindrical or stored
without stability;
F6-flick the cart port-tundish and hot cutting
machine;
F7-flip materials, parts - improperly stored or
accidentally hit the crane load;
F8-free fall tundishs, materials, spare parts etc. the
handling crane;
F9-leakage of liquid steel accidental ladle perforation
or transport tundishs;
F10-splashes of molten metal of the bubbling, ladle
opening, tiping ladle, release tundish with oxygen
barreled;
F11-diversion of materials, spare parts for their
transport cranes;
F12-balance of parts and materials transported by
cranes;
F13-recoil from using pneumatic hammer;

F14-jet, rash at the accidental cracking tracks energy
fluid or hydraulic systems;
F15-contact with surfaces or dangerous outlines rugs, fabrics or plastics reinforced;
F16 -high temperature of objects or surfaces accidental touch surfaces with high temperature;
F17-surprise the flame to the heating tube immersion,
in cutting pipe with O2;
F18-Electrocution by direct - current paths
unprotected and damaged;
F19-Electrocution by indirect contact - accidental
leakage current - corroded earthing systems;
F20-Working with flammable substances - hydraulic
oil;
F21-possibility of explosion of liquid steel at
accidental contact with dissociation water;
F22-high temperature of the air (according to analysis
bulletins);
F23-low temperature of the air in specific points in
winter;
F24-airflow natural draft, premises enclosures;
F25-high noise level - according to the attached
analysis bulletins determinations;
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F26-low level lighting on some routes and some

points of intervention - no lighting lamps;
F27-brightness - view incandescent material;
F28-radiation - in the vicinity of premises with liquid
steel, on the footbridge, near the ladle;
F29-natural disasters earthquakes;
F30-excessive dust - according to the attached ballot
determinations;
F31-accumulation of toxic gases - as attached
analysis bulletins;
F32-flammable or explosive gases or vapors explosive mixture of oxygen, methane, etc.;
F33-waiver of ladels weighing 260 t with 250 tf
cranes;
F34-forced postures or vicious - cleaning the gutters
cooling chamber, ignition tubes for heating slabs dip
molding machine control;
F35-dynamic effort - dust bag handling, materials,
etc.;
F36 -difficult decisions in short action;
F37-short cycle repetitive tasks - opening and closing
the casting plugs (for maintaining the steel
crystallizer);
F38-execution of contingency operations work load
or other way than technical provisions work;
F39-the wrong order in time to catch ladle crane hook
steel balance;
Nrg8 =
49
Riri
i=1
49
ri
i=1
F40-closing accidental cooling circuit of crystallizer,

during casting explosion;
F41-wrong position on the table of ladle bubbling , or
cooling slabs;
F42-setting wrong oxygen or gas flow;
F43-trouble with the crane;
F44-closing the circuit for cooling during casting;
F45-travel and stationary hazardous areas - close to
the liquid steel pots under high load funds, on the
access roads;
F46-fall on same level - uneven surfaces, materials
stored on the access roads, etc.;
F47-falls from heights: by stepping into the void, the
imbalance by sliding - to travel on walkways, stairs
access to interventions curved wire;
F48-failure to start circuit cooling crystallizer
explosion;
F49-failure personal protective equipment (E.I.P),
individual work equipment (E.I.L), and other means
of protection provided (which was granted by the
employer).
Using the risk factors for foundry workers can
calculate the overall risk level of the job using the
formula:
Nrg = Riri/ ri
In which: Riri - is the sum of risk factors
considered work area; ri - is the sum of the partial
workplace risk assessment.
3(7x7) + 0(6x6) + 9(5x5) + 4(4x4) + 30(3x3) + 2(2x2) + 1(1x1)

3x7 + 0x6 + 9x5 + 4x4 + 30x3 + 2x2 + 1x1
To work from casting after the introduction of

related parameters in formula diagram in Figure 1.
level of risk is achieved Nrg = 4.04.
4. Interpretation of the results of the

evaluation of risk factors
Overall risk level calculated for foundry
worker " is equal to 4.04, a value that it falls into the
category of jobs with unacceptable level of risk.
The result is supported by the "Assessment
Sheet job snitch" which is observed that out of 49 risk
factors identified (Fig. 1), and 16 above, as part of the
risk level, the 3: 3 fits to the category of high risk
factors (NVPR = 7), 0 falling within the category of
high risk factors 9 fits into the category of high risk
factors (NVPR = 5), and the other four factors falling
within the category medium risk (NVPR = 4).
715
177
= 4,04
The 16 risk factors that are unacceptable in the

range: F31, F33, F49, F2, F3, F7, F9, F16, F25, F27,
F30, F45, F10, F22, F35, F38.
To reduce or eliminate the 16 risk factors (which
is in the range acceptable) are required generic
measures listed in "Safety measures proposed" to
foundry worker.
Regarding the distribution of risk factors
generating sources, the situation is as follows (see
Fig. 2):
42.86%, factors belonging to the means of
production;
22.45% working environment factors;
10.20% work task factors;
24.49% factors belonging to the contractor.
The analysis of the evaluation form shows that
75.51% of the risk factors
identified may have irreversible consequences on the
performer.
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risk factors for work

tasks ; 4,26
risk factors of
contractor ; 25,53
risk factors of
environmental work
; 25,53
risk factors of
production means ;
44,68
Fig. 2. Distribution of risk factors inscuritatea on sources of job insecurity in casting
5. Measures and proposals

To ensure job security in the continuous casting
machine area, measures technical and organizational
proposed are:
For high risk factors, F 31, F33, F49 (NVPR =
7).
- Design and development of optical systems
and audible warning of the presence of toxic gases
interlocked with gas detectors placed at points likely
to accumulate toxic gases or toxic fumes;
- Work location routes of facilities containing all
the equipment necessary to report if toxic gases and
vapors;
- Acquisition personal protective equipment(
E.I.P). appropriate activity to be carried out according
to regulations.
For high risk factors, F2, F3, F7, F9, F16, F25,
F27, F30, F45 (NVPR = 5).
- Marking with warning signals at all areas with
potentially fluid flow with high temperature;
- Restriction on possible areas where fluid flow
is possible incandescent;
- Insurance against uncontrolled movement of
materials through, handling hazardous procedures,
leveling, anchoring etc.;
Not exceeded the maximum permitted
stacking the boot or casual;
- Leveling transport routes in the warehouse;
- Compliance dimensions of access roads and
removal of all materials that obstruct the way;
- Restriction on possible areas where there is a

possibility of contact with surfaces that have high
temperature;
- Measures against noise sources - is achieved
through design changes to the technical equipment if
possible, or by adopting special attenuators devices,
the choice of technical equipment in conditions
comparable technology, priority will be given to
those that produce less noise;
- Measures to combat noise at receiver - consists
in isolating the staff working in noise;
- Adopt, where possible, working methods with
minimum release of dust;
- Marking of access lanes and high action.
For environmental risk factors, F 10, F22, F35,
F38 (NVPR = 4).
- Training on the need for safety glasses,
protective masks and other means of protection;
- Checking and testing contractors on
compliance a labor protection rules;
- Appropriate signs at the workplace risk;
- Staff working in warm microclimate will
benefit from breaks ,will have to restore
thermoregulatory capacity, duration and frequency of
which are dependent on the intensity of exercise and
the values of parameters of microclimate;
- Will be built fixed spaces with proper
environment;
- Will ensure sparkling salt water (1g NaCl /
liter) in volume of 2-4 liters / person / exchange,
delivered at a temperature of 16-180 C;
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- To prevent risks caused by physical exertion

should be avoided:
- wrong job positions or fixed;
- extreme movements;
sudden movements;
- repetitive movements.
In this sense, the employer must:
- the criteria ergonomic design of workplaces
and work;
- adequate instruction and training employees on
how to conduct professional activities appealing to
security professionals and health;
- professional activities with great physical
effort, the distribution of workers over 45 years will
be done only with the occupational physician;
- medical examination of employees according
to the law;
- Training employees on the consequences of
non-compliance with security restrictions - not used
or incomplete use of means of protection, perform
operations that are not listed in the job etc.;
- Verifying by permanent control of the head
working group, from superiors.
6. Conclusions
For job security in hardware is required as the
following main conclusions:
- Clear identification and marking areas that
frequently occur or accidental toxic gas;
- Making clear procedures on how to act in case
of toxic gases and vapors issue alert;
- Training employees on the consequences of

non-compliance with security restrictions - not using
or use means of protection etc.;
- Verifying by permanent control of the head
working group, from superiors;
- A medical examination of workers according
to the law;
- conducting periodic measurements of
pollutants in the work environment;
- conducted periodic monitoring work processes
aimed at equipping managers and employees to use
protective equipment.
References
[1]. Darabon D., Evaluarea riscurilor de accidentare i
mbonvire profesional, Editura Virom, Constanta 2005.
[2]. Darabon D., Managementul securitii i sntii n munc.
Ghid de evaluare a confomrii cu cerinele legale, Bucureti,
Editura AGIR, 2010.
[3]. Instruciuni de lucru la masinile de turnare continua TC1UOR.
[4]. Standarde: Legea 319/2007, Legea securitii i sntii
muncii; HG 1425/2007, Normele metodologice de aplicare a Legii
319/2007; HG 955/2010, Modificri la HG 1425/2007; SR OHSAS
18001/2008, Sisteme de management al sntii i securitii
ocupaionale. Cerine; SR OHSAS 18002/2009, Sisteme de
management al sntii i securitii ocupaionale. Linii directoare
pentru implementarea OHSAS 18001/2007; SR EN ISO
9000/2006, Sisteme de management al calitii. Principii
fundamentale i vocabular; SR EN ISO 9001/2008, Sisteme de
management al calitii. Cerine; SR EN ISO 14001/2005, Sisteme
de management de mediu. Cerine cu ghid de utilizare;
Sr EN ISO 19011/2011, Ghid pentru auditarea sistemelor de
management.
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THE STUDY OF DENDROCHRONOLOGY AS AN ARCHEOMETRYC

METHOD FOR CHARACTERIZING OLD WOODEN ARTIFACTS
Raluca Anamaria CRISTACHE1, Ion SANDU1,2, Viorica VASILACHE1,
Ioana HUTANU1, Liliana NICA1, Anamaria BUDU1
1
Al. I. Cuza University of Iasi, ARHEOINVEST Platform, Blvd. Carol I 11, 700506, Iasi, Romania
2
Romanian Inventors Forum, Str Sf. Petru Movila 3, L11, III/3, 700089, Iasi, Romnia
email: ion.sandu@mail.dntis.ro
ABSTRACT
The paper presents the dendrochronological dating method for the
archeometric characterization of old wooden artifacts. The aim of this method is to
give a certain cutting date of the tree from which the artifact was made. The
dendrochronological dating is based on wood anatomy, on the annual ring
measurements and their limiting factors (wood species, humidity, temperature,
growth area, etc.). The actual dating is made by comparing and matching the
measurements of each annual ring of the artifact with the proper
dendrochronological series.
KEYWORDS: wood artifacts, annual rings, dating, dendrochronology
1. Introduction
Dendrochronology is a discipline belonging to
the science of biology and is used to determine the
age of wooden objects. This method, despite being
implemented for use in dating archaeological artifacts
and buildings, is also used to solve artistic-historical
issues. The main goal of this discipline is to give an
exact date of cutting the wood from which the artifact
is made [1]. The dating method was developed by
Strokes and Smiley in 1968, continued by Fritts in
1976 and Schweingruber 1983 [2].
According to the Explanatory Dictionary, the
word "dendrochronology" has the following meaning:
science which deals with determining the age of
woody plants based on the study of the annual rings
formed by increasing the thickness of the root and
stem, the term originating from the Greek dendron,
tree, chronos, time and logos, science [3]. In other
papers, the dendrochronology is explained as the
science of dating events and changes in
environmental factors by comparative study of
growth rings of trees (the exact years of formation of
growth rings) [4]. In other words dendrochronology
studies the annual growth rings of trees, with the aim
of establishing the year when the wood was cut (the
last ring present). However, this method can provide
a wealth of information that is stored in the annual
rings, namely the climate change, the composition of
air, water, of the geographical area in which the tree
grew, and more [5, 6].
Dendrochronology enjoys prestige in dating

wooden artifacts. With this method were dated
musical instruments [7], houses [8, 9], caskets [10],
paintings [11-14] and many others.
This dating method is based on the biological
specificity of the trees, on their anatomical
characteristics. Wood is a biological material
composed mainly of cellulose, lignin, sugar, minerals,
essential oils, resins, etc. The characteristics,
quantities, and their location differences lead to the
great diversity of trees and plants species, giving
them properties as hardness, elasticity, high or low
density and so on [15]. For the dendrochronology
dating, a very important aspect, is the growth of the
tree, which is complex and specific: under the bark is
a layer of cells forming the cambium, whose role is to
divide and form outward the bark, and inwards the
xylem [16]. The way in which the cambium develops
to form the two tissues, lead to observable structural
limits. These are the annual rings of wood, visible at
softwoods and hardwood species with ring-porous
distribution, and less noticeable for diffuse-porous
distribution [4]. The newly created timber is designed
to carry the tree sap. When the life of these cells ends,
they become inactive and are converted into
heartwood when they have a specific color, darker,
the cells decreasing in diameter and hardening.
Concentric bands composed of dark and light-colored
areas form the annual rings. The age of tree can be
measured counting the rings from marrow to wood
bark [17].
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The appearance of the annual rings will vary

depending on the climate and the environment in
which trees grow. For example, in temperate zones
the annual rings are distinct, alternating the dark and
light shades of the ring (ringporous and semi-ringporous) [16]. In the tropics, many species of trees are
missing these biological signs of early and late wood,
which makes dendrochronology dating not possible.
The annual rings also vary in thickness; as the tree
ages, the wood becomes denser and the rings are
narrowing, the trunk circumference growing harder.
The design that we see on a stem section is the result
of variation of early and late wood, however in some
trees there are no significant differences between the
growth rings [18].
2. The principles of the method

In order for dendrochronology to evolve as the
dating method, there were imposed over time a
number of basic principles. The Dendrochronology
principles are a number of condensed rules, improved
over time, written to summarize the aspects of this
science. Their role is not to restrict the evolution of
science but to establish some areas of development.
The first principle appeared in 1785, Principle of
Uniformity, and the last in 1987, among them being
written six other principles. Not all 8 principles are
only for dendrochronology, some of them are written
for dendrochronology adjacent sciences [2, 5]. All
dendrochronology,
dendroclimatology,
dendroecology studies should be based on these
principles to leave no errors.
The Principle of Uniformity implies that by
linking environmental factors with the appearance of
annual rings, the physical factors with the biological
ones, it can be seen a correspondent both in the
present and future. "The present is key to the past"
idea continued with "The past is the key to the future"
[4]. The same physical and biological principles that
make the link between the current environment and
the variance of tree growth were valid in the past, the
annual ring characteristics being determined by the
same environmental conditions, both in the present
and in the past when that parameter is identified. In
other words the same environmental factors will
produce the same biological changes regardless of the
period, thus over time varying only the frequency and
intensity with which they occur.
The Principle of Limiting Factors explain the
details which are interpreted in the analysis of growth
rings. Therefore this principle illustrates the influence
of environmental factors, particularly rainfall and
temperature in the biology of trees. In other words,
the presence and absence of rainfall in a geographical
area, leaves an imprint in the growth of the annual
rings of trees, (the annual rings are narrower as the
years are dryer) which is a limiting factor for the trees

in that area, as elsewhere the temperature and it's
variation leads to a accentuated thickening or even to
the death of trees [19]. For many trees, especially
those in temperate zones, the climate is not the
limiting factor. On the other hand the processes
related to the position of the tree (competition for
nutrients in the soil or light) can be the growth
limiting factor [20].
The Principle of Aggregate Growth Pattern
connects the tree growth factors and the pattern
development of the annual rings. According to these
aspects from the form of the annual rings there must
be extracted information, namely a signal. This signal
represents
an
information
coming
from
morphological parameters and details of the annual
ring, applicable to a given problem. Outside the
signal is noise, that is represented by information not
relevant to the current problem. This principle says
that any individual series of growth rings can be
"decomposed" into an aggregate of environmental
factors, human and natural, that led to the creation of
that growth pattern over time [19, 20].
In 1990 the researcher Cook summed this
principle in a complex mathematical formula which is
based on four signals: biological growth curve of
various shapes, the macroclimatic general signal of
the area, the endogenous or exogenous disturbances,
and the noise or inherent error [4].
The Principle of Ecological Amplitude refers to
the ability of a tree species to accommodate in an area
with different environmental factors, thereby it refers
also to the inability of tree species to adjust, leading
to restricted areas of development. From this point of
view, the most useful trees for dendrochronology are
found most often on the edge of their geographical
distribution.
The Principle of Choosing The Geographic Area
consists in the criteria on which is based the selection
of the area of interest, according to the objectives of
the study. This principle was developed to determine
the differences between the selection criteria based on
the research needed, so for a dendrochronology study
will take into account the species of trees, the area
where there are located and the trees themselves, and
for a dendroecological study it will be considered the
pollutants in the area, the positioning of the trees and
the exogenous aspects [4, 19, 20].
The Principle of Crosdating is the basis for the
dendrochronology dating method. This means
matching the pattern for one or more growth rings of
a sample, with rings dated from developed tree-ring
series, in other words its rings are placed in time.
Crossdating is possible because environmental factors
that led to a limitation of growth are similar in all
trees in a given geographical area, the limiting factor
signal being delayed in each series of rings. This
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principle of dating can be synthesized in six steps: a)

highlighting the annual ring characteristics: total
width, width of early wood and the late wood,
density, color, in a plot, b) the timing parameter taken
into consideration starts from a single ring provided
that this ring is formed in one year and meets all
biological requirements, Otherwise, the timeline will
begin before or after the ring, c) identification of
growth rings used as references by comparing with
other cores, d) comparisons and dating should be
repeated and the reference samples should be from
different periods to include periods when the climatic
factors were a limiting factor, e) using the general
characteristics of the annual ring to insert zero values
where the rings are missing or for combining two
coats in a ring, f) the last step involves comparing the
data obtained with other reference series from
geographically close ranges, but it is not always
useful because of the influences of variation that can
blur the variation of macro-areas [19-21].
The Principle of Repeatability was created to
reduce the noise of a tree-ring series. For this purpose
it is necessary that from a tree to retrieve multiple
samples in order to decrease the possibility of internal
variations, and from a geographical area to obtain
samples from a number of trees in order to minimize
the noise [4, 19, 20].
The Principle of Standardization is related to the
principle of repeatability because it refers to
obtaining the best possible signal. To obtain the
desired signal, it recourse to standardization by a
specific algorithm of the growth series, (expressed by
the width of growth rings or other parameter) and
transforming them into growth indices that represents
the basic series to obtain the reference
dendrochronological series [4, 19, 20].
3. Work method
Dendrochronology is based on annual
periodicity of growth that is controlled by climate,
temperature and rainfall. In the temperate area, a
season of hibernation is installed between the fall and
spring and a growing season occurs during the
summer. When the vegetative period begins in May,
new cells are formed to conduct water from the roots
at tips of branches, these large cells forms the early
wood. In summer, at the end of June, starts late cell
formation, in the middle of September the radial tree
growth ceases for about 7 months. The result is the
gradual accumulation of new cells grown in one
season, forming an annual ring. Favorable growth
conditions will be observed in a large ring width,
while the unfavorable ones will lead to the formation
of a narrow ring, so it can be known not only the age
of the tree, but also the climatic fluctuations over time
[23]. This is demonstrated by measuring the rings
from many trees in a small area and comparing the

measurements obtained. The values of the measured
rings are inserted into a graph showing on the vertical
line the rings width, and horizontally each rings year.
Overlaying the plots, we get the growth ring curve
[18]. The synchronization of two plots is called
crossmaching or crossdating, which aims to identify
the common positions between the reference series
and the undated series. If the position between two
sequences of rings is shifted even by one year there
will be no matching between plots [4, 19-21]. This
series involves a collection of information, indices,
features of an annual ring parameter and characterize
a single wood species from a given geographical area.
The dendrochronological series is defined as a time
series of a annual ring parameter (total width, width
of the early wood or late wood, density, etc.),
measured and converted using a specific method standardization - in a series of indices. A
dendrochronological reference series for a particular
species and ecological area may be defined as a series
of indices of growth the signal environment
containing macro-areas, which can be used for dating,
reconstitution of the environment, etc. [4].
The crossdating can be done and between trees
from different sites, as long as it is used a basic
chronology built for the whole area. To build a
longest possible dendrochronological series for a
trees species, it is necessary that the data to come
from different trees of different ages and that these
data are overlapped and replicated to provide a valid
series. From this series, a part of an undated tree plot
can be overlapped on the dendrochronological series
to see where it falls, thus on each ring, the year when
it grown can be read accurately [24].
However the dendrochronological dating
method has disadvantages. First, not all samples can
be dated, but only the rings present in the sample can
be dated. This is not necessarily the date of the
woodcutting, or when it was used. For certain result a
sample needs to have bark, the last ring before it is
the last year of life of the tree. If the bark and last ring
are not present then the dating is not accurate. It may
happen that in some years due to climate change or
due to another factor that will be missing from the
development of the tree, the annual rings can be very
narrow, or wide only in certain areas of the trunk, or
not appear at all. These rings are considered as partial
or missing, and may lead to the impossibility of
dating or to a wrong dating [25].
From a practical perspective, for a
dendrochronological dating of a painting an edge of
the wood support must exposed, which is usually not
painted, it should be cleaned with a blade or
sandpaper. After the rings were exposed, they will be
numbered and measured through with a optical
microscope most likely to 1/100 mm scale. The
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measurements will be recorded and with their help a

graph which is to be compared and overlapped with
other plots of the reference series. In order for the
dating method to be successful, it should be taken
into account some factors: the analyzed area must
have at least 100 annual rings to prevent false dating,
the wood should be cut radially for its quality, and
also it must not have nodes or other growth
aberrations. The easiest dating of a wood support it
would be when it contains both the bark and marrow,
but this case is not applicable when it comes to
paintings. The sapwood, approximately 15-30 rings
just below the bark, has sugars that makes it
susceptible to insect attacks or wood decay fungi,
therefore, this layer is removed for a better quality of
the wood support for painting [18]. Without the
presence of these rings from sapwood in the dating
process, they will be approximated, according to
geographic area and wood species, which leads to an
approximate dating and not to a definitive and
accurate one. For oak the sapwood rings are estimates
for geographical areas, varying from 32 9 in
Northern Ireland, 20 6 and 26 7.5 for Germany,
15 6 to the Baltic, and 26 9 to Aegean region
[22]. In other species of trees, the sapwood is very
narrow, or it does not differ from the cambium. A
crossdating method, used most often to check
crossdating graphics is through specialized software
[26-28]. Among them, the most used is COFECHA,
but in laboratories Tellerevo, WinDendro, TSAPWin, are used also. The role of those software is to
compare and verify the measurements made by
crossdating and to find sections in which the undated
plot matches. The role of these programs is to check
and compare measurements made with other tree-ring
series, and find the section where the undated fits
series thus finding the year when the tree was cut.
There will not be a straight answer unless the undated
series has all the annual rings underneath the bark to
the marrow [28].
4. Conclusions
Most religious objects, artworks, artifacts,
buildings that are in the Romanian Cultural Heritage
do not have a well known date of execution at the
time of the discovery. To date an artifact, first of all it
is required a group of researchers from different
fields: chemistry, history, art, conservation, biology,
archeology, etc. Wooden artifacts can be dated totally
or partially using dendrochronology. Once the
preliminary steps have been completed, will be
exposed an area with visible annual rings or wood
cores will be removed. Annual rings will be
measured, placed in a graphic and then, using an
international database on the required wood species,
the data will be compared in a specialized software, to
obtain compatible sizes of rings (between the undated

series and the reference series), and thus the
corresponding years for each year.
Acknowledgement
This paper was done with the help of the Project
POSDRU/86/1.2/S/62307.
References
[1]. R. M. Stockton, J. A. Wixom, A. E. Hessl, A comparison of
two techniques for measuring and crossdating tree rings,
Dendrochronologia, 29, 2011, pp. 237243.
[2]. D. A. Norton, J. Ogden, Dendrochronology: a review with
emphasis on New Zealand aplications, New Zealand Journal of
Ecology, l0, 1987, pp 77-95.
[3]. A. Canarache, V. Breban, Mic dicionar al limbii romne,
1974, Ed. tiinific. Bucureti.
[4]. I. Popa, Fundamente metodologice i aplicaii de
dendrocronologie, 2004, Ed. Tehnic Silvic, Bucuresti, p 229.
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POLYOXOVANADATE Na2(NH4)4[V10O28].10H2O THERMAL

BEHAVIOUR
Denisa C. M. SIMONESCU1, C. CAPATINA2,

E. PARASCHIV3, V. PUNESCU3
Department of Analytical Chemistry and Environmental Engineering Faculty of Applied Chemistry and
Materials Science, University Politehnica of Bucharest, 1-7, Polizu Street, RO-011061, Bucharest, Romania;
2
Department of Environmental Engineering, University Constantin Brancusi, 3, Genova Street,
RO-210152, Targu-Jiu, Gorj, Romania
3
Dacia High School Bucharest
email: claudiamaria_simonescu@yahoo.com
ABSTRACT
Red-orange
crystals
of
a
polyoxovanadate
compound
Na2(NH4)4[V10O28].10H2O, suitable for X-ray determination have been obtained
from the filtrate of the system Cu(CH3COO)2.H2O: NH4VO3: Na2S2O3.5H2O in
molar ratio 1:1:1 at 905 used in order to copper-vanadium mixed sulfide
nanoparticles obtained. After the slow crystallization at room temperature for the
two months the single crystals were obtained. Single crystal X-ray diffraction
revealed that the compound obtained consists of distinct polyoxovanadate anions
[V10O28]6- which negative charge is balanced by two sodium cations, and four
ammonium cations. The structural characterization of this compound is in
according to the other polyoxovanadate obtained by Fratzky and coworkers [1].
Thermal properties of the as-prepared product were studied by nonisothermal
techniques together with IR spectroscopy and X-ray diffraction in order to identify
phases obtained during different thermal decomposition stages.
KEYWORDS: crystal structure, polyoxovanadate, polyoxovanadate anion
[V10O28]6-, single crystal X-ray diffraction, thermal behaviour, vanadium, vanadate
1. Introduction
Polyvanadates are compounds with a great
importance because of their structural diversity based
on various types of {VOx} polyhedra (x=4, 5, 6) [2],
and due to their potential applications in
biochemistry, medicine, catalysts, and electrode
materials [3]. For polyvanadates have been reported a
series of crystal structures, such as [V3O9]3- [4],
[V4O12]4- [5], [V5O14]3- [6], [V6O17]4- [7], [V10O26]4[8], [V10O28]6- [9], [V10O30]11- [10], [V12O32]4- [11],
[V13O34]3- [12], [V14O36]4- [13], [V15O36]5- [14],
[V15O42]9- [15], [V16O38]n- (n = 3, 7, 12) [16-18],
[V16O42]n- (n = 4, 7) [19, 20] [V17O42]4- [21, 22],
[V18O42]12- [14], [V18O46]5- [23], [V18IVO42H9(VVO4)]6,
[V19O49]9- [24], [V22O54]6- [25], [V34O82]10-[26],
[27],
and
[{(V4O4)O4}V12IVV18VO74]10[H12V12VO36(VIVO4)]4- [28].
The most of these polyoxovanadates have a
structure which can encapsulate neutral or charged
molecules functioning as templates [29].
The decavanadate structure has been

characterised from a number of its salts:
Ca6V10O28.16H2O,
K6V10O28.10H2O,
.
K2Zn2V10O28 16H2O [30], (NH4)6[V10O28].6H2O [31]
(HMTA
=
[HMTA-CH3]4[H2V10O28].5H2O
hexamethylenetetramine)
[32],
(C4N2S2H14)2[H2V10O8].4H2O [33]. A few articles
concerning the thermal behaviour of polyoxovanadate
have been published [34-38].
In
this
work,
polyoxovanadate
Na2(NH4)4[V10O28].10H2O was obtained by slow
crystallization of the filtrate of reaction between
copper acetate, ammonium metavanadate and sodium
thiosulphate (1:1:1) at 905 oC used in order to
copper-vanadium mixed sulfide obtained. From this
filtrate single crystals were obtained.
These single crystals were characterized through
the determination of their structural and chemical
formula by using elemental chemical analysis, single
X ray diffraction, IR spectrometry, and thermal
analysis.
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2. Experimental Section
All of the raw materials were purchased from
Merck Chemistry Co. Ltd.
The filtrate obtained after the separation of the
complex compound Cu3(VO)(SO4)2S.H2O from the
system Cu(CH3COO)2.H2O: NH4VO3: Na2S2O3.5H2O
in molar ratio 1:1:1 maintained at 905 for 1 hour
was submitted to a slow crystallization at room
temperature for a while. All of these substances were
purchased from Merck Chemistry Co. Ltd. The single
crystals obtained after the two months crystallization
were characterized by IR Spectroscopy and single
crystal X-ray diffraction. The elemental chemical
analyses were performed by an Electronics SPD
1200A ICP emission analyzer with a pump flow of
1.85 mL.min-1 and a flow rate of the auxiliary gas (Ar
99.99%) of 0.5 l.min-1. The nitrogen and hydrogen
were determined by combustion with the Carb Erba
Elemental Analyzer type -1106, an organic
elemental chemical analyzer. The method consists on
the automatically combustion of a standard sample,
and after that the combustion of the sample in an
oxygen flow at 1080C followed by the resulted gases
chromatographic determination. The IR Spectra was
recorded on a FT-IR 620 (Jasco, Japan)
Spectrophotometer in the 400-4000 cm-1 range using
potassium bromide pellets. Single crystal X-ray
diffraction was performed on a Bruker SMART
diffractometer, using graphite-monochromated Mo
K radiation ( = 0.710 73 ). For this purpose the
crystals were attached with silicon grease to a
cryoloop. Data was collected at room temperature
(297 K). The structures were refined with anisotropic
thermal parameters. The hydrogen atoms were refined
with a riding model and a mutual isotropic thermal
parameter. For structure solving and refinement a

software package SHELX-97 was used [39, 40]. The
drawings were created with Ortep and Diamond
programs [41].
The thermal behaviour of polyoxovanadate
obtained was performed by using a Q-1500 PaulikPaulik-Erdey derivatograph, at heating rates of 2.5-5
K/min and with sample mass of 20 mg.

Synthesis. The system Cu(CH3COO)2.H2O:
NH4VO3: Na2S2O3.5H2O in molar ratio 1:1:1 in 50
mL distilled water was maintained at 905 with
continuously stirring. After 10 minute of the
beginning of the heating in the reaction system was
obtained a green- yellow earth precipitate and a light
green solution. At this time the system temperature
was 74 C. After other 5 minute of heating the
precipitate became dark green and the temperature
was 82 C. After another 10 minute of stirring with
heating the precipitate changed into a green-brown
precipitate and the temperature of the system at this
time was 92 C. The mixture formed by a greenbrown precipitate and a green solution was
maintained at 905 with continuously stirring for
one hour. At the end the brown-violet precipitate was
filtered, washed with distilled water and dried at room
temperature. The chemical analysis of this precipitate
revealed that this precipitate correspond to the
complex compound Cu3(VO)(SO4)2S.H2O.
The yellow filtrate obtained after the separation
of the complex compound was submitted to a slow
crystallization at room temperature.
After two months the red-orange single crystals
were obtained.
22
20
%T
10
0
4000
3000
2000
1000
400
Wavenumber[cm-1]
Fig. 1. Infrared spectrum of Na2(NH4)4[V10O28].10H2O single crystals
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The elemental chemical analyses of the single

crystals obtained showed that the single crystals are
polyoxovanadate Na2(NH4)4[V10O28].10H2O. Anal.
Calcd for Na2(NH4)4[V10O28].10H2O: Na, 3.66; V,
40.66; N, 4.46; H, 2.87; O, 48.40. Found: Na, 3.56;
V, 40.09; N, 4.22; H, 2.71; O, 49.42.
The IR spectra (figure 1) of the single crystal
confirmed the polyoxovanadate chemical formula.
As can be seen from this figure the observed
bands which are in the range of 3600-3200 cm-1, and
1623, 1401 cm-1 are characteristic for the water

molecules and ammonium groups.
The strong bands at 953cm-1 can be assigned to
the stretching vibrations of (V=O) bonds, which are
consistent with that of some known polyoxovanadates
[42-46]. The bands from 810cm-1, 740cm-1, 595cm-1,
519 cm-1 are assigned to the antisymmetric stretching
vibrations of V-O-V [31, 45].
X-ray Crystallography. The details of the
crystal structure determination for single crystals
obtained are given in Table 1.
Table 1. Crystallographic Data for Na2(NH4)4[V10O28].10H2O

Empirical formula
Molecular weight
Crystallographic
system
Space group
Unit cell parameters
Ratio between cell
parameters
Cell volume
Z
Calculated density
H36N4Na2O38V10
1255.71 g/mol
triclinic
P -1 (2)
a=8.4935(8) b=10.4201(10) c=11.2772(10) =68.54(0) =87.27(0)
=67.16(0)
a/b=0.8151 b/c=0.9240 c/a=1.3277
850.84(61) 3
1
2.45055 g/cm3
Single crystal X-ray diffraction obtained

revealed that the compound consists of distinct
polyoxovanadate anions [V10O28]6- which negative
charge is balanced by two sodium cations, and four
ammonium cations (Figure 2). Sodium cations are
hidratated with six water molecules, they are sharing
two water molecules. The polyoxovanadate anion
[V10O28]6- has a structure which consists of 10 V
centres in the structural unit. Four of the V atoms are
in a square pyramidal configuration. The V-O bond
length is between 1.5964(19) and 2.3546(17) and
O-V-O angles are in the range of 73.90(6) 174.85(8). The six of the vanadium atoms are in an
octahedral configuration. In this case the V-O bond

length is between 1.6828(17) and 2.1133(16) and
O-V-O angles are in the range of 78.39(7) 165.90(8). The VO6 octahedra are in an edge-sharing
mode. The terminal oxo-V distances for the eight
metal atoms (V2, V3, V4, V5, V7, V8, V9, V10) all
lie within the narrow range of 1.5964(19)-1.6175(17)
being similar with other V-O distances from other
polyoxovanadate [19].
Sodium ocurs as a pair of edge-shared NaO6
octahedra. In the octahedron, sodium is surrounded
by six water molecules. The Na-O bond distances are
in the narrow range 2,334(3)-2,433(3) (Figure 2).
Fig. 2. Polyoxovanadate Na2(NH4)4[V10O28].10H2O structural formula
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This structural characterization of the

polyoxovanadate
compound
Na2(NH4)4[V10O28].10H2O is in according to the other
polyoxovanadate structure [1].
The
thermal
decomposition
of
Na2(NH4)4[V10O28].10H2O (Figure 3) obtained from
system Cu(CH3COO)2.H2O:NH4VO3:Na2S2O3.5H2O
in molar ratio 1:1:1 at 905 starts with one

endothermic step corresponding to the evolving of ten
water molecules.
The reaction intermediate obtained in the
temperature range 310-630 C and the final
decomposition products were identified also by X-ray
diffraction investigations (Figures 4 and 5).
Fig. 3. TG, DTG and DTA curves obtained for polyoxovanadate Na2(NH4)4[V10O28].10H2O
obtained from the filtrate of the system Cu(CH3COO)2.H2O:NH4VO3:Na2S2O3.5H2O
in molar ratio 1:1:1 at 905 (heating rate=5/min)
Fig. 4. X-Ray pattern of the intermediate obtained from polyoxovanadate

Na2(NH4)4[V10O28].10H2O thermal decomposition at 310-630 C
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Fig. 5. X-Ray pattern of the intermediate obtained from polyoxovanadate

Na2(NH4)4[V10O28].10H2O thermal decomposition at 630-900 C
X-Ray patterns of the intermediates obtained
from polyoxovanadate Na2(NH4)4[V10O28].10H2O
thermal decomposition at different temperature fields
(Figure 4 and Figure 5) were used to establish the
thermal decomposition steps.
Thus,
the
thermal
behaviour
of
Na2(NH4)4[V10O28].10H2O obtained from the filtrate
of
the
system
Cu(CH3COO)2.H2O:NH4VO3:Na2S2O3.5H2O in molar
ratio 1:1:1 may be expressed by the following
equations:
and four VO5 pentahedra, two fitted above and two

fitted below the array by sharing edges. The IR
spectra, and the short distance (1.6017(18) 1.6111(18)) revealed that in the decavanadate anion
are V=O bonds. The sodium cations are hidratated
with six water molecules sharing two water
molecules.
Thermogravimetric studies reveal the complete
removal of all water molecules and ammonium
cations as ammonia in multiple steps ranging from 30
to 900 C.
Na2(NH4)4[V10O28].10H2O Na2(NH4)4[V10O28] +
10H2O
References
Na2(NH4)4[V10O28] + 1/2O2 Na2(NH4)2[V10O28] +

2NH3 +H2O
Na2(NH4)2[V10O28] + 1/2O2 Na2[V10O28] + 2NH3
+H2O
2Na2[V10O28] + O2 Na2O + 3Na0.76V6O15
Na2O + Na0.76V6O15 + O2 Na2O + V2O5 + NaV6O15
4. Conclusions
The polyoxovanadate Na2(NH4)4[V10O28].10H2O
was obtained as single crystals by an unconventional
method and its structure was determined by single
crystal X-ray diffraction. After the structure solving
and refinement it was concluded that the
decavanadate anion [V10O28]6- consists of 6 VO6
octahedra in a rectangular 2x3 array sharing edges,
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[43]. B. X. Dong, Y. H. Chen, J. Peng, Y. M. Kong, A. X. Tian,
H. S. Liu, J. Q. Sha, J. Mol. Struct., 788 (2006) 200.
[44]. T. Kurata, Y. Hayashi, A. Uehara, K. Isobe, Chem. Lett.,
2003, p. 1040.
[45]. B. Dong, C. J. Gmez-Garca, J. Peng, S. Banmansour, J.
Ma, Polyhedron, 26 (2007) 1310.
[46]. F. Gagnard, C. Creisner, W. Tremel., Inorg. Chem., 36
(1997) 352.
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COMMUNICATIVE TOOLS USED TO WORLDWIDE PROMOTION

OF INDUSTRIAL PRODUCTS
Carmen-Penelopi PAPADATU
Dunarea de Jos University of Galati, Romania
email: cpapadatu@ugal.ro
ABSTRACT
This paper will provide some aspects regarding communicative tools used to
worldwide promotion of metallurgical /industrial products.
The role of marketing communications includes distributing information,
promoting image and reputation, creating and stabilizing product and service
demand, providing competitive differentiation, generating sales leads, ensuring
customer retention and loyalty, and motivating staff. To accomplish these and other
objectives, there are many marketing communication tools available: advertising,
direct marketing and relationship marketing, sponsorship, event marketing, sales
promotion, public relations, and other, alternative strategies.
KEYWORDS:
promotion
communicative
tools,
1. Introduction
At present time, we can see that our life was
improved with so much news about everything,
including industrial product. We live together The
Information Age (also known as the Computer Age,
Digital Age, or a New Media Age).
This Information Age is a period in human
history which is characterized by the shift from
traditional industry to the industrial revolution
brought through industrialization, with an economy
based on information computerization. The onset of
the Information Age is associated with the Digital
Revolution just as the Industrial Revolution marked
the onset of the Industrial Age (source:
http://en.wikipedia.org).
During the information age, the digital industry
creates a knowledge-based society surrounded by a
high-tech global economy. This high-tech global
economy promotes its influence on the manufacturing
domain and on the service sector and it operates in an
efficient and convenient way.
In a commercialized society, the information
industry is able to allow individuals to explore their
personalized needs. It simplifies the procedure of
making decisions for transactions and significantly
lowers costs for both: producers and buyers
In 1970s appeared the electronic paper, e-paper
and electronic ink.
The electronic paper displays like ordinary
paper, theoretically making it more comfortable to
industrial
products,
worldwide
read, and giving the surface a wider viewing angle

compared with conventional displays.
The contrast ratio is available and displays since
2008. This might be described as similar to that of
newspaper.
An ideal e-paper display can be read using direct
sunlight.
Since 1970s until 2013, The Information Age
was adopted very well by the public from all over the
world. We mustnt neglect that in 1989 appeared the
Internet form which is the possibility to communicate
between the people more easy.
The audience passed without problems, in the
last
two
decades,
new
technologies
of
communication.
These
new
communication
technologies develop continuously, rapidly and help
spread information with very high speed among the
general public.
The fast evolution of technology in daily life, as
well as of the new style of life during of the
Information Age has allowed rapid global
communications development and a rapid
development of networking to shape modern society.
2. Communications tools
Communications tools used to worldwide
promotion of metallurgical/industrial product are: TV
Advertising, Press Advertising, Radio Advertising,
Cinema
Advertising,
Sponsorship,
Leaflet
Distribution, SMS or Internet way.
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2.1. TV Advertising
TV advertising is the purest form of direct
marketing. It is a numbers game the more people
impacted upon by a message, the greater the response.
TV not only builds audience coverage quickly,
but also lends credibility to your overall proposition,
allowing viewers to see your offer in the company of
its peers. Clever airtime planning can optimize
response levels and effectiveness whilst minimizing
media costs [1].
Sponsoring offers an opportunity to support well the

locally-based community events with real benefits for
your company.
2.6. Leaflet Distribution

Leaflet Distribution provides a means of
optimizing targeted impact within a specific and
controlled area.
The advertising flyers can be distributed with
newspapers (shared) by the Post Office.
2.2. Press Advertising
2.7. SMS Campaign
Press advertising also reaches substantial

numbers of people and a combination of national,
regional and ethnic publications should be
considered.
Press advertising describes advertising in a
printed medium such as a newspaper, magazine or
trade journal.
It is a form of communication for marketing
direction and its used to encourage or to manipulate
an audience formed by: viewers, readers or listeners.
The desired result is to drive consumer behavior
with respect to a commercial offering. This type of
work belongs to a category called affective labor.
Advertising market in Romania registered a
decrease of 3.6% in 2012.
The text messaging marketing works in a similar

way to traditional direct mail. Its a big advantages
because the message reach a person rather than an
address and that newly received text messages are
more likely to be opened and read than paper [1].
2.3. Radio Advertising

