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Construction and Building Materials 82 (2015) 192205

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Construction and Building Materials


journal homepage: www.elsevier.com/locate/conbuildmat

Compressive strength and durability properties of high volume y ash


(HVFA) concretes containing ultrane y ash (UFFA)
Faiz U.A. Shaikh , Steve W.M. Supit
Department of Civil Engineering, Curtin University, Perth, Australia

h i g h l i g h t s

 The addition of 8 wt.% UFFA improved the compressive strengths of HVFA concretes.
 Durability properties of HVFA concretes are also improved due to addition of 8% UFFA.
 The HVFA concrete containing 8% UFFA exhibited superior durability than ordinary concrete.
 UFFA reduces the porosity of the HVFA matrix and accelerates the pozzolanic activity.
 UFFA produces more CSH gel by consuming calcium hydroxide (CH) in HVFA concretes.

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents the effect ultrane y ash (UFFA) on compressive strength and durability properties
Received 24 October 2014 of concretes containing high volume class F y ash as partial replacement of cement. The compressive
Received in revised form 19 February 2015 strengths are measured at 3, 7, 28, 56 and 90 days, whereas the durability properties are measured at
Accepted 24 February 2015
28 and 90 days. Chloride induced corrosion, water sorptivity, volume of permeable voids, chloride ion
Available online 9 March 2015
penetration, chloride diffusivity and porosity of above concretes are measured in durability properties.
Microstructural analysis in terms of thermogravimetric analysis (TGA) is also conducted to identify the
Keywords:
reaction phases of calcium hydroxide in the HVFA matrix containing UFFA. Results show that the addition
Ultrane y ash
High volume y ash
of 8 wt.% UFFA signicantly improved the early age as well as later age compressive strengths of ordinary
Compressive strength and HVFA concretes. All above measured durability properties of HVFA concretes are also improved and
Durability in most cases the HVFA concrete containing 32% y ash and 8% UFFA exhibited superior durability prop-
Corrosion erties than ordinary concrete containing 100% cement. The results also indicate the effectiveness of UFFA
Porosity in producing high packing density and in accelerating the pozzolanic activity to produce more CSH gel
Concrete by consuming calcium hydroxide (CH) in HVFA concretes.
2015 Elsevier Ltd. All rights reserved.

1. Introduction which are effective in forming denser matrix leading to higher


strength and better durability [13].
For many years, the incorporation of y ash as partial replace- The use of high volume y ash as partial replacement of cement
ment of cement in concrete is a common practice. The quantity in concrete has also been studied. The main concern in this regard
of y ash to