The Radio stations, today, fight for their
advertising in clusters or sets, scattered throughout
the broadcasting hour. Advertising rates can vary
depending on the length of spot the advertisers elects
to run. Radio Programmes reaches audiences at times
and in circumstances that other media cannot achieve
(in their workplaces or in their cars for example). It is
also ideal for building up the frequency of impact, for
reinforcing of some key aspects of publicity
campaign, such as a free phone number. The Radio
Programmes acting as a call to action to potential
customers who may didn't know that these products
are actually in the market.
2.4. Cinema Advertising

It is an extremely cost-effective medium that can
be targeted to specific regional locations and for a
specific industrial product. It is used to reinforce
campaign messages within a relaxed and influential
environment.
The cinema advertising is not likely to generate
an immediate response but it is likely to be effective
as a low-cost, long-term reminder medium.
2.5. Sponsorship
The sponsorship is a fast way to reach an
audience in an increasingly crowded market.
3. The internet remains powerfull

The Internet will register a growth, a major
contribution coming from the area of performance
media corresponding to Zenith OptimediaAdvertising Expenditure Forecasts [2, 3].
In 2013, the Internet has reached a share more
than 12% of total consumption in Romania.
The investments in the field of television have
dropped with 3% from last year.
In 2013, Print media has registered a decrease of
15% in the case of newspapers and a decrease of 10%
in the case of magazines.
Data report press released by Zenith
Optimedia, assure that the global market looks an
development of advertising for industry product and
marketing. It has increased by 3.5% this year [2].
It is expected an increase of publicity for
industry product with at least 4% in 2014.
The dramatic growth in Internet usage was
transformed into a major global communications
tools.
The internet has become a major source of
information,
communication,
entertainment,
promoting: news, movies, Science, Technical
evolutions, information from medicine applications....
But, first of all, the internet has become a veritable
point of virtual meeting for millions young people.
There have been three phases in the
development of the internet as a communications
tools.
In the first phase it was used by experts, or by
the global scientific community, to communicate
information to each other.
In the second phase, the internet way was used
by organizations, business men and governments to
communicate.
In the third phase, we had the horizontal
communication, which it means the possibility to
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create networking sites or internet blog. It means the

possibility to discuss with everybody from each part
of the world about everything.
As a result of these phases, 56% of the people
from European Union used social networking sites in
August 2007 and more than 61% - in December 2012.
Internet way evolution
70
60
[% ]
50
40
Internet way evolution
30
In Europe, in December 2007, all media users

used most: TV set -36%; radio -26%, internet sites
24%, newspapers only 7% [2].
In December 2009, all media users used most:
TV set-30%; radio-25%; internet sites - 36%;
newspapers only 6%.
In December 2012, all media users used most:
TV -18%; radio-17%; internet sites -61%. More than
45% from internet messages were dedicated for
industry promotion.
In figures 1-2 were presented the evolution of
some communications tools evolution in European
Union.
4. Conclusions
20
10
0
2006 2007 2008 2009 2010 2011 2012 2013
Many of us have struggled through one boring

and non-productive video-conference in which the
images lagged behind the audio to the point of
distraction and many of us have sent an e-mail
message in an emotional moment.
Online communication is a new phenomenon. It
appeared into the world existence toward the end of
the 20th century. Online communication is growing at
one of the fastest rates of any new form of
communication between people, in all over the world
and its long-term impact is expected to be substantial.
More than 45 % from internet blogs/messages
were dedicated to industrial product promotion.
Year
Fig. 1. Internet way evolution during last five

years
[% ]
TV audience evolution
40
35
30
25
20
15
10
5
0
2006
References
2007
2008
2009
2010
2011
2012
2013
year
Fig. 2. TV audience evolution during last five

years
The Internet way is overtaking other more
conventional media as a source of information.
[1]. www.info@prlimited.co.UK.
[2]. www.ec.europa.eu/education.
[3]. Belanger, F., Jordan, H. Diana, Evaluation and
implementation of distance learning: technologies, tools and
techniques, Library of Congress Cataloging in Publication Data2000, ISBN 1-878289-63-2.
[4]. Papadatu, C. P., The Environment politics in Balkans, Editura
Fundatiei Universitare Dunarea de Jos Galati, 2008,ISBN 978973-627-414-5.
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CONTRIBUTIONS CONCERNING INTEGRATED SCIENTIFIC

CONSERVATION OF CULTURAL AND NATURAL HERITAGE
Petronela SPIRIDON1, Ion SANDU1, Viorica VASILACHE1,
Irina Crina Anca SANDU2
1
Alexandru Ioan Cuza University of Iai, Interdisciplinary Research and Education Platform ARHEOINVEST,
Laboratory of Scientific Investigation and Conservation of Cultural Heritage,
2
Requimte e Ncleo do Departamento de Conservao e Restauro, Faculdade de Ciencias e Tecnologia,
Universidade Nova de Lisboa, Campus da Caparica, 2829-516 Caparica, Portugal
ABSTRACT
Term conservation is attributed to the ensemble of complex and differentiated
activities, sequential or not to valorization of the cultural and natural heritage
assets. Today we talk about Conservation Science like new field, interdisciplinary,
which assume the modern concept of integrated conservation. It includes a system
of measures developed during the valorization in museums and has in attention,
protection and valorization of the natural and cultural heritage assets, in an
integrated manner to enable socio-economic and cultural development, both at the
micro and the macro- system. In this context, the aim is development and use of
generally accepted principles and norms so that integrated conservation to be
priority and to be stimulating for all involved in this process. Regarding these
aspects, the current work treats the current national and international policies, by
placing the emphasis on the role of community members and public, correlated with
research, training and institutional development infrastructure, in the work of
integrated conservation, sustainable for the regions with tangible value heritage.
KEYWORDS: conservation science, national and international policies,
principles and codes of ethics, terminology, investigation, research, archaeometry
1. Introduction
At present, the term conservation is attributed to
the ensemble of complex and differentiated activities,
sequential or not to valorization the cultural and
natural heritage assets [1, 2]. Among these are [3]:
- Development of standards for the protection
and tutelage of cultural assets;
- Establishing principles and systems/means for
classification, cataloging and research;
- Interventions of maintenance, protection and
preservation (acclimatization, treatments to halt the
destructive physical-structural processes and the
evolutionary alteration);
- Development of scientific research focused on
priority areas: new materials and procedures of
preservation and restoration, new methods and noninvasive investigative techniques, new systems of
museum display and enhancement, new systems of
protection and so on;
- Developing their infrastructure and

partnerships with institutions, workshops and
laboratories on new research topics;
- Formation of networks of such centers, which
have attention to valorization of the assets less
known or newly discovered ones, especially those
from disadvantaged areas.
In a broad sense, generic, the term conservation
includes
distinctly
investigatigation/research
activities, preservation and restoration.
Conservation Science, like new field,
interdisciplinary, which assume the modern concept
of integrated conservation includes a system of
measures developed during the valorization in
museums.
This has in attention, protection and valorization
of the natural and cultural heritage assets, in an
integrated manner, to enable socio-economic and
cultural development, both at the micro and the
macro-system. It aims in this way, development and
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use of generally accepted principles and norms, so

that integrated conservation to be priority and to be
stimulating for all involved in this process and for all
society actors, including public and community
members from the regions with tangible value
heritage.
It must therefore, a strict control of the influence
of all domestic and industrial activities in the same
area, with the total elimination of pollution sources,
the directed development of urban infrastructure,
regulating the movement and transport demarcation
of protection and development status/their functions,
increase cultural and environmental education etc.
[4].
2. Principles in Conservation Science

The fundamental principles governing the rules
applied in conservation science through: regulations,
orders, codes of ethics/ laws, decrees, orders,
decisions, etc. are:
- Conservation is a complex field, with global
character, scientific (theoretical) and technological
(applied) that requires a gradual - sequential approach
to
the
specific
activities
required
from
discovery/acquisition
to
display/valorization/hoarding, neglect of any activity
can cause negative effects on the conservation status
of assets [5].
- Conservation include public interest activities
and their achievement must be consistent with the
national and international standards [6].
- Conservation requires the approach "less is
more"[7] - scientific analysis can be initiated only
after a careful examination and a sufficient
justification, the physical preservation of the object
being a priority [8].
- Conservation is based on the principle of
professional confidentiality.
At these fundamental principles, in the field of
conservation science, it is added a series of specific
principles [9], namely:
- Keeping entirely on the original parts of the
object/minimal intervention (Primum non nocere).
- Compatibility of the materials and the
interventions.
- The use of some materials, substances, etc. and
application of some methods that were originally
studied and tested.
- The use of some materials, substances, etc.
reversible, which may subsequently be removed
without affecting the status of the object.
- Legibility of the interventions.
- Restoring through the reintegration stops
where begins hypothesis - will not be made
completions in the absence of more than 50% of the
original (unless there replicas, copies or photographs

document allowing such an initiative).
Monitoring the evolution of the conservation
status of the restored object by performing periodical
checks.
3. Deontological aspects
According to the document entitled The
conservator - restorer - a definition of the profession,
ICOM-CC presented in Copenhagen in 1984, the
term conservator-restorer means a professional who
practice conservation and restoration of cultural
heritage [8]. This dual formulation of the profession
is adopted by international organizations as:
ICCROM, UNESCO, ECCO, but was never accepted
in the UK and USA. Moreover, in recent years
endeavoring a dissociation and definition of terms,
implicitly of the profession of restorer or conservator,
Swiss National Museum was the first European
national institution that introduced the name, still
unused to Kurator (curator) eliminating the
ambiguous meaning given by the double formulation
specified above [4], and Romania became the first
and only country who create at the level of museum
institution the function of conservator [4].
As regards the identification and formulation of
the professional conduct aspects, Antony J. Duggan
noted in 1984 [10] that any code of ethics is almost
certainly incomplete, because the social conventions
changes continuously and carry with them new
models of professional practice.
According to the Code of Ethics promoted by
E.C.C.O. in 2003, the specialists operating in the field
of conservation science enjoy principally of the
following rights: to act directly on cultural assets
being responsible towards author, owner and the
society, to deny any request for intervention that is
contrary to the ethical code and obtain the all relevant
information for the conservation a cultural object
from the owner/custodian.
The same code of ethics mentioned above
defines the responsibilities, respectively the specific
obligations of specialists in the field (scientific
conservator,
investigator,
curator,
restorer,
museographer) towards: cultural property, the
owner/custodian, colleagues and profession. Also
included are the responsibilities and obligations
towards the public, which we find stipulated in
chapter IV, art. 10 of the ONU Convention for the
Safeguarding of Intangible Cultural Heritage in 2003
[11], pursuant to which it must developing and
promoting educational programs, information and
greater public awareness to a deeper understanding of
all activities in the field of Conservation Science.
In the majority the codes of ethics proposed by
the international organizations at the European level,
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the specialists from conservation science are

encouraged to conduct research and to understand the
methods of scientific research.
4. Fields of activity
The Conservation Science concerns all activities
that aimed at preserving unaltered the appearance of
heritage objects (and the messages they send), as
close to the original, the process of the valorization
continues, integrated social and with the preserving of
historical stratification (traces of certain significant
events), putting together the efforts of preservation
and restoration, and the security guard [2, 12].The
specialists in the field operate in several lucrative
subdomains that highlights the route they have
generally, all heritage assets, namely [1]:
- Discovery/acquisition/transfer, taking into
custody and itineraries.
- Scientific investigation.
- Typological classification and grouping (by
material, artistic technique, conservation status etc.),
cataloging and documentation of cultural asset.
- Passive preservation (preventive) or
acclimatization.
- Active preservation (curative) or treatments to
halt of deterioration and degradation evolutive
processes.
Restoration
(consolidation,
structural,
chromatic and environmental reintegration).
- Valorization (museistic and touristic).
Hoarding
researching
the
new
historiographical
and
archaeological
sources
(documents, archives).
- Protection (guard against thefts, vandalism,
fire and disasters) and maintenance (cleaning,
acclimating, lighting, etc.).
Of these scientific investigation is conducted
focusing on six expertises:
- Authentication - establishing paternity (author,
school custodian, owner).
- Asset evaluation (share stock exchange and
catalog).
- Establishment of conservation status
(mechanisms, processes, developments on damage,
degradation identified).
- Studies of compatibility (compatible new
materials and processes used in interventions to
preserve/restore).
- Monitoring behavior of interventions during a
fixed period of six months, a year or two years.
- Ongoing monitoring of the conservation status
(environmental
factors,
conservation
status
display/storage).
Of these expertises, the authentication and the
establishment of the conservation status requires
corroboration of the analytical methods from various
disciplines related involved in the conservation

science respectively, co-assisting between two or
more instrumental techniques. In carrying out those
expertises, an important role it plays the
Archaeometry, which through the transformation of
the archaeological information in one quantitative,
measurable offers clarifications that allow dating,
establishment of paternity, heritage assessment and
establishment of conservation status.
Lately, referring to the scientific investigations
specific of the integrated conservation, more and
more authors [6]. highlights the importance of the
setting up a team that, in addition to the conservator
and the consecrated specialists in the field (curator,
conservator, etc.), should Include the representatives
of the pure sciences (Geology and Mineralogy,
Chemistry, Biology, Science applied, Environmental
science), of the technology areas, of the art history [6]
and even the members (artists and local native) of
communities from regions with tangible value
heritage.
This inter-multidisciplinary collaboration offer
support to the conservator in his work, not only in
that will be supported in investigating treatment
options, in finding materials and identifying the
techniques used by the artists, in establishing the date
of manufacture and investigating the optimal
materials (including from the cultural and
ethnographic perspective), but will get a
contextualization and justification of scientific data
through visual inspection and through the results of
historical research (oriented to knowledge of the
cultural original context).
Inclusion in the specialist teams of some
members of communities from the regions with
tangible value heritage may be surprising, but shall be
aligned to the modern concept of integrated
conservation, according to which followed up the
elaboration and use of some principles, standards and
practices unanimously accepted so as to be simulative
for all actors involved in this process.
However, even if the concept of integrated
conservation is modern, the attempts to attract the
public/community members in the activities aimed at
preserving cultural heritage are not very recent.
This approach was subtly made since 1964 by
the International Charter for the Conservation and
Restoration of Monuments and Sites, adopted at the
Second International Congress of Architects and
Technicians of Historic Monuments, in Venice [13],
in which specify that monumental works of the
peoples are considered as a common heritage and,
vis-a-vis future generations, it is necessary to protect
them responsible for transmission in the fullness of
their authenticity and was affirmed in 2003 by ECCO
Code of Ethics [14, 15], which mentions that the
work of preservation/restoration is an activity of
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public interest and should be conducted in accordance

with national laws and international
5. Conclusions
Involving community members in the scientific
investigation process specific of the integrated
conservation may have a fundamental role in the
management of the cultural heritage and may be even
a means of guaranteeing the right of public access at
cultural value resources, both now and in the future.
Moreover, through this approach, the public can
be educated and transformed into a actor sociocultural active, into a collaborator in the
preservation/restoration process of the cultural and
natural heritage assets and even into a promoter of
cultural, ethnographic and religious value.
It impose the integration of active participation
of the population in the cultural heritage conservation
policy, so that later it can be supported and promoted
through the cultural policies and measures developed
in accordance with the social and economic, and
adapted to each level geo-political (level local,
national, regional or international).
Such participation shall be based on the access
to knowledge, a condition by which informing the
public is an important element of integrated
conservation and that has a direct effect on cultural
expressions of individuals/groups/companies.
References
[1]. I. Sandu, Aspecte interdisciplinare ale tiinei conservrii
patrimoniului cultural, International Workshop Cercetarea
romnesc n context european, Ed. Universitii Alexandru Ioan
Cuza, Iai, 2013, pp. 67-92.
[2]. I. Sandu, I. G. Sandu, A. Dima, Restaurarea i conservarea

obiectelor metalice, Ed. Corson, Iai, 2002.
[3]. G. Perusini, Il restauro dei dipinti e delle sculture lignee.
Storia, teorie e tecniche, Del Bianco Editore, Udine, 2004.
[4]. A. Moldovan, Conservarea preventiv a bunurilor culturale,
Ediia a IV-a revizuit i adugit, Ed.Cetatea de Scaun,
Trgovite, 2010.
[5]. ***, Professional Guidelines (II): Code of Ethics, ECCO,
2003.
[6]. J. H. Stoner, Changing Approaches in Art Conservation: 1925
to the Present, n (Sackler NAS Colloquium) Scientific
Examination of Art: Modern Techniques in Conservation and
Analysis Proceedings of the National Academy of Sciences, pp. 4057, (2005), http://www.nap.edu/catalog/11413.html.
[7]. H. Jo-Fan, Data and interpretation: enhancing conservation
of art and cultural heritage through collaboration between
scientist, conservator, and art historian, IOP Science, 2012, IOP
Conf. Ser.: Mater. Sci. Eng. 37 012003, pp.1-6,
http://iopscience.iop.org/1757-899X/37/1/012003.
[8]. H. C. von Imhoff, Aspects and development of conservatorrestorers profession since WWII, E-conservation. The on-line
Magazine, No. 8 (2009), pp. 53-61, http://www.econservationline.com/content/view/717.
[9]. ***, HOTARREA nr. 1546 din 18 decembrie 2003, pentru
aprobarea, Normelor de conservare i restaurare a bunurilor
culturale mobile clasate, art. 32, Ministerul Culturii i Cultelor,
Bucureti, 2003.
[10]. A. J. Duggan, Ethics and the curator, Manual of curatorship.
A guide to Museum Practice, (edited by John M.A. Thompson),
Museum Association, Butterworths, London, 1984.
[11]. ***, Convention ONU for the Safeguarding of Intangible
Cultural Heritage, (chapter IV, art. 10), Paris, 2003.
[12]. I. Sandu, Nomenclatura patrimoniului cultural, Ed.
Performantica, Iai, 2004.
[13]. ***, International Charter for the Conservation and
Restoration of Monuments and Sites, adopted at the Second
International Congress of Architects and Technicians of Historic
Monuments, Venice, 2003.
[14]. ***, Professional Guidelines (II): Code of Ethics, ECCO,
Copenhaga, 2003.
[15]. ***, Carta for Protection and Management of the
Arheeological Heritage, ICOMOS, Roma, 1990.
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MATERIALS AND TECHNIQUESSHAPING THEM INTO ART

Gh. FLOREA1, L. D.DRAGOMIRESCU2, L. PARASCHIV3,
E. PARASCHIV4
1

Theoretical high school Alexandru Ioan Cuza of Bucharest
3
Politehnica University of Bucharest
4
Dacia High School Bucharest
email: gflorea@ugal.ro
ABSTRACT
This article presents some of the materials used to produce art works in close
connection with human evolution from its beginnings until today.
There are also short presentations of their making techniques, which, with few
exceptions, remained the same until today.
KEYWORDS: materials, techniques, art
1. Introduction
2. Materials and works of art
Art appears at the beginning of the Upper

Paleolithic period and ends at the end of the Iron Age,
and in some parts of the world eaven earlier,
approximately between 40000-10000 BC, traces of its
being discovered all over the world.
Stone, bone, wood, horn, coral, clay, metals,
ivory, glass, pearls are materials that art has been
repersented by and in some cases they still are.
For several tens of thousands of years after the
appearance of the human being, stones, animal bones
and horns, wood and clay were the main materials
used to make tools, household items or weapons and
ornaments, statues etc.
Archaeological discoveries have revealed tools,
weapons and artifacts dating from this time, made just
from these materials that are used even today to make
similar products, when the material range has
expanded considerably.
If objects made of stone, bone or horn, ivory and
clay can still be found, not the same can be said about
wood objects due to its perishability they havent
resisted the passing of time.
The human evolution and the discovery of
metals and fire led to an even greater diversity of
materials used in the mans daily life and among them
are works of art.
Since the Paleolithic, art began its transition
from being made with common non-metal materials
to the noble and precious metals.
Experts say that the earliest works of art that

have been preserved without degradation were made
from burnt clay, although the oldest sculpture in the
world seems to be dating back more than 400,000
years, made from stone and was found in Morocco.
It is in this case a stone object showing clear
changes made by man: some pitting that suggests the
neck, arms and legs, and on its surface can be seen
some red spots, possible remnants of a coat of paint
In the late Paleolithic, about 35,000 years ago
began to appear more frequently, small stone
sculptures and figurines representing animals or
women
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Fig. 1. Venus Lespugue
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One of the figures of this kind is a statue known

as the Venus of Lespugue.
She represents a woman with generous forms
and dates back approximately 20,000 years, a period
corresponding to primitive art intuition, the geometric
shapes were still not relevant to man, the artist using
his instinct to find the way to the most surprising
expressions.
In the same category we can find statue of
Willendorf, much older than Venus.
If we think of them, as historians say,
personifications of fertility, we can imagine their
magical thinking in making them; we also must not
fail to notice their aesthetic appearance.
The Neolithic marks the transition to polished
stone and the first appearance of large statues and
statues and stone ornaments.
Fig. 2. Phidias - panateneelor Procession,

Parthenon (frieze)
Starting with the Sumerians, with the first stone
statues, and continuing with the Egyptians and
Greeks, we reach the end of antiquity in Ancient
Rome, each leaving us impressive reliefs and statues.
honor of the goddess Athena and on the walls are

presented battles between centaurs and Lapita.
Perfection in stone sculpture (marble) is also
achieved in Italy in the Renaissance through
Michelangelo Buonaroti.
And today stone of various types (granite,
marble, etc.) is processed by sculptors and specialized
exhibitions and museums are housing many of their
works.
Being the most common material on Earth's
surface and can be easily softened and processed, clay
could not go unnoticed and it was used since ancient
times, if not the same period as stone but at least a
period close.
Clay was easy to shape by soaking in water and
the forms which were given only depend on the
ingenuity of the craftsman and possibly on the
customers demand.
Since the beginning there where household
objects made from clay, molded by hand, followed by
air drying, burning and glazing.
These objects, with the advent of decorations,
turned into works of art.
Primitive man has shaped from mud, since the
Paleolithic, a number of animals, creating the first
sculptures whose designs were taken from the
surrounding life in nature (bison, reindeer,
mammoths, etc.) also proving more spirit of
observation. Regarding the use of modeling strictly in
the artistic way, small statues of Tanagra were and
remain true works of art.
Fig. 4. Tanagra figurine

Fig. 3. Michelangelo's David
The Greek Parthenon, a remarkable work of
architects and artists, is decorated with statues
depicting various scenes of mythology, frieze,
executed by Phidias, depicting organized feasts in
They were made of clay subjected to molding

and painting and represent beautiful women and girls
that charms with tenderness and delicacy.
The originals are spread throughout the Greek
world, and in time start to appear on the periphery,
with changes made to them by local customs.
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A mold to obtain these figurines was found in

Dobrogea Callatis.
Even today, clay is used in the production of
various household items or decorative objects, fantasy
and craftsman of the artist playing an important role
in the artwork.
The beginnings of metal casting are also linked
by stone and clay.
The first permanent forms, open or closed, were
made of stone, clay was used to make forms of parts
made from wax models, using them for wrapping.
Lets not forget the casting of statues whose
materialization starts with modeling clay for taking
the desired shapes.
These models are obtained by artists through a
series of additions (bonding) of inert material on the
inside frame then pressing and removing
progressively to the final form.
Convexity, concavities and open spaces of the
model are set to reach a final form.
When the artist is working in clay, he certainly
wants to complete his work by casting it.
This makes the creative process more difficult
because he has to design the form, spaciousness and
light surfaces that his work will take, for example,
bronze may have different colors, enhanced
toughness and allows obtaining larger openings than
stone.
Using metal, not only in art, is linked to its
presence in a native form on the Earths crust; copper
was also added to the precious metals mentioned
above.
Copper is a very malleable and ductile metal at
both high and low temperature, and quickly found its
use not only to obtain weapons and household objects
but also in the making of ornaments or small
figurines.
As a first procedure of obtaining copper, plastic
deformation is the first in casting, even if jewelers
obtained ingots from precious metals melting and
casting them in a mold.
Archaeological excavations on the site of
settlements dating back from millennia VII - V BC (
Siparra in Mesopotamia ) revealed evidence that at
the time people were working native metals,
especially copper, by hammering, obtaining a number
of household items and jewelry.
The appearance of bronze and its casting process
led to its adoption by artists.
Artists such as, Phidias, Miron, Polyclitus or
Praxitele realized works of an inestimable value for
the universal art, showing the simple beauty of the
human body and the great love for freedom of the
people, serving as a model both for contemporary
artists and for those of future generations.
Even if their works remained preserved mostly

by copies made in marble, they have a perfect shape
and exquisite craftsmanship of the sculptors work.
Among the few exceptions is the statue in
bronze of a warrior, 1.98 m high, discovered offshore
at Reggio di Calabria.
This was done at the mid fifth century BC and is
characterized by quality and smoothness of the
molding details (hair style, eye color, teeth leaved for
viewing through the mouth ajar) that turns into a
piece of classical Greek representative.
Fig. 5. Greek Warrior Statue

Today aluminum and bronze is frequently used
from which can get both statues and other ornaments
as necklaces, lockets, earrings, brooches, rings,
pendants etc.
It is resistant to atmospheric corrosion, and has a
color close to that of gold. Furthermore, it may be
gilded with gold.
According to a certain timeline in the evolution
one can not omit iron metallurgy and VII century en
when China discovers this material.
In China the lion statue in the garden of the
church Tsang-Cion, and in Europe the oldest cast iron
objects are dating from the fourteenth century is
found on a tomb slab of a church in Sussex
(England).
From iron they began to pour pots with handles
and feet and inlaid figures, stove plates, cannon
barrels and even jewelry.
Iron jewels followed the steel ones but were less
agreeable.
Today, iron is used more for molds.
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Aluminum is currently used in art but it does not

enjoy it too much use.
It can be processed and shape without any
difficulty, it easily melts, and is rolled and welding is
also easier.
It is used more to obtain decorative pieces and
architectural decoration.
However, it can be an exciting and formidable
competitor for bronze.
Bronze sculpture has a special significance: its
potential of changing over time, expressed by the
appearance of patina and the modification of its color
and specific gravity.
Instead, it is "devoid of weight settled,
decorative and universal in nature and can maintain
almost any shape, giving it skills and becoming a
mandatory component of artistic achievement.
Because of this aluminum presents interest in
arts although is more moody and complex.
Use of aluminum jewelry dates back less time
and does not spread higher than among people with
reduced resources.
3. Techniques for shaping materials

into art
As can be inferred from the presentation of the
rock material used in art, its processing could be done
only by grooving.
If the first objects present only light incisions
using sharp tools on the surface of stones shaped by
the artist closer to the desired shape, antiquity marks
the beginning of the actual carving with small
interruptions that continued until today.
The method consists of a phases in which the
material from carving is gradually removed.
The process applies not only any kind of stone
(marble, limestone, basalt, etc.) but even to wood or
polystyrene.
Each material used by sculptor presents many
opportunities for the treatment of the surface, ie
finishing the only artist who decides to change the
work surface through specific processes or process
used to highlight the vision leaving traces of the
carving tools, if this is thought to influence the
viewer's reaction to the work. Differences that make
the difference between model and sculpture are those
that reflect the artist's ingenuity and physical effort,
motivated by the desire to achieve a work with unique
features. If the work is made of black granite, for
example, sanding and polishing only made after
grooving, lead to an enhancement of the color of the
material but also to highlight the complete contours,
shapes or getting a light reflection.
Casting statues begins with the production
model using modeling techniques.
Like carving, modeling is a traditional method

that originated in antiquity.
It is a gradual process that involves the addition
of a reinforcing material.
Sculptor leaves a core, reinforced or not
(depending on the size of the paper), which adds soft
material, clay.
When the work is ready, pour a plaster mold that
serves casting, bronze or cast iron, casting a specific
work of art by procedeeele.
Previously Eighth Dynasty (third millennium century BC), foundries Thebes (Egypt) knew to get
through a process similar to the lost wax statues
hollow and lightweight.
The first major piece of hollow representing a
woman's head, poured in about 650 BC Crete, art
casting height is reached, all in Crete, during 650-600
BC and, later, in Greece the years 600-500 BC.
Also in Greece, Rhoicos sculptor, the late sixth century, he discovers technique "bronzuluii empty",
borrowed from Egyptian clay core is wrapped in wax,
which was then modeled by the sculptor.
The form was coated with clay which is
practiced in a number of channels for the flow of the
wax.
Fig. 6. Greek vas

Molten bronze was then poured into the mold of
clay, causing melting wax flowing through channels.
The assembly was further cooled by the statue
was released (discussed) and cold finish
Work whistleblowers in ancient Greece to
achieve a statue is pictured in a series of drawings
represented on ancient cup diameter 30 cm, dating
from the period 460-440 BC.
On a portion of the circumference of the vessel
are represented three employees, of which two are
near the furnace, and the last fixed arm of a statue
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whose head, still on the floor, waiting for their turn

installation.
The other half sun depicted two workers smoothed
statue of a warrior under the watchful eye of two
spectators. In the feudal era began to widely apply the
template formation to obtain forms for casting bells.
Comparing the old technologies of obtaining the
objects of art today, we can see that they are almost
identical, the differences between them are due to the
time evolution of equipment and materials.
Compared to traditional jewelry jewelry
bimetallic meet today, ordinary metal jewelry gold or
silver etc.
Such jewels are made of common metals can be
gold or silver using balvanice bathrooms. Typically
the copper base metal is used. To achieve the twin
jewels are increasingly using only common metal that
will be in contact with a precious metal gold. This is
all copper metal in general. Double jewelery is to
support a thicker metal plate of nickel, zinc, tin,
especially copper, on which the hot-pressing is
applied to the thin gold foil and reproduce finest
details. This enables wafer grinding jewel without
any problem and without identifying the process of
obtaining.
4. Conclusions
We can say that, from all that we have
mentioned above, each historical era is tied to an art
chapter.
Along with bronze and later with iron, made

history in art stone (marble, granite, limestone), clay
(porcelain, burned down), wood and ivory for later
use and a range of metals (aluminum for example)
and equipment "non-traditional".
The metal has made a specific contribution to
the development of the means of expression in the
arts.
By its characteristics, it has enabled the
realization of enduring works, durable, which allowed
a specific structure plans artworks.
Regarding the use of metal in art, their
beginnings starts with vessels and ornaments of
precious metals and ordinary figures appearing much
later.
Casting and art had evolved over time
independent, but at times, when the artist's interest for
metal foundry appeal met with selected forms,
strongly emphasized the fine details, well-defined,
two, punched in Joint work managed to make works
of art.
References
[1]. Gh. Florea, Al. Chiriac, I. Marginean, Gh. Croitoru,
Turnatoria de arta. Materiale metalice, Editura Europlus, Galati,
2008.
[2]. Gh. Florea, Al. Chiriac, I. Marginean, Procedee performante
de puinere in forma, Editura Europlus, Galati, 2008.
[3]. C. Baraschi, Tratat de sculptura, Editura Meridiane,
Bucuresti, 1962.
[4]. ***, http://commons.wikimedia.org.
[5]. ***, http://en.wikipedia.org.
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INVESTIGATION METHODS AND TECHNIQUES FOR ANALYSIS OF

PANEL PAINTINGS STATE OF CONSERVATION
Ana-Maria BUDU, Silvea PRUTEANU,
Viorica VASILACHE, Ion SANDU
Arheoinvest Interdisciplinary Platform, Laboratory of the Scientific Investigation,
Al. I. Cuza University of Iasi
ABSTRACT
The art objects affected by external agents and factors can be analyzed by
different methods, more or less invasive. Thus, the deterioration of panel or
painting layer can be studied by optical methods (SEM, X-Ray, colorimetry etc.).
The identification of panel and painting layer degradation can be realized through
different modern semidistructive techniques, like spectroscopy (FTIR,
microRaman), GC-MS and X-Ray diffraction. These techniques allow us to clarify
the mechanism of degradation processes and to choose compatible procedures for
the preservation-restoration of the old panel paintings.
KEYWORDS: panel paintings, deterioration, degradation, analysis methods and
techniques
1. Introduction
The state of conservation of an art object is
defined as its state of degradation and deterioration at
a given moment. Depending on that it is determined if
the object can be exhibited, if it needs interventions
or if it must be kept in a deposit due to its advanced
degradation.
The deterioration of an object refers to the
changing of its physical state by external factors.
They act upon the panel and painting layer, creating
panel lacunae, cracks, fractures, detachments, loss in
strength, shape changes (in the support), cracks,
cleavages, exfoliations, abrasions, lacunae, blisters
(on the painting layer).
The degradation is the result of physicalchemical, microbiological or biochemical processes,
which affect the materials chemical nature and it is
irreversible [1].
The materials oxidize under the influence of
light, temperature, moisture, pollutants and they
decompose, leading, in time, to visible modifications
which affect the aspect of art object. The wood
changes its colour, becomes fragile, the unstable
pigments take a more stable form and change their
original colour, the varnish becomes darker or
whitish.
This paper will present a few investigation

methods used in panel painting analysis of
deterioration and degradation.
2. The analysis of panel and painting layer

deterioration
There are used different 3D imagistic methods,
like holograms, to analyze the deformations which
occur on the panel. The hologram is the recording of
interferences realized by a light beam of a certain
wavelength with another light beam of the same
wavelength which comes from an object [2].
An example is holographic interferometry which
uses the laser. Through this method there are recorded
and interferometrically compared two light beams,
scattered by an object, at different moments (the
images are recorded on the same holographic plate
[3].
The differences in objects positions create
fringes (emphasizing the changes in panel paintings
flatness). These differences are small (few microns)
and can be obtained by heating the object with an IR
lamp. With the help of a computer the fringes can be
analyzed and a map of deteriorations (detachments,
xylophagous attack) can be created (Fig. 1 a, b) [4].
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Fig.1. a - The panel painting of Saint Sebastian, attributed to Raphael, and its holographic
interferogram, b - details of the defects seen in the interferogram [4]
A type of holography less sensitive to
vibrations, which can be used in situ, is conoscopic
holography (Fig.2 a, b). This method needs a video
camera with a conoscopic module (a uniaxial
birefringent crystal put between two circular
polarizers) which captures the reflected and scattered
light from the objects surface. The light that reaches
the crystal is split into two beams (ordinary and

extraordinary) which create an interference model
that depends on the angle of beam aperture. By
measuring the distance between the fringes we can
find the distance of investigated point. Using software
we can analyze and visualize 3D images that can be
rotated in any direction [5].
Fig.2. Detail of the da Vincis painting Madonna dei Fusi: a- the 3D model obtained by conoscopic
holography, b- the coloured imaged superimposed on the 3D model [5]
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The radiography of a panel painting shows the

intensity of xylophagus attack. There is also used the
computed axial tomography (CAT scan) [6]. It is
based on computer storage and correlations of
radiographies, so that cross sections images are
created. It helps observe inner defects, the shape and
density of objects [7]. Scanning electron
microscopy (SEM) offers details about crystalline
structure, or about material texture [8]. For example,
SEM shows the degree of deterioration of cellulose
fibers [9]. A method used for observing internal
defects is thermography. An object can absorb or
release electromagnetic radiation IR, and the

temperature differences on its surface are registered
with thermographic cameras, which distinguish
differences less than 0.1 C.
The obtained images are in black and white, the
warmer areas being lighter in colour. In the case of a
painting with cleavages, after warming and cooling
the painting layer we can locate the cleavages and
determine their size, because the air under the
cleavage delays the thermal equilibrium. This method
can also be used to verify the efficiency of
consolidation interventions [10].
Fig. 3. Images obtained by thermography, showing the effectiveness of a consolidation (the last frame
indicates the area where consolidation wasnt successful) [10]
An optical method used in evaluation of colour
changes which occur in painting layer, under the
influence of physical or chemical factors from the
deposit or exhibition environment is colorimetry. It
measures the physical characteristics of colours: the
hue, the saturation, the luminosity. It is based on the
fact that all colour shades can be obtained by
combining the primary colours: red, blue and green,
in different quantities, and by their overlapping
results white.
For colour analyses it is used CIE L*a*b
diagram, a 3D representation of colour distribution,
where L is the vertical axis and represents
luminosity, and a and b are horizontal axis, with
a going from green to red, and b varying from
blue to yellow.
With the help of this diagram we can establish
how much a shade is different from another. The
painting surface is analyzed with a colorimeter, which
gives quantified information about colour variation,
varnish and medium ageing under microclimate
action [11, 12].
3. The analysis of panel and painting layer

degradation
Reflection spectroscopy was used to analyze
the effects of microclimate upon paintings. It is based
on the fact that different molecules absorb different
radiations of certain wavelengths, the rest of them
being reflected. The spectrometer examines the
reflection spectrum which has gaps (absorption
bands) characteristic for these molecules. Thus, the
composition can be determined [13].
An analysis of painting layer composition can be
realized with IR spectroscopy. Each functional group
absorbs certain wavelengths of IR radiation, this fact
helping in their identification [14]. It can determine
the modifications which appear in the painting layer
(varnish degradation). Also, FT-IR spectroscopy
helps identify the functional groups from the
inorganic (sulphates, carbonates, nitrate, phosphates,
silicates) and organic (oils, animal glue, waxes,
resins) compounds.
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Fig. 4. IR spectrum for lead white and egg yolk medium [15]
Micro Raman spectroscopy enables pigment,
media and varnishes identification. It is based on
inelastic scattering of light as a result of radiation
interaction with molecular vibration, without energy
absorption. The obtained spectrum is characteristic to
a certain molecule. The microscope attached to the

spectrometer offers a spatial resolution of a few
microns. A holographic filter helps eliminate the
elastic scattered light, which doesnt allow Raman
peaks visualisation in spectrum [1].
Fig. 5. Raman spectra of media used in tempera paintings: a - albumin; b - casein;

c - gelatin; d - isinglass; e - fish glue [16]
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X-ray fluorescence spectroscopy is used to

determine the chemical composition of materials, but
also, the thickness of films. The X-rays dislocate
electrons from the lower energy shells which results
in atoms instability and a higher state of energy. The
electrons from higher energy states drop on lower
energy shells, yielding energy as photons. The atoms
of every element have electronic shells with specific
energies, hence the spectra created by the photons
help identify the corresponding element [17]. The
evaluation of wood degradation, varnish oxidation
can be examined by gas-chromatography/massspectroscopy (GC-MS) [9, 18]. Gas-chromatography
makes possible the separation of mixture compounds,
so they can be analyzed through spectroscopy. This
method helps realize a quantitative and qualitative
analyse of substances [19].
X-ray diffraction helps analyzing the

crystalline structure of mineral pigments used in
painting. Its based on wave dispersion by the atoms
electrons of a crystalline structure. The condition for
diffraction is that the radiation wavelength is equal to
the distance between two crystalline layers (0.15 - 0,4
nm) and its accomplished by X-rays (0.01-10nm)
[20].
The scattered radiations are recorded with a
camera for X-rays or with a detector installed on a
goniometer (the ensemble made by the device used to
support the sample, detector and the corresponding
equipment).
The spectrum will appear as a graphic with
peaks that depend on the radiation intensity and
distance d and its compared with reference spectra
[21].
Fig. 6. XRD spectra of three different samples of ultramarine [22]
4. Conclusions
The results of different research methods
presented in this paper help to correctly and
completely evaluate the state of conservation of panel
paintings, of deterioration and degradation degree.
They are also useful in analyzing the impact of
certain environmental factors and understand the
degradation mechanism. The non-invasive methods
are preferred for monitoring the evolution of
deterioration
and
degradation
in
different
microclimates.
References
[1]. Sandu I., Sandu I. C. A, Vasilache V., Geamn M. L.,
Modern Aspects Concerning the Conservation of Cultural
Heritage, vol. IV, Ed. Performantica, Iai, 2006.
[2]. Jeong, T. H., Basic Principles and Applications of

Holography,
http://spie.org/Documents/Publications/00%20STEP%20Module%
2010.pdf, (3.09.2012).
[3]. ***, Holographic interferometry, Rice University, 2003
http://www.owlnet.rice.edu/~dodds/Files332/holography.pdf,
(3.09.2012).
[4]. Tornari V., Optical and Digital Holographic Interferometry
Applied in Art Conservation Structural Diagnosis, e-Preservation
Science, 3, 2006, pp. 51-57.
[5]. Fontana R., Gambino M. C., Pampaloni E., Pezzati L.,
Seccaroni C., Panel Painting Surface Investigation by Conoscopic
Holography, in 8th International Conference on Non Destructive
Investigations and Microanalysis for the Diagnostics and the
Conservation of the Cultural and Environmental Heritage, Lecce,
2005, pp. 1519.
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Radiographic Study of Some Panel Painting Icons from the
Beginning of the XXth Century, International Journal of
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[7]. ***, Computed Tomography, Education Resources - NDT
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[9]. Popescu C. M, Dobele G., Rossinskaja G., Dizhbite T.,
Vasile C., Degradation of lime wood painting supports. Evaluation
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[10]. Verdelli M., Presenti N., Aldrovandi A., Thermographic
and Radiographic Studies of Vacuum Consolidation of the Paint
Layers of Panel Paintings, Internal Article, 2, 2008,
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[11]. Lorusso S., Natali A., Matteucci C., Colorimetry applied to
the field of cultural heritage: examples of study cases,
Conservation Science in Cultural Heritage, 7, 2007, pp. 187- 208.
[12]. Antonioli G., Fermi Oleari F. C., Reverberi R.,
Reflectoscopic analysis of cultural goods for knowledge and
preservation, Universit degli Studi di Parma, Dipartimento di
Fisica Istituto Nazionale per la Fisica della Materia, 2000.
[13]. Khoshhesab Z. M., Reflectance IR Spectroscopy, Payame
Noor University, Department of Chemistry, Iran, 2004.
[14]. Hsu C.-P. Sherman, Infrared Spectroscopy, Handbook of

Instrumental Techniques for Analytical Chemistry, ed. F.Settle.
Upper Saddle River, N. J. Prentice Hall, 1997.
[15]. Tsang J.-S., Cunningham R. H., Some Improvements In The
Study Of Cross Sections, JAIC, 30, 2, 1991, pp. 163-177.
[16]. Vandenabeele P., Wehling B., Moens L., Edwards H., De
Reu M., Van Hooydonk G., Analysis with micro-Raman
spectroscopy of natural organic binding media and varnishes used
in art, Analytica Chimica Acta, 407, 2000, pp. 261274.
[17]. Brouwer P., Theory of XRF. Getting acquainted with the
principles, vol. 1, Netherlands: PANalytical B.V., 2010.
[18]. Dietemann P., Higgitt C., Klin M., Edelmann M. J.,
Knoch R., Zenobi R., Aging and yellowing of triterpenoid resin
varnishes - Influence of aging conditions and resin composition,
Journal of Cultural Heritage, 10, 2009, pp. 30-40.
[19]. Hites R. A., Gas Chromatography Mass Spectrometry,
Handbook of Instrumental Techniques for Analytical Chemistry,
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[20]. Birkholz M., Thin Film Analysis by X-Ray Scattering, WileyVCH Verlag GmbH &Co. KGaA, 2006.
[21]. ***, Basics of Xray Diffraction, Scintag Inc., 1999, Chapter7,
http://epswww.unm.edu/xrd/xrdbasics.pdf. (2.09.2013).
[22]. Hochleitner B., Desnica V., Mantler M., Schreiner M.,
Historical pigments: a collection analyzed with X-ray diffraction
analysis and X-ray fluorescence analysis in order to create a
database, Spectrochimica Acta Part B: Atomic Spectroscopy, 58
(4), 2003, pp. 641649.
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QUANTIFICATION OF ATMOSPHERIC POLLUTION BY

QUALITATIVE ANALYSIS OF PRECIPITATION AS SNOW
Adrian LEOPA1, Daniela TRIFAN2
1
Dunrea de Jos University of Galai, Engineering Faculty of Brila,

Research Center for Mechanics of Machines and Technological Equipments
2
Agricultural Research and Development Station of Brila
emails: leopa.adrian@ugal.ro, dana.trifan@yahoo.com
ABSTRACT
Air pollution is a direct consequence of industrial development, evolution and
diversification of means of transport as well as urbanization. Considering the
factors of air pollution, it is obvious that the largest urban agglomeration raises
issues about this type of pollution with negative impact on human health factor. Due
to the specific urban congestion, air pollution can not be eliminated but can be
taken to mitigate its efforts. The first stage of work to reduce air pollution in urban
centers is detailed knowledge of the phenomenon by identifying the sources
generating harmful environmental chemicals.
This paper proposes a methodology for identification of air pollution in Braila
city on the quality indices of rainfall. In their fall to the ground, rainfall records a
second pollution by cleaning the atmosphere of dust and microorganisms and
dissolved gases added, which is even stronger as the atmosphere is polluted.
We took samples of snow in two repetitions of 20 sites of the city and that the
three villages of Braila County, Romania, which were brought to the same
temperature and laboratory testing to determine the main physical, chemical and
biological indices. Snow samples from the Traian and Silistraru localities were the
controls of this experience. Based on the results obtained we established
correlations between qualitative indices studied and we created the map of the air
pollution in Braila city, Romania.
KEYWORDS: air pollution, snow, qualitative indices, atmosphere
1. Introduction
Living organisms are constantly influenced by
physical, chemical and biological environment, there
is a balance between environment and organisms that
inhabit it. When the environment becomes polluted,
there is a constraint, a change in the average balance,
affecting living organisms, the more polluted the
environment factor that is less abundant.
Meanwhile, among physical, chemical and
biological environment there is interdependence, their
activity positively or negatively correlate with
quantitative increase of a factor. The most obvious
action of environmental factors on living organisms is
exerted through pollution and pollution occurs when a
particular environmental factor is in excess, causing
imbalances in biotic or abiotic environment.
Therefore, it was necessary to introduce control
and environmental monitoring, which requires the
development and maintenance of systems for
surveillance of environmental factors in addressing

the imbalances that occur.
There are several ways to study the relation
existing between environmental factors and living
organisms, of which the most used are: investigating
factors
permanent
environmental
simulation
laboratory experimental methods, methods of
investigation of living organisms on which factors act
environmental, statistical and mathematical methods
of interpreting the data obtained by previous methods.
Atmosphere has one of the ecological systems of
the biosphere, which balances the mutual relations
between man and environment, therefore, watershed
protection of population centers against air pollution
to be considered as an important issue of
contemporary, period of rapid development of
industrialization and urbanization (I. Bumbu, 2006).
In the literature, are remarkable studies by a
team of Japanese researchers on the snow in the city
of Sapporo in Hokkaido, located near mining
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Toyobira River basin. The study aimed at evaluating

the content of heavy metals in snow deposited in
urban areas, to determine the degree of atmospheric
pollution due to mining. From this study, this paper
examines other quality parameters of water from
snow to quantify the degree of pollution of the
atmosphere. The cumulative effect gives us the
possibility to evaluate urban pollution snow provides
a period of time (Hiromitsu, 1985). It is known that
atmospheric precipitation, liquid form of snow, trap
their way to ground some of the existing particles in
the atmosphere. So, the atmosphere is polluted with

both physicochemical and biological analyzes of
water will be the modified precipitation than normal.
2. Material and methods

Experience consisted of taking samples of snow
in two rehearsals, the 20 sites of Braila, Romania and
the three rural areas during January-February 2012
(Fig. 1).
Fig. 1. The map of variants of experiment

Snow samples were brought to the same
temperature, in laboratory and were determined
following qualitative indicators (Burtea, 2009; Trifan,
2011):
- pH and electric voltage (mV) - Potentiometer
method.
- CTSS and electrical conductivity (S) conductivity method.
- microbiological load - Microscopic method
micrometers.
The statistical interpretation of results was
performed using MS Excel, ANOVA test and
Correlation test, to determine the interdependence of
quality indicators studied.
Based on the results, two dimensional and three
dimensional maps were made using software package
MATLAB R14 with all quality indicators studied in
the observation areas most polluted in the city,

compared with control.
3. Results and disscusion

The results of laboratory determinations of
water quality index of precipitation as snow, recorded
from January to February 2012 the area of Braila,
Romania, were statistically processed by method
variance (ANOVA test) (Table 1). Applying the
ANOVA test, we found that the experience is
statistically F=10.63>Fcrit=2.44. Significances of
differences were summarized in Table 2.
It may be noted that there were variations with
negative differences from the witness experience, but
statistically uninsured, instead most quality indicators
recorded positive difference to the witness as follows:
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- Positive significant differences in electrical

conductivity variants V4 and V7;
- Positive significant differences in variant V5
CTSS and positive significant distinct differences for
variants V3, V4, V6;
- Positive significant differences from controls

for electric potential, the V15 variant, distinct variants
significant for V3, V16 and V23 and positive very
significant differences for variants V4, V6, V8, V9.
Table 1 The variance analysis of experience with ANOVA test
Count
Sum
Average
Variance
ANOVA: Single Factor

SUMMARY
25
25
25
25
25
178,4
1691
768,55
987,15
1037
7,136
67,64
30,742
39,486
41,48
0,88659
3837,80
297,62
429,58
1002,01
SS
47391,02
133629,9
181020,9
df
4
120
124
MS
11847,76
1113,583
F
10,63
Groups
pH
Electrical conductivity
CTSS
Electric potential
Microbiological charge
ANOVA
Source of Variation
Between Groups
Within Groups
Total
The control of experience was average between

M1 and M2, respectively average of rural variants:
M=
M1 + M 2
2
[1]
P-value
2,06
F crit
2,44
Differences significations are represented by: *

(positive significant difference); ** (positive
distinctive significant difference) and *** (positive
very significant difference) or (negative significant
difference); 00 (negative distinctive significant
difference) and 000 (negative very significant
difference) between every variant and the control of
experience.
350
300
250
200
150
100
50
pH
V1
0
V1
1
V1
2
V1
3
V1
4
V1
5
V1
6
V1
7
V1
8
V1
9
V2
0
V2
1
V2
2
V2
3
V1
V2
V3
V4
V5
V6
V7
V8
V9
M1
M2
Electrical conductivity [S]
CTSS [mg/l]
Electric potential [mV]
Microbiological charge
Fig. 2. Chart with quality indices of water precipitation as snow
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Differences &
Significances
Differences &
Significances
M1
M2
V1
V2
V3
62,7
28,25
51,85
75,25
153
17,23
-10,82
-30,72
-17,87
-5,37
37,89
-23,80
-67,56
-39,30
-11,81
34,65
14,75
27,6
40,1
78,5
9,95
-9,95
2,9
15,4
53,8
40,28
-40,28
11,74
62,35
217,81**
15,45
18,95
24
24,65
36,75
-1,75
-10,17
1,75
10,17
6,8
39,53
7,45
43,31
19,55 113,66**
7
13
32
29
27
-3
3
22
19
17
V4
V5
V6
V7
V8
V9
V10
V11
V12
V13
V14
V15
V16
V17
V18
V19
V20
V21
93,2
320
147
74,3
44,05
43,85
57,7
34,7
43,7
45,3
70,4
56,85
53,2
29,4
41,5
47,5
33
34,7
33,03
3,88
-2,32
32,03
-5,97
-22,02
-22,57
-14,77
-27,17
-22,32
-21,62
-8,32
-15,22
-17,07
-29,87
-23,37
-19,67
-27,77
72,64*
8,53
-5,10
70,44*
-13,13
-48,43
-49,64
-32,48
-59,75
-49,09
-47,55
-18,30
-33,47
-37,54
-65,69
-51,40
-43,26
-61,07
49,35
43,15
77,5
39,5
23,45
22,9
30,7
18,3
23,15
23,85
37,15
30,25
28,4
15,6
22,1
25,8
17,7
18,3
24,65
18,45
52,8
14,8
-1,25
-1,8
6
-6,4
-1,55
-0,85
12,45
5,55
3,7
-9,1
-2,6
1,1
-7
-6,4
99,80**
74,70*
213,77**
59,92
-5,06
-7,29
24,29
-25,91
-6,28
-3,44
50,40
22,47
14,98
-36,84
-10,53
4,45
-28,34
-25,91
45,7
23,65
39,55
18
40,3
47,25
54,25
70,1
73,1
41,9
46,55
33,1
35,4
15,9
51,9
52,5
13
102
28,5
6,45
22,35
0,8
23,1
30,05
37,05
52,9
55,9
24,7
29,35
15,9
18,2
-1,3
34,7
35,3
-4,2
84,8*
165,70***
37,50
129,94***
4,65
134,30***
174,71***
215,41***
307,56***
325,00***
143,60***
170,64***
92,44*
105,81**
-7,56
201,74***
205,23***
-24,42
493,02***
51
25
37
23
21
32
17
11
35
14
26
21
65
37
96
87
125
110
41 410***
15 150***
27 270***
13 130***
11
110**
22 220***
7
70*
1
10
25 250***
4
40
16 160***
11 110***
55 550***
27 270***
86 860***
77 770***
115 1150***
100 1000***
V22
V23
29,2
20,4
-27,17
-25,07
-59,75
-55,14
16
9,8
-8,7
-14,9
-35,22
-60,32
28,5
34,7
11,3
17,5
65,70
101,74**
47
49
37
39
370***
390***
45,47
24,7
0,00
17,2
0,00
10
M=
M1 + M 2
2
Abs.
Rel.
Abs.
Rel.
Electric
potential
[mV]
Electrical
conductivity
[S]
Differences &
Significances
Variants
CTSS [mg/l]
Differences &
Significances
Microbiologi
cal charge
Table 2. Significances of differences between variants and the control of experience
DL0,1% = 125% DL1% = 93,43

To see how the water quality indices of
precipitation interact with one another, we calculated
the correlation coefficients were seen in the setting of
Abs.
Rel.
Abs.
Rel.
-30
30
220***
190***
170***
% DL5% = 68,74 %
significant positive correlations between CTSS and

electrical conductivity and electric potential between
microbiological loads (fig. 3).
0,800
0,600
0,400
0,200
0,000
-0,200
-0,400
pH
Electrical conductivity [S]
Electrical
conductivity [S]
CTSS [mg/l]
-0,091
-0,028
-0,253
0,028
0,650
-0,175
-0,204
-0,105
-0,226
CTSS [mg/l]
Electric potential Microbiological

[mV]
charge
0,261
Electric potential [mV]
Fig. 3. Chart with correlation indices between quality indices of water precipitation as snow
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The two and three-dimensional maps provide

information on the degree of dispersion and
concentration of urbanpollutants, based on these
indicators can be taken several measures to mitigate

pollution in areas of maximum value.
a. 2D representation
b. 3D representation
Fig. 4. Maps of pH values in variants of experience

Electrical conductivity was generally low,
witness to the experience, the highest valuesbeing
recorded for variants V3, V5, V6, V14, that in areas
of the city's main roads and the railway station (Fig.

5).
Fig. 5. Maps of electrical conductivity in variants of experience

Total content of water soluble salts of
precipitation as snow was very high at V3 and V6
variants compared with controls, respectively Way
areas Galati and Radu Negru areas represent the main

roads that connect with other counties, very
circulated, also (fig. 6).
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Fig. 6. Maps of CTTS in variants of experience
Fig. 7. Maps of electric potential in variants of experience

The highest electric potential was recorded in
experimental variants V11, V12, V21, i.e. areas that
are parks and vegetation is more abundant (fig. 7).
Correlations established between the electrical and
other indices were negative, except for

microbiological load was positive.
Experimental variants with biological load were
the largest downtown, V18, V19, V20, V21, that in
most populated areas and high traffic (Fig. 8).
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Fig. 8. Maps of microbiological charge in variants of experience

pollution reduction strategy, in order to decrease the
effect of global warming.
4. Conclusions
The analysis of water from precipitation as
snow can cause air pollution, watching some quality
indices of snow deposited on the ground.
The areas most polluted chemically motor
vehicles are the highly circulated that influence pH
and electrical conductivity CTSS, there is a coverage
map almost identical to the three indices mentioned.
Recreational areas are those where the
electric potential is much higher than other areas,
while also increasing the biological load of the
atmosphere, evident by the values of these indices in
precipitation as snow.
Research on the quantification of air
pollution by analyzing water from precipitation must
continue in order to take the best measures in terms of
References
[1]. Bumbu I., Bumbu I., Vrlan L., Controlul i monitoringul
mediului, Curs de lucrri practice i laborator, 2006, Chiinu.
[2]. Burtea C., Cantemir G., Agrochimie Lucrri practice de
laborator, 2009, Brila.
[3]. Hiromitsu S., Tanenori S., Kazuo S., The presence of Heavy
Metals in Urban Snow, Environ. Sci. Hokkaido, 1985.
[4]. Trifan D., Burtea C., Pedologie Lucrari practice de
laborator, 2011, Brila.
[5]. Gilat, A., MATLAB: An Introduction with Applications 2nd
Edition, Wiley edition, 2004.
[6]. Viskari EL, Rekil R, Roy S, Lehto O, Ruuskanen J,
Krenlampi L, Airborne pollutants along a roadside: assessment
using snow analyses and moss bags, Environmental Pollution,
Volume 97, Issues 12, 1997, Pages 153-160.
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TESTING SOME TECHNOLOGICAL SOLUTIONS ALIGNED TO

NATURAL CONDITION IN AMELIORATING RICE PADDIES
Marcel BULARDA, Ionel IVAN,
Daniela TRIFAN, Ioan VIINESCU
email: scdabraila@yahoo.com
ABSTRACT
The experiments described in this paper are part of an activity included in the
second phase of the project "Research on improving rice cultivation technology in
ameliorating rice paddies on salted soils under improvement" developed in the
Agricultural Research and Development Station of Braila, Experimental Center
Polizeti. To establish a technology solutions aligned with the natural and
increasing developed in this project were addressed two experiences, namely:
- Establishing the influence of crop rotation practice in rice cultivation
technology.
- Testing of varieties of the technology "Clearfield".
The purpose of these experiments is to highlight the advantages of using
technology Clearfield and crop rotation in the culture of rice considering that this
culture is less known and widespread.
The results of implementing these technological solutions have shown that
monoculture rice production decreases by 41%, while Clearfield technology brings
significant increases production, increasing economic efficiency compared to
conventional technology, with a profit of between 364.5 to 1818 lei / ha.
KEYWORDS: crop rotation, rice culture, rice padding, economic efficiency,
clearfield technology
1. Introduction
Cropping and crop rotation is a technological
solution that harmonizes the natural protection of the
soil with agricultural production, giving it a durable
nature. Growing the same plant on the same plot for
several years or even in monoculture, will increase
the potential for attack by pathogens of pests, to
increase the amount of weed seeds and vegetative
material capable to reproduce weeds, and reduce soil
resources in plant nutrients, soil humus, the changes
in pH and therefore to reduce crop production. As a
result, crop rotation crops in space and time is the
only solution to avoid these imbalances that can
produce them in the agro ecosystems. Crop rotation
are the means at hand and less costly to fight weeds,
diseases and pests, to achieve high yields and also to
protect the soil and the environment. In crop rotation,
with rotation of crops takes place also rotation of the
system works, the system of fertilizer, herbicides,
insecticides and fungicides used etc. At the same
time, Clearfield technology is part of a advanced
strategy work has been extended to rice crop and

requires use of the Pulsar to disproof mono and
dicotyledonous weeds in rice in the early stages of
their development. This technology is able to replace
the use of a large number of chemicals for weed
control in rice cultivation, which are used alone or
combined, both on the ground and vegetation.
Clearfield technology is able to deal effectively with
wild rice infestation plot, something that tends to
grow in areas that use lower quality seed.

Experimental Centre Polizeti from Braila
County is located at the intersection of parallel
4450'49" North latitude and the meridian of
2748'34" East longitude, in the Eastern Romanian
Plain, the Plain North Baragan, on the left Danube, at
an elevation of 4.00 m, according to Google Earth
(Fig.1). Experimental field has an area of 31 ha,
located in the Eastern county of Braila, situated in a
complex area of physical contact between various
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geographic units: the Danube Meadow, Clmui
Meadow and Braila Plain.
Fig. 1. The map of Experimental Centre Polizeti from

Agricultural Research and Development Station of Brila (Google Earth)
In the experiment with crop rotation in rice
plantation, to establish a culture system version and
version monoculture crop rotation with rice in two
crops, sunflowers and wheat respectively. In the
Clearfield technology experience working method
consisted in the establishment of a field test with
foreign varieties specifically designed for this
technology was applied to the specific technology and
work were highlighted productions.

EC Polizeti climatic conditions in 2012, is
presented in Table 1. Note that the rice crop in 2012
recorded a rainfall of 58.5 mm higher than the annual
average, and the average temperature during the
growing season was higher by 2.17 oC. Relative
humidity was higher by 1.0%.
Table 1. Climatic elements during the growing period of rice in 2012

Average monthly values
Climatic elements
Rainfall
(mm)
Zonal
(Braila)
CE
Polizesti
Temperatures in air
(oC)
Relatively humidity
in air (%)
Normal
Agr. year
2012
Deviation
Agr. year
2012
Deviation
Normal
Agr. year
2012
Deviation
Normal
Agr. year
2012
Deviation
IV
VI
VII
VIII
IX
36
52
63
47
42
29
Total/
Average of
growing
period
269
39
137
51
23
74
35
359
+3
+85
-12
-24
+32
+6
+90
35
103
76
17
63,5
33
327.5
-1
10.9
+51
16.9
+13
20.7
-30
22.8
+21,5
22.1
+4
17.5
+58.5
18.48
14.0
18.3
22.8
26.4
23.6
18.8
20.65
+3.1
70
+1.4
67
+2.1
66
+3.5
64
+1.5
65
+1.3
62
+2.17
65.67
66
72
70
59
61
72
66.67
-4
+5
+4
-5
-4
+10
+1
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Elements of technology applied in the

experiments regarding the influence of practicing
crop rotation in rice cultivation technology, in C.E.
Polizeti in 2011-2012 agricultural year are presented

in Table 2.
Table 2. Elements of rice cultivation technology applied in Experimental Centre Polizeti

Specification
Surface (ha)
Pre-cultivation plant.
Base fertilization
Soil works
Weeds disproof on
soil
Variety/hybrid
Treatment of seeds
Norm of seeds (kg/ha)
Sowing time
Other works
Fertilized phased
Herbicide sprayer
Diseases treatment
Pests treatment
Biological purified
Weeded out
Irrigation
Harvest
Production (kg/ha; %)
V1
Rice in rotation on three years with
sunflower and wheat
8.00
Wheat
Complex fertilizers 300 kg/ha 1 ha exp
- disc 2 treceri + nivelat 2 treceri + 1 disc
Stomp 5.3 l/ha
16.05.2012
Polizesti 28
246
14-15.05. 2012 Polizesti-28
7-30.05 exp.
Rogued weeds
Urea 243 kg/ha
7.05.2012
Dicopur 1 l/ha
Alert 0.7 l/ha
Continuous submersion
variable water layer
05.11.2012
Abs. 5.200 kg/ha; Rel. 100%
The results of implementing this technological

solution with rotation have shown that in monoculture
rice production decreases by 41%, compared with
rotation after wheat. In the experience with Clearfield
technology aimed efficacy Pulsar applied dose
1-1,2L/ha once or repeated, if necessary, the rice
V2
Rice in monocultivation
0.50
Rice
Complex fertilizers 300 kg/ha 1 ha exp
-disc 2 treceri + nivelat 2 treceri+ 1 disc
Stomp 5.3 l/ha
16.05.2012
Polizesti 28
246
14-15.05. 2012 Polizesti-28
7-30.05 exp.
Rogued weeds
Urea 243 kg/ha
7.05.2012
Dicopur 1 l/ha
Alert 0,7 l/ha
Continuous submersion
variable water layer
05.11.2012
Abs. 3.100 kg/ha; Rel. 59%
paddies established with varieties resistant to

Imazamox.
Pulsar herbicide was applied early postemergence to control both dicots and monocots the
year.
The results are presented in Table 3.
Table 3. Determination results for productivity indices of rice varieties studied

No
Variety
Density
Density
1
2
3
4
Sirio
Luna
CL 26
CL 71
plants/mp
458
460
504
500
panicle/mp
640
592
624
660
Panicle
emergence
03-08
08-08
07-08
12-08
Panicle
length
cm
20,3
16,2
19,9
21,0
To track and analyze the effectiveness of

technology Clearfield through the productions made
in the report and compared with working version that
uses products used for weed control in rice by
conventional technology (the most effective herbicide
is one that uses Gulliver).
Total
seeds
Dried
seeds
107,2
74,0
100,6
129
18,6
8,2
37,4
22,6
Height
cm
84
87
88
87
Production
15,5 % U
kg/ha
%
8.768
100
9.706
110,7
9.737
111,0
9.521
108,58
Difference
MT +/kg/ha
Mt.
+ 938
+ 969
+ 753
They took into account the performance of the

first three varieties tested in other experimental
fields. The results of biometric measurements and
productions recorded at different rice varieties grown
by classical technology Clearfield technology is
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Length panicle
cm
Total seeds
Dried seeds
Percent dried %
Height cm
568
27-07
19.00
76.8
10.2
13.28
110
8.525
100
Mt
Mt
Sirio
458
640
03-08
20.3
107.2
18.6
84
8.768
102.9
243
2.9
Luna
460
592
08-08
16.2
74.0
8.2
87
9.706
113.9
1.181
13.9
CL 26
504
624
07-08
19.9
100.6
37.4
88
9.737
114.2
1.212
14.2
CL 71
500
660
12-08
21.0
129
22.6
87
9.521
111.7
996
11.7
Osmangic
300
368
06-08
15.80
76.0
10.2
13.42
116
11652
136.7
3.127
36.7
Selenio
504
633
07-08
18.40
95.0
9.2
9.68
90
12207
143.2
3.682
43.2
Centaur
534
700
03-08
18.40
81.2
14.0
17.24
89
12355
144.9
3.830
44.9
Ronaldo
408
588
11-08
13.90
76.2
8.0
10.38
80
7850
92.1
-675
-7.9
Difference
MT +/-
Panicle emergence
time
396
Density of
plants/ m2
Polizesti
28 Mt
Variety
No.
Density of
panicles/m2
Production
15.5 % U
Table 4. Biometric measurements at different rice varieties compared to Control (classical technology
of Polizesti 28 variety)
kg/ha
kg/ha
3.425
3.525
10
Vasco
410
540
08-08
13.70
101.8
6.0
17.33
76
5100
59.8
11
Fast
324
400
08-08
14.10
126.0
14.0
15.64
72
5000
58.7
12
Elida
240
272
05-08
18.5
136.8
28.2
20.6
111
9146
107.3
621
7,3
13
Impuls
404
480
07-08
19.5
101.8
14.2
13.94
120
8700
102.1
175
2,1
14
Magic
360
552
07-08
17.0
109.4
34.4
31.4
113
10752
126.1
2.227
26.1
Situation of biometric measurements at different

rice varieties grown by classical technology compared
-40.2
-41,3
to different varieties of rice cultivated with Clearfield

technology is presented in figure 2.
Fig. 2. Graph with results of biometric measurements for rice varieties

cultivated by classical and Clearfield technologies
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Compared with the control (Polizeti 28)

Clearfield technology cultivated species density was
much higher, 108 pl / m2 CL26, 104 pl / m2 CL71, 73
pl / m2 Month and 62 pl / m2 Sirio.
Among other varieties grown by classic
technology, Centaur and Selenio only Italian varieties
had higher densities compared to the control,
respectively 138 pl / m and 108 pl / sq.
Panicles density was also superior at varieties
grown Clearfield technology compared with controls,
with 92 panicles / m2 at line CL71, 72 panicles / m2
the variety Sirio, 56 panicles / m2 at line CL26 and 24
panicles / m2 Luna variety.
Among the varieties grown by classic
technology, higher values for number of panicles in
square meters, compared to the control were recorded
at Centaur Italian varieties (132 panicles / m), Selenio
(63 panicles / m) and Ronaldo (20 panicles /
m). Regarding of panicle length, only three of the
four Clearfield varieties had higher values compared
to the control, respectively CL 71 (+2 cm), Sirio (1.3

cm) and CL26 (0.9 cm) and the other 10 varieties
grown by classic technology, only Pulse recorded a
higher value compared to the control (+ 0.5 cm). In
terms of plant height, Clearfield technology cultivated
varieties showed a medium of 86.5 cm, a difference
of -23.5 cm, compared to control (Polizeti 28) and a
difference-8cm from the average of all the 14
varieties studied.
For the total number of seeds, in correlation with
the percentage of dry and shriveled grains, the best
results, carried out with the control, were obtained
from all varieties grown Clearfield technology. Thus,
recalculated healthy grain yield by decreasing the
grain dry and shriveled, it was found that Clearfield
varieties, with a smaller percentage of dry and
shriveled beans, got made very significant differences
from the control: variety Moon (2713 kg / ha) LC 26
(2119 kg / ha) 1917 kg / ha (CL71) and Sirio (1556
kg / ha) (Figure 3).
Fig. 3. Differences in yields from cultivated rice varieties in Clearfield technology

and traditional technology, from control Polizeti 28
In Table 5 are showed the costs of rice
production per hectare for conventional technology
and Clearfield technology, following the calculation
of economic efficiency for the species studied.
In terms of economic efficiency of rice varieties
studied, significant differences were recorded Italian
varieties Centaur (5745 lei / ha), Selenio (5523 lei /

ha), Osmangic (4690.5 lei / ha), while cultivated
varieties with Clearfield technology were significant
differences compared to the control, as follows: CL26
(1818 lei / ha), Luna (1771.5 lei / ha), CL71 (1494 lei
/ ha) and Sirio (364.5 lei / ha) (Figure 4).
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Table 5. Technological estimate rice varieties grown in the experimental center Polizeti in 2012 (lei)
Polizesti
28 Mt
Sirio
Luna
CL 26
CL 71
Osmangi
c
Selenio
Centaur
Ronaldo
Vasco
Fast
Elida
Impuls
Magic
Base fertilization
23
23
23
23
23
23
23
23
23
23
23
23
23
23
Soil works
Herbicides sprayer on soil
Sowing
Weeded out works
Fertilization on vegetation
period
Weeded sprayer in vegetation
Diseases treatment
Irrigation
Harvest
Total expenses mechanical
works
2.Materials
Seeds 250kg/ha
Complex fertilizers 300kg/ha
Stomp 5l/ha
Urea 243kg/ha
Guliver 40g/ha
Nominee 40ml/ha
Dicopur 1 l/ha
Pulsar 2x1l/ha
Water for irrigation
Total material expenses
Total expenses
Productions obtained
Income obtained
Profit obtained
Difference of profit compared to
control
560
560
560
560
560
560
560
560
560
560
560
560
560
560
19
19
19
19
19
19
19
19
19
19
19
19
19
19
120
120
120
120
120
120
120
120
120
120
120
120
120
120
100
100
100
100
100
100
100
100
100
100
100
100
100
100
22
22
22
22
22
22
22
22
22
22
22
22
22
22
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
23
50
50
50
50
50
50
50
50
50
50
50
50
50
50
350
350
350
350
350
350
350
350
350
350
350
350
350
350
1290
1290
1290
1290
1290
1290
1290
1290
1290
1290
1290
1290
1290
1290
1 . Mechanical works
2250
2250
2250
2250
2250
2250
2250
2250
2250
2250
2250
2250
2250
2250
770,57
770,57
770,57
770,57
770,57
770,57
770,57
770,57
770,57
770,57
770,57
770,57
770,57
770,57
245
245
245
245
245
245
245
245
245
245
245
245
245
245
419,37
419,37
419,37
419,37
419,37
419,37
419,37
419,37
419,37
419,37
419,37
419,37
419,37
419,37
217,5
217,5
217,5
217,5
217,5
217,5
217,5
217,5
217,5
217,5
226,28
226,28
226,28
226,28
226,28
226,28
226,28
226,28
226,28
226,28
25
25
25
25
25
25
25
25
25
25
328
328
328
328
4447
4447
4447
4447
4447
4447
4447
4447
4447
4447
4447
4447
4447
4447
8600,72
8459,94
8459,94
8459,94
8459,94
8600,72
8600,72
8600,72
8600,72
8600,72
8600,72
8600,72
8600,72
8600,72
9890,72
9749,94
9749,94
9749,94
9749,94
9890,72
9890,72
9890,72
9890,72
9890,72
9890,72
9890,72
9890,72
9890,72
8525
8.768
9.706
9.737
9.521
11652
12207
12355
7850
5100
5000
9146
8700
10752
21312,5
21920
24265
24342,5
23802,5
29130
30517,5
30887,5
19625
12750
12500
22865
21750
26880
12787,5
13152
14559
14605,5
14281,5
17478
18310,5
18532,5
11775
7650
7500
13719
13050
16128
364,5
1771,5
1818
1494
4690,5
5523
5745
-1012,5
-5137,5
-5287,5
931,5
262,5
3340,5
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Fig. 5. Economic efficiency of rice varieties studied, from witness Polizeti 28
4. Conclusions
References
Rice is the culture that exploits the salt saturated

soils and in Romania can achieve about 10 t / ha
rice, provided the use of appropriate
technologies.
Monoculture of rice decreases production by
41% compared to rotation of culture after wheat.
Study on application of Clearfield technology
(Sirio, Luna, CL 26, CL 71) that record better
economic efficiency compared to the classical
(variety Polizesi 28), with a profit between 364.5
to 1818 lei / ha.
[1]. Albescu, I. 1979 Polizeti 28 an intensive rice variety well

adapted on salin soil. Producia vegetal Cereale i plante
tehnice, nr. 4: 35-37.
[2]. Alionte, GH., 1983 - New aspects of rice cultivation
technology. Agricultural Issues 3.
[3]. Alionte, GH., Melachrinos, FL., Onita, E., Stefan D., 1985 Results obtained by the method of induced mutations in rice
improvement. Fundulea, IL: 59-70.
[4]. Bumbu, I., Bumbu, I., Vrlan, L., - Controlul i monitoringul
mediului - Curs de lucrri practice i laborator, 2006, Chiinu.
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RECYCLING METHOD FOR FLAT AND CONTAINER GLASS
Gheorghe FLOREA1, Camelia NEAGU-COGLNICEANU2,

Irinel NEAGU- COGLNICEANU3
Dunarea de Jos University of Galati-Romania, Domneasca Street, No. 111, Galati-Romania

Gheorghe Asachi Technical University of Iasi-Romania, Department of Machine Manufacturing Technology,
Blvd. Mangeron No. 59A, 70050 Iasi, Romania
3
Pro Ideas Trade SRL, Independentei Street, 810112, Braila-Romania
emails: gflorea@ugal.ro, proideastrade@yahoo.com, neaguirinel@yahoo.com
ABSTRACT
The paper aims to develop sustainable method for convert the waste glass (flat
and container) in custom glass products with aestethic properties.This recycling
method lead to saving energy and natural resources, reduce the quantity of waste
glass, reduce CO2 emissions,creating new glass objects.
KEYWORDS: glass, 3D model, design, digital fabrication, thermal forming,
sagging, bending, recycling
1. Introduction
Over the past years the targets for waste glass
recovery, recycling has increased significantly in
Romania, in line with EU Directives. In the European
glass industry, the major sector is: a) container or
packaging glass (~56% of total production) and b) flat
glass (~25% of total production) [1]. The total
amount of waste glass generated in the EU-27 in 2007
was 25.8 Mt (include both pre and post-consumer
waste glass). In 2007, total collection rate was ~58%
and total recycling rate was ~46%. According to
FEVE [2], recycling rates and recovery rates for glass
container, in 2011, vary from country to country. Fig.
1 present the collection rate for recycling container
glass in year 2011 and Fig. 2 present recycling rates
available across Europe.
Fig. 1. Collection rates for recycling container

glass in year 2011, in Europe,according
FEVE,adapted from [2]
Fig. 2. The rate of recycling glass container for

EU27 Member States 2011, adapted from FEVE
[2]
Container and flat glass are the principal
constituents of the waste glass. For flat glass, most of
the waste is pre-consumer. Ideally, the whole quantity
of recovered waste glass could be used as raw
material to produce new glass (in a closed loop
system). In the real world, it is a practical limit to
this, due the following factors: the high standards of
the glass manufacturing industry (the need to be
color-sorted, contamination tolerance,particle size of
glass cullet), the high cost of transport to glass
manufacturing facilities, the imbalance between
production and arisings of specific waste glass
stream. For example, to production flat glass, only
flat glass cullet can be used [1]. Glass is 100%
recyclable but 100% recovered glass cannot be used
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in glass manufacture. For this nonrecyclable waste

glass, since 1963, according Ling et al. [3], research
has been carried out for use of waste glass as concrete
aggregate. Recently, the results of the studies realized
by Ling et al. [3] have shown that is feasible to use
100% crushed glass cullet as a decorative aggregate
in the manufacturing in glass architectural mortar and
as replacement of cement in concrete in production of
concrete products (concrete blocks, self-compacting
concrete). In order to recycling glass cullet for noncontainer glass is used different routes: as raw
material in ceramic industry, as road aggregate
substitute, as an alternative aggregate in bituminous
materials (glasphalt); as an alternative filter medium
in water treatment, as an abrasive blast media for
blasting as sand substitute, as an alternative to sand in
the sports turf industry, for manufacturing of foam
glass [1, 4]. According to Neville, Glass is too
valuable to be thrown away as aggregate: glass
should be recycled as glass [5].
The purpose method in this paper consist in
processing the waste glass (flat and bottle) using
slumping process for convert in utility and decorative
products. This method have double significance:
addreses of manufacturers and designers who made
glass products unique or small series and evaluated
the feasibility of manufacturing glass objects from
waste glass from one process without CO2 emissions.
2. Materials and methods

2.1. Glass slumping technology
In glass industry, for architectural and
automotive applications, is used the bending
processes [6, 7]. For shape windshields, distinguish
two basic processes: a) the sag bending (gravity sag
bending) and the press bending technology. Glass
thermal slumping utilizes similar process conditions
as compression molding, e.g. heating, molding, and
cooling. The only difference is on the pressing force
in the molding stage.In both cases,exists similar

processes: e.g. heating,slumping and cooling.It is
necessary to heat the glass to the temperatures around
the softening temperature, to the region of plastic
deformation and after slumping process followed by a
controlled cooling (annealing); the difference in this 2
methods consist in: the gravity bending technology
uses only a one-piece mold (an refractory steel ring)
and glass is shaped though the action of gravity (Fig.
3 a); in addition,the press bending method, use,
during the heat treatment, in the molding stage, a
vertical or orizontal applied force by placing a die
(die assist sag bending) or use two ceramic dies witch
press the glass sheet to give a precisely formed
surface.(Fig. 3b).
Fig. 3. Schematic illustration of the glass

bending and glass compression [7]
Glass thermal forming processes can be adapted
for manufacture of spherical optical elements [8-11],
for Progressive Addition Lenses (PAL) [12], for
decorative glass industry [13] and complex buiding
elements.
Function of the form of mould, the slumping
technology can be:
i) direct slumping (glass is placed on the mould;
the mould is typically made of metal because the
metal contract more than glass as shows Fig. 4a;
ii) indirect slumping (glass is placed in the
mould) as shows Fig. 4b.
Fig. 4. Schematic illustration of direct slumping (a) and indirect slumping (b) , adapted from [14]
2.2. Experimental procedure

The proposed procedure for this work follows 4
distinct steps, as shown in Fig.5:
1. making a plaster mould;
2. preparing the waste glass;

3. setting the parameters of the thermal
treatment;
4. thermal processing in electric kiln.
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Fig. 5. The flowchart of recycling method for waste glass
3. Making the plaster mould

The digital fabrication starting with a
image.This image was enhanced using digital
processing software in order to adjust colour
saturation, colour density and contract. The relief
surface was maked with ArtCam software and the
result was a sculptural model (fig. 6), than was
converted the CAD file to the STL (Standard
Tesselation Language) format. It is known fact that
the 3D models represented the most efficient way of
evaluate a project before even existing in the real
world [15, 16]. It is possible to used reverse
engineering technique, the object being scanned 3D
and the point cloud is processed in STL file. The
virtual model was transferred to CNC (Computer
Numerical Control) machine via *STL files. The
parameters required to processing on CNC machine
was set, in order to obtaining the shape desired.
Because the milled foam method is a low cost method
for custom manufacturing moulds, autors used this
route.For roughing was used a EndMill 6 mm,
stepover 1.2 mm, 50%, spindle speed 15000 rpm,
feed/plunge rate 20/60 mm/sec. For finishing was
used an Ball Nose 1.5 mm step over 0.15 mm, 10%,
spindle speed 15000 rpm, feed/plunge rate 10/4
mm/sec.
The following figures represents the: figure 6 the virtual model, figure 7 - the mesh creator process;
figure 8 - detail of the mesh; figure 9 - the roughing
toolpath; figure 10 - the finishing toolpath; figure 11 the milling process; figure 12 - the negative cavity
obtained.
Fig. 7. The mesh creator process
Fig. 8. Detail of the mesh
Fig. 9. The finishing toolpath
Fig. 10. The finishing toolpath
Fig. 6. The virtual model

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The plaster slurry was poured into foam cavity

created by CNC machining. After the mixture has air
dried, the plaster mould was backed at elevated
temperatures to remove all moisture prior to use.
4. Preparing the waste glass

For this experiment, a total of 5 sodalime glass
samples has been tested.
The samples includes flat glass post-industrial
cullet collected from a glass processor and postconsumed container glass (green, amber and colorless
bottle glass) from pub.
The waste glass was cutting, beveling (only flat
glass), washing and drying. This glass have Softening
Point = 715 C; Annealing Point = 548 C and Strain
Point = 511 C (according ASTM C 338, ASTM
336), Coefficient of Linear Thermal Expansion (CTE)
(25275 C) = 8.3 x 10-6 K-1.
Fig. 11.The milling process
5. Parameters of thermal treatment
Fig. 12. The negative cavity obtained

The plaster mould was obtained by casting a
plaster slurry in the foam cavity. Plaster or plasterbonded molds are used for casting nonferrous metals
such as aluminium-, zinc-, or copper-based alloys.
The advantages of plaster moulds consist in
dimensional accuracy, excellent surfaces, economical
for low volume production. The plaster compound
was prepared by mixing 66% gypsum and 33% water
(according to manufacturer recipe).
Parameters of thermal treatment must

determinate taking in account the next conditions:
type of glass (CTE, the thermal history, size of glass
piece), characteristics of the mold (dimensions,
complexity of mould, the form), the features of
electric kiln (type of electrical resistances, load of
kiln).
For choice of thermal treatment, it is necessary
to considering the dependence viscosity-temperature.
The viscosity is the most significant property in glass
processing and is highly dependent on temperature
and the composition of the glass [17-19]. Fig. 13
shows the viscosity of a glass as a function of
temperature.
Fig. 13. a) Viscosity temperature relationship for a glass[4]; b) viscosity versus temperature diagram
for different types of glass [18]
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6. Thermal processing in electric kiln
7.Results and discussions
The thermal processing was made using a

electric kiln, Nabertherm F220, from Pro Ideas Trade
company. The thermal cycle used is described in Fig.
14.
This recycling glass method using plaster molds

proved the fact that is feasible to convert waste glass
in utility and decorative products. In Fig. 15 is
presented different objects manufactured with this
method.
Fig. 14. The thermal cycle used
Fig. 15. Objects obtained from recycled glass
8. Conclusions
The following conclusions are derived from the
results of this experiment which evaluated the
feasibility of manufacturing glass objects from post
consumer and post industrial waste glass. Soda-lime
glass waste, virtual modelling method, glass slumping
technology was investigated with aim to use this
waste glass for producing custom glass articles.
This recycling method also proposed solution
for reducing the environmental impact and helps
reduce the amount of the raw materials, energy and
CO2 emissions and give opportunity to designers and
manufacturer to explore this option in obtain products
with high artistic value.
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The advantages are:

- low cost cost moulds;
- low cost for producing unique and small
series;
- possibility of obtaining good surface details
with high accuracy;
- small investment for enterprises, designers and
craft industry;
- the range of glass products obtained from this
method is large: domestic glass, decorative
objects,splashback,clocks so on;
- use a low temperature comparing to other
recycling glass method;
- CO2 emisions is almost zero except in case of
use organic compound for decorating.
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The disadvantages are:

- the need to produce a new plaster mould for
each item;
- the thermal cycle need to adapt to each glass
item and each type of glass (flat,container);
- it is recommended to use only controlled glass
source.
References
[1]. Vieitez, E. R., et al., End-of-Waste Criteria (EoW) for Glass
Cullet:Technical
Proposals,
Available
from:
http://ipts.jrc.ec.europa.eu/publications/pub.cfm?id=4940. Accesed:
01.08.2013.
[2]. FEVE - the European Container Glass Federation, Available
from: http://www.feve.org/. Accesed: 18.03.2013.
[3]. Ling T.-C., C.-S. Poon, H.-K. Wong, Management and
recycling of waste glass in concrete products:Current situations in
Hong Kong. Resources, Conservation and Recycling, 2013. 70, p.
25-31.
[4]. Available from: http://www.wrap.org.uk/. Accesed:
14.02.2013.
[5]. Neville A., Concrete: Nevilles Insights and Issues, London:
Thomas Telford Publishing, 2006.
[6]. Velea V., Flat Glass, Bucharest: Editura Tehnica, 1986.
[7]. Balta P., Glass technology, Bucharest: Editura Didactica si
Pedagogica.
[8]. Winter A., M. Vongehr, P. Friedrich, Light weight optics
made by glass thermal forming for future x-ray telescopes, Proc.
SPIE 7732, Space Telescopes and Instrumentation 2010:
Ultraviolet to Gamma Ray, 77320B (July 29, 2010),
doi:10.1117/12.857147, 2010, San Diego, California, USA.
[9]. Mika M., et al., Glass and silicon foils for X-ray space
telescope mirrors, Ceramics-Silikaty, 2011, 55, (4), p. 418-214.
[10]. Mika M., et al., Lightweight Mirrors for Space X-Ray
Telescopes, World Academy of Science, Engineering and
Technology, 2011, 58, p. 319-323.
[11]. Sveda L., et al., Thermal Forming of Glass - Experiment vs.
Simulation, Acta Polytechnica, 2011, 51, (6), p. 72-75.
[12]. Lochegnies D., 3D Modelling of Thermal Replication for
Designing Progressive Glass Moulds, New Journal of Glass and
Ceramics, 2013, 03, (01), p. 34-42.
[13]. Silva A., F. Jorge Lino, R. J. Neto, Design of glass artifacts
through rapid prototyping and rapid tooling, in 5-th International
Conference on Mechanics and Materials in Design, 24-26 July
2006, Porto-Portugal.
[14]. Residential Glass Bending Guidelines, Available from:
http://www.climaguardglass.com/cs/groups/climaguard/documents/
web_content/dev_005414.pdf.
[15]. Florea G., A. Chiriac, I. Saracin, Technology of casting and
reparing some parts using the mehod of rapid prototyping-RP by
experimental tests, INMATECH-Agricultural Engineering, 2010,
30, (1), p. 83-86.
[16]. Nedelcu D., et al., Some aspects concerning the physical
models obtained using high performance composite material, in
Proceedings of the 13th International Conference on Modern
Technologies, Quality and Innovation, ModTech2009 - ISI
Proceedings, pp. 455-459, ISSN 2066-3919.
[17]. Fluegel A., Glass viscosity calculation based on a global
statistical modelling approach, Glass Technology: European
Journal of Glass Science and Technology, Part A, 2007, 48, (1), p.
13-30.
[18]. Brill R. H., A note on the scientist's definition of glass, The
Journal of Glass Studies 1962, Available from: ww.cmog.org.
[19]. Axinte E., Glasses as engineering materials: A review,
Materials & Design, 2011, 32, (4), p. 1717-1732.
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GROUNDWATER EXPLOITATION BY GROUND-IRRIGATION

ON AGRICULTURAL TERRITORIES FROM
THE BIG ISLAND OF BRAILA
Ioan VIINESCU, Marcel BULARDA, Daniela TRIFAN
e-mail: scdabraila@yahoo.com
ABSTRACT
Land of the Danube and the river meadows interior totaling an area of
approx. 2,100,000 hectares - 14% of arable land, of which 513 900 ha 442,000 ha
Danube and Delta are fertile land with low energy consumption for pumping
irrigation water in enclosures can be dammed and against drought oases. Meadow
soils crops receive significant amounts of water from the shallow aquifer located by
lifting it by capillarity in the root system of the plant. On these soils is the factor
mainly water and vegetation inclusive of other factors, resulting in good supply of
crops, and the negative phenomena of excess water with damaging implications for
physical and chemical characteristics of the soil, thus affecting agricultural yields.
Research conducted on the Big Island of Braila model (Lysimeter) in the field,
have revealed the groundwater contribution (the amount of high water by
capillarity) for major crops in different soil conditions and depths of
groundwater. Were highlighted as two technological aspects of groundwater
capitalization of plants grown in the meadow, on the one hand the need to
differentiate the system of irrigation (watering rules, number of watering, every
application) depending on soil hydrological conditions (measurement intake water)
and on the other hand, the opportunity to shape conformation groundwater
reservoir (its depth) to ensure optimal positions such underground irrigation
(under-irrigation) crops. Efficient use of natural water resources in irrigation
facilities in the floodplain provide such reducing irrigation water, and conserve the
fertility of soils, while avoiding degradation processes in excess water and
secondary salinization.
Groundwater reservoir water management involves conducting a survey and
its highlighting features utility plant. In this regard, the paper presents case hydro
geological framework (conformation tank water) in 2012, 3 farms of the Big Island
of Braila, Stavilaru residence and Marasu, pedo-hidrologic representative farms
for all agricultural holding Big Island of Braila. On this basis could district
groundwater intake within farms and also to differentially applied crop irrigation
regime, taking into consideration the volume of water available to plants in
aquifers. To characterize the groundwater reservoir utilization and intensity of
groundwater supply plant in a given territory (farm, plot) have established specific
two indices: the use of groundwater reservoir (Guf), showing the proportion of
territory (%) in the groundwater reservoir is effective for plants and groundwater
index useful contribution (Ifu), measuring the volume of water (m / ha) plant
accessed tank water.
KEYWORDS: groundwater intake, under-irrigation, hydro geological regime
1. Introduction
Meadow soils crops receive significant amounts
of water from the shallow aquifer located by lifting it
by capillarity in the root system of the plant. On these

soils is the factor mainly water and vegetation
inclusive of other factors, resulting in good supply of
crops, and negative phenomena of excess water with
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damaging implications for the physical and chemical

properties of soil, thus affecting agricultural
yields. Big Island of Braila farm is a reference entity,
with natural features, hydro and specific
organizational system.
The natural environment of the enclosure is
characterized by a dry climate specific in North
Baraga, with average annual rainfall value of 447
mm, the temperatures of 10.9 C with fertile alluvial
soils with good permeability to water, groundwater,
the located at depths quality levels within the limits
0.5-2 3.5-4 m enclosure, with an area of 72,000 ha
was dammed in 1964 and designed the drainage and
irrigation in 1965-1980.
Research conducted on the Big Island of Braila
model (Lysimeter) and in the field, have revealed the
groundwater contribution (the amount of high water
by capillarity) for major crops in different soil
conditions and depths of groundwater. Efficient use
of natural water resources in irrigation facilities in the
floodplain provide such reducing irrigation water, and
conserve the fertility of soils, while avoiding
degradation processes in excess water and secondary
salinization.
hydrogeology and groundwater intake. It was

designed so the fund of technical information upon
which to operate a scheme for agricultural irrigation
(watering rules, number of watering) differentiated
areas with crops correlated with soil and hydro
geological context (depth of ground water level). To
determine the intensity of water supply from
groundwater and differentiation of crops irrigation
regime, Hypsometer measurements were performed
using the Big Island of Braila, which accurately
measure groundwater intake depending plant
vegetation stage, depth of groundwater level and soil
textural type. In order to determine the use and
intensity of water supply plant of groundwater in the
tank farms were developed pedohydrological two
indices: the use of groundwater reservoir (Guf) and
groundwater index useful contribution (Ifu) indices
indicating the farmer for any area in the state of water
supply farm soil and water intake plant ensured.
In order to characterize the operational

potentiality in crop water supply groundwater
reservoir in the territory of pilot farms were
developed two indices pedohydrological, Table 1,
adding:-utility ratio of groundwater reservoir to
supply water to the crops by capillary ascent - Guf groundwater reservoir utilization (%), with the extent
of areas with groundwater depths below 2 m, the
actual areas that are very active in crop water supply,
as resulted from research undertaken;-crop useful
measure groundwater contribution The agricultural
territory, namely groundwater index useful
contribution - Ifu (m / ha), commeasuring in average
water supply per hectare cultivated on the farm, a
weighted average of the areas well stocked and poorly
supplied groundwater.
To capitalize resource for groundwater intake

plant requirements and reducing irrigation water
meadow soils were chosen to analyze three pilot
farms, representative in terms of natural conditions,
soil,
geomorphology,
hydrology,
specific
improvement of facilities (irrigation, drainage,
drainage) of hydrological unit complex natural
landscaped Big Island of Braila, farms Stavilaru
residence in irrigated conditions and Marasu in
irrigated conditions. In these farms made a network of
wells to measure groundwater depth, was made a
permanent program of observation, observation data
being processed periodically (monthly, seasonal) in
the form of maps of the intensity zoning

3.1. Pedohydrological indices to
characterize the groundwater supplies
Table 1. Pedohydrological indices of groundwater supplies on the territories of pilot farms

Pedohydrological indices
Farm
Pondered average rate

of farm land (m)
The percent use of groundwater

supply Guf (%)
Groundwater contribution
useful index Ifu (mc/ha)
Stavilaru
4,24
82
1720
Edera
4,43
24
490
Marasu
4,89
37
762
* Categorize Guf values: high-60%-large 40-60%, moderate 20-40%, 0-20% lower

As hydro geological indices shows in Table 1
for the three farms studied in work are highlighted
three different conditions:
- farm Stavilaru with the ground below (weighted

average rate 4.24 m), with the highest degree of using
groundwater reservoir Guf = 82% and the highest
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value of the index groundwater contribution useful

Ifu = 1.720 m / ha;
- farm Edera with middle position weighted average
share of land (4.43 m), but with a degree of use of
groundwater reservoir small;
- 24% (the smallest of farms analyzed) and

groundwater contribution useful index lowest Ifu =
490 mc / ha Marasu-farm, from the middle ranks
hydropedological (Guf = 37%, Ifu = 762 mc / ha).
Table 2. The contribution of ground fine textured soil (Lysimeter measurements in

Big Island of Braila)
Crop
Wheat
Maize
Sunflower
Soybean
Green
Alfalfa
Depth of
groundwater
(m)
IV
VI
VII
VIII
IX
Total rate of
groundwater in
vegetation period
(mm)
0,5
24
65
92
181
1,0
44
77
129
1,5
19
67
91
2,0
12
21
2,5
0,5
12
28
111
129
70
350
1,0
65
103
70
253
1,5
23
77
44
154
2,0
20
2,5
15
0,5
80
170
100
365
1,0
50
150
100
304
1,5
27
68
100
198
2,0
10
45
40
98
2,5
12
20
38
0,5
47
120
140
100
415
1,0
23
65
80
90
263
1,5
15
30
40
93
2,0
21
2,5
14
0,5
40
107
126
130
150
100
653
1,0
35
91
90
115
130
100
561
1,5
30
86
70
93
122
100
501
2,0
71
60
80
90
85
292
2,5
31
50
46
59
70
281
3,0
20
25
30
35
35
150
3,5
10
10
10
10
15
60
Monthly rate of groundwater (mm)
Note: The contribution of groundwater on soils with medium-coarse texture diminishes the fine texture
compared to the 10% at depths of groundwater level below 2 m and 20% at depths of groundwater level greater
than 2 m.
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rigorous research data determined in the Lysimeter

station in climatic conditions of the Big Island of
Braila.
In Table 2 are presented the experimental results
on the contribution of monthly groundwater caused
Lysimeter in Big Island of Braila, for a period of 25
years, 5 tested crops: wheat, corn, sunflower,
soybean, alfalfa, 5th depths of groundwater level (0,
5m, 1m, 1.5 m, 2m, 2.5m) soil conditions with fine
texture
and
medium
to
coarse
textured
soils. Determinations hydrogeology in 2012 within
the 3 farms monitored fund basic hydrological
research of groundwater reservoirs Table 3.
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Intake water, the essential element the

hydrological balance of the soil inside the Big Island
of Braila, is an extremely effective fertility farms in
this area. Previous research undertaken in the field of
irrigation and experimental models (Lysimeter
station) allowed obtaining valuable explanations on
how crops harness this element of balance.
3.2. Groundwater contribution of crop

farms within pilot
In order to determine the contribution of
groundwater within the 3 pilot farms were valued
Table 3. Zoning hydrogeology in the spring, summer and autumn pilot farms
Big Island of Braila
Zoning of groundwater depth level (%)
Zone with
groundwater
depth
Stavilaru Farm
Edera Farm
Marasu Farm
Spring
Summer
Autumn
Spring
Summer
Autumn
Spring
Summer
Autumn
0-1 m
26
10
1-2 m
60
70
70
23
18
25
42
38
26
2-3 m
14
19
21
59
47
34
14
25
30
3-4 m
13
35
40
38
35
43
4-5 m
Pondered
average depth
(m)
1,38
1,62
1,62
2,32
2,67
2,65
2,40
2,45
2,69
26
9
24
0
24
5
26
5
26
7
23
2
250
43
150
35
38
26
25
25
14
13
50
1
10
10
100
18
19
21
23
26
30
34
35
38
42
16
2
47
200
40
13
8
40
20
16
2
50
30
300
59
60
60
14
Zoning depth of groundwater level
70
70
70
80
0
%
0
Spring
Summer
Autumn
Stavilaru Farm
0-1m
Spring
Summer
Autumn
Edera Farm
1-2m
2-3m
3-4m
Spring
Summer
Autumn
cm
Marasu Farm
4-5m
Series6
Ponderal average depht (cm)
Fig. 1. Season hydrogeological zoning on pilot farms from the Big Island of Braila
In Tables 4, 5 and 6 are exposed the results on
the contribution of groundwater in total vegetation
period on the 3 pilot farms for corn, soybeans and
sunflowers. In
determining
the
groundwater
contribution was taken into account zoning on depth

groundwater level of the 3 pilot farms (Fig. 2) in the
vegetation periods of the three cultures and measure
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the water supply of groundwater from Lysimeter
determinations presented in table 2.
Fig. 2. Hydro geological situation in spring 2012 at Edera Farm

From the results, we can notice the following
conclusions:
Stavilaru Farm by morpholitological
conformation of the land was the most favored by the
natural, namely:
- depth-weighted average groundwater level reduced

the vegetation period of spring crops - 1.54 m;
- to provide such a contribution in groundwater
weighted average farm 1,583 m / ha of maize, 1,942
cubic meters / ha for sunflower and 1,270 m / ha in
soybean.
Table 4 Groundwater contribution during the vegetative ground of corn, sunflower and soybean
on fine textured soil at Stavilaru farm
Groundwater contribution (mc/ha)
on districts depths of groundwater
level (%)
Pondered average values
Culture
0-1 m
15 %
1-2 m
67 %
2-3 m
18 %
3-4 m
0%
Maize
3.500
1.540
150
Pondered average groundwater contribution 1.583 mc/ha
Sunflower
3.650
1.980
380
Soybean
4.150
930
140
Pondered average depth during the vegetative ground 1,54 m
Edera Farm had water supply conditions crop

of groundwater reservoir lowest morpholitological
correlated with context (land situated at higher rates
and coarse textured soils in depth) that: depthweighted average groundwater level in vegetation
periods of spring crop of 2.54 m;
Groundwater-weighted average intake is

lowest of the three farms, namely 479 mc / ha for
maize, 687 mc / ha for sunflower and 353 mc / ha in
soybean.
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Table 5 Groundwater contribution during the vegetative ground corn, sunflower and soybean
on fine textured soil at Edera farm
Groundwater contribution (mc/ha) on
districts depths of groundwater level
(%)
Ponderal average values
Culture
0-1m
2%
1-2 m
22 %
2-3 m
47 %
3-4 m
29%
Maize
3.500
1.540
150
Pondered average groundwater contribution 479 mc/ha
Sunflower
3.650
1.980
380
Soybean
4.150
930
140
Pondered average depth during the vegetative ground 2,54 m
Marasu farm though in conditions unfavorable

improvement (not operational planning irrigation) has
some natural conditions more favorable to the Edera
farm and had secured an additional contribution in
harnessing groundwater favorability follows:
- weighted-average depth of the groundwater and

values ranged from 2.53 m in the growing season of
crops sown in spring.
- correlated with the geological conformation, each
hectare benefited from a water intake weighted
average of 643 cubic meters / ha of maize, 853 mc /
ha for sunflower and 441 mc / ha in soybean.
Table 6 Groundwater contribution during the vegetative ground of corn, sunflower and soybean
on fine textured soil at Marasu farm
Groundwater contribution (mc/ha) on districts
depths of groundwater level (%)
Pondered average values
Culture
0-1m
2%
1-2 m
35 %
2-3 m
23 %
3-4 m
39%
4-5 m
1%
Maize
3.500
1.540
150
Pondered average groundwater contribution

643 mc/ha
Sunflower
3.650
1.980
380

853 mc/ha
Soybean
4.150
930
140

441 mc/ha
By Figure 3, based on previous research on the

contribution of soil water table in the Big Island of
Braila is levied essentially biological, hydrological
complex phenomenon for 4 cultures, including:
- progressive decrease groundwater intake and
increase in groundwater depth, causing descent
capillary fringe and thus different levels of access to
groundwater by plants, groundwater supply,
- the amount of differentiation between cultures,
consisting of progressive increase starting from poor
rooting crops, wheat and Biological shallow-water
reduced, the crop rooting deeper and higher
Pondered average depth during the vegetative ground

2,53 m
consumption of water, corn, and sunflower and

alfalfa;
- rainfall that enters the soil water balance is
added to the reserves provided aquifers causing
changes in irrigation water requirement and irrigation
default regime, correlation regime irrigation (watering
rules, number of watering, every application)
Measure water supply plant in aquifers and
atmospheric precipitation for maize, is illustrated in
figure 4 to reflect the realities of the field, the farmer
known by close monitoring of hydro climatic factors.
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Fig. 3. The results of research on the supply of groundwater and soils with fine texture influence on
irrigation water requirements in Big Island of Braila
Fig. 4. The contribution of groundwater to corn ground fine texture and differentiation of irrigation
regime
4. Conclusions
The meadow soils crops receive significant
amounts of water from the shallow aquifer located by
lifting it by capillarity in the root system of the plant.
Measure groundwater reservoir full operation

in water supply plant pedohydrological is evidenced
by two indices: the use of groundwater reservoir
(Guf), expressing the proportion of area (%) in the
groundwater reservoir is effective for plants and
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groundwater index useful contribution (Ifu),

measuring the volume of water (m / ha) tank plant
accessible water.
Studies in three farms of the Big Island of
Braila representative stated correlation between
geomorphologic conformation revaluation of land and
groundwater measurement for plants that Stavilaru
farm with the land below was provided the highest
degree of using groundwater reservoir (48 %) and the
highest value of the index useful groundwater intake
(1,000 m / ha), while the highest odds Edera farm the
land, the use of groundwater reservoir was lowest
(24%) and the contribution of groundwater index
useful lowest (490 mc / ha);
Pedohydrological characteristics of land and
permanent observation tank conformation from
conformation wells, groundwater hydrogeology,
farmer ensures the necessary technical information
correct operation of the irrigation water management,
water saving and protection of soil quality.
References
[1]. Botzan M., Haret C., I. Stanciu, Visinescu., Buhociu L.,
1991 - Recovery of hydro-Romanian Danube floodplain and
delta. Editorial Agricultural Machinery Propaganda, Bucharest:
112-143 (Romanian language).
[2]. Visinescu I., 1994 - Optimizing Agropedology factors of
agricultural production on the floodplain soils. National
Conference of Soil Science, Bucharest: 159-170. - (Romanian
language).
[3]. Visinescu I., V. Zamfirache 1998 - New Guidelines to exploit
soil hydrological and agricultural meadow, Fundulea INCDA
scientific works, vol XX, no. 1-2: 53-74. - (Romanian language).
[4]. Visinescu I., Bularda M., May 2013 - Using reversible
arrangement of drainage-drainage and irrigation (underirrigation) in Big Island of Braila, Fundulea INCDA Symposium,
Bucharest. - (Romanian language).
*** Results research project ADER 2.2.4 - Research for the
effective use of natural water resources in irrigation facilities to
reduce irrigation water consumption and conservation of soil
fertility status, vol 1-2011, Vol 2-2012, manuscripts. - (Romanian
language).
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STUDY ON THE CHEMICAL PARAMETERS OF POLLUTED

GROUNDWATER IN SOME AREAS OF BRILA COUNTY
Mariana Carmen BURTEA, Anca SERBAN, Gheorghe CANTEMIR
Dunrea de Jos University of Galati, Engineering Faculty of Brila,
Calarasilor Street, 29, RO-810017, Braila, Romania
emails: carmen.burtea@ugal.com, anca.serban@ugal.ro, gheorghe.cantemir@ugal.ro
ABSTRACT
The paper contains the physico-chemical parameters of water found in several
fountains in the area of Lacu Srat, Scarlatesti, Tudor Vladimirescu, Gropeni etc.
to determine the quality of the drinking water and the suitability for irrigation, as
well as the influence of weather and antropic activities.
Very high levels of salts, nitrogen compounds, in some samples even heavy
metals can affect human and animal health, as well as the soil quality in those
areas. Monitoring the water quality leads to the conclusion that the physicochemical parametres of groundwater changes due to: weather, the use of well,
adjacent soil parameters, agricultural and domestic activities taking place in the
area.
KEYWORDS: groundwater, water parameters, pollution
1. Introduction
2. The study results
Water resources, especially in groundwater

aquifers have a high risk of pollution both short and
long term, with the direct consequence that they can
not be sources of drinking water for the population in
many areas of country.
Major pollutants affecting groundwater quality
can be grouped into the following categories:
petroleum products from industrial processes,
chemicals used in agriculture, heavy metals,
household products, products of zootechnics. Since
the processes of infiltration, water involves various
pollutants at the ground surface these substances ether
reach in groundwater or are deposited in aquifers
beds. As a result there is a deterioration of
groundwater quality that makes them unfit for use.
This phenomenon occurs in all forms of
groundwater, but is most intense in ground water,
because of the shallow depth at which it is located
[1]. This process can become so intense that it
becomes irreversible.
This paper highlights the changes that took place
in 2011-2012 on the physico-chemical parameters of
water from several wells drilled in the county of
Braila in order to establish the degree of drinking and
suitability for irrigation and pollution indicators
dynamics for identification of factors that influence
the evolution of water quality studied.
There were collected water samples from

villages Cazasu, Tudor Vladimirescu, Bertesti,
Victoria in 2011-2012. For samples were determined
chemical parameters that show some degree of water
pollution from wells: pH, chloride content, nitrate
content, nitrate content, ammonia. The chemical
analysis of water to determine water natural
ingredients and ingredients coming from pollution.
Water samples were collected from the public
network and from wells.
In the study the following results were obtained:
1. Cazasu village (fig. 1, 2): pH value of the
wells water from 7.5 to 7.6 in 2011 and 7.75 to 8.06
in 2012. There is an increasing pH limits exceeding
the permissible limit, according to STAS 1342/1991.
Chloride content of the well water has valuesfrom
538.99 mg/l to 765.94 mg/l in 2011 and between
206.16 mg/l and 792.64 mg/l in 2012. There was a
decrease and exceeding limits. Nitrate content of
wells water had values of 395.54 mg/l to 425.99 mg/l
in 2011 and 526.46 mg/l to 540.50 mg/l in 2012.
There is a growth exceeding limits. Nitrite content of
wells water had values from 1.25 mg/l to 3.37 mg/l in
2011 and 0.70 mg/l to 0.82 mg/l in 2012. There was a
decrease in 2012 in excess of the permissible limit.
2. Tudor Vladimirescu (fig. 3,4): pH value of
water wells from 6.97 to 7.38 in 2011 and 6.9 in
2012.
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Nitrate content ofwells water had values of

13.49 mg/l to 38.2 mg/l in 2011 and 12.1 mg/l to 30.0
mg/l in 2012. It is noticed that did not exceed
permissible limits, according to STAS 1342/1991.
Nitrite content of water wells had values from 1.05
mg/l to 2.83 mg/l in 2011 and 0.43 mg/l to 1.2 mg/l in
2012. There was a decrease exceeding permissible
limits, according to STAS 1342/1991.
Fig. 1. Dynamics of groundwater chemical

parameters of Cazasu

parameters of Tudor Vladimirescu

parameters of Cazasu
There is a decrease in pH that does not exceed
the permissible according to STAS 1342/1991.
Chloride content of water wells had values from
53.18 mg/l to 95.32 mg/l in 2011 and between 42.55
mg/l and 70.92 mg/l in 2012. It is noticed that does
not exceed permissible limits, according to STAS
1342/1991.
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parameters of Tudor Vladimirescu
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3. Gropeni (fig. 5, 6): pH value of water wells

were from 7.86 to 8.13 in 2011 and 7.75 to 8.56 in
2012. There is an increasing pH in excess of
Chloride content of well water had values from
297.86 mg/l to 390.06 mg/l in 2011 and between
288.41 mg/l and 749.1 mg/l in 2012. Increases and
decreases are found exceeding limits, according to
STAS 1342/1991. Nitrate content of water from wells
had values from 9.93 mg/l to 15.25 mg/l in 2011 and
13.12 mg/l to 18.89 mg/l in 2012. There was an
increase that did not exceed limits, according to
STAS 1342/1991. Nitrite content of water wells had
values from 0.78 mg/l to 3.75 mg/l in 2011 and 0.22
mg/l to 1.75 mg/l in 2012. It appears that two values
do not exceed but the other are beyond limits,
according to STAS 1342/1991.

parameters of Gropeni

parameters of Gropeni
4. Scarlatesti (fig. 7, 8): pH value of the water
wells were from 7.60 to 7.84 in the third quarter of
2011 from 7.16 to 7.67 in the fourth quarter of
2011from 7.78 to 8.38 in 2012. There was a decrease
of pH in the fourth quarter from the third quarter and
an increase in 2012 compared to 2011 that exceed
Chloride content of well water registred values from
226.55 mg/l to 262.4 mg/l in the third quarter of
2011, from 60.28 mg/l to 535.45 mg/l in the fourth
quarter of 2012 and between 364.7 and 676.96 in
2012. There is an increase in the first quarter of 2012
compared to 2011 that exceed the permissible limits,
according to STAS 1342/1991. Nitrate content of
water wells had values from 17.54 to 457.13 in the
third quarter of 2011, from 114.27 mg/l to 500.25
mg/l in the fourth quarter of 2011 and 186.51 mg/l to
529.63 mg/l in the first quarter of 2012. There is an
increasing excess of permissible limits, according to
STAS 1342/1991. Nitrite content of water wells had
values from 0.65 mg/l to 8.65 mg/l in the third quarter
of 2011, from 0.65 mg/l to 8.25 mg/l in the fourth
quarter of 2011 and to 1.27 mg/l to 1.33 mg/l in 2012.
There was a decrease exceeding permissible limits,
according to STAS 1342/1991.
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from 0.05 mg/l to 0.1 mg/l in the fourth quarter of

2011 and 0.2 mg/l to 0.3 mg/l in the first quarter of
2012. There is an increase in 2012 but does not
exceed permissible limits.

parameters of Scarlatesti

parameters of Lacu Sarat

parameters of Scarlatesti
5. Lacu Sarat (fig. 9, 10): pH value of the water
from wells was from 7.8 to 7.9 in the fourth quarter of
2011 and 7.92 to 8.6 in the first quarter of 2012.
There is an increasing pH in excess of permissible
limits, according to STAS 1342/1991. Chloride
content of the well water had values from 63.83 mg/l
to 123.24 mg/l in the fourth quarter 2011and from
53.9 mg/l to 63.12 mg/l in the first quarter of 2012.
There was a decrease but did not exceed limits.
Nitrate content of water from wells was in the range
of 15.01 mg/l to 34.5 mg/l in the fourth quarter 2011
and 16.2 mg/l to 43.7 mg/l in the first quarter of 2012.
There is a slight increase in 2012, exceeding the
limits. Nitrite content of water from wells had values
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Fig.10. Dynamics of groundwater chemical

parameters of Lacu Sarat
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6. Chiscani (fig. 11, 12): pH value of the water

from wells was from 7.8 to 8.8 in the fourth quarter of
2011 and 7.7 to 8.59 in the first quarter of 2012.
There is an increasing pH in excess of permissible
limits, according to STAS 1342/1991.
8,8
8,6
8,4
8,2
pH
8
7,8
2011
7,6
2012
7,4
7,2
7
1
sample
sample
CMA
2011
2012
Chloride content of the well water had values

from 138 mg/l to 426 mg/l in the fourth quarter of
2011 and from 426 mg/l to 532.5 mg/l in the first
quarter of 2012. The samples from Chiscani exceed
limits of chlorides content in water. Nitrate content of
water from wells was in the range of 50 mg/l to 79
mg/l in the fourth quarter of 2011 and between 45
mg/l to 100 mg/l in the first quarter of 2012. There
are increases in both years exceeding the limits.
Nitrite content of water from wells had values from
0.05 mg/l to 1 mg/l in the fourth quarter of 2011 and
0.04 mg/l to 1 mg/l in the first quarter of 2012. There
is an increase exceeding permissible limits in both
years only for sample 4.
Dynamics of physico-chemical parameters
indicated a change in their concentration in 20112012. In some wells, the values remained the same
while the others grew or low in concentrations. The
causes are multiple: from the weather, the
groundwater level, the activities in the study area and
the hydrological regime at this time of year. By
monitoring these deep aquifers we could conclude
that the study area is polluted at the groundwater
level.
4. Conclusions
200
400
600
Chlorides, mg/l

parameters of Chiscani
100
80
Nitrate,
m g/l
60
CMA
40
2011
20
2012
0
1
sam ple
1
0.8
N it r i t e,
mg / l
0.6
CMA
0.4
2011
0.2
2012
0
1
sa m pl e

parameters of Chiscani
Human activities can negatively influence the

quality (through air, soil or surface water) and
groundwater quantity (by irrational use of water).
Natural causes are primarily the small amount of
drought or lack of rainfall [2].
Surface water or groundwater contamination is
favored by the following issues [3]:
- Water in the liquid phase at variations in
temperature causes to engage in its flow various
impure substances;
- Water is an environment for physico-chemical
reactions (as dissolution of artificial or natural
substances, sedimentation of suspended solids etc.).
Worrying values are nitrates and nitrites, and
heavy metals that cause serious diseases of the human
body. Groundwater in the studied areas can produce
major disrupt on animal health and degrade the soil
by its high mineralization [4]. Exceeding the
permissible values makes these waters become unfit
to household waste, watering cattle and crop
irrigation.
Water quality monitoring leads to the conclusion
that during a calendar year, physico-chemical
variations in the groundwater are caused by [5]:
climatic conditions;
the use of fountain;
limitrophe soil parameters;
agricultural and domestic activities in the area;
hydrological regime in 2011-2012;
Groundwater levels.
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The wider use of nitrogen fertilizers to increase

agricultural production has led to a significant
increase in soil nitrate content in some food products,
surface water and groundwater. The increasing nitrate
concentrations found in the environment led to a
higher incidence of nitrate poisoning [4]. The
farmland fertilization with manure and synthetic
nitrogen fertilizers in particular, is the main cause that
led to increased nitrate content in soil, vegetation and
water sources. In heavily fertilized lowland territories
where agriculture is intensive, well water contains
traces of nitrates that reach or exceed 100 mg/l.
The main conclusions of the study are that:
- pH does not fall within the limits of STAS
1342/1991 (7.4), but respected the limits of exception
(8.50);
- chloride content is predominantly greater than
the limit (250 mg/l), and some areas beyond
acceptable limits exception (400 mg /l);
- content of nitrites/nitrates exceeds the
permissible limit (0.3 mg/l /45 mg /l) can lead to
poisoning of the population.
The mineral content of the water had high

values and the wells water has not the proper quality
for drinking and if would be used for irrigation it
would lead to soil degradation by salinization.
Recommendations on consumption of the wells
water after treating the water with various physico chemical methods such as: softening by ion
exchange, demineralization by reverse osmosis,
active carbon filtration, ultrasonic treatment,
treatment with ozone, microwave, UV [6].
References
[1]. Ciobanu D., Ciobanu R. C., Chimia Mediului Ambiant, Ed.
Tehnico-Info Chiinu, 2001.
[2]. Ciurea A., Cartas V., Stanciu C., Popescu M.,
Managementul mediului, vol. 2, Editura Didactic i Pedagogic,
RA, Bucuresti, 2005.
[3]. Lupea A. X., Branic A. G., Ardelean A., Ardelean D.,
Fundamente de chimia mediului, Editura Didactic i Pedagogic,
2008.
[4]. Surpeanu M., Elemente de chimia mediului, Ed. Matrix
Rom, Bucureti, 2004.
[5]. Rojanschi V., Protecia i ingineria mediului, Editura
Economic, Bucureti, 2000.
[6]. Ciomos V., Alimentarea cu ap a populaiei prezent i viitor,
Editura Hidrotehnica, Vol. 50, Nr. 2-3, Bucuresti, 2005.
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METHODS OF OBTAINING BIOPLASTIC

Dorin EFTIMIE, Aurel CIUREA
Dunarea de Jos Galati, Facultatea de Inginerie Braila
emails: deftimie@ugal.ro, aciurea@ugal.ro
ABSTRACT
This paper presents the need for bioplastics materials that goes into
packaging to eliminate environmental pollution. Experiments may be the
development of industrial technologies in order to obtain the ideal bioplastic
material.
KEYWORDS: bioplastic materials, bioplastic technologies
In 1907 in the United States, the belgian Leo
Baekeland was setting up a material that would
revolutionize the consumer market: ordinary plastic,
which began to be used to produce the various items.
Plastic waste resulting from human activities
and production, is a particular problem due to the
continue increase in their quantities and types, which
by infestation and degradation in the natural
environment presents a danger to the environment
and human health (fig. 1).
"green": bags, boxes, films and any container that

serves to packaging products of all kinds (fig. 2).
Fig. 2. Biodegradable packaging
Fig. 1. Polluted waters with plastic material

Applying
a sustainable plastic
waste
management involves major changes to current
practices. Currently waste management priorities are
not in accordance with the law.
Another disadvantage is that traditional plastics
is not inherently biodegradable. Biological polymers
began to be used as raw materials for plastics. These
materials are a new generation of bio-plastics that are
more environmentally friendly than those made from
petroleum.
For more than 10 years, it has been talking about
biodegradable packaging. A true fashion or genuine
concern for protecting the environment. However, the
demand is growing. Packages have began to become
A product is called biodegradable when it

transforms, it breaks down and is eliminated
naturally. A biodegradable packaging consists of
molecules that can be converted into smaller
molecules and less polluting, transformation that
occurs because of micro-organisms that live in the
wild: bacteria, mushrooms, algae, etc.
The result of this transformation process must be
water, carbon dioxide or methane. Even plastics can
be biodegradable. Their origin is synthetic or on
plant-based resources. Although it is attempted the
making of biodegradable plastics that break down as
naturally as paper and wood.
As far as we know, there are two technologies
for production of packaging:
A.
Hydro-biodegradable technology
"Hydro-biodegradability" involves producing
bioplastic packaging materials based on natural
ingredients products (starch, gluten, biopolymers). In
these conditions biodegradation is initiated by
hydrolysis, and the microparticles are transformed
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into biomass by microorganisms, with releasing of

CO2 and methane, according to some studies, the
phenomenon is known as the compostability. It is a
phenomenon similar to the one, in which vegetable
waste (leaves, straw, etc.) buried in the ground turns
into compost.
Advantages:
Technology is regarded as the most
"sustainable", in fact the biggest advantage of this
technology is virtually non-polluting.
The wastes are composted, and can be used
as fertilizer.
Does not contain any heavy metals or other
pollutants.
It complies with the essential requirements
of European directives in this area, the Directive
94/62/EC - Packaging, packaging waste and related
harmonized standards.
Disadvantages:
The resulted packagings are not sustainable,
they degrade, pshysically speaking, in a very short
time. Based on natural ingredients it is clear that
dedicated cultures will be required to the production
of this type of packaging, possibly from genetically
modified plants.
Does not recycle.
Their manufacture possess serious use of
water resources and consumption of energy higher
than traditional packaging.
At the end of the life cycle of packaging, the
resulting waste involves use of industrial composting
facilities.
B.
Oxo-biodegradabile technology
Involves the use of an additive (often it contains
magnesium, cobalt, nickel and so on - heavy metals)
in the manufacture of packaging. This finely
dispersed additive in the polymer matrix of
packaging, has the ability to convert an inert product
to biodegradation, such as polyethylene, in a
biodegradable product which is basically a plastic that
degrades in a relatively short time, 3 to 24 months.
Advantages:
It is the cheapest option for producers of
classic packaging. Introducing new technology
involves a minimal costs of adapting machines.
Packaging can be recycled.
There are as reliable for use as traditional
plastic.
The resulted waste can be stored in landfills
at no extra cost.
Disadvantages:
It is and remains a plastic that under certain
conditions
(temperature,
humidity,
sunlight)
degrades. Hence the numerous disadvantages with

common traditional plastics:
The waste must necessarily collected and
stored in landfills or recycled;
The degradation lasts up to 24 months, the
waste can threaten the life of aquifer.
Some additives may contain heavy metals in
excess, as such packaging manufacturers must carry
out additional testing of products (bags) to
demonstrate the compliance with the essential
requirements of the European directives.
The main types of biodegradable packaging:
biopolymers resulting from plants (starches,
cellulose, etc.);
biopolymers
produced
by
chemical
polymerization which asosciates the use of renewable
raw materials with industrial polymerization
processes;
biopolymers produced by micro-organisms
genetically modified; synthetic polymers.
Today's technologies are not advanced enough
to impose a future solution for biodegradable plastics
and research has been done for the diversity of
obtaining raw materials:
- chicken feathers, raw material for
biodegradable plastics;
- biodegradable packaging, from sugar;
- genetically engineered organic plastic;
- biodegradable plastic from bones and flesh of
animals;
- ecological plastic - from clay and milk;
- eggshells, raw material for biodegradable
plastics;
- bacteria, for the production of biodegradable
plastics;
Many biomaterials plastics can be processed
with conventional injection molding equipment and
converted into packaging and other products. A
problem is that new plastic materials are usually more
expensive than traditional oil-based. Recent advances
in production technology have enabled cost reduction
of biodegradable resins, but more needs to be done in
this regard. Some recyclable materials explored to
obtain biodegradable plastics are:
starch
polylactic acid (PLA)
cellulose and lignin in wood and cotton
cellulose
polihidroxialcanoai (PHA)
pullulan
In Romania, there is processing capacity
exceeding 20 000 t/year starches and the starch
obtained from maize, varying the last two years from
12 000 t/year - 15 000 t/year, with a growing
domestic market and export opportunities.
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Biodegradable plastic materials processing

includes operations similar to those used in the
making and shaping of plastic materials.
Biodegradable materials can be cast, molded,
processed and merged, can be processed with relative
ease in many forms and with few operations.
Biodegradable materials are melted or deformed at
relatively low temperatures, unlike metal, are easy to
handle and require less energy to be processed.
Properties of plastic subassemblies and components
are, however, influenced by the method of
procurement, manufacturing process parameters, so
strict control of these conditions is important for the
quality of subassemblies.
Biodegradable material is usually transported to
processing units under the form of grains or powder
and is melted (thermoplastic materials) just before the
modeling process. Biodegradable material is available
under the form of sheet, flat form, rods and tubes
which can be molded into a variety of products.
Currently, the most significant areas of
application, in order of consumption, bioplastics are:
biodegradable bags for household waste;
foils for food and non-food packaging;
shock fillers;
food bags;
catering products: cups, plates and cutlery;
protective films for agriculture;
Horticultural compostable items.
Fig. 4. The result of the test (viscous solution)

Eperiment number 2 using materials
A simple recipe for obtaining bioplastic and
more clear it involves the following ingredients
shown in the figure:
15 g of food starch;
60 ml distilled water;
5 ml of glycerin (glycerol concentrated,
100%);
5 ml of vinegar (acetic acid).
The two performed laboratory experiments

reveal the composition and concentrations of
substances in order to obtain relevant bioplastic
material, presented in fig. 37.
Fig. 5. Getting gelation mixture

From the experiment result the following
conclusions:
- Without being buried in the ground the
samples were placed randomly in environmental
factors (fig. 6):
1. Traditional plastic foil;
2. Biodegradable plastic foil;
3. Biodegradable starch-based foil.
Fig. 3. Preparation of the solution

Experiment number 1 using materials
- 2.5 grams of corn and potato starch,
- 2 ml of anhydrous glycerol (which acts as a
binder),
- 3 ml of concentrated hydrochloric acid,
- 3 ml of a solution of sodium hydroxide
(NaOH), which is added at the end and is designed to
reduce viscosity.
Fig. 6. The three types of foil

After about a month it was observed that the
normal plastic was not affected, the biodegradable
plastic bag turned into flakes and starch based plastics
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fell (was cracked and deteriorated) and are shown in

fig. 7.
Fig. 7. The types of plastic
There is a higher biodegradation of starch-based

plastic material and can be considered that through
expansion and research studies, the production
technology of this type of plastic will develop.
The conclusion can only be one: human
consciousness has not proven that it can save
humanity from the morass bags and plastic bottles.
Pollution today will be nothing compared to
tomorrow's pollution.
References
Conclusions
In conclusion, it has been showed
biodegradation of samples in the experiment.
the
[1].*** - Green plastics http://green-plastics.net/

[2]. *** - Metabolix http://www.metabolix.com/
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RESEARCH CONCERNING THE IMPACT OF THE POLLUTION ON

WATER AND SOIL RESOURCES FROM DANUBE DELTA
Gelu MOVILEANU1, Maria VLAD2, Tamara RADU2, Stefan DRAGOMIR2
1
Environment Engineering and Biotechnology, Faculty of Valahia University, Trgoviste, Romania

2
Material and Environment Engineering, Faculty of Dunarea de Jos University, Galati, Romania
email: mvlad@ugal.ro
ABSTRACT
This paper presents research on the impact of pollutants on aquatic and
terrestrial ecosystems in different areas of the Danube Delta. The main quality
indicators evaluated on a three-month period were pH, turbidity and heavy metal
content of water in four areas and soil pH as well heavy metal content in water and
soils collected from different areas. Given the great influence of heavy metals on
ecosystems, the values determined for samples of soil and water in areas Enisala
belt Canal, Canal Enisala Iancina Cape, Cape Dolosman were compared with the
maximum values indicated by Norm 161/2006. Metal transfer along aquatic food
chains relevant to environmental health research for several reasons. First, the
accumulation of metals in aquatic organisms may have as final result the trophic
transfer of metals to people, leading to a potential risk on public health from the
consumption of contaminated aquatic products.
KEYWORDS: heavy metals, turbidity, water, soil
1. Introduction
Natural water has pH values between 6.58.
Deviation from these values indicates pollution with
inorganic compounds [1]. Concentration of hydrogen
ions in water and soils is an important factor that
determines the reactivity of water or soil and can thus
assess whether media can be for developing various
bodies etc. Heavy metals and their compounds
generally have high density and are toxic even at low
concentrations. The toxicity potential of metals
depends on the bioavailability and physicochemical
properties of the bodies. These properties depend on
the atomic structure of the metal. Metals are divided
into the following categories: alkaline, alkaline earth,
transition, metals. Metals which show a higher
relevance to the environment in terms of toxic effects
are: cadmium (Cd), chromium (Cr), copper (Cu), lead
(Pb), nickel (Ni), zinc (Zn).
Distribution of heavy metals in water, soil,
plants, with concentrations above the admitted limits
influences the structure and their operation. In water a
large proportion of the heavy metals are combined
with suspended materials and are listed in the calm
water area. In sediments, heavy metals are capable of
endangering ecosystem when they are re-mobilized.
In particular, the fine sediments (fraction of sand or
silt less than or equal to 63 m) can accumulate large
amounts of heavy metals on the surface of mineral

and organic particles. Therefore analyzes of these
sediments can give reliable information of local
contamination. The toxic effects of pollutants have
repercussions at the cellular level, tissue or organism
level, thus changing population integrity and finally
the entire ecosystem. [3, 4]. The response to the
impact of contaminants varies from hours to
molecular and cellular level up to several years at the
population level and community. Temperature is a
particularly important factor influencing metal
toxicity, since most aquatic organisms are
poikiloterme. Living organisms have a certain
selectivity in metal accumulation, therefore is
necessary to distinguish between essential and nonessential metals. Essential metals such as copper,
zinc, manganese, iron and cobalt are vital components
of many enzymes and respiratory pigments. The
deficiency of these metals, but equally accumulation
over certain levels, produce harmful effects [5].
Essential metals (lead, arsenic, mercury,
cadmium) are highly toxic, even at very low levels,
especially if accumulated in the metabolically active
sites. The body is forced to limit the accumulation of
inessential metals or pass them in nontoxic forms.
Toxic metals interfere with normal metabolic
functions of essential elements. By binding to the
protein macromolecule is produced a disruption of the
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normal biological function [6]. Metal-catalyzed

formation of oxygen free radicals is involved in the
production of several pathological changes including
mutagenesis, carcinogenesis and aging. Heavy metals
even in relatively low concentrations are toxic [7].
2. Specific methods of physico-chemical

indicators analysis
2.1. pH values
pH values are a measure of acidity or basicity of
a solution. Determination of pH in water or aqueous
solutions was made in accordance with ISO
10523/1997 using a calibrated pH- meter, figure 1.
Fig. 4. Lake Golovita - water/soil samples
Fig. 5. Port Jurilodvca water/soil samples

Fig. 1. pH-meter COND 720
For analyzes in order to determine the pH of
water, soil and water turbidity from different areas of
the Danube Delta have collected water and soil
samples from the areas shown in Figures 2 to 5.
Turbidity of water samples taken from areas

Canal Dranov, Canal Enisala, Port Jurilodvca, Lake
Golovita was done with turbidimeter, Figure 6.
Fig. 6. Turbidimeter
3. Specific methods for heavy metals

analysis
Fig. 2. Complex Enisala Razimwater/soil

samples
3.1. Atomic absorption spectrometry
Fig. 3. Canal Dranovwater/soil samples
Analysis method by atomic absorption (AA) is

based on the phenomenon known almost one hundred
years before (1859) - discovered by German GR
Kirchhoff. Established principle on experimental
basis, it can be enunciated in the form of physical law
- Kirchhoff's law -as follows: each chemical element
absorbs those rays that may issue in the same well
defined temperature and pressure. Atomic absorption
spectrometer measures the absorbed radiation by the
atoms remains in the ground state. Their number is
usually much higher than those excited. Atomic
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absorption spectrometry (AAS) is a method that is

characterized by a much better sensitivity, at least to a
temperature of 5000 K. Resonance absorption is one
of the most used lines in chemical analysis by atomic
absorption. Therefore, in order to achieve a good
selectivity, the radiation source emitting the beam to
go through the cell, it must be a monochromatic
source with a frequency equal to the resonance line of
the atoms of the sample.
Fig. 9. Canal Enisala
3.2. Determination of heavy metal by X-ray

fluorescence
Heavy metals from soil samples can be
determined with X-ray spectrometer, Figure 7.
Fig. 10. Cap Dolosman heavy metals in

water/soil
Fig. 7. Portable X-ray fluorescence analyzer
(Model: Alfa)
To achieve the determination of heavy metal
contents in soil and water of the Danube Delta,
samples were collected from the areas shown in
Figures 8 11.
Fig. 11. Cap Iancina
4.1. Experimental results on the impact of
environmental factors on ecosystems
Experimental data collected on water turbidity
in the 4 points of the Delta are shown in table one,
and graph, Figure 13.
Fig. 8. Belt Canal Enisala heavy metals in

water /soil
Table 1. Water turbidity values in the 4 points of the Delta

Sample
P1-Canal Dranov
P2-Canal Enisala
P3-Port Jurilodvca
P4-Lake Golovita
April, 2013
85.2
24
1122
790
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Turbidity (NTU)
May 2013
104,6
30.9
12 75
843
June, 2013
99.9
27.0
1225
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Turbidity (NTU) in April, 2013

Turbidity (NTU) in June, 2013
Turbidity (NTU) in Mai, 2013
1400
Turbidity [NTU]
1200
1000
800
600
400
200
0
P1-Canal
Dranov
P2 -Canal
Enisala
P3-Port
Jurilodvca
P4 -Lake
Golovita
Fig. 12. Variation of water turbidity analyzed 4 to par, in April, May, June 2013
For analyzed water samples were observed that
the highest values of suspended solids content were in
May and June, especially in Lake Golovita Jurilodvca
port. This may be due to increasing the amount of
water in these months as a result of the default rains
which caused increasing the amount of silt brought by

the Danube. Determination soil and water pH in the 4
areas are shown in Tables 2 and 3.
Based on experimental data were plotted graphs
mentioned in Figures 14, 15.
Table 2. Water pH values in the 4 areas of the Danube Delta

Water pH
Sample
P1-Canal Dranov
P2-Canal Enisala
P3-Port Jurilodvca
P4-Lake Golovita
April, 2013
May 2013
June, 2013
8.65
8.72
9.10
7.87
8.03
8.37
8.81
7.56
7.75
7.98
8.09
7.36
Table 3. Soil pH values in the 4 areas of the Danube Delta

soil pH
Sample
April, 2013
8.4
7.9
8.9
7.8
P1-Canal Dranov
P2-Gradistea
P3-Port Jurilodvca
P4-Lake Golovita
May, 2013
8.9
8.7
9.4
8.5
water pH in April, 2013

water pH in June, 2013
June, 2013
8.6
8.3
9.2
8.1
water pH in May, 2013
10
water pH values
9
8
7
6
5
4
3
2
1
0
P 1-Canal
Dranov
P2 -Canal
Enisala
P 3-Port
Jurilodvca
P 4 -Lake
Golovita
Fig. 13. Variation of water pH in 4 areas analyzed in April, May, June, 2013
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Figure 13 shows that analyzed water pH has

the highest values in April and May, especially in
Port Jurilodvca and Canal Dranov, Canal Enisala. The
main cause of this variation is pollution, especially in
port and lower amount of vegetation which lead to

decreased content of nitrates, phosphates from the
water.
soil pH in April, 2013

soil pH in June, 2013
10
soil pH in May, 2013
soil pH values
8
7
6
5
4
3
2
1
Golovita
P4 -Lake
Jurilodvca
P3-Port
P2 -
Gradistea
Dranov
P1-Canal
Fig. 14. Variation of soil pH in 4 point analyzed in April, May, June, 2013
Graph 14 shows that analyzed soil pH has the
highest values in May and June, especially in port
Jurilodvca and then Canal Dranov and Canal Enisala.
The main cause is pollution, in the port and the
greater amount of vegetation by consuming nitrates,
phosphates from the water which will increase these
substances in soil sediment. According to Standard

161/2006, maximum permissible concentration for
heavy metals analyzed in water and soil samples in
the 4 Danube areas were not exceeded, Tables 4, 5.
Based on the determined values were drawn graphs,
Figures 15, 16.
Table 4. Content of metals in water

Source
Cr
Ni
Pb
Zn
Cu
As
Limit according to Standard

161/2006 - class II quality
mg/L
0.05
mg/L
mg/L
0.025
mg/L
mg/L
0.01
mg/L
mg/L
0.2
mg/L
mg/L
0.03
mg/L
mg/L
0.02
mg/L
Belt Canal Enisala

Canal Enisala
Cap Iancina
Cap Dolosman
0.034
0.037
0.021
0.023
0.006
0.009
0.003
0.006
0.138
0.149
0.081
0.118
0.022
0.025
0.020
0.018
0.010
0.012
0.008
0.011
0.021
0.019
0.016
0.017
Table 5. Content of metals in soil

Source
Limit according to
Standard 161/2006
Cr
mg/kg
100
mg/kg
Ni
mg/kg
35
mg/kg
Pb
mg/kg
85
mg/kg
Zn
mg/kg
150
mg/kg
Cu
mg/kg
40
mg/kg
As
mg/kg
29
mg/kg
Belt Canal Enisala

Canal Enisala
Cap Iancina
Cap Dolosman
14.656
15.201
6.090
14.798
5.275
4.558
4.933
4.426
5.446
5.162
3.735
3.648
41.392
53.854
24.327
36.641
14.706
11.047
2.262
6.302
2.580
3.116
2.548
2.905
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Cr
Ni
Pb
Zn
Cu
As
metals content in water [mg/L
0.25
0.2
0.15
0.1
0.05
0
Limit
according
Standard
Belt Canal Canal

Enisala
Enisala
Cap
Iancina
Cap
Dolosman
Fig. 15. Variation of heavy metals content in water collected from areas belt Canal, Enisala,
Canal Enisala, Cap Iancina, Cap Dolosman
Cr
Ni
Pb
Zn
Cu
As
metals content in soil [mg/kg
160
140
120
100
80
60
40
20
0
Limit
according
to Standard
Belt Canal
Enisala
Canal
Enisala
Cap
Iancina
Cap
Dolosman
Fig. 16. Variation of heavy metals content in soil collected in areas belt Canal Enisala,
Canal Enisala, Cap Iancina, Cap Dolosman.
5. Conclusions
1. Analyzed water pH values had the highest
values in April and May, especially in port Jurilodvca
then Canal Dranov and Canal Enisala.
2. Soil pH values had the highest values in May
and June, especially in port Jurilodvca then Dranov
and Canal Enisala.
3. According to Standard 161/2006, maximum

permissible concentration for heavy metals analyzed
in water and soil samples from areas belt Canal
Enisala, Canal Enisala, Cap Iancina, Cap Dolosman
was not exceeded.
4. Significant environmental impacts in Danube
Delta have the agriculture and tourism.
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5. Soil and water resources management must be

done so that to ensure economic efficiency and
harmonious relationship with the environment.
References
[1]. Gtescu P., tiuc R., Delta Dunrii Rezervaie a Biosferei,
Tulcea: Editura CD Press. 400, 2008.
[2]. Wepener V., Van Vuren J. H. J., Du Preez H. H, Uptake
and distribution of copper, iron and zinc mixture in gill, liver and
plasma of freshwater teleost Tilapia sparrmanii, http:
www.wrc.org.za, 27, 2001, p. 99-108.
[3]. Oel V., Bnrescu P., Nalbant T., Baboianu C., Rezultatele
investigaiilor ihtiologice din teritoriul Rezervaiei Biosferei Delta
Dunrii, Analele ICPDD, 2, Tulcea, 1993, p. 145-162.
[4]. Oel V., Actual status of ichthyofauna in the Danube Delta

Biosphere Reserve-Romanian sector: systematic and conservation,
The 10-th Europ. Congr. of Ichthyology Praga, Book of Abstracts,
2001, p. 61.
[5]. Srbu I., Benedek Ana Maria, Ecologie practic, Edit. Univ
Lucian Blaga, Sibiu, 2004, p. 260
[6]. Stara M., Nvodaru I., Schimbri n structura ihtiofaunei ca
efect al modificrii caracteristicilor biotopului, In Analele
tiinifice ale Institutului Delta Dunrii, Tulcea, 1995, IV/1, p. 223239.
[7]. indrilariu P. D., Bacalbaa-Dobrovici N., Freyho F. J.,
Wolter C., The juvenile fish community of the Lower Danube and
Danube Delta, Internat. Assoc. Danube Res., 2002, p. 517 526.
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INVENTORY ACTIVITY OF MACHINES USED ON CONSTRUCTION

SITES FOR ENVIRONMENTAL EMISSIONS EVALUATION
Carmen DEBELEAC
"Dunarea de Jos" University of Galati, Engineering Faculty of Braila
Calea Calarasilor no. 29, 810017 Braila, Romania
email: carmendebeleac@yahoo.com
ABSTRACT
In this paper the author presents requirements imposed for non-road
construction machinery emissions according to European regulations and
methodology for emissions testing. The inventory tasks of construction machines
used on site (excavators, loaders, bulldozers, graders, scrapers, etc.) will be
described. The paper deals information about best practices for collecting the
required data for each construction machine/equipment in view of environmental
emissions evaluation.
KEYWORDS: emissions, site, construction machines, diesel engine
1. Introduction
Nowadays, the control emissions of non-road
mobile sources at construction site plays an important
role to protect the workers, the around public and air
environment. Through good design and planning of
activities that are developed at construction site,
exceeding of regulated limits refereed to non-road
mobile sources can be avoided just before starting
works. Non-road mobile sources contain any mobile
machine, transportable industrial equipment or
vehicle with or without body work, not intended for
the use of passenger - or goods - transport on the
road, in which an internal combustion engine is
installed [2].
In this paper, the authors taking into
consideration only sources called non-road mobile
machinery - NRMM that find wide applications in
construction sites (e.g. excavators, loaders, trucks,
vibratory hammers, compactors, graders, etc.).
Main activities in the construction area consist
by following (non exhaustive list):
- work
involving
embankments
soil
(stabilization, foundation, excavation, compaction
etc.);
- demolition works;
- installation of several devices;
- repairs, modifications, preservation, cleaning
and maintenance works;
- renovation and restoration works.
Construction machinery engine operation leads
to air emissions of carbon monoxide (CO), the
emissions of hydrocarbons (HC), of the oxides of
nitrogen (NOx) and the emissions of particulate
matter (PM). There are several criteria for

establishing concentration limits for each pollutant
sources above-mentioned that varies with engine
type, mode of operation, and type of fuel used.
The emissions factors mean a measure of the
grams of pollutant per HP or kW and per hour of
operation. According to a statistical analysis
performed in 2005 [2], with 32% and 30%
respectively, construction machinery is the second
highest source of non-road emissions of nitrogen
oxides and particulate matter.
2. Legislation and standards applied on

construction site
As a developing country, construction is one of
the most active industries in Romania. Excessive
noise, vibration and emission levels can result in
many activities developed at the constructions site
with negative impact for surrounding occupants
including surrounding residents, site workers,
atmosphere, ground, etc. [3].
In Romania, the Law no. 265/2006 assures the
general frame for environmental protection and
Governmental Regulation HG 622/2004 includes
types of products under certification by the
certification scheme with the decision of
implementing regulations.
Recently, Directive 2010/26/EU specifies
technical details on the testing and approvals of Stage
III B and Stage IV engines [6].
The legislation has been developed in
cooperation with the U.S. Environmental Protection
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Agency to achieve worldwide harmonization of

emission limits. In many countries (EU, USA, Japan),
regulatory authorities have harmonized emission
standards for non-road engines with gradually
applicability: I, II stages [4], and III, IV [5]. The goal

of the stage III B consist on implementation of tier 4
engines with low emissions level such is shown in the
Table 1.
Table 1. EU Emission Standards for Non-road Diesel Engines - Stage III B

Category
Power,
in kW
Validity date
L
M
N
130 P 560
75 P<130
56 P<75
37 P<56
CO
Emission (g/kWh)
HC
NOx
January 2011
January 2012
January 2012
3.5
5.0
5.0
0.19
0.19
0.19
January 2013
5.0
These limit values apply to all non-road diesel

engines mounted into constructions machinery that
operate on site.
Evolution in time of regulated emissions of air
pollutants is shown in Fig.1 where the reference year
represents 2010.
Percentage (%)
500
400
PM
2.0
3.3
3.3
0.025
0.025
0.025
HC+NOx=4.7
0.025
Based on graphic into fig.1 its observed that

reductions in NOx and PM are significant, over 400%
reduction compared with machines from a fifteen
years ago. In our country there is Best Practice
Guidance builds based on EU norms and apply to
smaller industrial activities at construction site.
Emissions from machinery associated with
construction sites can significantly add to levels of
local air pollution, so it is important that best practical
means machine emissions reducing to be applied.
3. Methodology
300
The general requirements for emission control

strategy applicable for stages IIIB and IV of non-road
engine based on monitoring of speed and torqueoperating range of the engine over a test cycle (e.g.
steady or/and transient cycle depending on non-road
machine type) [6]. Actual Regulations provides
information about general procedures for non-road
engine inventory through the next technical details
identification as follows: machine category, machine
type, engine type, engine-power class, etc. An
example for excavator equipments is shown in Table
2.
200
100
0
1990 1995 2000 2005 2010 2015
Fig. 1. Comparison of on-road and nonroad emissions requirements

() CO; () HC; () NOx; () PM
Table 2. Sub-categories inventory for non-road segment of construction machinery

Machine Category
Machine Type
Engine Type
Construction
Machinery
Hydraulic Excavator
Komatsu, SA6D114E1
Caterpillar, C6.4
JCB, Isuzu A4BG1T-S1
If we have vehicle type means that we know

type of engine and fuel, engine power, year of
construction, and other technical specification with
influence over the air emissions. Based on these data
Pollutant
NOx
PM
Engine-power
class
170 kW
110 kW
63 kW
and according with actual methodology it is verified

if the machine achieves the limit levels of emissions.
In Table 3 is presented the NOx and PM pollutant
limit values in respect with engine-power class.
Table 3. Engine-power class for each pollutant from construction machines [2]
Engine-power class
<18 kW
18-37 kW
37-75 kW
75-130 kW
130-300 kW
300-560 kW
27.35
29.25
35.30
36.75
35.34
34.24
5.38
3.69
2.88
1.89
1.72
1.71
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Based on the estimated activity and the load

factors of the main equipments used in building
construction (Table 4) it can be calculate the baseline
mass emissions in air from each engine in respect

with annual operation time.
Table 4. Annual operation time for engine of non-road constructions machinery [1]
Size
Hours per
year operating
<300 HP
1800
>300 HP
2000
All
All
<300 HP
>300 HP
2000
1500
2000
2500
Rollers
All
1000
Pavers
All
1200
<300 HP
1800
>300 HP
All
All
All
All
All
2000
2000
1800
1500
1500
1800
Equipment type
Excavators
Dozers
Graders, Compactors
Scrapers
Wheeled Loaders
Off-Road Trucks
Stabilizers
Drilling equipment
Skid Steer Loaders
Backhoes
After machines inventory, the next stage

consists on mass emissions evaluating depending on
number of hours of operation per year, manufacturer
year and many other factors. Analytic, non-road
emissions engine are calculated with the next formula
[2]:
0.59
0.43
0.21
which contents a number by 8 - mode cycles (named

C1 steady-state test). Table 5 summarizes some
conditions regarding non-road transient cycle test.
Table 5. Description of non-road transient cycle

Indicator
Average speed
Average torque
Test repeat
E m = N H P k CF1 CF2 CF3 (1)
where: Em represents emissions per equipment type

(tonnes per year);
N - number of machines;
H - hours of operation (in hours per year);
P - mean engine rated power (in kW);
- emission factor (g per kWh);
k - load factor;
CF1 - correction factors for deviation of
effective load from standard load of duty cycle;
CF2 - correction factor for dynamic work regime
of equipment;
CF3 - correction factor for wear and tear of the
equipment.
According to [6, 7, 8], non-road engine
emissions are measured at constant-speed engines and
during real conditions with a new test procedure
Load
factors
Value
67.7%
39.3%
2
For construction machines the test cycle

contains a sequence of test points each defined by
speed and torque which are described through the
engine operation mode under the steady state or
transient work conditions (Table 6).
The measurement of pollutant emissions
developed over the entire work cycle of the machine
was described in Directive 2010/26/EU, which
provides calculation methodology of many indicators
such as:
- specific emissions (in g/kWh);
- mass emissions (in g/test);
- mass flow (in g/test) for each individual
component.
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Table 6. Engine load according by the ISO 8178 C1 [8]

Mode
1
2
3
4
5
6
7
8
Engine speed
rated
rated
rated
rated
intermediate
intermediate
intermediate
Low idle
Torque %
100
75
50
10
100
75
50
0
4. Case study for Romanian

manufacturers in the construction
machines field
In Romania, the construction machines industry
have relative low representation such as market level,
comparative with the EU in the same area.
The strategy adopted by the National
manufacturers of non-road construction equipments
consists by the full acquisition of these machines or
only some main components which are assembled
using the local labour force.
Among imported components from UE it can
enumerate engines, pumps, actuators, electronic
Weighting factor
0.15
0.15
0.15
0.10
0.10
0.10
0.10
0.15
devices and other technical systems, due to high

technical performances, efficiency, maintenance, and,
last but not least, environmental emissions rate.
In Table 7 are show the results of an inventory
act about emissions of construction machineries
manufactured in Romania, in 2013.
A partial concluding remark shown that standard
emissions of these machines are over-passed (e.g. it
has to have Stage IIIB, but it actually accomplish
Stage II).
The actual effort of Romanian manufacturers of
construction equipments must be focuses to
implement the higher cleaner engine technologies for
emissions level decreasing.
Table 7. Inventory of non-road construction equipments made in Romania

Romanian
construction
machinery
Diesel
engine dates
Standard
emissions
Excavators
Manufacturer: Promex S.A. Braila
S1205
Perkins
1106C E60TA
4 stroke
P=125 kW
2200 rev/min
EC Stage II
USA EPA Tier 2
S 1811
Perkins
1106C E60TA
4 stroke
P=159 kW
2200 rev/min
EC Stage II
USA EPA Tier 2
S 3602
Deutz BF6M1015C
P=273 kW
2100 rev/min
EC Stage II
P851 HyEI
Perkins
1104C-E44TA
P= 97 kW
2200 rev/min
EC Stage II
Table 7. Inventory of non-road construction equipments made in Romania (continued)

Romanian
construction
machinery
Loaders
Compactors
Manufacturer
Promex S.A. Braila
Diesel engine dates
IF 50
Kubota
V2003-T-EBB-EC-1
36,5 kW
2800 rev/min
CVM 10
Deutz
P6L912
P=78 kW
2800 rev/min
Standard emissions
EC Stage II
EC Stage II
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Tractor for loader

and excavator equipments
Manufacturer
Manufacturer
S.C. Geda
Nicolina Iasi
Prodexim S.R.L.
U 650
UTB U 650
Brasov
Deutz
U 650
BF4M2012
P=47,8 kW
P=60.5 kW
1800 rev/min
2500 rev/min
EC Stage II
EC Stage II
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5. Conclusions
References
The paper presents European frame for

environmental emissions of non-road construction
machines. The EU regulation of NRMM must
implement in Romania and this legislative process
cant begin without an inventory of all equipments
used, in this particular case, on construction sites.
For the scientific world, the implementation of
Stage III B and IV goals through the introduction of
tier 4 engines, represents a major progress because
will added to work together engineers with different
specializations such as materials science, design,
thermal and fluid science, electrical, electronics, and
informatics engineers who will developed new
products and technologies with higher performances.
Most of the NRMMs in Romania are imported
by the local dealers which sell both new and second
hand machine. In the case of used machine, they
arent always accompanied by certificates that could
give information on their emission standards.
For this reason, the Romanian Authorities must
impose the concrete and effective measures to tackle
NRMM emissions specifically.
[1]. Environmental Protection Agency - EPA, Median Life,

Annual Activity, and Load Factor Values for Nonroad Engine
Emissions Modeling, NR-005c (EPA420-P-04-005), U.S.
Environmental Protection Agency, Office of Transportation and
Air Quality, Ann Arbor, MI, 2004, available at www.epa.gov.
[2]. Environmental Protection Agency - EPA, Users guide for
the final NONROAD 2005 Model, EPA-420-R-05-013, U.S.
Environmental Protection Agency, Office of Transportation and
Air Quality, Ann Arbor, MI, 2005, available at
http://www.epa.gov.
[3]. Picu, M. and Nastac. S., A study concerning the driver comfort
improvement as regards the transmitted vibrations by the vehicle
running on roads in Romania, Carpathian Journal of Earth and
Environmental Sciences, Vol.6(2), 2011, ISSN Printed: 1842
4090.
[4]. ***, Directive 97/68/EC contains measures against the
emission of gaseous and particulate pollutants from internal
combustion engines to be installed in non-road mobile machinery.
[5]. ***, Directive 2004/26/EC contains amendments to Directive
97/68/EC.
[6]. ***, Directive 2010/26/EU contains amendments to Directive
2004/26/EC.
[7]. ***, Directive 2012/46/EU amending Directive 97/68/EC of
the European Parliament and of the Council on the approximation
of the laws of the Member States relating to measures against the
[8]. ***, ISO 8178-2:2008 - Reciprocating internal combustion
engines - Exhaust emission measurement - Part 2: Measurement of
gaseous and particulate exhaust emissions under field conditions.
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STUDY ON THE USE OF NATURAL ECOLOGICAL MATERIALS

FOR CONSTRUCTION AND INSULATION OF BUILDINGS - REEDS
Ovidiu Dima
email: odima@ugal.ro
ABSTRACT
A major action, regulated by European and national legislation is thermal
rehabilitation of buildings and isolation of new buildings to reduce consumption of
fuel and energy needed to ensure thermal comfort. The paper analyzes the
possibility of using natural organic materials for insulation and recommends in this
regard, precast reeds. Experimental researches have shown the possibility of
increasing the fire resistance of structures of reeds with fireproofing solution of
sodium silicate from grade III to grade V resistance. A comparative calculation
showed also reduced more than four times the energy consumption designed to
ensure thermal comfort in a home insulated reed plate, to a house of the same size,
thermally not insulated. The same proportion is estimated and reduced emissions.
KEYWORDS: thermal insulation,
fireproofing, reduced pollution
1. Introduction
The energy performance of a building is
determined by reference to amount of energy
consumed to ensure standard operating conditions. In
the case of housing is the main energy consumption:
central heating and hot water, cooling and ventilation
systems operate, home lighting, etc.. Based on these
consumption, buildings fall into the seven energy
classes. It is estimated that over 50% of the energy is
used for heating or cooling, the main cause of this
high percentage is inadequate insulation.
Thermal insulation is constructive action to
reduce losses or excessive intake of heat to maintain a
certain temperature inside the building. An insulated
building provides thermal comfort and operating
economy. The amount of energy decreases and
lifetime increases. Record It is also appropriate
behavior from the point of view of transfer of
humidity and freeze-thaw phenomena related to the
external elements of the building.
2. Insulation materials and their

characteristics
Most common insulation materials are natural
and artificial materials.
Distinguish between artificial materials: glass
mineral wool , mineral wool , expanded polystyrene ,
extruded polystyrene , polyurethane foam insulating
polymer films incorporating bubbles, cellulose fibers
natural
organic
materials,
reeds,
obtained from recycling of paper , cardboard, wood

waste , sawdust , chips etc. They may be mixed with
the polymer and flame retardant . It highlights the
trend of recovery of waste for the production of
prefabricated insulation with positive economic
effects and environmental protection .
Natural building materials and insulation were
used along time and they are: stone, wood, cork,
wool, straw, adobe clay, hemp, reed and bulrush etc.
In recent decades, however, their use has suffered a
strong setback. Today, plans to build eco led to the
use of natural materials , materials that can be found
easily in nature and does not involve an extensive
process. Compared with artificial materials, natural
ones have the following advantages: does not require
extensive industrial processing, the processing does
not cause nuisance due to low power consumption,
non-toxic and after leaving the service of the building
are readily degradable and environmentally friendly
behavior.
Reed insulation. Reed was one of the traditional
materials for the construction of a roof, especially in
rural areas. After a period of ignorance, he returns to
the present, because of indisputable quality: reed
grows spontaneously in moist areas and cleaning of
these areas require periodic harvesting, the cost of
harvesting is reduced, whether natural or processed in
different formats provide both thermal insulation and
a proper waterproofing in all seasons. Reed
construction can be used as: plate granular, woven
reeds or reed wall, Figure 1.
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a)
b)
c)
Fig. 1. The use of the reed forms: a) granular plate, b) woven reeds, c) wall
As destination precast reed may be used in:
a) inner insulation in which case reed plates
about 5cm thick wall cling. In these plates may enter
the heating system in the form of plastic or metal
tubes, Figure 2a.
a)
b) external wall insulation at least 10cm thick

layer of mortar attached directly to the wall, Figure
2b.
c) thatched roofs, Figure 2c.
b)
c)
Fig. 2. Intended use of precast reeds: a) inner insulation, b) exterior insulation, c) roofs
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3. Increased fire resistance of precast reed

insulation
Most natural materials used for insulation are
combustible and therefore need to increase their fire
resistance. Operation through which the increasing
resistance to fire of combustible materials,
fireproofing called. A correctly executed fireproofing,
maintained over time, can improve the fire resistance
of a building from grade III to grade V resistance and
other protective measures can reduce more expensive.
Also fireproofing to provide: fire location at initial
outbreak, of mind of the residents, lower costs to end
insurance policies. In addition retardant functions as
insecticide-fungicide against pests.
Most of the fire retardant solutions are based on
sodium silicate and the following characteristics
Table 1.
Table 1.
Basic solution
pH-ul
Vscozity
Color
Odor
Density
Number of layers
Layer thickness
Application
Specific
consumption
Surface drying
Drying2 coats
Sodium silicat (Na2SiO3)

11,46
3.2%
Beige-brown
Slightly pungent
1.33g/cm la 20 oC
2
20075m
Spraying, brushing, dipping.
Both types of samples were subjected to

burning, having previously been moistened locally
with a solution flammable. In unprocessed samples, it
was found that the fire burned and Integrity in
samples fireproof fire burned until exhausted
flammable solution. The fabric is colored reed local
and then the fire extinguished, Figure 3.
The test demonstrated the beneficial effect of
fireproofing process.
4. Comparative study on the benefits of

thermal insulation housing
0.7-0.8kg/m
1 or
48 ore
Stages of fireproofing are preparing the material,

treating the material with fire retardant solution by
spraying, brushing or dipping to form a layer of about
200m, superficial and deep drying materials
outdoors.
To test the fire resistance of precast fireproof
reed compared to those in the natural state, have
prepared two samples of woven reeds.
One type of samples was kept in its natural state
and the other to fireproof coating with sodium silicate
solution.
a)
b)
Fig. 3. Reed fabric samples for trying to fire a)

original sample fireproof b) sample fireproof
after fire
The main advantage of a home insulation is

lower power consumption for maintaining thermal
comfort conditions and at the same time protecting
the environment by using less fuel quantities to obtain
this energy. To prove this we conducted a
comparative study on the energy performance of a
building with thick concrete walls =30cm
uninsulated and a similar building with concrete walls
insulated with thick reed plates 10cm.
Calculation of heat loss through exterior walls
was done taking as example a house with one level
with external dimensions: L = 8m, W = 8m, h = 2.5 m
and S=80m wall surface.
They were considered too climatic conditions in
the south-eastern Romania respectively: a period of
winter for 5 months, 150 days, with a difference in
average temperature between inside and outside
t=20 C for a period of summer for 3 months about
90 days with a mean temperature difference t=5 C.
For the remaining four months of transition between
cold and warm considers the existence of a thermal
equilibrium between the inside and outside of the
building heat transfer is negligible.
From the technical point of view, the heat loss
Q, depending on the temperature difference [K], the
total area of the outer wall [m], the coefficient of
heat transfer.
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k[
W
]
m2 K
Q = k S t where k =
Q=
Rc is derived by applying corrections to the

theoretical strength;
For concrete wall were considered values:
concrete=1.7; concrete=0.3; Rc = 0.27.
For insulated concrete wall plate 10cm reeds
following calculations resulted Rc = 1.18.
Energy expended is calculated using the
formula: E=Q x T [Wh]; where T- the time in hours
and E = Q x T x 3600 [J].
For the calculation of fuel is envisaged its
calorific value. If methane gas calorific value is
q=55.5 [MJ/kg]. Knowing the energy consumption
and fuel value we can calculate the mass of fuel
required by the relationship: m = E/q [Kg].
1
and k =
Rc
1
S t and Q =
S t [W ]
Rc
- thermal conductivity [
W
]
m K
wall thickness [m];

Rc - actual wall thermal resistance corrected;
Case 1- Concrete Walls 30cm
Rc=0.27
Winter 5 months x 30 days x 24h = 3600 ore
Q=1/0.2780 20=5925W
Ewinter=59253600=21330000Wh=21.33MWh
Summer 3 months x 30 days x 24h =2160 ore
Q=1/0.2780 5=1481W
Esummer =1481 2160=3198960Wh=3.2MWh
Etotal=24.53MWh=88.3GJ
Annual consumption of methane m = 1591Kg
Analyzing the data obtained it is shown a

reduction theoretically considerable energy to thermal
comfort, four times where home plate isolated walled
reeds house versus non-insulated walls.
Combustion heating in turn generate emissions. The
amounts of contaminant results, calculated on the
basis of the balance of the combustion reaction are
shown in Table 2 and Figure 4.
Table 2
Nuisances
from
burning
methane
[kg/GJ]
NOx
CH
CO
CO2
NH3
46
2.5
25
56
0.15
Concrete
Concrete
Walls
Walls
reeds
30cm
insulation
10cm
88.3 GJ
20.16 GJ
annual emissions (t)
4.06
0.93
0.22
0.05
2.2
0.5
4.95
1.13
0.013
0.003
5. Conclusions
6
5
4
Neizolat
Izolat
2
1
0
1
Fig. 4. Annual emissions of pollutants.

Comparative presentation
Case 2- Housed reeds plate 10cm

Rc=1.18
Winter 5 months x 30 days x 24h = 3600 ore
Q=1/1.1880 20=1355W
Ewinter =13553600=4878000Wh=4.87MWh
Summer 3 months x 30 days x 24h =2160 ore
Q=1/1.1880 5=338W
Esummer =338 2160=730080Wh=0.73MWh
Etotal=5.6MWh=20.16GJ
Annual consumption of methane m = 363Kg
Increasing the energy efficiency of housing is a

very important step in protecting the environment. By
5-10 cm insulation of external walls with reeds
houses, we can achieve great energy savings
(theoretically consumption is 4 times less), and
therefore make a significant contribution to
environmental protection by reducing noxious
emissions in the same proportion. In addition
fireproofing prefabricated reeds improves the safety
of the buildings and the physical and psychological
comfort of the occupants.
Benefits of using natural organic materials are
organic materials are taken from nature and do not
require large amounts of energy for processing, after
processing their results in a reduced amount of
pollutants, natural materials are non-toxic and
environment friendly behavior, are easily degradable
without affecting the environment after use. Is
nonetheless a rational exploitation of all natural
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materials to determine imbalances in ecosystems not

difficult to repair and unpredictable effects on the
human community.
References
[1]. ***, STAS 3010-1952 Stufitul.
[2]. ***, Normativ privind folosirea plcilor de stuf (stufit) la
lucrrile de construcii, Ed. de stat pentru arhitectur i construcii
Buc. 5.02.1953.
[3]. I. Albu, Chimie i materiale de constucii, I. P. Cluj Napoca

1983.
[4]. I. Buchman, s.a., Materiale de construcii, Universitatea
tehnic Timioara, 1995.
[5]. C. Bob, P. Velica, Materiale de construcii, EDP Buc. 1978.
[6]. V. Athanasovici, V. Muatescu, I. S. Dumitrescu,
Termoenergetic industrial i termoficare, Bucureti 1981.
[7]. T. Chifu, Tipuri de stufriuri din Delta Dunrii; alctuirea i
caracterizarea lor, An. t. I.C.P.D.D. Tulcea 1993.
[8]. G. Gheorghe, Distribuia i utilizarea gezelor naturale, Ed.
Tehnic Bucureti, 1972.
[9]. LEGEA nr. 372/2005 privind performanta energetica a
cladirilor.
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SAWDUST RECYCLING TECHNOLOGY IN INSULATION

BOARDS MANUFACTURING
Dorin EFTIMIE, Dumitru POPA
Dunrea de Jos University of Galati, Braila Engineering Faculty

emails: deftimie@ugal.ro, dpopa@ugal.ro
ABSTRACT
The paper proposes a technology for manufacturing the insulation plates by
mixing of sawdust waste with cement adding polystyrene or mineral wool. The
boards have thermal and sound absorbing properties and are used to make
partitions, the partitions of buildings, masking of installations in attics walls and
facades.
KEYWORDS: insulation boards, waste sawdust, technology
1. Introduction
Environment
protection,
public
health,
maintenance of biological diversity and fragile
ecosystems balance are some of the current problems
facing humanity.
When the amount of pollutants exceeds the
neutralizing capacity of the environment, the
ecosystems suffer their alteration and destruction
process, resulting total living areas lacking.
In recent years many economic agents have
emerged in the wood processing industry, especially
in mountainous areas where raw material is plentiful.
Without proper management of waste in the form of
sawdust resulting from the processing, this sector can
become an important source of pollution, especially
ground. Sawdust from the amounts of the sawmills
have been a problem in recent years.
According to the National Institute of Wood [1],
in Romania, waste sawdust resulting from wood
exceed 1.5 millions m3.
Typically, shells and sawdust are organic

materials, in principle, should not pollute the
environment. In fact, in many cases sawdust is used
to improve soil texture, together with the nitrogen in
fertilizers, manure, lime, etc. But, when large
quantities are left on the ground, near watercourses,
this type of waste is very pollutant (fig. 1 and 2).
Fig. 2. Discharge of sawdust
Fig. 1. Pollution with sawdust
Landfilled on the ground, the sawdust alter the

quality and composition of the soil, changing the ratio
carbon/nitrogen from the soil. Soil bacteria which
consume carbon, also consume nitrogen (essential for
the metabolism of plants) soil that remains is
insufficient for plant growth.
The impact of the water environmental factor is
similar to the bacteria that consume the carbon in the
cellulose wood chips and the oxygen in the water,
asphyxiate the fish and other organisms. The
leachates of the sawmills were caused by rain, snow
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or water used by employees to reduce the spread of

dust by the wind. The leachate gently penetrate the
medium and pollute groundwater or the river/lake
nearby involving dissolved materials, including
substances used in wood treatment. In addition, the
process releas the lignin in the water (lignin is a
complex compound, a part of the plant cell walls,
which protect the trees from pests while still is green,
but it may leak into the water, poisoning it).
In Canada, an ample operation to determine the
environmental impact of the sawmills proved to be
too expensive for owners of the sawmills, so many
small sawmills prefered to close rather than to pay
new fees of the Ministry of Environment for the
assessment and sawdust storage [2].
In the process of integration, environmental
protection is a priority, each economic agent has a
duty to act in accordance with the requirements to
protect the environment, human health and ensuring
their work. The waste is covered by the European
Directive 94/62. Implementation of this directive on
waste management is a major problem. Its approach
is based on the integrated management and long term.
Integrated waste management system has the
following principles, in order of priority:
- prevent (a responsibility of all economic agents
and consumers of goods);
- reuse/recycling;
- energy recovery;
- storage.
This is why it is necessary to find other possible uses

for waste sawdust.
As reuse there is a solution found by Hungarian
engineers who designed a construction material from
a mixture of sawdust and cement. This material
combines the resistance of cement with the heat of the
wood, it being able to manufacture different casings
modulation in the form of bricks used in construction.
These are not removed after concreting. The name
given to this material is FABETON meaning woodconcrete (fig.3).
Alternatively, the use of wood-cement mix is
the sound absorbtion panels, used to make the
partitions, the partitions of buildings, masking some
installations, the attic walls, as well as the facades.
The mixture of wood-cement from small
fragments of sawdust mineralized and cement is
poured into the mold, getting the material which can
be used to manufacture the insulating boards of
120x50 cm with different thickness: 2.5 cm; 4 cm, 6
cm, 8 cm or 10 cm, single or multi-layer of
polystyrene and mineral wool (fig. 4 and 5).
Add to the fire retardant composition solution
with the following properties:
- properties fire (ignition of wood is very
difficult and slow flame retardant);
- water-repellent properties (preventing, absorb
water from the atmosphere);
- increasing resistance to external factors that
may attack the timber (decay, fungi, or
microorganisms).
Fig. 3. Bricks FABETON

As to energy recovery, both briquetting and
pelleting sawdust, are viable solutions to save
environment from waste sawdust, but, because of the
quite expensive installations, required finished
products are obtained with a cost price rather high.
Fig. 4. Polystyrene insulation board

The insulation boards are weather resistant but
must be protected against the action of groundwater
and fire.
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Items are resistant to thinners used in

construction, so you can use any known method for
waterproofing protection. Due to the rough surface,
the elements are an ideal base for coating. It can be
used as prepared mortar stations and the on-site
preparation.
- Walling dry all year round (comfort) through a

continuous transport of humidity from the air to the
outside, without condensation.
- Minimum storage humidity. Outstanding
features takeover and elimination of water through
open-pore structure on wood (water retention capacity
of 0.7kg/m, water removal capacity 2.1kg/m per
hour).
- Short time drying of walling. This means that
products are faster available for use and the walling
behaves completely devoid of problems if rainfall
occurred on site (there are considered all seasons,
even the winter).
- Low specific weight. The low density of the
sawdust is that the material obtained has a specific
weight which is about 1/3 of that of the other
materials of construction. This feature makes the
material to be easy to carry and handle.
Fig. 5. Mineral wool insulation board

The items do not absorb water, as a result, the
coating that is obtained will have an ideal strength
and no cracks (the water evaporates more slowly).
You can apply any type of coating, coating in 3
layers, special coating materials or products made on
site in the factories (dry coating). Once there are
coated, surfaces can be painted with any paint, it is
possible direct painting on items without coating. For
faience, it is recommended to apply a layer of
coating, for low of adhesive use.
The sound and thermal absorbing boards are
used to make facades (fig 6, 7).
The advantages of using soundproofing panels
are:
- Optimal thermal insulation. Outstanding
thermal properties by design,
highly effective
biological combination between sawdust-cement and
the isolation by integrated polystyrene insulation.
- Walls warm and dry. Optimal capacity for
absorbtion/dissipation of humidity garantees the
climate comfort and pleasant living conditions.
- Integrated thermal insulation. By using the
sawdust-based boards there is no need of
supplemental thermal insulation or added after. There
is no need of adhesive for joining material.
- Optimal soundproofing. Through such
combination, shall be provided to minimize the stress
caused by noise.
- Optimal diffusion of water vapors
Fig. 6. Making insulation
Fig. 7. Insulated wall

The equipment needed for sound-absorbing
boards is shown in fig. 8 and is made of the following
components:
A mixer with two-shafts;
B - screw conveyor;
C - hydraulic press.
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Fig. 8. Equipment for manufacturing boards

Adouble shaft mixer; Bscrew conveyor; Chydraulic press
1mixer engine; 2elastic coupling; 3gear box; 4coupling part; 5,6gears; 7drum mixer;
8,9shafts mixed; 10propeller; 11funnel; 12flexible tube; 13screw conveyor; 14transfer drum;
15pipe DN 12; 16flexible coupling; 17spacer; 18press electric engine; 19adjustable pipe elbow
and nipple; 20pipe nipple; 21DN13 pipe; 22hydraulic pump; 23side plate; 24,25hydraulic
cylinders; 26upper poanson; 27mold
Fig. 9. Images from the test
Tests to determine material composition

and mechanical properties of sound
absorbing boards
In the determinations was performed
experimentally a mold with sizes 400 x 250 x 70 mm,
with sliding lid inside. The mold was made in welded

construction.
As raw material were used:
sawdust, two grains;
Portland cement;
water.
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homogenized by light vibration, before being

subjected to pressing on the hydraulic press (fig. 9).
In fig. 10 and 11 there are checking for flexure
on specialized equipment.
The results are summarized in table 1.
Fig. 10. Flexure test

Samples were done on a hydraulic press of 20tf.
There were samples of a mixture of sawdust
with two granulations and Portland cement in various
proportions (1/8, 1/4, 1/3), as follows:
The samples were made by mixing manually,
Fig. 11. Test value
Table 1. Material properties obtained

Technical
parameters
density
flexural
strength
roughness
Symbol
The value obtained
Unit
P1
P2
P3
P4
P5
P6
Kg/m
580
588
590
592
595
596
N/mm2
0.1
0.12
0.22
0.25
0.3
0.3
1.5
1.4
1.3
1.2
1.1
Conclusions
Material density increases with the increase in
the cement/sawdust ratio, being higher for sawdust
material containing small grain. Comparing the
density of FABETON, which is 500 kg/m3, note that
the values obtained are a little higher.
In terms of flexural strength, it increases with
increasing of the ratio cement/sawdust being also
higher if the material contains less grain sawdust.
Roughness was determined by observation,
taking as standard sample no.6, which was assigned a
value of 1. Was increased roughness as decreasing
ratio cement/sawdust, being higher in the case of
material containing higher grain sawdust.
The next objective is proposed further study on

the determination of the composition of materials and
the mechanical properties of the insulation boards, as
measured by compositions containing different
particle sizes, and different species (pine, beech, oak,
etc.).
References
[1]. National Institute of Wood http://www.inl.ro/.
[2]. Canadian Geographic, 2009
http://www.canadiangeographic.ca/magazine/jf09/.
[3]. Panasyuk G.P., Azarova L.A., Voroshilov I.L., New ways of
recycling of a wood sawdust,
http://www.isasf.net/fileadmin/files/Docs/Arcachon/posters/p150P115%20Panasuyk%20Proceeding.pdf
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THE EXPERIMENTAL ANALYSIS OF ULTRASONIC TREATMENT

EFFICIENCY OF WASTEWATERS FROM FISH FARMS
Anca ERBAN, Adrian LEOPA
emails: anca.serban@ugal.com, adrian.leopa@ugal.ro
ABSTRACT
The fish breeding within the fish farms provides an important quantity of food
necessary for human survival while excluding the intensive fishing which implies
most of the fish species extinction. The fish breeding in optimal conditions in the
fish farms primarily involves ensuring a high quality of water. In order to ensure
the quality parameters according to the current standards the wastewater is treated
by various processes of which the most modern equipments use the ultrasound
technique.
The experimental study investigated the efficiency of ultrasound treatment
applied on wastewaters from the fish farms of Turcoaia village, Tulcea County, by
comparative analysis of some quality water parameters before and after the
ultrasound treatment.
KEYWORDS: wastewater treatment, ultrasound, water indicators
1. The current water treatment methods

in aquaculture systems
The water quality of natural water bodies is an
important objective of national and European
legislation for the quality and quantity of natural
sweet water is one of the key factors of a healthy life.
Arguments as discharges causes contamination and
damage natural ecosystems, wastewater requires high
taxes led to finding effective and affordable treatment
methods for aquaculture wastewater.
The efficiency of nutrient removal was obtained
by combining different types of wetland such as
stabilization ponds, fish tanks, and ponds with
Macrophytes plants. Furthermore, the integration of
valuable fish and plants, these nutrients may be
converted into secondary selling products.
Merging the fish in one tank leads to the reuse
of a certain proportion of discharged nutrients in the
flesh of fish, and the required level of dissolved
oxygen provides favourable conditions for aerobe
processes. In ponds with Macrophytes those that
tolerate the waste water, assimilates a considerable
amount of nutrients for biomass production that can
be used to obtain bio energy. Regarding the
recirculating aquaculture systems, there are processes
and equipments designed for wastewater treatment
based on principle as:
- removing residual solids by sedimentation

tank, cyclone, site parking, site rotating, vibrating
sieves, filters with granular material;
- removing fine and dissolved solids by agent
porous filters, filters with active carbon, ion
exchangers, separators foam;
- removing carbon dioxide by diffusers and
packed bed;
- oxygenation by descendants contactors with
bubble, contactors with lateral injection, packed
columns enclosed, multiple contactors with pressure;
- aeration by gravity aerators, depth aerators,
surface aerators;
- water disinfection with ultraviolet radiation or
ozone [1].
Both for the intensive and recirculating systems
the aim is reducing the water and energy
consumption, minimizing the volume of discharged
wastewater, improving the nutrient application by
using well-prepared diets for fish and optimal culture
conditions.
In this respect the Directive 2000/60/EC in the
field of water policy refers directly to the Nitrates
Directive 91/676/EEC concerning the diffuse
pollution of water with nitrates from agricultural
activities with the extent on phosphate is intended to
maintain the natural balance of nutrient in soil and
influence the use of phosphorus in farm practices.
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2. Applications of ultrasound on
wastewater parameters
Conventional methods for reduction turbidity
and Total Suspended Solid (TSS) in water treatment
process are rapid and slow filtration, microfiltration,
ultrafiltration and coagulation/flocculation. The
recent studies with variation of time, power and
frequency of US irradiation showed the reducing of
turbidity at 28 kHz of frequency at 1 hour of
irradiation time [2] and a decrease of 4 times for the
ultrasound generator operating at 27.2 kHz frequency
at 30 seconds [3]. The reduction of TSS due to
various power density ultrasonic irradiation increased
significantly at 30 minutes of ultrasonic irradiation
but became unstable from 60 minutes to 120 minutes
of irradiation at all power density [4].
The water disinfection with ultrasound
irradiation is based on the acoustic cavitations and
inactivates microorganisms due to chemical attack by
the hydroxyl radicals generated by ultrasound, to
high pressure and temperature resulting from bubble
collapse that can cause cell death and also to shear
forces induced by microstreaming occur within and
consequently damage bacterial cells [5].
The cost of ultrasound techniques is an
impediment to its use in wastewater treatment but
there are alternatives to conventional energy forms
that reduce the cost of installation operation.
The Microphone was positioned at a distance of

1 meter from the sonic generator and perpendicular to
the flow direction of the generators air flow. The
data processing namely the spectral representations of
acoustic signal was achieved with the program
Samurai version 2.0.
In the figures 1-7 are shown the spectrograms of
acoustic signals acquired and their analysis notice that
the regime characterized by the dominant spectral
components in the range of ultrasound was obtained
when the generators nozzle was set at 3.8 mm and
the working pressure of 1 respectively 2 bar.
Fig. 1. Nozzle 3.8 mm - Pressure 1 bar
3. The experimental evaluation of

pressure-frequency function
The working frequency of ultrasound generator
depends on the compressed air pressure and therefore
the research required an experimental stage of setting
the optimal working regime under which the
dominant frequencies are within the ultrasound field.
Thus there was recorded and analyzed the acoustic
signal of the ultrasound generator during its
operation, for different combinations of nozzle size
and compressed air pressure, as in Table 1.
Nozzle
[mm]
3.8
3.9
5.3
5.5
Pressure [bar]
1
1
1
1
2
2
2
2
In order to achieve the experimental signal it

was used an acquisition board type Harmonie Octav
SINUS with 8 channels, one Microphone with
integrated amplifier ICP-IEPE, PCB 130 E20 and the
required connectors.
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The higher and constant ultrasonic frequency

was obtained at the pressure of 2 bar for the
generators nozzle of 3.8 mm and 5.5 mm. Thus, it
was chosen the nozzle of 5.5 mm and the operating
pressures of 1 and 2 bar for the experimental study.
4. The experimental study of ultrasound

technique application on aquaculture
wastewaters
The raw water samples were taken from the fish

farms of Turcoaia village, Tulcea county from seven
different locations presented in fig. 8 (3 lakes, 3
ponds and the pump). The water samples were
analysed and thus it was chosen the water sources for
the final experiment.
Fig. 8. The fishing complex of Turcoaia

Raw water parameters
450
400
350
300
250
200
150
100
50
0
L1
L2
L3
P
I1
DO [mgO2/l] Cl-[mg/l] HCO3 [mg/l]
I2
I3
TDS [ppm]
Fig. 9. The physico-chemical indicators of raw

water
In figure 9 is shown the results of physicochemical water analysis.

The water indicators in lakes L1 and L3 both
with the pump area recorded the higher values for
TDS, while TDS value in the water of pond P1 and
lake L2 is the lowest.
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Thus it was chosen for further analysis and

experimental ultrasound technique the water sources
of lakes 1 and 3. The other water parameters such as
dissolved oxygen, chlorides and bicarbonates are
within the limits imposed by legislation.
TDS (ppm), phosphate (mg/l PO43-) and ammonia

(mg/l NH4+) content. The phosphate and ammonia
parameters were analyzed as they influence the
evolution of aquatic ecosystem and follow the
concern of water nutrient loading from agricultural
sources.
4.1. The experiment progression

4.2. Results and discussion
The experimental installation consisted in a
compressed air source connected to the sonic air-jet
generator (fig. 10) and a control system with a control
valve and manometer (fig. 11) in order to eliminate
fluctuations in the pressure generated by the
compressor and provide flow and pressure during
ultrasonic treatment.
The water samples analyzed had a normal pH

considering their source and their values were within
the regulated limits of 6.5 to 9.0 pH units (fig.12).
p=1 bar
pH 10
8
6
4
2
0
0
10
20
30
40
L1
50
60
70
t [s]
L3
p=2 bar
pH 10
8
6
4
Fig. 10. The sonic air-jet generator
The water samples of 0.5 liter were exposed to

ultrasound treatment in a glass tank and the operating
parameters were the working pressure of 1 and 2 bar
and the exposure time of 5, 15, 30, 45 and 60 seconds
for the first pressure, and 5, 15, 30, 35 and 45 seconds
for the second pressure. The working pressure and
time exposure mentioned were applied for both
sample series from lakes 1 and 3.
0
0
10
20
30
40
50
t [s]
L1
L3
Fig. 12. The pH indicator of water samples

Also the pH evolution is about the same at 1 bar
pressure for both type of samples, but for the higher
pressure it was recorded the lower values of pH for 15
and 45 seconds of ultrasound exposure.
The TDS analysis indicated as in case of pH a
constant and similar evolution at 1 bar pressure and
for both water sources, but the ultrasound emitted at
the pressure of 2 bar and the time variation had a
detectable influence on TDS in lake 3, as in figure 13.
p=1 bar
TDS [ppm]
300
250
200
150
100
Fig. 11. The control system of the

experimental installation
50
0
Physico-chemical parameters of water samples

treated with ultrasound technique were pH (pH units),
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20
30
40
L1
L3
50
60
t [s]
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ultrasound registred an increase of ammonia once

with the exposure time.
p=2 bar
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TDS [ppm]
176
174
172
170
168
166
164
162
p=1 bar
NH4 [mg/l]
10
20
30
40
L1
t [s]
8
7
6
5
4
3
2
1
0
50
L3
Fig. 13. The TDS indicator of water samples
10
20
30
40
L1
TDS concentration of treated samples had much

lower values than the one of raw water presented in
figure 9.
The content of nutrient as phosphate in treated
water samples is up to 15 times higher than the
allowed concentration of 0.1 mg/l PO4 in lake 3 and
five times higher in lake 1 (fig. 14).
50
60
L3
t [s]
70
p=2 bar
NH4 [mg/l]
10
8
6
4
2
p=1 bar
PO4 [mg/l]
10
20
30
L1
3
40
t [s]
50
L3
Fig. 15. The ammonia concentration of water

samples
2
1
The ammonia concentration in samples from

lake 3 is up to 25 times higher than the allowed limit,
but also it is noticed a decrease once with the
exposure time.
The study aim of proving the influence of
ultrasound waves on water characteristics under
certain operating conditions was achieved and arised
from the dynamics of water indicators in terms of
time exposure and working pressure of sonic air-jet
generator during the experiment.
0
0
10
20
30
40
L1
50
60
t [s]
70
L3
p=3 bar
PO4 [mg/l]
3.5
3
2.5
2
1.5
1
0.5
0
0
10
20
30
L1
40
t [s]
4. Conclusions
50
L3
Fig. 14. The phosphate content of water

samples
This situation might be explained by enriching
the water with nutrients as phosphorous derived from
fish metabolism, excess fish food or agricultural
activities that use phosphorus based fertilizers.
The water samples from both lakes had a high
content of ammonia that can be explained by
denitrification of nitrates in ammonia under the action
of some specific bacteria living in water.
The samples from lake 1 had ammonia concentration
up to 7 times higher than the limit concentration of
0.3 mg/l N-NH3 and the samples exposed to
The water pH is slightly influenced by the

ultrasound emission of the air-jet generator. The TDS
content in water is modified with the increasing of
time exposure, but there are needed more tests to find
the optimal time exposure and working pressure in
order to achieve the best results. The phosphate
concentration is also slightly influenced by the
ultrasound treatment, but it is noticed its decrease at
the first lake samples and a pressure of 1 bar. The
ammonia behaviour with ultrasound assistance is not
considerable, but there are certain conditions that
determined its concentration to decrease such as 30
seconds and 1 bar or 20 seconds and 2 bar. The
experiment requires more tests in order to establish
correctly the optimal operating parameters of the
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installation in order to achieve the best results for

each water indicator.
References
[1]. Cristea V., Grecu I., Ceap C., Ingineria sistemelor
recirculante din acvacultur, Ed. Didactic i pedagogic, R. A.,
Bucureti 2002.
[2]. Mutiarani Irsyad M., Trisnobudi A., Ultrasonic Irradiation
in Decreasing Water Turbidity, 2009.
[3]. Stefan A, Balan G., The Chemistry of the Raw Water Treated
By Air-Jet Ultrasound Generator, Rev. Roum. Sci. Tech-Mec.
Appl., 56(1), 85-92, 2011.
[4]. Chua S. Y., Adul Latif P., Ibrahim Sh., Effect of Ultrasonic
Irradiation On Landfill Leachate, Proceedings of Postgraduate
Qolloquium Semester 1 2009/2010, 2010.
[5]. Joyce E., Phull S. S., Lorimer J. P., The development and
evaluation of ultrasound for the treatment of bacterial suspensions.
A study of frequency, power and sonication time on cultured
Bacillus species, Ultrasonics Sonochemistry 10, 315- 318, 2003.
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THE IMPACT OF AGRICULTURAL PESTICIDES

ON THE ENVIRONMENT
Gabriela Alina CIOROMELE, Aurel CIUREA, Nicoleta AXINTI
Faculty of Engineering Braila, Dunarea de Jos University of Galati,
29, Calea Calarasilor Street, Braila, Romania
emsail: Alina.Cioromele@ugal.ro, Aurel.Ciurea@ugal.ro, Nicoleta.Axinti@ugal.ro
ABSTRACT
Currently Environmental protection is an important issue facing humanity.
Thus, due to the rapid growth of the global population, ecological agriculture
is a practical alternative to intensive overuse of pesticides to increase agricultural
production and ensure.
The main role of organic agriculture is to implement and at the same time to
promote a balanced range of technologies to prevent environmental pollution.
Big Island of Braila in groundwater that are due to shallow uncontrolled
application of herbicides can have a powerful impact on the environment and
consequently on agricultural production.
KEYWORDS: agriculture, pesticides, pollution
In the last few years, due to economical

competition, the agriculture was subjected to an
excessive intensification through the usage of large
quantities of fertilizers and pesticides.
The protection of the environment and the
rational usage of natural resources (especially of the
soil) is one of the biggest problems in the world and
the present and future of human kind depend on it [1].
Thus, the quality of the soil resources is an
essential problem and keeping the soil productive
should be a permanent concern for development.
Damaging the soil resources reduces both the quality
and the quantity of multiple resources that humans
use directly [2].
Improper application of wrong doses of
herbicides shows a negative effect on both the
environment and especially on the ground. Thus, for a
long time, residual herbicides in soil is especially
visible in the production plants.
Different factors are occasionally involved in
herbicides failure under field conditions which most
due to human mistakes lead to improper application
technique [3].
Another way herbicide resistance may develop
that is thought to be less contributory is a genetic
mutation. This occurs after the herbicide has been
applied and provides resistance to the herbicide [4].
In developing countries, chemical weed control
is not widely practiced because of relatively cheap
labor, high chemicals prices and lack of technical

extension and experience in herbicides application
which leads in most cases to the misuse of these
chemicals and crop injury , failure of selective
herbicides and weed control operation, soil and air
pollution and limitation in crop rotation options [5].
2. Study area and the location of the

experiment
The research was conducted in a single location
from the Large Island of Brila, for two years on
eutric gleysol on which corn was grown.
The experiment took place on a surface of 1 ha,
each experimental version having 2000 m2 , the rates
of herbicides applied in experiments are given in
fig.1.
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MARTOR
NETRATAT
1. Introduction
V1
V2
V3
V4
Dicopur
M
(250 ml)
Lontrel
300
(EC)
0,125
ml
Mistral
4 SC
250 ml
Turbo
Flo
(SC)
0,1 l
Fig. 1. The experimental design
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In order to observe the influence of pesticides on

the soil, we used the following herbicides:
V1 Dicopur herbicide M (SL) at a dose of
1 l/ha.
V2 we used the Lontrel 300 herbicide (EC)
at a dose of 0.5 l/ha.
The Mistral 4 Herbicide SC was used in V3
at a dose of 1 l/ha.
For V4 we used the Turbo herbicide FLO
(SC) at a dose of 0.4 l/ha.
The control was untreated.
All four herbicides were applied postemergently, when the corn was in the 4-6 leaves
phenophase.
In order to study the influence of pesticides on
the properties of the soil, we took soil samples on
12.04.2011 and 17.04.2012, a day before sowing.
The second batch of samples was taken after the
harvesting of the corn, on 18.09.2011 and 14.09.2012.
Fig. 3. The temperatures registered
During the entire 2010-2011 crop year the

ammount of rain was 515 mm which exceeded the
multiannual average (447 mm) by 68 mm, attesting
an year with values that are over the average (fig. 2).
The apparent density in the experimental field

registered values fluctuating between 1.07 and 1.12
g/cm3 in the 2010-2011 crop year and between 1.10
and 1.16 g/cm3 in the 2011-2012 crop year at a profile
depth of 0 to 20 cm (table 1).
Tab. 1. The apparent density in the experimental

field (g/cm3)
The
crop
year
2011
2012
2011
2012
2011
2012
2011
2012
Fig. 2. The precipitation registered
2011
Higher values of rainfall were recorded in April

2012 agricultural year, when average rainfall was
91mm. The crop year 2011-2012 can be characterized
as being a good year in terms of rainfall, registering a
surplus of 161 mm compared to the multiannual
average. The temperatures registered in the 20112012 crop year showed higher values compared to the
normal average, an exception being the month of
February when we registered a value of -7 C (fig.3).
2012
Depth
(cm)
05 april
Variety
V1
V2
V3
V4
V
martor
Depth
(cm)
21 october
020
1.12
2040
1.21
4060
1.23
020
1.18
2040
1.16
4060
1.15
1.12
1.17
1.15
1.14
1.15
1.13
1.08
1.12
1.11
1.09
1.15
1.14
1.10
1.13
1.11
1.14
1.15
1.13
1.11
1.14
1.12
1.14
1.13
1.12
1.09
1.11
1.10
1.10
1.12
1.11
1.07
1.12
1.09
1.09
1.11
1.10
1.10
1.15
1.13
1.12
1.17
1.14
1.11
1.18
1.21
1.10
1.10
1.09
1.16
1.16
1.12
1.11
1.08
1.10
Under the action of pesticides we can observe

that the values of apparent density decreased
compared to the control version, these values being
lower with approximately 0.06 g/cm3.
Compared with the control, values of apparent
density variations recorded in the experimental field
recorded significantly higher values in V1 after
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harvesting, the profile depth of 0-20 cm in the

agricultural year 2010-2011.
To note is that in version V4 values of apparent
density grew 0.06 g/cm from the first experimental
year
The total humus contents in the soil from the
experimental area was observed at a profile depth of 0
to 50 cm.
From the data analysis, it was found that the
humus reserve in the herbicide versions was lower
throughout the entire profile depth in each
experimental year with approximately 0.01% (fig. 4).
Fig. 5. The soil reaction

From the data obtained and shown in table 2, we
can observe that the density of the plants varied
between 81% and 96% sprung plants, the version
treated with Turbo Flo registering the smallest
percentage of sprung plants.
Tab. 2. Density of the plants and the production

Variety
V1
V2
V3
V4
V martor
Fig. 4. The total humus contents in the soil from

the experimental
Total humus content ranged between 3.9 and
5.44 in depth profile. Higher values were recorded in
the 2010-2011 crop year, when total humus content
ranged between 4.2 and 5.44.
In the agricultural year 2011-2012 can be seen
from the data shown in the figure 4 as total humus
content decreased significantly in the V3.
The soil reaction for the entire profile depth (030 cm) is weakly alcaline with pH values between
7.52 and 8.24.
The pH increased progressively with the depth
on all experimental versions, except from the samples
taken at a depth of 10-20 cm in the first experimental
year.
Compared with the control, the data shown in
figure 5 it can be seen that V3 and V4 recorded
significantly higher values in the depth profile in the
agricultural year 2011-2012.
Density of the
sprung plants
(%)
2011
2012
98
96
93
83
97
92
91
81
100
100
Production
(kg/ha)
2012
7100
6930
7240
6901
7400
The remanence of the herbicides applied in the

first experimental crop year was more pronounced in
the versions treated with Lontrel and Turbo Flo, the
percentage of sprung plants fluctuating between 81%
and 83%. The production varied between 6901 and
7400 kg/ha, residual herbicides is visible in the year
agricultural 2011-2012.
4. Conclusions
The data obtained confirmed the fact that using
pesticides influences the physical and chemical
properties of the soil.
The humus reserve of the experimental
veersions was influenced by the remanence of
herbicides.
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The culture density and the corn yield can be

diminished because of the corn crop sensitivity to
Lontrel and Turbo based herbicides residuu.
Diminishing the remanent effects of the Lontrel
and T urbo herbicides applied throughout multiple
years within a monoculture is achievable by the
interruption of the treatment and controlling the
weeds with herbicides based on another active
substance.
References
[1]. Berca M., Teoria gestiunii mediului i a resurselor naturale,
Ed. Ceres, Bucureti, 1998.
[2]. Rusu T., Albert I., Bodis A., Metode i tehnici de producie n
agricultura ecologic, Ed. Risoprint, Cluj- Napoca, 2005.
[3]. Ross, M. A., C. A. Lembi, Comprehensive review of general
weed science principales and weed management options including
in depth evaluation of herbicide families, Applied weed Science
1999.
[4]. Harger A., Wax L., McGlamery M., Pike D., Herbicide
Resistance in Weeds, University of Illinois Extension. Last
accessed April 14, 2003 (www.weedresearch.com /Articles/5049).
[5]. Su Shao-quan, Crop injury from herbicides and its prevention
in China. Xiandai Nongyao, 5(4), 1-4, 12 (2006).
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STUDIES REGARDING SOIL AND GROUNDWATER RESOURCES

FROM THE BIG ISLAND OF BRAILA
Ioan VIINESCU, Daniela TRIFAN, Marcel BULARDA
ABSTRACT
This paper presents the agrochemical study of soil and groundwater resources
on three farms from The Big Island of Brila (Edera Mrau and Stvilaru) and
studies that have been prepared as an activity included in the project "Research on
the efficient use of natural water resources in irrigation facilities to reduce water
consumption irrigation and conserve the soil fertility."
The purpose of this study is to investigate the state of soil and groundwater
quality, in terms of reaction (pH), the total content of soluble salts (CTSS) and the
supply of macronutrients (nitrogen, phosphorus, potassium), as based on the results
analyzes to make recommendations on rational and efficient management of
chemical and organic fertilizers and amendments, use good quality groundwater for
irrigation to ensure a large agricultural productions in terms of quantity and
quality, on all plots.
Based on recommendations, soil fertility can be increase, and it can prevent
soil and groundwater pollution with chemical and / or organic residues. At the
same time, the studies represent the first phase of a larger study that will take
several years and will seek to analyze the dynamic indices of soil and groundwater
quality in pilot farms Edera, Mrau, and Stvilaru from the Big Island of Braila, to
be correlated with agricultural technologies applied in regional climate conditions.
KEYWORDS: soil, groundwater, resources, quality, pollution, Big Island of
Braila
1. Introduction
1.1. The main types of soils and their
fertility potential
Geomorphologic, land study is part of the North
(Stvilaru and Edera farms) and the south (farm
Mrau) of dammed floodplain of the Big Island of
Braila. Existing soils on farms Stvilaru residence
and Mrau are undeveloped soils, which are in Class
Protisoils, Aluvisoil type with different subtypes,
depending on the area. These soils are formed on the
alluvial deposits of different textures, characterized
by the heterogeneity of both vertically and
horizontally. Silt vertical in homogeneity is
determined by the variation of flood volume, which
has the effect of alternating coarse material submitted
to large floods, with fine materials deposited in small
floods.
Alluvial soils the size composition very different
that soil texture ranges from coarse and fine sand
banks found in the lowland areas, and by increased
content of carbon (between 153 and 265 mg/100g

soil) these soils are carbonate. Alluvial soils are
developed under the influence of a permanent surplus
of moisture in the profile due to the high level of
groundwater.
Humus content is varied between 1.92 and
5.76%. In general, soils within Stvilaru farm
residence and Mrau have high fertility due to
nutrient-rich and nutrient assimilated good content,
and fluid level higher than other soils.
Frequent floods caused embankment before soil
processes and pseudo- gleyzation and depression
areas affected almost every year of the phenomenon
of excess moisture due to high levels of the Danube
and suffered a process of low salinity.
1.2. Elements of climate zones

Which area on the pilot farms is characterized
by a temperate continental climate, with hot and dry
summers, with low rainfall and cold winter. Aridity
index is around 22:
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I = P / T x 10
(1)
where: P = average annual rainfall, T = average
annual temperature.
The average annual temperature is 10 - 11oC.
The coldest month is January (- 2 - 5C) and the
warmest period is in June, July, August, exceeding
25C, there is a period of intense growth and
fructification of plants, irrigation is necessary.
Multi-annual rainfall below 450mm, and their
distribution is quite uneven on the vegetation, long
periods of drought ascertaining the late summer and
early autumn. Values of evaporation-transpiration
potential over 700mm, exceeding an average of 200 250 mm rainfall amount, reflecting their poor
character. The wind has a frequency of 75% versus
25% days with calm winter chill wind beat, which is a
cold wind beat NE and Austral summer, which is a
warm wind, causing drought and beat SE) [7]. Early
white frost occurs in late September, often in
October, and the latter are in April and even May.

Agrochemical soil samples for analysis were
taken from distinct geomorphologic areas where the
groundwater level is different, realizing Edera by 6
polls farms and farm surveys Mrau and 7 Stvilaru
on by 6 layers of 25 to 25cm, the from 0 to 150 cm.
In total were brought to the laboratory a number of
114 soil samples from the pilot farm area and 19
water samples. After preparation and pulverization of
soil and water filtration, samples were analyzed in the
Agrochemical laboratory S.C.D.A. Braila, performing
the following determinations [8]:
- In all soil samples (analysis of large series),
collected over 6 layers (depths) and the samples
groundwater: soil reaction in aqueous suspension
ratio soil: water 1:2.5 and reaction (pH), determined
potentiometer with a pH meter; total content of
soluble salts in the soil water extract ratio: 1:5 water
directly from groundwater in mg / l, conductivity was
determined by using conductivity-meter HI 933310.
permanent and temporary alkalinity (bicarbonate and
carbonate content) in aqueous extract ratio soil: water
1:5 and directly from groundwater by micrometric
method.
- A part of the samples (analysis of several small),
that is, the top layer of soil (0 - 25 cm) and all the
ground water samples: the content of nitrate nitrogen
and nitrate nitrogen in parts per million (ppm N-NO-3
and ppm N-NO2) was determined by the Photometric,
with Photometric HI 83200. In the same working
methods were determined contents of nitrate and
nitrite and sodium nitrate. phosphorus content
expressed in parts per million (ppm P) was
determined by Photo colorimeters by using
Photometric HI 83200. mobile potassium content

expressed in parts per million (ppm K+) was
determined by Photo colorimeters by using
Photometric HI 83200. at harvest soil samples from
depth 0 - 25 cm to more determined and humus
content by wet oxidation method and dosage titration
by Walkley-Black method, the Gogoa modified.

3.1. Statement of soil quality
Regarding soil reaction, synthetic situation
Edera, Mrau, and Stvilaru farms, in surveys is:
soil on Edera and Mrau farms has a slightly
alkaline pH in 100% of the surveys;
soil on Stvilaru farm 14.2% has a low pH acid
soil, 14.2% has neutral pH and 71.4% of soil pH
is slightly alkaline.
To lower the pH level by areas of weak acid neutral - slightly alkaline, it is recommended nitrogen
fertilizer with physiological acid reaction, such as
ammonium nitrate and ammonium sulphate,
without
being
subject
to
phosphogypsum
amendments.
Accumulation of soluble salts in the surface soil
horizon in our country is caused by the hydrogeology
of groundwater from shallow correlated with poor
drainage. Soils on Edera, Mrau and Stvilaru farms
content of soluble salts were between 89.16 mg/100g
soil and 215 mg/100g values, which characterizes
them as normal soils in terms of salt content soluble,
except for S7 of Stvilaru farm, where there is a low
saturation (Fig. 2).
Nitrogen is one of the most complex chemical
and important role in plant life and can not be
replaced by any other nutrients, organic matter and
humus is made, converted or are in various stages of
processing, and which has as an essential component
humic acids.
Humic acids are formed due to intermediate
products of decomposition of the organic matter as a
result of slow biochemical oxidation, followed by
condensation
reaction
and
the
resulting
macromolecular compounds [1].
The soil is rich in humus, and its fertility is
higher. In the formation of humus, are retained and
accumulated nutrients for the plants, substances
which are then gradually released through
mineralization. Humus is important for cation
exchange properties and protects a range of ions
leaching (Ca, Mg, K, Na, NH4), which then makes
them available to plants and microorganisms [2].
The presence of humus in the soil gives it a
grainy structure, very good hydro properties,
improving the physical properties of extreme textured
soils (clay and sand).
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8,2
7,8
6
7,6
5
7,4
4
7,2
3
7
S2
S3
S5
Stavilaru
125-150cm
75-100cm
50-75cm
S6
100-125cm
0-25cm
25-50cm
125-150cm
75-100cm
100-125cm
0-25cm
50-75cm
25-50cm
125-150cm
100-125cm
50-75cm
S4
Edera
75-100cm
0-25cm
25-50cm
125-150cm
100-125cm
50-75cm
75-100cm
0-25cm
25-50cm
125-150cm
50-75cm
75-100cm
100-125cm
0-25cm
25-50cm
125-150cm
75-100cm
100-125cm
0-25cm
S1
50-75cm
25-50cm
125-150cm
100-125cm
6,6
50-75cm
0
75-100cm
6,8
0-25cm
25-50cm
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S7
Marasu
Fig. 1. Soil pH values on depths in the survey conducted on Edera, Stvilaru and
Mrau farms (October 2012)
Fig. 2. Included in total soluble salts in the soil at pilot farms of the Big Island of Braila
[mg/100g soil]
60
50
40
30
20
10
0
S1
S2
S3
S4
S5
S6
S1
S2
Marasu
S3
S4
S5
S6
S7
Stavilaru
Humus %
azot nitrat ppm
S1
S2
S3
S4
S5
S6
Edera
azot nitrit ppm
Fig. 3. Supply situation and humus soil nitrogen in Mrau, Stvilaru and Edera
farms, October 2012
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Soil humus supply values are in the range of

1.93% to Stvilaru S3, up to 5.76% to Mrau S3,
indicating a low to medium supply on the first point
and good in other sections of the survey (Fig. 3). To
increase the humus content of the soil is
recommended to apply organic fertilizer or green
manure on plots with low humus content.
Another important nutrient for plant element is
phosphorus, which is located in the soil in the form of
organic and inorganic compounds. The total content
of phosphorus will vary depending on the nature of
the soil formation rock, soil age, factors of soil
forming,
chemical
fertilizers
and
organic
administration [4]. Because it performs complex
functions in the plant, phosphorus can not be replaced
by any other nutrient [3]. Therefore, it must be
ground to the needs of each crop plants, according to
the fertilizer applied. Regarding soil phosphorus
supply (Fig. 4), the territory of pilot farms recorded a
low to medium phosphorous content, recommending
calculating phosphorus fertilizers doses, depending
on the specific consumption of the crop, in
conjunction with expected production and supply
condition of the soil in this element.
Like phosphorus, potassium is a very important

element in plant life because: stimulates cell division
and young tissue growth, indirectly stimulates active
absorption of nutrients in plants, stimulates the
synthesis and activation of enzymes plays a role in
the process of photosynthesis, has a role in transport
raw sap, regulates intracellular osmotic pressure, has
a role in opening and closing the stomata, has a role
in regulating water balance in plants, causing their
resistance to drought, determine plant resistance to
breaking and falling, causes resistance to pest and
disease attack, increases ability of grain twinning
causes a high amount of plant: roots, leaves, fruits,
seeds and increased resistance to storage products,
especially potatoes [5].
Regarding soil potassium supply (Fig. 4), within
the three pilot farms, the situation is quite good, the
supply of potassium and potassium oxide being
between 10 and 25 ppm, except S3 on Mrau farm
and S4 on Stvilaru farm, where the potassium
content is zero. This element must be provided as
according to the requirements of crops according to
the fertilizer, with particular attention should be
administered either in excess or less, its role in plant
nutrition, described above.
Fig. 4. Soil nutrient supply situation in Mrau, Stvilaru and Edera farms, October
2012
3.2. Groundwater quality situation in the

three pilot farms
In good conditions of soils well supplied
groundwater from the Big Island of Braila,
groundwater is an element of soil fertility, as an
additional source of water for crops, but may cause
some negative processes such as the accumulation of
salts in the soil, and gleyzation. Situation of mineral
residue content in groundwater samples taken in

October 2012 is as follows: Stvilaru farm water
quality is good, with the exception of S7 survey (Fig.
5 and 6 b), the value of mineral residue exceeds the
Normal (2.489 g/l). Edera farm, the 6 water sampling
points, the total soluble salts were rated good to
satisfactory water within 4 points and 2 points S4 and
S6 were located in poor water group (Fig. 5 and 6 a).
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Marasu farm (farm under irrigated) in all

sampling points of water, water quality is good and
satisfactory, except two locations (S1 and S5), where
the waters below 2 g / l proved to be unsatisfactory
for irrigation (under-irrigation) (Fig. 5 and 6c).

Summary of the situation in October 2012, the total
content of soluble salts in groundwater is shown in
Figure 5.
Fig. 5. Mineral residue content of groundwater in Edera, Stvilaru and Mrau farms, October 2012
Fig. 6. Statement of total content of soluble salts in groundwater in pilot farms Edera (a), Stvilaru
(b) and Mrau (c), October 2012
In terms of pH values of all samples analyzed
attests good water (6.5 to 7.2) and tolerance for
irrigation (7.3 to 7.6), exceptional one point S6
Stavilaru farm, in which water is unsatisfactory, (Fig.
7). Phenomenon sweeten and salt concentration in the
groundwater was observed in the chemical analysis of
the previous research is correlated with the intake of
fresh water from the Danube and precipitation. 2012

was a dry year with low intake of water during the
warm season and lowered levels of the Danube to the
area normal circumstances, being favorable
phenomenon in salt concentration of groundwater.
Synthesis of pH values of groundwater in pilot farms
in October 2012 is shown in Figure. 8.
Fig.7. PH values of the groundwater situation in pilot farms Edera (a), Stvilaru (b) and Mrau (c),
October 2012
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8
7,91
7,8
7,6
7,69
DESECARE
7,63
7,49
7,43
7,4
7,25
7,45
7,41
7,4
7,36
7,32
7,24
7,2
7,18
7,17
7,1
7,03
7,03
6,98
6,93
6,8
S1
S2
S3
S4
S5
S6
S7
6,6
STAVILARU
MARASU
EDERA
Fig. 8. pH values of groundwater on Edera, Stvilaru and Mrau farms, October 2012
Content analysis of minerals in groundwater
fertilizers supply showed a good to very good, as is
observed in synthetic maps obtained by extrapolating
the values determined from surveys Cased at farms

throughout the pilot (fig. 9.).
Fig.9. Groundwater nitrate supply situation in pilot farms Edera (a) Stvilaru (b) and Mrau (c),
October 2012
Analysis on groundwater nitrate content,
revealed that Mrau farm (farm under irrigated)
groundwater total lack of nitrite, while Stvilaru and
Edera farms nitrite content is higher, the highest value
(over permissible limits) is the point of the farm

Stvilaru S1 (Fig. 10.), which requires closer
monitoring of mineral nitrogen fertilization in this
area.
Fig. 10. Statement of nitrite in groundwater on farms Edera (a) and Stvilaru (b) - October 2012
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Statement of phosphorus and potassium in

groundwater showed an adequate supply of
phosphorus and potassium supply very good in all
pilot farms (Figure 11, 13.) For farm Mrau (fig. 12)
was found to maintain the limits normal content of
nitrate and nitrite, as phosphorus and potassium
content has exceeded the allowable S3 survey of

ground water with 0.14 mg/l l and 5 mg/L for K also
found a very high level potassium ion and potassium
oxide drainage channel (85mg/l K + and 105mg/l
K2O).
Fig. 11. Groundwater supply situation with P2O5 (mg / l) in pilot farms Edera (a) Stvilaru (b)
and Mrau (c), October 2012
Fig. 12. NPK content in various forms in water samples collected from surveys on Mrau farm
Fig. 13. Groundwater supply situation with K2O (mg / l) in pilot farms Edera (a) Stvilaru (b)
and Mrau (c), October 2012
The content of nitrate and nitrite in water
samples collected from the surveys, the farm Edera
was increased for surveys S1, S3 and S5 (Fig. 14).
For farm Stvilaru noted a very high content of all

track quality parameters of water samples S1 and S7
surveys (Fig. 15).
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Fig. 14. NPK content in various forms in water samples collected from surveys, Edera Farm
Fig. 15. NPK content in various forms in water samples collected from surveys, Stvilaru farm
4. Conclusions
Existing soils in the three pilot farms have a high

fertility, relief and ground water quality which
provides some of the necessary plants by underirrigation water, dissolving the mineral elements
in the soil and root absorption helping them.
There are limited areas, according to maps made
in the recommended application of organic
fertilizers and green manure to increase the
humus content, which would substantially
improve soil fertility and increase crop
production and more later.
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Polls of groundwater can be used for irrigation,

according to the recalculation of doses of
mineral fertilizers in conjunction with crop
requirements.
It imposes strict future monitoring of
groundwater quality in conjunction with
monitoring the status of soil fertility in pilot
farms to allow fertilization plans are correct,
depending on the specific consumption of the
crop, and thus to avoid excessive application of
nutrients can lead to groundwater pollution.
Results
are
provisional
subsequent
determinations will better define the processes
dynamics of saline groundwater and soils and
their quality in terms of nutrient content.
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References
[1]. Andries, S., Changing humus content in the soils used in
agriculture, 2005, Chiinu (Romanian language).
[2]. Berca M., Soil ecology issues, 2010 Ceres Publishing House,
Bucharest (Romanian language).
[3]. Burnea I., I. Popescu, Neamu G., E. Stancu, Lazr t.,
Chemistry and Biochemistry plant, 1977, Didactic and Pedagogic,
Bucharest. (Romanian language).
[4]. D. Davidescu, Davidescu Velicica, Agrochemical Agenda,

1978, Ceres Publishing House, Bucharest. (Romanian language).
[5]. Davidescu D., V. Davidescu, Agrochemical Horticulture,
1992, Romanian Academy Publishing House (Romanian
language).
[6]. Lctuu R., Agrochemical, 2006, Terra Nostra Publishing
House, Iasi (Romanian language).
[7]. Elena Stancu, Pedological potential of agricultural land in
Braila county, 2009, www.portal_braila.ro (Romanian language).
[8]. Trifan D., Burtea C., Pedology - Practical Laboratory , 2011
Braila. (Romanian language).
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THE EXPERIMENTAL METHOD OF INVESTIGATION AND

DIAGNOSIS OF HUMIDITY IN STRUCTURAL ELEMENTS OF
HERITAGE BUILDINGS
Stefania IONESCU, Adrian LEOPA
Dunrea de Jos University of Galati, Engineering Faculty of Braila,
Research Center for Mechanics of Machines and Technological Equipments
29, Calea Calarasilor Street, RO-810017, Braila, Romania
emails: stefania.ionescu@ugal.com, adrian.leopa.@ugal.ro
ABSTRACT
This study is based on experimental evaluation of walls humidity located in
the basement of the Engineering Faculty of Braila in order to identify the source of
humidity and solutions to attenuate and remediate the infiltration. On the wall in
question was drawn a grid in which nodes were made experimental determinations
to detect humidity source. Based on these values were made 2D and 3D maps of the
wall humidity that were used to identify the source of moisture. The excessive
humidity sources found in buildings elements has a higher relevance taking into
account the pathogenic effects derived from this.
KEYWORDS: building, heritage, humidity, investigation
1. Introduction
The main role of a building is to ensure its
inhabitants a healthy, enjoyable and comfortable
environment, less depending on outdoors conditions,
especially acoustic and meteorogical. Current
requirements relating to this aspect are much more
restrictive than those accepted in previous historical
periods due to the changes which have occurred in the
nature and complexity of actions (exterior and
interior) what shall be exercised on the buildings, on
the one hand, and in the light of the development of
user requirements, on the other hand. Meeting these
requirements, directly related to the use of energy, it
is just as important as those of safety and stability to
mechanical action, and that its appearance
architectural-aesthetic or framing in the environment.
In the light of the above, it is necessary to an
evaluation of the potential of the degradation of the
elements of masonry caused by water ingress,
buildings assets which at the time their construction
have not benefited from current technologies
waterproofing. In Braila town are a series of these
buildings which are faced with water ingress to the
elements of the Foundation, one of these being
established Faculty of engineering in Braila. At its
basement have been identified that water has
penetrated inside outer walls of brick, appearance to
the negative implications both on the health of
construction as well as the quality of the environment.

For these reasons, the work of the experimental
constitute an investigation of the degree of infiltration
of the water on one of the walls of the hall S18, on
the basis of the results obtained being proposed
methods for the reduction or even elimination of this
problem.
2. Current state of mentality studied

Both European and world level, there are
concerns for investigation deficiencies in design or
operation of buildings, for the application of a set of
measures that are intended to ensure or to increase
comfort of the occupants. A special category of
buildings covered by these investigations is, heritage
buildings, which form part of cultural heritage of any
nation. True works of art, witnesses credible history
of nation which they built, these monuments he ask
for entitlement to rehabilitation and consolidation, in
order to be able to transmit future generations what
we have shared with us and the new. Therefore, we
have not only a debt engineering judgment to repair
the damage produced by the lapse of time, but also a
moral obligation to restore these buildings dignity he
expects sometimes resigned. An analysis of a
relationship energy consumption - internal quality of
the environment, the buildings housing and
administrative has been carried out in the European
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project HOPE (Health Optimization protocol for

Energy efficient Buildings), carried out with 14
participants from 12 European countries during the
period 2002-2005 [7]. They have been investigated
more than 160 buildings in the sector of dwellings
and administrative, half of them showing power
consumption relatively low. The investigation
consisted of a general inspection, a discussion with
the superintendent of the building, and distributed
questionnaires occupants.
The results obtained have denied as well as
sentence relating to direct relationship of
proportionality between power consumption and
quality of the environment, allowing framing
buildings which have been formed under
investigation into 4 categories:
- buildings with high energy consumption and
adequate quality interior environment;
- buildings with high energy consumption and
low quality of the environment inside;
- buildings with low power consumption and
poor quality of the environment inside;
- buildings with low power consumption and
quality of the environment.
Thus, it was found that the energy consumed do
not depend only interior temperature value, the rigors
of climate and ventilation rate but also to an extent
even greater than architectural solutions and
constructive and of the mode of operation.
There was a high percentage of dissatisfaction in
buildings in which consumes a large amount of
energy for mechanical ventilation but not careful
attention should be given moisture, employment or
protection to noise. And vice versa, buildings with
reduced power consumption, natural ventilated, has a
healthy interior environment and comfortably.
Ideally, the characteristics of the breather offices
and dwellings should be correlated with the levels of
moisture, in such a way as to minimize chemical
processes speed that will cause discomfort and
disease once they are present in sufficient quantity,
[5].
ecosystems environmental niches and provide

ecology in their environment built, which enable the
development pathology in the construction industry.
The most common health problems that occur as a
result of exposure to fungi and bacteria speeds are:
bronchial asthma, such as rhinitis, eczema and less
villages, but extremely dangerous extrinsic allergic
alveoli is are also considered and bronchopulmonary
aspergilosys, resulting from exposure to high
concentrations of spores of molds site and its
surroundings as well as Cladosporium and Serpula
Lacrymans. The fungicides species known for
causing respiratory allergies in humans are: alternaria,
Aspergillus, cladosporium, andpenicillium. For
example, in Great Britain, bronchial asthma is a
disease very frequency affecting approximately 3
million people (5% of the adult population) and to
children represents the most widespread chronic
disease.
4. Objective review
Building on Route Calarasilor no. 29 is one of
public buildings representative of Braila city date in
use in the year 1891. The building belongs to Braila
county council and is included in List of Historical
Monuments in Braila County.
Functions have been distributed as follows: on
the ground floor - the tribunal with two sections, less
aggressive body, the Prosecutor's Office, two cabinets
of inquiry and reassign lawyers; upstairs - prefecture
with health service county school the veterinary
service of the county.
3. Pathology buildings in the balance sheet

Pathology in construction, interior air quality
management, bio-damage and health problems that
may arise in buildings are complex problems that
require
multi-disciplinary
investigations
and
monitoring of the environment. Lack of maintenance,
neglecting chronic and execution faults which can
lead to water ingress, the emergence condensation
and moisture go often to toxic molds proliferation of
pathogenic and other microbial and biological effects
which may cause allergic reactions sensitive
individuals and lead in general to the appearance sick
building syndrome. Buildings are working as spatial
Fig. 1. Engineering Faculty of Braila
5. Experimental study of humidity from

the elements of construction
The basement has its headquarters building
where Faculty of engineering have been identified
water has penetrated inside internal walls of brick,
appearance to the negative implications both on the
health of construction as well as the quality of the
environment.
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For these reasons, has been carried out an

investigation of experimental Presence of damp in
one of the walls of the hall S18, on the basis of the
results obtained being proposed methods for the
reduction or even elimination of this problem.
To be able to identify and characterize more precisely

moisture sources in the wall affected, experimental
measurements have been carried out over a period of
two seasons: fall and spring. Thus, a first set of data
was recorded in November 2012, fig. 3 and 4.
Justitiei Street
Fig. 2. Positioning wall studied in part of the

building. Basement Plan
Fig. 3. Studied wall review
Table 1. Measured values for temperature and relative moisture for the first experimental
measurement
Vertical
point
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
Horizontal
point
1
2
58.4
80.5
23.5
23.9
43.7
65.7
23.6
23.5
54.5
55.1
23.9
23.9
49.9
60.3
24.2
24.1
24.5
57.4
24.9
24.2
21.2
50.2
24.8
23.4
83.4
23.7
59.1
23.1
88.3
23.5
52.1
24.1
36.3
23.2
33.6
22.8
Fig. 4. 2D analysis moisture from the wall

for the first case

for the first case
On the basis of these numeric values of

moisture, with program Matlab R14, have been drawn
up by interpolation in 2D and 3D charts, which shall
constitute tools on the basis of which can be clearly
identified source location of water infiltration.
It should be noted that their accuracy for the

identification of the source depends on the number of
points in which they were carried out experimental
determinations. The second set of experimental data
was determined in February 2013. Representations in
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the form of 2D and 3D maps, of the relative humidity

are shown in Fig. 5 and 6. From the comparative
analysis of the two sets of experimental
measurements corresponding to November and

February, is observed that spring the wall shows
excessive moisture values for a larger area.
Table 2. Measured values for temperature and relative moisture for the second experimental
measurement
Vertical
point
Horizontal
point
1
2
3
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
68.2
90.3
71.6
23.6
22.8
23.6
52.1
45.8
68
23.9
24.6
24.8
52.2
47.8
48.7
24.1
24.1
24.4
49.4
43.1
50.1
23.9
24.5
24.8
46.8
49.9
56.6
24.8
24.5
24.9
50.3
42.8
41.4
25.2
24.8
24.6

for the second case

for the second case
The last set of data was recorded on the date
March 2013, fig. 7 and 8.
This set of experimental measurements

highlights, compared to data recorded in November, a
larger area of the wall affected by moisture.
Table 3. Measured values for temperature and relative moisture for the third experimental
measurement
Vertical
point
Horizontal
point
1
2
3
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
M
(%)
T
(oC)
58.4
80.5
83.4
23.5
23.9
23.7
43.7
65.7
59.1
23.6
23.5
23.1
54.5
55.1
88.3
23.9
23.9
23.5
49.9
60.3
52.1
24.2
24.1
24.1
24.5
57.4
36.3
24.9
24.2
23.2
21.2
50.2
33.6
24.8
23.4
22.8
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6. Conclusions
In connection with the carrying out of this
experimental study it can be concluded that:
- drawing up maps humidity in the elements of a
building, shall constitute a modern instrument with a
view to the identification of areas affected by
moisture;
- case study analysis showed the existence of
some important areas with excess moisture, derived
by infiltration water from ground, which is in contact
with the wall.
- of the three periods of the year, in which they
were carried out experimental measurements, winterspring proved period that promote water ingress in
structural elements of the building.
Fig. 8. 2D analysis moisture from the wall for

the third case
After the interpretation of these maps of
moisture, it is found that the wall studied presents
excessive moisture on upper and lower sides,
appearance explainable by a lack of a waterproofing
correctly.
Fig. 9. 3D analysis moisture from the wall for

the third case
References
[1]. Roulet C.-A., Ostra B., Foradini F., Cox Ch, Designing
healthy, comfortable and energy efficient buildings: lessons from
enquiries within the European, HOPE Project. CISBAT 2005.
[2]. Bliuc I., Baran I., Methodology for optimal solution for
thermic rehabilitation of buildings, International Symposium
materials, components and structures for composite construction,
Timisoara 2005.
[3]. Quality assurance internal environment with minimal energy
consumption - attribute of sustainable architecture, Grant CNCSIS
2004-2006.
[4]. Brightman H S, Moss N, Sick building syndrome studies and
the compilation of normative and comparative values, In: Spengler
JD, Samet JM, McCarthy JF, editors, Indoor air quality handbook.
New York: McGraw-Hill, 2000.
[5]. Baughman A V, Arens E A, Indoor humidity and human
health Part 1: Literature review of health effects of humidityinfluenced indoor pollutants, ASHRAE Trans 1996, 122:193211.
[6]. Irina Bliuc, Elemente de fizica constructiilor, 1995.
[7]. Vagner I., Diaconu A., Cozma L., Rehabilitation of collective
housing ensembles made of large precast concrete panels - general
aspects, Revista Constructii, Vol. 14, No. 1, 2013.
[8]. Bardahan S., Tehnici si metode de investigare si reabilitare a
constructiilor afectate de umiditate, Project Graduation, 2013.
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DECONTAMINATION OF POLLUTED SOIL BY COMPOSTING OIL

WITH THE HELP OF MUSHROOMS
Dorin EFTIMIE, Aurel CIUREA
Dunarea de Jos Galati, Facultatea de Inginerie Braila
emails: deftimie@ugal.ro, aciurea@ugal.ro
ABSTRACT
This paper presents bioremediation using Pleurotus mushrooms of soil
pollution with organic compounds derived from crude oil, showing how the
pollution is produced and its effect on the soils.
KEYWORDS: soil pollution by oil, bioremediation, Pleurotus mushrooms
There is no doubt that the soil is the most
precious capital, which man has for the satisfaction of
his needs and ambitions. After all, at least until the
invention of artificial photosynthesis, we all depend
upon the thin and fruitful layer from Earths surface,
from where the majority of the resources necessary to
life are extracted. However, one of the great
paradoxes is that man tends to jeopardize the source
of life through ignorance, negligence, greed, or other
causes. This is how its done, that while modern
techniques allows man to introduce in the productive
cycle millions of hectares of land, which until
yesterday were considered inert forever, on the same
note, other millions of fertile acres become unfit for
cultivation, still because of human action.
Fig. 1. Area polluted with oil

Although for a long time it was long thought
that the soil has an infinite capacity to degrade
pollutants, today it is proved that the soil surface can
only degrade about 30 t of dry material/ha/year.
Romania as a country with a tradition of
producing and processing oil, is unfortunately
affected, by unwanted phenomena that lead to the
pollution of the environment with crude oil, oil

products and residue from oil processing.
In most cases, the thickness which soils are
affected by oild pollution is of 30-40 cm, due to the
viscosity that causes a heavy movement through the
soils aggregates, and because of the fat substances
(the mineral oils) it contains, it dresses the soil
particles with a greasy film that hinders or prevents
water movement in the soil.
Oil radically alters the soil properties, both
physical and chemical, but biological ones too. It
forms a waterproof film on the surface of the soil,
which prevents water movement in the soil and
exchange of the soil and atmosphere, producing the
asphyxiation of roots and promoting the
manifestation of the reduction process. As the soil
becomes more anaerobic, it decreases the number and
metabolic activity of bacteria. Oil, being rich in
organic carbon (98% hydrocarbons), increases the
C/N ratio in the soil, negatively influencing the
microbial activity and nutrition of plants with
nitrogen.
The immediate effect of soil oil pollution is
reflected in the very disturbance of soil
microbiological activity. During the first weeks after
the discharge, depending on the intensity of the
pollution, the reduction of microbiological activity in
the soil, a situation confirmed by analysis of the
breath surface (release of carbon dioxide) and
enzymatic activity (dehydrogenase).
In areas of oil extraction, the problem of soil
pollution due to this activity becomes even more
complicated because, concomitant with oil residue
pollution, it is also occurring an waste and salt water
pollution, capable of causing a strong salinization of
soils polluted with oil. In the conditions of such a
pollution, the soil becomes virtually unproductive,
being removed completely from the economic circuit.
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According to some authors plant life begins to

suffer when on the soil is drained oil at a quantity
greater than 1 L/m2. [1]
After the established assessment in 2010 at the
Research Institute for Soil Science and
Agrochemistry, it has been settled that a considerable
area, more than 50,000 hectares of terain, is polluted
with such products, the largest areas to meet are in the
districts Teleorman, Braila, Bihor, Dolj, Dmbovia,
Giurgiu and Gorj.
Given that oil pollution, oil waste products and
residues affect the actual ability of soils to sustain
life, the development of a methodology for remedial
adapted to the conditions in Romania is absolutely
necessary.
Depending on the principles of remediation
technology, there are currently used technologies
based on physical, chemical, thermal and biological
methods.
Soil pollution by petroleum products is a reality,
the remediation technologies are specific for each
case. In general the principle of classical technologies
are not on the bio principle.
Biological soil remediation technologies include
this three categories of methods:
a) Biodegradation
b) Bioaccumulation
c) Biolixivierea
Bioaccumulation biological technology includes
decontamination of polluted soil by composting oil
with mushrooms.
Mushrooms
are
effective
against
the
disassembly of toxins, that have long molecular
chains, the mushrooms break the chains and turn
them into less toxic compounds. They also remove
heavy metals from the soil accompanying them in
their bodies and thus removes them from the ground,
essentially using these toxins as nutrients.
Mycelial enzymes can break down some of the
most resistant materials created by man or nature,
because many ties that retain herbal substances are
similar to linkages found in petroleum products such
as diesel oil, and many pesticides or herbicides. These
toxins can degrade pharmaceutical products based on
estrogen.
There are mushrooms that can degrade several
types of toxins, others are limited to certain toxins.
Using mushrooms as starting species in
bioremediation projects involve other organisms in
the rehabilitation process. Once the toxic barriers
have been removed by specific mushrooms, a synergy
between at least four systems (mushrooms, plants,
bacterias, animals) enters the habitat and converts the
toxins into derivatives which may be useful for some
some and harmful for others.
The decontamination procedure was performed
according to the depth of infestation in the soil, the
concentration in oil products and the time required for

the decontamination.
The decontamination of heavily contaminated
soils having the TPH concentration above 20-70 g/kg,
is made by stripping and incineration.
The decontamination of soils with the TPH
concentrations below 20 g/kg is achieved by means of
biodegradation.
The technological phases of soil remediation
are:
1. Sampling and analyzing to determine the
degree of contamination of soils.
2. Setting the decontamitation way.
3. Decontamination of soil contaminated
environment.
4. Controling the level of decontamination
achieved.
The first step in carrying on the investigation of
soil pollution from the location SC Petrom SA Parc
5 Oprisenesti consisted of soil sampling in two
different locations (fig. 2).
Fig. 2. Sampling of contaminated soil

These soil samples where mechanically
processed to reduce grittiness, step necessary to
conduct further chemical analyzes. Moving on, it has
been used the laboratory equipment site soil testing
kit system.
Fig. 3. Samples 2 and 3 of contaminated soil

With the help of Soxhlet method, the oil has
been extracted from the soil samples no. 2 and 3 with
ethyl ether (fig. 3).
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The Soxhlet technique (fig. 47) involves the

solubilization of extractable components by dripping
of a cold solvent from the reflux of a condenser, thus
requiring a full time job.
Fig. 6. Oven drying the ball collector
Fig. 4. Weighing 2g of contaminated soil
Fig. 7. Laying and weighing of the ball collector

in a desiccator and on the scale
The thermal shock is performed by lowering the
temperature in the first few days from 21 C to 8-9 C
for 3-4 days or at the temperature 3-4 C for one day,
followed by the return to optimum temperature for
fructification at 12-15 C.
The appearance of primordials imposes the light
factor, which is essential for the development of
carpophores.
Fig. 5. The Soxhlet apparatus

The numerical value obtained from this analysis
for hydrocarbons is 0.2 g/100g soil from sample
number 2 less contaminated soil and 0.8 g/100g from
sample number 3 of soil heavily contaminated with
oil. The incubation is carried out at a temperature of
20-24 C over a period of 10-15 days, with the
relative humidity of 75-80%. Ventilation must be
reduced semi- aerobically conditions must be met,
currents must not exceed 0.2 m/s. Light is not
necessary for the growth of mycelium, so that at this
time, the light will be used only for internal guidance.
Fig. 8. Pleurotus progress of the day 8

After 18-20 days after sowing, the incubation
period is deemed complete and a phase of maturation
follows (fig. 9).
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The Pleurotus mushroom initially weighted 1.1

g and the weight after the extraction was 0.9 g.
Conclusions
Fig. 9. Pleurotus progress of the day 20

To determine how much oil have absorbed the
Pleurotus mushrooms from samples 2 and 3, one
mushroom from each sample has been taken and each
mushroom has been cut and weighed using the
electronic analytical balance.
Following the extraction of oil it has been found
that:
Sample no. 2 soil little contaminated with oil.
The Pleurotus mushroom initially weighted 0.9
g and the weight after the extraction was 0.7 g.
Sample no. 3 soil very contaminated with oil.
Although the remediation technology is unstable

(due to specific solutions for fungus growth) and
specifies a degree of oil pollution of soil, this
experiment can be a step for future research in
developing a viable and competitive technologies in
terms of cost.
References
[1]. tefan Ghe., Metode de analiz a solului (biologic,
enzimatica i chimic), Probleme de Agrofitotehnie teoretic i
aplicat, ICPT Fundulea, vol. XXI, 1999.
[2]. Calinoiu M., Tehnici de extractie a poluantilor din sol, prin
aplicarea metodelor fizice de depoluare, Analele Universitii
Constantin Brncui din Trgu Jiu, Seria Inginerie, Nr. 3/2011.
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RESEARCH ON WATER EVACUATION REUSE IN RICE PADDING

ON AMELIORATIVE SALTY SOILS BEING IMPROVED
Marcel BULARDA, Ioan IVAN, Ioan VIINESCU,
Daniela TRIFAN
ABSTRACT
Rice padding for agricultural production are complex systems whose proper
functioning do contribute a series of objectives that represent a series of works
made large investments in the hydro-technical, of land improvement and land
reclamation, the irrigation facilities, providing specific equipment necessary
mechanization of irrigation water management in the mentioned works and how to
achieve agricultural and cultural works themselves.
To conduct proper activity in rice fields and greater efficiency in rice
production it need to be technical and economic contribution of all the ranges
shown on line functionality safe, continuous and low cost as their enrolling and
maintaining permanent paddy on the modernization of technical equipment in order
to achieve efficiencies working as high efficiency line of business organization and
minimal manipulation of irrigated water to minimize the losses on the line optimum
use of natural working framework.
Use of water discharge channels make it possible to reduce energy
consumption required for water feed in rice plantation. It is also possible to reuse
nutrients contained by dissolving and washing water outlet and unused
plant. Experience is aimed to determine the need and type of transfer technical
solutions to water evacuation channels in rice paddies.
KEYWORDS: rice paddies, water quality, reused water, environment protection
-channel drain of plots (tertiary channels, side
channels, the main collector and exhaust).
1. Introduction
Aim of experience is the determining discharge
water quality by measuring pH, alkalinity, total
dissolved salts content and content of nitrite, nitrate,
phosphorus and potassium, in order to establish the
possibility of using it to irrigate rice without danger
of damage of crop and soil.
It can also determine the amount of total salts
removed from plots by draining loaded with salt.
You can determine the speed of improvement of
soils in rice fields. The main components of rice
fields in EC Polizeti are:
- floating station for pumping irrigation water
from the Danube to the top level of 5 m from the
discharge rate;
-channel water from irrigated rice fields (supply
channel, main channel power, channel power side (by
plot) and sector or distribution) rice-plots;
Fig. 1. Plug the water supply from the Danube

to the EC Polizeti rice paddies of SCDA Braila
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Fig.2. Building structure and functional arrangement rice padding in EC Polizeti of SCDA Braila

The research method consists in sampling the
water from leaking into the duct of the plot and
analysis laboratory pH meter, Conductivity,
Photometric and classical titration methods. The
complex analysis can determine the amount and type
of salts (ground) water contained in the exhaust.
Methods Laboratory were:
- determination of pH by potential-metric
method;
- determination of total dissolved salts (TDS) by
conductivity-metric method;
- determination of water alkalinity by titrimetrical method;
- determination of nitrite, nitrate, phosphorus
and potassium by photometric method.
To check the efficiency of water use practices in
the discharge channel to irrigate rice were used
mobile pumping units operated from the tractor.
In the analyzes of water from the discharge
channel can determine the following parameters:
- water quality of discharge
- rate of desalination as a process ameliorative
soil washing with water irrigation;
- use potential for irrigation water discharged
later,
- setting nutrient levels content and recalculate

doses of fertilizer.
In terms of pH, natural waters fall into seven
groups, Table 1.
Table 1. Normal values of quality indices of

water for irrigation apply
Indices
Normal
value
< 1.0
6.5 8.3
13
< 50
< 3.0
Mineralization, g/l
Reaction (pH)
Sodium absorption report (SAR), units
Magnesium parameter (PMg %)
Chlorine content, me/l

The pH value was correlated with alkalinity,
conductivity
and
total
dissolved
salts
content. Existing mineral elements content in water
discharge channel, correlated with demand for rice
culture in these elements, drain water reuse for
irrigation. Acceptable values of indices for assessing
water quality for irrigation is displayed in tables.
Water quality test results collected from the
outlet channel of EC Polizeti compared to water
Danube is tabulated in table 2.
Conductvity
mS
TDS
g/l
mg CaCO3
/ l water
Nitrogennitrate
(NO-3-N)
mg/l
Nitrate
(NO-3)
mg/l
Nitrite
(NO-2)
mg/l
Phosphate
(phosphate
PO3-4)
mg/l
Phosphorus
pentoxide
(P2O5)
mg/l
Potassium
(K+)
mg/l
Potassium
oxide
(K2O)
mg/l
Danube
water
Water
from
outlet
channel
Differen
ce
pH
Water
sample
Table 2. Values of quality indices of water determinate in agricultural year 2012
7.43
0.33
0.165
153
2.2
9.4
0.4
1.4
30
40
7.30
1.92
0.960
275.4
0.2
60
70
-0.13
+1.59
+0.795
+122.40
-2.2
-9.4
-0.4
-1.2
+30
-30
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Note that the amount of dissolved salts (TDS) in

water outlet is higher 0.795 g / l than in the Danube,
but that requirement quality irrigation water. Also, the
content of calcium carbonate is increased by 122,40
mg / l water (Figure 3).
In terms of this we can say that it is possible to
use water for irrigation canals drain the rice culture,
but with caution, either by using partial, as filling the
water of the Danube, there is a dilution of the
negative characteristics or by loading alternative
parcels once Danube water once water evacuation to
avoid re-salted problems. This solution should be
checked periodically discharge water quality analysis.
The solution technique used for pouring water
discharge channels in rice fields is to use a pump with
tubing. Absorption metal pipe fitted with whirlpool
and discharge piping fabric with great length and
weight. Pump with suction pipe is fitted to the tractor
lifting mechanism and acts from his PTO (fig. 4).
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Fig. 3. The results of analyzes of water quality

collected from channel against Danube water
Table 3. The results of measurements are presented tabular information.

Specification
Tractor type
Pump debit
Difference of pump level
The filling of a plot of 1

hectare of water to 10 cm
Consumption
of diesel
Irrigation water
taken from the
exhaust
135-145 CP
250-750 l/s
3.3-4.0 m
1-1.5 hours
10.8 l
An economy calculation shows that, for an area

of one hectare, the average amount of irrigation water
required 15,000 cubic meters (15 t water) rises to spill
a lower rate of 1.5 m and transfer the a distance of 10
m, compared to the classic situation in which water

from the Danube to be built at a rate of 8-10 m
depending on the river channel and transfuse a
distance of 3-5 km.
Fig 4. Technique solution used for pouring water discharge channels in rice paddies
Given that periodic determinations prove the
validity of the method of water-saving irrigation
using water discharge channels, key points can be
made stationary pumping stations to use electricity.
4. Conclusions
For the development of technical solutions for
the recovery phase of the operational capacity of
rice fields known to be constructive and
functional elements of its technical condition and

problems that arise in operating the technical
equipment, the parameters that characterize the
soil and irrigation water, etc.
In the economic efficiency the development
scheme of rice fields are the most important
elements: power supply, the network of escape
routes and technical equipment for land
reclamation and agricultural works specific.
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Develop a set of technical solutions for the

recovery phase of the operational capacity of
paddy through extensive rehabilitation must take
into account the structural and functional
elements of it, on which are necessary remedial
action.
Technical solutions correlate each of the
parameters starting work mainly to the need for
plant needs and the extent that these solutions
apply and manifest.
References
[1]. Albescu, I. 1979 Polizeti 28 an intensive rice variety well
adapted on saline soil. Production vegetal Cereals and technique
plants, nr. 4: 35-37.
[2]. Alionte, GH., 1983 - New aspects of rice cultivation
technology. Agricultural Issues 3.
[3]. Alionte, GH., Melachrinos, FL., Onita, E., Stefan D., 1985 Results obtained by the method of induced mutations in rice
improvement. Fundulea, IL: 59-70.
[4]. Bumbu, I., Bumbu, I., Vrlan, L., - Controlul i monitoringul
mediului - Curs de lucrri practice i laborator, 2006, Chiinu.
[5]. Fadil Glawat, Mitsuyasu Yabe, - Profit efficiency in rice
production in Brunei Darussalam: a stochastic frontier approach,
J. ISSAAS Vol. 18, No. 1:100-112 (2012).
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CORELLATIONS BETWEEN OPERATING MODES AND

ENVIRONMENTAL EMISSIONS OF NON-ROAD MACHINES AT
CONSTRUCTION SITES
Carmen DEBELEAC
"Dunarea de Jos" University of Galati, Engineering Faculty of Braila
Calea Calarasilor no. 29, 810017 Braila, Romania
email: carmendebeleac@yahoo.com
ABSTRACT
This paper focuses on environmental emissions reducing for non-road diesel
engines of construction machines, such as excavators, loaders, bulldozers, graders,
scrapers, etc. The criteria for pollutant reductions implemented by known
construction machinery manufacturers are reviewed. The paper deals information
about the influence of machine operating mode and fuel consumption, implicit over
the environment emissions rate. Thereby, those key factors that are taking into
account to estimate the machine emissions are speed, acceleration, and operating
mode over entire working cycle. Results presented in this paper offer arguments for
all users to work on site with construction machines using adequate operating
procedures with depth impact over the emissions reducing for diesel engines.
KEYWORDS: emissions, construction machines, operating mode
1. Introduction
At present there are three approaches available
to reduce emissions from diesel engines:
- refuel: use a cleaner diesel fuel formulation
which reduces engine-out emissions;
- retrofit: represents the reducing of emissions
by treating exhaust gas with an oxidation catalyst, a
diesel particulate filter or selective catalytic
reduction;
- replace/repower/rebuild: replacement an
existing engine with a new lower emissions engine
that incorporate cleaner technologies.
Worldwide, more than ten years, the
manufacturers have been improved their diesel
engines to reduce exhaust pollution and changes
include: improvements to the combustion chamber
for a cleaner burn; electronic, high-pressure, fuel
injection systems for improved fuel management;
variable-geometry turbochargers and charge-air
coolers that precisely regulate air; exhaust-gas
recirculation technology to keeping emissions at low
level.
2. Solutions and technologies adopted by

main construction machinery
manufacturers
For most of construction machines type
manufacturers proposed general operating procedures
applicable during working process, called "good

operating skills" that are essential to keep machines
in good condition, such as: choosing the right
machine to match the work requirements; optimizing
loads and number of cycles; optimize equipment
position to minimize working distance; reducing
displacement
speed
and
limit
rapid
acceleration/deceleration into operating mode, using
Economy or Power mode only it is needed.
Actual
emissions
regulations
require
construction equipment manufacturers including
Komatsu, John Deere, Caterpillar, Case, Volvo,
among others to implement new solutions for
developing cleaner construction machines.
Thereby, John Deere Inc. is continuously
developing and testing the "PowerTech" engines to
achieve the final Tier4/Stage IV emissions
regulations [12, 13, 14, 15]. Their approach uses
cooled exhaust gas recirculation for NOx reduction
and an integrated exhaust filter for particulate matter
reduction.
Caterpillar Inc. adapts emissions reduction
technologies to existing products to reduce emissions
output through implementation of emission upgrade
group, diesel oxidation catalyst and diesel particulate
filter. Most engines of Caterpillar Inc. have natural
gas versions.
In 2006, Komatsu Inc. developed a new engine
generation called "Tier3 Engine ecot3" from leading
construction equipment suppliers provide very low
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emissions levels to meet the latest environmental

regulations. Additional solutions are given by
Komatsu Inc. for decrease of fuel consumption for
main non-road construction machinery shown in

Table 1 [8].
Table 1. Solutions imposed by Komatsu manufacturer for consumption fuel efficiency

Recommendations
Type construction machinery
For excavators:
use variant b)
instead of the
conventional variant
a).
a)
b)
For loaders:
shorten the distance
for loading and
minimize the
loading V-angle.
Optimum values: D=0.8L (L - machine length), =300.

For example, in Canada, in 2007, has estimated
that the costs of retrofit programs for non-road
construction machinery it is possible to reach the
values given in Table 2.
The results carried out on a truck are shown in

Table 3 and on a loader with bucket capacity by 3.4
m3 in Table 4 [11].
Table 3. Influence of truck operating mode

Table 2. Cost estimation per tonne reduction
emissions
Pollutants
NOx
PM
Operating mode
Non-road construction machinery

$ 2.100 - $ 20.900
$ 20.000 - $ 86.700
Repeated acceleration and

deceleration*
Work at constant speed*
Work from inertia**
According to [2] the key factors used to

estimated machine emissions are: speed, acceleration,
and operating mode, all over steady or transient work
cycle.
Making an analysis of heavy-duty diesel truck
activity and emissions data results that non-road
machines spend a lot of time on working cycle at
high-speed and at idle. In consequence, a smaller
percentage of time machines operated under transient
engine/duty cycle [5, 9].
In case of trucks, it must to avoid repeated
acceleration and deceleration operating mode during
transport for reducing of fuel consumption.
The type of tasks (e.g. excessive speed and
acceleration, inefficient deceleration, wrong gear and
engine speed) can influence the engine load of the
equipment.
Fuel consumption,
l/h
100%
87%
62%
Notes: *test conditions consist in repeated

acceleration and deceleration two times between 20
km/h and 30 km/h, over a distance of 300 m;
**
test conditions: truck loaded by 90 tonnes
moving on 120 m distance from inertia.
A bulldozer motion with loaded blade imposes a
higher load on the engine than motion with the empty
blade.
Air emissions increase with the engine load of
the equipment, as can be seen in figure 1 [10].
For excavators, almost 50% of the total NOx
emissions results in 29% of working cycle time when
average engine speed and hydraulic pressure in drive
system acquire very higher values. Mass per time
emission rates developed in non-idle operating modes
(e.g. moving arm and boom, using bucket) can
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become on average 7 times greater than for the idle

operating mode [1].
Table 4. Influence of loader operating mode

Indicator
Productivity, in t/h
Fuel consumption, in l/h
Fuel efficiency, in t/l
Working
distance
0.8 L
1.0 L
1.5 L
0.8 L
1.0 L
1.5 L
0.8 L
1.0 L
1.5 L
Percent
117%
100%
93%
101%
100%
101%
116%
100%
92%
PM (g/h)
In construction machinery fields, the use of

biodiesel was tested on excavators, graders, tracks
with good results regarding on engine environmental
emissions.
Thereby, tests performed on four categories of
dump trucks, for two fuels (B20 biodiesel and
petroleum diesel) demonstrated that used fuel average
and CO2 emission rates were approximately the same,
but average emission rates of NO, CO, HC, and PM
decrease by 10, 11, 22, and 10%, respectively, for
B20 biodiesel versus petroleum diesel. Also, used
fuel average and emissions rates increased 26 to 35%
when dump trucks have load, respectively, unload
operating modes [3]. In case of grader equipments, on
average, using of B20 instead of petroleum diesel
leads to a negligible decrease of 1.6% in NOx
emission rate, and decreases of 19-22% in emission
rates of pollutants: CO, HC, and PM [4].
4. Conclusions
1,5
The paper contains some recommendations for

operational practices with construction machines.
Mainly, the factors, which influence air emissions,
are fuel properties, machine weight, speed,
acceleration, and operating mode with the equipment.
Also, decreased idle time of construction machine
leads to total emissions decreasing for construction
activity. In addition, reduced fuel consumption means
reduced maintenance, and in this way will increase
engine life.
As the main concluding remarks of this study
reveals that fuel consumption strongly depends on
machines operating mode and for tested equipments
was observed an average of 15...20 % diminishing of
environmental emissions in respect with a large range
of transitory regime reduction as a function of
machines type and category.
0,5
0
Idle
Forvard
Reverse
Blade
Fig. 1. Average PM emissions for phases of

bulldozer working cycle
Also, for scrapers, weight has influence over the
particulate matters emissions.
It was tested a Caterpillar 613 scraper type
during two phases of working cycle (empty and
loaded) and resulted two times greater PM emissions
than empty mode operation, as can be seen in Table 5
[6, 7].
Table 5.Scraper emissions factors
Average
Mode
Scraper
Speed
PM10, in
(mass, in
type
in km/h kg/vehiclet)
km
Empty
24
2.2
CAT
(16)
613
Loaded
19
4.2
(29)
References
[1]. Abolhasani S., Frey H. C., Kim K., Rasdorf W., Lewis P.,
Pang S.-H., Real-world in use activity, fuel use, and emissions for
non road construction vehicles: a case study for excavators.
Journal of the Air Waste Management Association (58), 2008, pp.
1033-1046.
[2]. Clark, N. N., Vora, K. V., Wang, L., Gautam, M., Wayne,
W. S., Thompson, G. J., Expressing cycles and their emissions on
the basis of properties and results from other cycles,
Environmental Science & Technology, Vol. 44 (15), 2010, pp.
59865992.
[3]. Frey, H. C., Kim, K., Operational Evaluation of Emissions
and Fuel Use of B20 Versus Diesel Fueled Dump Trucks, Report
No. FHWY/NC/2005-07, Prepared for the North Carolina
Department of Transportation by North Carolina State University,
Raleigh, NC 2005.
[4]. Frey H. C., Kim K., Pang S.-H., Rasdorf W., Lewis P.,
Characterization of real-world activity, fuel use, and emissions for
selected motor graders fueled with petroleum diesel and B20
biodiesel. Journal of Air Waste Management Association (58),
2008, pp. 1274-1287.
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[5]. Garjendran P., Clark N. N., Effect of Truck Operating

Weight on Heavy-Duty Diesel Emissions. Environmental Science &
Technology, 37(18), 2003, pp. 4309-4317.
[6]. Gregory E. Muleski, Chatten Cowherd Jr., Kinsey J. -S.,
Particulate Emissions from Construction Activities. Journal of. Air
& WasteManagement Association, (55), 2005, pp. 772783.
[7]. Helms H., Lambrecht U., The potential contribution of lightweighting to reduce transport energy consumption, International
Journal of Life Cycle Assessment, 12(2)-140/2007, 2007, pp. 58
64.
[8]. Karino H., Andou H., Takanuki H., Development of Tier3
Engine ecot3, Komatsu Technical Report, Vol. 52, No.157, 2006.
[9]. Huai T., Shah S. D., Miller J. W., Younglove T., Chernich
D. J., Ayala A., Analysis of heavy-duty diesel truck activity and
emissions data. Journal of Atmospheric Environment (40), 2006,
pp. 23332344.
[10]. Lewis P., M. Leming H. C. Frey, Rasdorf W., Assessing the
Effects of Operational Efficiency on Pollutant Emissions of Non-
road Diesel Construction Equipment. TRB 11-3186, Proceedings,

90th Annual Meeting of the Transportation Research Board, 2011.
[11]. Sarbu L., Revue from tools and equipments (Revista de
unelte & echipamente), Year XII, No. 9 (131), September 2011, pp.
48-61.
[12]. ***, Directive 97/68/EC contains measures against the
[13]. ***, Directive 2004/26/EC contains amendments to Directive
97/68/EC.
[14]. ***, Directive 2010/26/EU contains amendments to Directive
2004/26/EC.
[15]. ***, Directive 2012/46/EU amending Directive 97/68/EC of
the European Parliament and of the Council on the approximation
of the laws of the Member States relating to measures against the
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ENVIRONMENTAL RISK AT URBAN WASTEWATER TREATMENT

Lucica BALINT, Doru MATEI,
Simion Ioan BALINT

email: lbalint@ugal.ro
ABSTRACT
A risk assessment involves identifying all risk factors and quantifies their size.
Risk assessment is required the following steps: a) identification of risk factors, b)
setting out the consequences, c) determining the probability of occurrence; d)
assignment of risk levels depending on the severity and likelihood of consequences
of risk factors. Determination was made qualitative consequences for each risk
category in part determining the maximum foreseeable consequence. The study was
carried out on a wastewater treatment plant.
KEYWORDS: risk management, environmental factor, wastewater
1. Introduction
Risk management seeks to identify and assess
the probability of occurrence of undesirable events
that may or may lead to serious consequences and
estimation of the proportions that we can have these
consequences.
Centralized water and wastewater treatment
systems develop, modernize impressively, covering
large areas, serving thousands of residents and
operate continuously using new and complex
techniques to achieve the norms and quality
standards. Environmental risks are due to technology,
equipment and materials used in the purification
process. These risks can occur directly on the

equipment, personnel, spaces in the immediate
vicinity of the business environment in general and
all its components. For each environmental risk
measures shall be adopted to be managed to achieve
results consistent with legal requirements.
The study was carried out on a wastewater
treatment plant.
2. Investigation
Identification of risk factors and risk analysis:
A. Environmental Risks;
A1. Environmental factor "water"
A13
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Partial level of
risk
A12
Pollution over the limit permissible effluent by economic units discharging

wastewater into the sewage system (according NTPA 002)
Reduction of microorganisms activity used in treatment by inhibiting
substances in the effluent discharge
Damage to the sewage system and waste water adduction system to
discharge the effluent (uncontrolled leakage can lead to groundwater
pollution)
Probability
A11
Risk
Severity
No.
Consequences
Table 1. Levels of environmental partially risk factor for water
large
large
medium
A18
A19
Partial level of
risk
A16
Probability
FA
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A15
medium
medium
medium
large
large
Risk
Damage to above ground structures - grids station, aeration tanks, final

sedimentation tanks, etc. (can cause accidental discharges of wastewater
and groundwater pollution)
Effluent pollution through improper treatment of wastewater process
parameters resulting from failure of maintenance program
Envoy pollution by accidental admission of rainwater due to increased
flow (exceeding the treatment capacity of the plant);
Pollution from activity products used in automobiles, electric generator,
maintenance work (oil, fuel filters, accumulators)
Pollution from discharged wastewater from laboratory work (biohazard
waters neutralized insufficient)
A14
Severity
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The level of environmental risk factor for water

will be calculated by the relationship:
n
Nr =
Ri
i=1
i=1
where:
Nr = the overall workplace risk level;
ri = rank risk factor "i";
Ri = level of risk for the risk factor "i";
n = number of risk factors identified in the

workplace.
The result will be:
NrA1 = 3.5
The value of overall risk level environmental
factor is marginally acceptable (<3.5). Has been
identified a risk factor value 5 (A11 - pollution over
the permissible limit influenced by economic agents
discharging wastewater into the sewage system).
A2. Environmental factor soil"
A23
A24
A25
Flooding the station by accidental admission of rainwater due to

increased flow (discharge on the ground by exceeding the maximum
wastewater basins).
Soil pollution due to discharge of activated sludge (accidental spillage of
transport and treatment facility, exceeding the maximum intermediate
sludge storage tanks).
Overcoming the storage capacity of treated sludge plant (soil pollution
by discharging sludge outside concrete platform).
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Partial level of risk
A22
Soil pollution from clogging and damage to the sewer system, the
wastewater feed pipe system to discharge in the effluent, to circuit of
activated sludge, etc.
sedimentation tanks, reservoirs and routes excess activated sludge or
recycled, etc. (can cause accidental discharges on the ground)
Probability
A21
Risk
Severity
No.
Consequences
Table 2. Levels of environmental partially risk factor for soil
medium
medium
large
medium
medium
The level of soil environmental risk factor will

be: NrA2 = 3.32
The value of overall risk level for soil
environmental factor indicates a placement in the
acceptability (<3.5). We identified three risk factors
Accidental discharges of auto transport sludge on route to the final

disposal site (in case of technical incidents, traffic accidents, failure
load, etc.)
Pollution from products used in automobiles, electric generator,
maintenance work (oil, fuel filters, batteries, etc.).
Pollution from laboratory waste (chemical waste, biological waste).
Probability
Risk
Severity
A28

Consequences
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A26
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medium
large
large
than 4 two factors due to the internal activity (A27,

A28) and one due to possible mismanagement of
rainwater (A23).
A3. Environmental factor air"
A32
Damage to the sewage system and waste water adduction system to

discharge in the effluent (air pollution by generating specific odours).
sedimentation tanks, etc. (air pollution by releasing specific odor).
Probability
A31
Risk
Severity
No.
Consequences
Table 3. Levels of environmental partially risk factor for air
small
small
A33
Odor pollution through improper treatment of wastewater process

parameters resulting from failure or breach of the maintenance program.
small
A34
Air pollution due to sludge fermentation products (CH4, H2S, etc.)
large
medium
medium
large
large
negligible
A38
Overcoming the storage capacity of treated sludge plant (particulate air

pollution resulting from partial dehydration of sludge stored).
Accidental discharges of dust resulting from sludge dewatering sludge
auto transport route to the final disposal site (in case of technical
incidents, traffic accidents, failure load, etc.).
Pollution from emissions in transportation, electric generator, from
boiler.
Pollution from emissions due to accidental releases from the storage
facility, transport and use GPL.
A39
Noise pollution due to increased noise in the blower.
A35
A36
A37
Overall risk level to environmental factor air

will be:
NrA3 = 3.53.
The value of overall risk level for air
environmental factor has a slight value in
unacceptability.
There are two risk factors with value 5 (A34,
A38). It is necessary to find and immediate
implementation of measures to reduce the risk level

of air pollution.
The overall environmental risk factor will be:
NrGM = 3.45
In the linear operating conditions the overall
risk environment that has the value 3.45 performs
within acceptable limits (<3.5).
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The next step is to determine the global risk

level where risks are taken into account natural and
technological risks.
B. Natural risks
Small
Small
Small
Large
The overall level of natural risks will be:

NrB = 2.00
The natural risks has the value 2 which category
you fall into very low risk levels. This shall be taken
Earthquakes
Floods
Landslides
Extreme weather events
Probability
B1
B2
B3
B4
Risk
Severity
No.
Consequences
Table 4. Levels of environmental partially risk factor for natural risks
2
2
2
4
1
1
1
2
1
1
1
3
into account since the choice of location for the

station site.
C. Technological risks
C3
C4
C5
C6
C7
The collapse of the construction, installation or facilities.
C8
Failure utilities: systems, facilities and equipment which causes

shutdown interruption of water supply, gas, electricity and heat.
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C2
Industrial risks due to technical incidents (major technical

incidents, the collapse of major equipment, etc.).
Risks due to manipulation and accumulation of dangerous
substances - irritant (e.g. polymers used for sludge thickening,
etc.).
Risks due to handling or accumulation of dangerous substances toxic and harmful to humans and the environment (e.g. oils,
battery electrolyte from batteries, petroleum products, reagents
used in laboratory work, accumulation of fermentation gases,
etc.).
substances - Flammable (e.g. fuels, petroleum products, reagents
used in laboratory work, paper and plastic packaging, etc.), the
risk of fire.
substances - explosive (e.g. emissions from LPG installation,
accumulation of unburned gas from the LPG plant, fuel oil, etc.),
the risk of explosion.
substances - with biohazard (e.g. working in areas with high
biological load - organisms potentially pathogenic microbiology
lab work, etc.).
Probability
C1
Risk
Severity
No.
Consequences
Table 5. Levels of environmental partially risk factor for technological risks
serious
small
small
very
serious
very
serious
very
serious
very
serious
large

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The overall level of technological risks will be:

Nrt = 4.10
This technological risk level will determine

special attention and take the necessary protective
measures and control.
The global risk level (NrG) from SEAU Brila
will be:
The technological risk has the value 4.10 which

is inacceptable. This value is greatly increased level
of biological risk (C6 - risk level 7) due to
manipulation and accumulation of dangerous
substances - with biohazard (e.g. working in areas
with high biological load - organisms potentially
pathogenic microbiology laboratory work, etc.)
N rG =
Ri ri
i =1
3
ri
3.45 3.45 + 2.00 2.00 + 4.10 4.10

= 3.42
3.45 + 2.00 + 4.10
i =1
4.5
4.1
Risk lavel
4
3.45
3.5
3
2.5
2
2
1.5
1
0.5
0
Environmental
risk factor
Natural risks
Technological
risks
Fig. 1. The diagram of global risk level (NrG) from SEAU Brila
3. Conclusion
By calculating the global risk level from SEAU
Braila plant, taking into account natural risks and
technological risks, the global risk factor reached to
near the limit of unacceptability.
Is necessary to establish measures to prevent,
reduce, treatment and eliminate the risks identified.
References
[1]. Moraru R., Bbu G. - Cadrul general al managementului
riscului de mediu, Buletinul AGIR nr. 3/2006, iulie-septembrie, p.
103-107.
[2]. Bbu G., Moraru R. - Environmental risk characterization

principles, Proceedings of the 6th Conference on Environment and
Mineral Processing, part. I, p. 17-21, VB-TU Ostrava, Cehia, 27 29.06.2002.
[3]. Ozunu A., Anghel C. I. - Evaluarea riscului tehnologic i
securitatea mediului, Editura Accent, Cluj-Napoca, 2007,
[4]. Radu Tamara, Maria Vlad, Marius Bodor - Environmental
risk management at hot-dip galvanizing, The Annals of Dunrea
De Jos University of Galai, Fascicle IX Metallurgy and Material
Science, special ISUE, May 2011, pag.263.
[5]. SR EN 292-1/1996.
[6]. Lucica Balint, Tamara Radu, Simion-Ioan Balint Environmental Risk Assessment On coke Plant Decommissioning,
International Scientific Conference Ugalmat 2011.
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RESEARCH CONCERNING HEAVY METAL POLLUTION OF SOIL

AND VEGETATION IN THE AREAS BORDERING TO THE
DEALLOCATED FACTORY OF HEAVY EQUIPMENTS
Aurel CIUREA1, Marian BORDEI2, Mariana Carmen BURTEA3
1

2
Dunrea de Jos University of Galati, Faculty of Science and Environment,
Domneasc Street, 111, RO-800201, Galati, Romania
3
Research Regional Interdisciplinary Center in Vibro-Acoustic Pollution and Ambient Quality
emails: Aurel.Ciurea@ugal.ro, Marian.Bordei@ugal.ro, cburtea@ugal.ro
ABSTRACT
The paper illustrates the influence of heavy engineering activity on soil and
vegetation quality of the bordering areas, carried on in a factory. The toxicity
induced by the presence of heavy metals to the level of environmental factors over
human health was the basis of thoroughgoing study of toxicological research in the
areas liable to contamination. The defense mechanisms of the organism against
pollution with heavy metals are physiologically limited, so it is necessary to monitor
the chemical parameters of soil pollution and to elaborate preventive measures of
pollution and rehabilitate the bordering areas in case of accidental pollution. The
determination of lead, cadmium, and zinc concentrations from plant and soil
samples allows us to quantify the degree of pollution generated by the industrial
activity.
KEYWORDS: heavy metals, pollution, industry
1. Introduction
Heavy metals in the soil which are subject to a
biological buildup, arrives in the plant, where they
pass through consumption of animal and human.
Each of them gets in the food chain and are the
subject of specific processes. In the circuit heavy
metals, acts different biological barriers to whom
there has been a selective bioaccumulation in order to
defend living organisms against excess these items.
However, biological barriers action is, in general,
limited, and, most often, there has to be a
concentration by build the point of view of
concentration and its role in the body, metallic ions
are classified into several groups which include:
A. Macroelemente, such as Na, K, and Mg,
found in high concentrations, essential and which
human beens normally may maintain them at levels
by using physiological homeostatic systems.
B. Essential micronutrients, found in organisms
in concentrations below 0.01 % (tissue dry)
comprising Fe, Zn, Cu, Co, Ni, Cr, Mo, Mn, V, is, I,
and, F, Al, Sn, Li.
C. Essential trace elements as possible, such as

Ba, Br, Rb, Sr, As, Ge, Ti.
D. Toxic elements, such as Pb, Hg, Cd, U.
Lead causes serious disturbances in metabolism
studies in microorganisms, affecting, in particular, the
processes of breathing, for the propagation of cells.
Zinc occurs in soil, in general, in concentrations
of 10-300 ppm, most often between 30 and 50 ppm.
In the plant, zinc becomes toxic at levels greater than
400 ppm (dry substance), due perhaps, the fact that
prevents absorption other essential elements. In the
soil, zinc seems to be mobile.
Cadmium is considered currently one of the
most dangerous heavy metals are very toxic to
humans and animals, so that any appreciable increase
in the cadmium content in food and feed is extremely
dangerous. Naturally, soils contain less than 1 ppm
Cd. Mercury is found, used, in the ground in
quantities of 0.01 -1 ppm, sometimes reaching to 500
ppm, and tolerable limiting being of 2 ppm.
Nickel is found, used in quantities of 2-50 ppm
flaw, sometimes, at 10 000 ppm, the quantity
tolerable in the soil being 50 ppm Ni.
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In general, the concentration in soil solution is

0.005 0.05 ppm and the contents in healthy plants
shall not exceed 1 ppm, the dry matter content.
Chrome. Ground pollution chrome, rarely
contituie a problem, because it is toxic to plants only
when it is in the form of anion oxidised (hexavalent
chrome), the form which can only arise under certain
conditions of pH and potential oxidizability, but
which do not takes more time in the ground. Chrome
is found, used, in soil, in conditions of 2-50 ppm Cr.
Arsenic is found, used, in soil, in quantities of
71 - 20 ppm, arriving at 8000 ppm in soils polluted.
In tolerable limiting ground, after some authors, is 20
ppm as, while others, claim that when a mobile
containing arsenic in the soil 5 ppm as, may be
affected plant growth.
Sampling was carried out in a number of 4

points (P1, P2, P3, P4). Sampling was made from the
following depths: 0 m; 0.5 m; 1 m; 1.5 m, fig.1.
4. Results obtained
As a result of analyzes carried out it was found
a large degree of contamination of the soil with heavy
metals fig. 2-9.
2. Purpose of paper
Fig. 2. Heavy metals content- xray method
Purpose of the work was to determine the

degree of contamination with heavy metals in the soil
of a disused industrial area. The study has been drawn
up with a view to provide data with regard to the
solution of clean-up to environmental factors, waste
management results and preparing for new activities
in the case decommissioning an area.
They have been studied the following
possibilities:
- The contribution and involvement in the
process of current decontamination always and has
been switched off and on again in the circuit of
industrial industrial areas without economic
efficiency;
- Identification possibilities of recovery and
applicability of the methods of clean-up and
continuous monitoring of the areas exposed to
contaminants with various pollutants.
3. Material and work method

Samples were taken and analysed in accordance
with the standards and have been sampled in order to
obtain the aggregate samples which are representative
of the characteristics of average plot.
Fig. 5. Heavy metals content- AAS method
Fig. 1. Disused factory location
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Natural Attenuation controlled

Is the process which occur naturally in the soil
and groundwater, without human intervention, the
purpose of which is to reduce mass, toxicity, mobility
or volume of the contaminants concentration
5. Conclusions
The strategic goal of protection for the
environment is to improve quality of life in Romania
by ensuring a clean environment, which will
contribute to an increase in the levels of living of the
population, improvement of the quality of the
environment, to preserve and improve the state
natural assets of which Romania benefits.
Specific objectives are:

reducing soil pollution caused by industrial
activities
reduction of pollution caused by soil
infiltration and deposition of heavy metals etc.
conservation eco features of the soil
development of a system of monitoring the
quality of the soil.
A major problem of the stage in which we find

ourselves is a multiplicity of disused industrial sites,
where it remains present all the history of the activity
carried out.

A proposal from the clean-up methods: ashing
in situ
This process consists in washing soil without
excavation areas (saturated and unsaturated) by water
injection (and mobilizing agents in solution) upstream
or right source of pollution. Subsequently, the water
polluted is pumped, treated on the surface and then
discharged in networks of sewage/water drencher,
surface water.
Biodegradation of pollutants most biological
treatment techniques in situ using micro-organisms,
mainly bacteria, in order to degrade pollutants totally
or partially.
References
[1]Avram N., Parpala D, Vasilica Dina Daniel Nagy, Mirela
Sohaciu, Cristian Predescu, Dan Constantinescu, G. G. Path "Theory generation processes of pollutants", Printech Publishing
House, Bucharest, 2006;
[2]Ecaterina Matei, Daniela Manea, Irina-Diana Parpala,
Andra Mihaela Stoica, Avram Nicolae - "Characterization of
pollutants ", Printech Publishing House, Bucharest, 2007;
[3]A. Ciurea, Cartas V., Stanciu C., Popescu Maria "Management of the environment" - "Management of the
environment" - vol I, II, Educational and pedagogical Publishing
House, R.A. , Bucharest, 2005;
[4[Radu Olinescu, Maria Greabu - "Defenses of the organism
against chemical pollution", Technical Publishing House in
Bucharest,1990.
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THE INFLUENCE OF ARID CLIMATIC CONDITIONS ON THE

DEGRADATION OF SOILS IN THE N-E ROMANIAN PLAIN
Mariana Carmen BURTEA1, Aurel CIUREA2, Luxia RNOVEANU1
1
Research Regional Interdisciplinary Center in Vibro-Acoustic Pollution and Ambient Quality

2
emails: cburtea@ugal.ro, Aurel.Ciurea@ugal.ro, Luxita.Risnoveanu@ugal.ro
ABSTRACT
The paper presents the characterisation of certain soils in the Braila county to
determine the influence of climatic factors over the pedogenetical process and the
degradation of the evolved soils. Also the purpose of the research was to establish
measures to prevent rainlessness effects on soil quality. The results show that
climate changes influences the desertification process and the drought in the
studied area has a highly negative impact on the ecosystem balance.
KEYWORDS: desertification, salt affected soils
1. Introduction
2. Purpose of paper
DesertifIcation represents the process of

degradation of the land caused by changes in the
climate and human impact. Particularly affects dry
land which are already fragile from the environmental
point of view. Desertification takes place in areas of
land where the rain drops are weak and the climate is
harsh. The result is destruction fertile layer followed
by loss of capacity soil to support crops, grassland or
other human activities [6].
As far as Romania is concerned, the areas
affected by the phenomenon of desertification are
located to the south, south-east of the country. Braila
County is one of the counties affected by
desertification. Here soil quality is affected either by
natural factors, such as climate, gentle relief, features
edaphic data shall be recorded. Factors may act in a
negative direction having as a result the drop in
quality of the soil or even losing its fertility. Land that
may have been damaged in Braila is 33.57% of
county area.
Restrictions relating to soil quality degradation
and potentially productive reduced shall be found by
a group of soils in the country were widespread.
In Braila county wooded areas are very small in
comparison with the rest of the country in fact that
promote production combat desertification.
Also in Braila, small desserts are to be found in
Big Island - 500 ha, Faurei - 600 ha, Insuratei 200ha, Stancuta - 300ha, Tichilesti - 400ha, Gropeni 100ha and Vadeni 57ha [7].
It was to determine the condition of a fertility

ground in area Gropeni Braila county with a view to
the establishment of climatic factors influence on the
process of soil development and, by default, on the
types of soil and which have evolved year Danube
river, by performing a pedological study.
The research was also aimed at establishing
measures with a view to preventing and combating
desertification effects on soil quality, the
establishment of doses of fertilizers to be applied for
the correction of the fertility status of the soil.
3. Conditions in the studied area

The area is characterized by a temperate climate
continental. Summers are warm and dry due air
masses continental values under the influence of solar
radiation, precipitation being reduced by character
hard outside and unevenly divided; the winters are
cold, a layer of snow stable and continuously. Annual
average temperature is between 110C. Highest values
recorded in June, July and August. In July average
temperature is 230C. Where the late spring may
appear until in the second decade of April (cases of
exception being up for the second decade of the
month of May). This fall, where early shall be
recorded at the end of October.
The precipitation will be multiannual average
442.4mm. The deficit of water recorded is 188300mm with a maximum recorded in the months of
July, August, September[4].
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4. Results obtained
5. Interpretation of results
Samples were taken and analysed in accordance

with the standards and have been sampled in order to
obtain the aggregate samples which are representative
of the characteristics of average plot. Sampling was
carried out in a number of 4 points (P1, P2, P3, P4)
table 1, fig.1.
Chemical determinations carried out have
resulted in obtaining the results needed for
interpretation of the environmental conditions
influence extent of accomplishments on physicochemical and morphological characteristics of the soil
in the area Gropeni commune.
PLOT P1 shows low content of salts on the

surface of that allows you to grow and the
development of a corn crops, but soil likely increase
the salinity by migrating its salts from depth to the
surface. This alkali carbonates and bicarbonates and
leading to a very high pH at depth 60-80cm.
Fertilizing with nitrogen fertilisers and good supply
of phosphorus counteract negative effect of salt. It is
recommended that fertilizing with livestock manure
for the restoration of the soil organic matter and
maintain salt level poor for otherwise it is not from
the content of salts will increase in arable layer but
also the exchangeable sodium content which would
reduce by more than land-use for crop corn.
PLOT P 2 - changes in soil conditions in the
steppe can vary from a square meter to another as a
result of differentiation rock composition presents an
alkalinity may low, a salination lower, a salination
sulphate-chlorine that provides more fertile ground
than the chlorine-sulphate degradation.
Soil from this plot is in the same batch in
Gropeni, is not affected by salt layers in 0-20cm and
20-40cm but moderate to heavy layers affected in 4060 and 60 80 cm pH.
Low alkali to heavy alkali in depth, texture
contrast conditions as a result of the river. Danger of
migration to the surface salts is eminent but currently
soil allows a beautiful crop of alfalfa.
It is recommended that organic fertilization and
maintaining salt affected effects at this stage by the
application of rules of irrigation in time, providing a
system via percolatif.
PLOT P 3 -soil is moderate to heavy salt
affected, this alkali carbonates and bicarbonates and
lead to pH values huge, supplies low with organic
matter. All of these features illustrate cumulative
effect of conditions giving rise to the process of
desertification. It is to be noted that the change of this
scheme via ground exudatif has led to accumulation
of salts on the soil surface, much more than in depth.
Soil has evolved in this plot different the others
as a result of the existence of a bottom embossed so
that the ground is salt effected evenly over the entire
depth and the sodisations is high throughout the
profile from the ground.
PLOT P 4
As to the plot P4 is recommended improving,
organic fertilization, fertilizing chemical fertilizers
with acid reaction. Soil has established saline soil
aspect. High cost of improvement make this land is
not cultivated at this time. As to the plot 4 is
recommended improving, organic fertilization,
fertilizing chemical fertilizers with acid reaction
(fig.2-6).
Table 1. Sampling points

Nr.
crt
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Nr.
plot
P1
P2
P3
P4
Depth
cm
0-15
15-30
30-45
45-60
0-15
15-30
30-45
45-60
0-15
15-30
30-45
45-60
0-15
15-30
30-45
45-60
Physico-chemical
analysis required
pH, salt content,
organic matter,
available
phosphorus content,
exchangeble sodium
content
Fig. 1. Experiment location

Developments in soil took place under the
influence of environmental factors in such a way that
the regime of non-calcareous area has led to a ground
contrast-textured, low organic matter; the pH alkaline
is low in the top layer and strongly alkaline in depth
due to the influence of desertification process which
result in the formation of salt affected soils and
sodium affected soils.
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Fig. 1. Total soluble salts (mg/100 g soil)

Fig. 6. Exchangeble sodium percents
6. Conclusions
Fig. 2. Soil pH values
Fig. 3. Organic matter content (H), %
100
50
0
1
Conditionst he area Gropeni led to the

formation of soils very different compared with the
ideal. Correcting the level of supply of nutrients it is
recommended to be carried out in conjunction with
optimal reports between nutrients. The doses of
chemical fertilizers will be calculated on the basis of
soil and subject to expected crop. Moderate
phosphorus content comparable to mislead unable
aqusition by plants of nitrogen supplied by organic
matter or the addition of chemical fertilizers with
nitrogen therefore will apply binary fertilizer nitrogen
and phosphorus alkaline reaction reduces accessibility
of phosphorus in the plant; the plots with alkaline pH
will be cultivates tolerance plant alkalinity and
measures shall apply ameliorative. Subject to the
organic matter it is recommended that it be enhance
by fertilization with manure; it is in this situation
because of destruction of protection curtains
represented by those clumps of forest land which was
the purpose to oppose the wind rose dry summer or
for plotting, which do not allow snow to settle
compact and to keep moisture in the atmosphere.
Braila ordered at a given time these clumps of forest
land which has to be cut, but, during the communist
regime to increase arable surfaces. One of the main
ways to combat desertification of the extension is
planting of trees and other plants which maintain
quality of the ground and rational exploitation of its.
Fig.4. Available phosphorus content (ppmP)
Fig. 5. Soluble anions and kations percents
References
[1]. Florea N. , Dumitru M. - Soil Science in Romania in the
twentieth century-XX century, 2002.
[2]. Ielenicz M., Ileana Ptru, Laura Comnescu, Mihai B.,
Nedelea Al., Oprea R. (2004) Dicionar de Geografie Fizic
ediia II revizuit, Editura Corint, Bucureti.
[3].R.Lacatusu - Agrochemistry, Iasi, 2003.
[4]. Oanea N. - General soil science, Alutus Publishing House,
Bucharest, 2005.
[5].Oanea N. Soil improvement, Bucharest, 2003.
[6]. St. Puiu, Adrian Basaraba- Soil science, Bucharest, 2001.
[7]. Research Resort Agricultural Development Braila Drought and agriculture in drought conditions, Olympic Games
Publishing House, Braila, 2010.
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STUDIES ON THE BIOCOMPATIBILITY OF TITANIUM BASED

ALLOYS USED IN ORAL IMPLANTOLOGY
Elisabeta VASILESCU1, Vlad Gabriel VASILESCU2
1
Dunrea de Jos University of Galati, Faculty of Materials and Environmental Engineering,

47, Domneasc Street, RO-800008, Galati, Romania
2
Carol Davila University of Bucuresti, Faculty of Dentistry Medicine,
37, Dionisie Lupu Street, Bucuresti, Romania
email:elisabeta.vasilescu@yahoo.com
ABSTRACT
The main issues to be considered in general when using metallic materials as
biomaterials in dentistry (dentures, implants) are corrosion, release of toxic metal
ions, wear and lack of elasticity. Toxicity of metal ions as particles resulting from
wear are major disadvantages since they can induce multiple tissue reactions,
including osteolysis, degradation of the normal structure of the bone, granulomas,
fibrous capsule, inflammatory and immune reactions. Biomaterial surface reactivity
and living tissue response are measured by the degree of biocompatibility. Ideally,
a biomaterial is considered biocompatible when does not react with the body where
it is implanted and does not release toxic products for the body. Metals and alloys
are the oldest types of materials for oral implants. Currently it is used almost
exclusively titanium and its alloys, tantalum and Co-Cr-Mo alloys. Titan shows the
highest corrosion resistance of all metals (P. Ducheyen) and is considered an inert
material in contact with the tissue because it is rapidly inactivated by forming a
thin, tenacious and protective layer of oxide. Surface oxide consists of TiO,
TiO3,Ti2O3, Ti3O4 that attracts and binds biomolecules (Kasemo 1983). The
disadvantages, however, of using titanium are the difficulty in casting (now it is
obtained by dissociation in vacuum at 1400 C having a purity of 99.85 to
99.95%), on the one hand, and on the other the fact that in vitro and in vivo Ti4 +
ions has been shown to inhibit osteoelastic activity and reduce protein synthesis of
osteoblast. Titanium alloys (eg Ti-6Al-4V, Ti-Al-Nb) are even better tolerated than
pure titanium as the oxide layer providing corrosion resistance has greater
thicknesses, estimated at about 10-20 m. Recent research has shown that the oxide
layer, TiO considered stable, regenerates every nanosecond. Reoxidation is a major
advantage due to minimizing the risk of biodegradation. Recent studies show,
however, that the release of vanadium ions in the body may cause serious damage
to organs and breathing system producing blood platelets [25]. There are also invitro studies which have shown that exposure of bone marrow cells from the
particles of Ti-6Al-4V alloy induce a significant increase in the release of pro
inflammatory and radiolucent mediators and are responsible for the loss of
prostheses [25]. The paper summarizes the results of a detailed study on the types
of titanium -based alloys used in oral implantology with examples illustrating the
harmful effects of alloying elements and also the progress in improving the
biocompatibility and implant osseointegration of titanium based alloys.
KEYWORDS:
titanium,
oral
biocompatibility, implant osseointegration
1. Introduction
The history of dental implant and their surgical
insertion can not be separated from the materials they
implantology,
alloying
elements,
were made of. All metal implants have resistance as

basic characteristic Initially, the metallic materials
have been selected for ease of manufacture. Given
that one of the most important features of the implant
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is that it comes in contact with living tissues of the

body, biocompatibility with bone and soft tissues and
longevity became in time the most important
selection criteria [4]. In general biocompatibility of
dental material dipend on their composition and
localization alon with the interactions at mouth level.
The material response to the pH modifications, when
applying forecs or to the degrading effects of the
biological fluids can all akter its biocompatibility.
Jakubik, in 1986 underlined that, depending on the
dominant factors of biocompatibility of dental
materials, there is a chemical form and a functional
(or mechanical) one (table 1).
Table 1. Determinants of biocompatibility

Biocompatibility
Chemical
Functional
BIOCOMPATIBILITY
Bio-tolerate
Bio-inert
Determinants
-insolubility
-corrosion resistance to pH
of 6,7-7,5
-electrical neutrality
-biostability
-shape
-macroscopic
(implant morphology) surface micromorphological
structure
Bio-active
M E C HA N I C A L P R O P R E R T I E S
Fig. 1. Relationship between biocompatibility and mechanical properties of materials used in the
manufacture of dental implants [6]
Comparing the biocompatibility and mechanical
properties of the materials used in the manufacture of
dental implants, Jukubik found an inverse ratio
between these two categories (Fig. 1).
It is known that when a biomaterial is placed in
the human body as a medical device, human tissue
responds in different ways, depending on the type of
that biomaterial used. Phenomena occurring at the
interface are of great interest because they ultimately
determine the success or failure of the implant, both
as immediate reaction and as long-term answer. The
nature of the biomaterial determines the biological
response as a result of the tissue-implant interaction
which can be characterized as follows:
- If the material is toxic, the surrounding tissue
dies;
- If the material is non-toxic and biologically
inactive (almost inert) a fibrous tissue of variable
thickness;
- If the material is non-toxic and bioactive, an
interfacial bond is formed;
- If the material is non-toxic and soluble
(absorbable) the surrounding tissue replaces it.
From this point of view, metallic biomaterials
for implants have a number of features which will be
described in the following.
Stainless steel widely used in the past especially
due to its good mechanical properties is still a
material susceptible to corrosion in saline
environments such as tissue fluid. The corrosion
avors the released of corrosion products which causes
inflammatory side effects. In the endosseous
implants, inflammation prevents osseointegration
and favors the fibrous capsule formation [4]. Cobalt -
chromium -molybdenum alloys have been used in

dentistry as subperiosteal saddles/bridges and
endosseous plates and transosseous implants.
Connective tissue forms a fibrous capsule around
these implants in weeks or months after their
placement. Although less than in the case of stainless
steel, this fiber reaction is also accounted for by
components released from the implant [4]. Titanium
implants have been successfully used as root devices,
untensiones devices that are left in the mucous
membrane for several months before being used as a
support for the prosthesis. The titanium - aluminum vanadium (Ti6A14V ) alloys have been successfully
used for this purpose, but remains the issue of safety
use as aluminum and vanadium are released into
tissue.
In soft tissue, the epithelium forms a bond with
titanium, a morphologically similar connection with
dental insert, but this interface has not been fully
characterized. Connective tissue does not seem to
attach to titanium, but forms a tight junction, which
limits penetration of bacteria and their products.
Techniques have been developed that limit retraction
of epithelium and reduction of bone height around
implants that may cause implant failure.
2. Considerations on the biocompatibility

of titanium based alloys used in oral
implantology
Titan was originally used as pure metal. It is
considered an inert material as in contact with the
tissue is rapidly inactivated by forming a thin layer of
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surface oxides (carbon monoxide, carbon dioxide,

trioxide) that confers resistance to corrosion 400
times higher than stainless steel. Titanium meets the
best features compared to other metals, being an
almost ideal material for endosseous dental implant.
It was discovered in 1791 by William Gregor,
isolated in 1939 by WJKroll. It was processed into
the form endosseous plates and roots, but the process
introduces impurities at surface level, which can
deter mine bone side effects, if manufacturing is not
extremely careful. Although the titanium is
considered to be a biocompatible metal, in vitro and
in vivo, Ti4+ ions inhibit in vitro osteoclast activity
and reduces the osteoblastic protein synthesis. In one
study [22] which uses a cellular line of MG -63
human osteoblasts, defined as proliferating
osteoblasts, Shida &Co have shown that Ti4+ ions
induce the production of IL -6 and thus activate
osteoclastogenesis. There is also data showing contact
dermatitis in response to the implantation of titanium.
In vitro testing of the titanium (in cell culture, tissue
culture, in the solid and in the form of metal salts)
indicates that the response of human fibroblasts in
culture in contact with titanium powder is within 72
hours as follows: the phagocytosis of fine particles of
titanium, without toxicity, cell density decreases very
little, solid titanium in cell culture can determine: cell
clumping on the titanium edge, a slight cell alteration,
human fibroblasts in contact with titanium salts suffer
no inhibition after 72 hours but titanium interact with
fibroblasts cell membrane
It is accepted today that the alloys most widely
used in medicine are "conversion" titanium based
ones that successfully bring together the corrosion
resistance, biological compatibility, resistance and
price. Corrosion resistance can be increased by
alloying with molybdenum, zirconium, rhenium,
niobium, chromium, manganese (eg, Ti-Al-V, Ti-AlMo, Ti-Al-Cr, Ti-Al-Cr-Co). The Ti-6Al-4V alloy is
the most widely used of all titanium alloys, its total
production is approximately equal to half of all
titanium alloys. It is an alloy of alpha - beta ( + )
containing 6% Al and 4% V, characterized by
excellent mechanical properties, very good corrosion
resistance, light weight and high degree of
biocompatibility.
The frequent choice of this alloy for implants is
determined by a combination of the more and more
favorable features, which include corrosion
resistance, durability, low modulus of elasticity and
the ability to adhere to bone and other tissues
(osseointegration). However there are a number of
issues related to the effects alloy components may
have. Metal ions released from corrosion and wear
can induce prothesis loss after a period of
implantation, especially because of the potential
adverse effects of vanadium. Aluminum compounds
are absorbed slowly, the target organ being the brain.

Aluminum adversely affect bone metabolism in that it
inhibits the phosphorylation and ATP synthesis,
thereby reducing cellular energy reserves. When the
amount of aluminum is very high in bone, its
mineralization is altered, thus causing pathological
fractures. The level of vanadium in the human body is
very small, normal values not exceeding 0.1 ppm.
Although it has some physiological effects (eg
growth, lipid metabolism, bone mineralization),
vanadium has toxic effects too. Vanadium lowers the
concentrations of coenzyme A and Q by disinhibition
of the oxidative phosphorylation, interferes with
many enzyme systems and can induce irreversible
disruption. Its high solubility contribute to the toxic
effects that are estimated to be 10 times larger than
those of the Ni -Co -Cu complex.
A careful analysis of the possible reactions of
prolonged contact of the living tissues with the
alloying elements of titanium alloys showed that the
use of alloys containing large quantities of vanadium,
cobalt and nickel is not recommended. On the other
hand, the introduction into the titanium alloy of
alloying elements such as molybdenum, niobium,
zirconium, tantalum is not limited in terms of
quantity. They increase the corrosion resistance helps
to increase resistance and are compatible with living
tissues. In the attempt to remove the toxic elements
and improve biocompatibility some titanium alloys
have been investigated. Starting from the fact that
although it is a long term process, the release of
vanadium ions in the body may cause serious damage
to organs and breathing systems and the patelets
producing systems, it was sought to replace V with
Nb in Ti - Al- Nb and Ti - Zr Al alloys [22, 25].
Research has shown that the alloy Ti - 6Al - 6Nb has
a higher mechanical strength and corrosion resistance
than Ti - 6Al -4V alloy It has also been shown that
aluminum and vanadium content should not exceed
6%, and the content of elements Fe, Cr, Mn, Ni, about
1%. In vitro studies showed that the cells behave
differently in the presence of debris generated by the
wear of the two alloys. There is an increased release
of prostaglandin E2 in response to contact with Ti 6Al -4V particles, and an increase in the release of
other inflammatory cytokines compared with Ti - AlNb particles. These data suggest that Ti - 6Al -4V
stimulates phagocytic cells more than the Ti - Al- Nb
or than pure titanium. Exposure of bone marrow cells
to Ti - 6Al -4V particles induces a significant increase
in the release of proinflammatory and osteolytic
mediators who are responsible for loss of prostheses
[25]. For this reason it is preferable to use Ti - Al- Nb
alloy instead of Ti- Al- V.
In order to investigate the issue of base metal
and alloying elements release in vitro research has
been done [18,19,20, 25] of the following categories
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of biomaterials: 316L stainless steel, Co-Cr-Mo

casting alloy grade 2 commercially pure Ti, Ti-6Al4V, Ti-6Al-7Nb without vanadium and Ti- 15Zr4Nb-4Ta. They were introduced in different solutions
as follows: alpha-medium PBS (-), calf serum, 0.9%
NaCl, artificial saliva, 1.2% L-cysteine, 1% lactic
acid and 0.01 % HCl.
The summary results of the investigation show
that:
- there is no significant difference with respect
to the content of Co released from the Co-Cr-Mo
casting alloy into the solution being tested;
- the amounts of Ti released in: alpha-medium
PBS (-), calf serum, 0.9% NaCl, artificial saliva are
much smaller than those released in: 1.2% L-cysteine,
1% lactic acid and 0.01 % HCl;
- the amount of Fe released from stainless
steel 316L decreases linearly with increased Ph of the
tested environments; on the other hand, the amount of
Ti released from the biomaterials studied increased
with decresing pH and is significantly attenuated
(over 4 times) with PBS;
-the amount of nickel released from stainless
steel decreased gradually with increasing pH;
- the quantities of Al released from Ti-6Al-4V
and Ti-6Al-7Nballoys decreased gradually with
increasing pH;
- a small V content is highlighted in: calf serum,
PBS (-), artificial saliva, lactic acid 1%, 1.2% and
0.01% L -cysteine HCl;
- the quantity of Ti released from Ti-15Zr-4Nb
4Ta alloy is less than that released from the alloy Ti 6Al -4V and Ti - 6Al - 7NB in all solutions tested
(about 30 % of lactic acid 1%, 1.2 % L- cysteine and
0.01% HCl);
- the quantity of (Zr + Nb + Ta) is considerably
lower than that of (Al + Nb) or (Al + V) released.
Therefore, in vitro research demonstrating that
the amount of metal released with Ti - 15Zr - 4NB 4TA alloys is low, shows that the alloy is suitable for
high durability implants. In other words, the
combination of alloy elements (Zr + Nb + Ta) is
preferably to the combination of (Al + Nb ) or (Al +
V) in terms of free ions. Improved biocompatibility of
titanium based alloys for implants has been an
important concern and sustained over time, starting
from surface treatment to provide passivity and good
osteointegration. Recent research assessed in vivo the
osseointegration of the titanium implant surface
treated mechanically and chemically by coating with
a hydroxyapatite film.
There were studied the morphological and
histological aspects in animal experiments and also
the osteoregenerative process of titanium implants
settling osteoregenerative dynamic processes and
osseointegration of the implants for various periods of
time.
Research results mainly showed that obtaining

surface micro retentions contribute to the implant
osseointegration.
-In
recent
year,
preparations
with
hydroxyapatite in different forms (powder, ceramic
granules, colloidal) are widely applied in the dental
medical practice. The surface treatment with
hydroxyapatite (HA) [27] showed better bone
apposition around the implant, especially in the early
period of healing. Osteogenesis occurs from the
periphery of the bone defects to the implant, therefore
there is a centripetal bone growth, in the interface
area being present non formed bone tissue limited by
mature bone blades. Initially a cancellous bone is
formed, which will be replaced by lamellar bone in a
few weeks. Thickening is observed in peripheral
areas, along with the frequency of bone trabeculae
and increasing bone mass.
In the late phase of bone healing finalizing of
implant osseointegration occurs, the image suggesting
lamellar concentric bone formation. Hydroxyapatite
[27] is a mineral which is acceptable in practice since
1970, forming new bone structures, but it is a
biocompatible nonresorbable bone substitute which
supports connective tissue matrix a long time, has
osteoinductive capacity, stimulates the growth and
differentiation of precursor cells of bone tissues. The
material stimulates the activity of fibroblasts and
osteogenic cells and also creates long-term fixing
conditions for calcium and phosphorus needed for
inductive bone matrix and mixing of its basic
substance. The use of hydroxyapatite in complex with
biopolymers
(polyethylene,
polypropylene,
polystyrene, Teflon, collagen) increases bone healing
effect. Implantology today is at a crossroads caused
by the conceptual developments of implants, passing
from classical implant to teeth implanted
bioartificially or biomimetically, offering new
advantages by shortening post-operative healing.
According to biomimetic principles [30], including
more biological structure, i.e. life, into the
implantable system leads to a more pronounced
similarity of the implant to the native tissue, to the
point that biomimetic implant participates in normal
tissue remodeling. Modification of metal surfaces
implantable with biomimetic coating means new
concepts and strategies promoted by techniques of
regenerative medicine and tissue engineering [30, 31].
3. Conclusions
- This paper is a synthesis of all knowledge about the
performance and limitations of use of titanium and its
alloys in dentistry, mainly in oral implantology.
- It is relevant the concept of biocompatibility
characteristics (chemical, mechanical / functional) of
titanium and its alloys in comparison to other alloys
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(stainless steel, cobalt-based alloys) used in

implantology while emphasizing the superiority of
titanium alloys and titanium based conversion alloys
and the need to improve their composition by
alloying with non toxic elements.
- It highlights the known techniques to improve the
characteristics biosurface of the dental implants and
the strategies of the new concept of tissue
engineering, the techniques for amending metal
surfaces implantable with biomimetic coatings.
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Publisher's Name and Address:

Contact person: Antoaneta CPRARU
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Phone:+40 336 130139, Fax: +40 236 461353
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Email: mbordei@ugal.ro
The papers published in this issue were presented at

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AND MATERIALS ENGINEERING
GALATI, 28-30.10.2013
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42. Ioan VIINESCU, Marcel BULARDA, Daniela TRIFAN - Groundwater

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THE ANNALS OF DUNAREA DE JOS UNIVERSITY OF GALATI.

ALUMINIUM ALLOYS MATRIX COMPOSITES FORMED BY

Aluminium-Magnesium alloys are attractive

Experimental procedure for obtaining composite

Table 1. Experimental parameters

Table 1 presents the material and process

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The entire assembly has been introduced into the

also holds the closed box supporting and adjustable

Fig. 1. Experimental installation. 1) melting

3. Results and discution

Fig. 2. a) SEM analysis to highlight the general

3.1. SEM/EDS Microstructure of

The composition of the isolated particles (SEM

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EDAX ZAF Quantification (Standardless)

Fig. 4. a) SEM analysis to highlight the general

3.2. SEM/EDS Microstructure of

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EDAX ZAF Quantification (Standardless)

Fig. 5. a) SEM image of the composite matrix

3.3. SEM/EDS Microstructure of

Fig. 6. a) SEM analysis to highlight the general

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Fig. 8. Change in percentage of AlN particles

SEM microscopy images taken by the three

Fig. 7. a) SEM image of the alloy renders the

The experiments made have corroborated that

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[3]. Jingzhong Zhaoa, Jiqiang Gao, Zhihao Jin, Preparation of

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PROPERTIES IMPROVEMENT OF MICRO ALLOYED CARBON

but they each produce exceptional grain refinement to

2. Material and procedures

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pressure of 20, 30, and 50 MPa. The deformation

2.2. High Pressure Torsion method

of rotation, time of torsion, were determined to obtain

2.3. Investigation equipment

3. Results and discutions

3.2. Severe deformation process parameters

where hi is initial height and hf is final height after

where: r is the radius of the disc, N is the number of

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phases (A + F) or above critical point Ac3.

crystalline grains of grain boundaries simultaneously

Fig. 1. HPT motor parameters

3.3. Optical microscopy

carbides of accompanying elements. The average of

3.4. Scanning electron microscopy

the nanometer-scale structure of the sample. In this

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3.5. Scanning electron microscopy

Fig. 4. EDS spectra. HPTed at =2.9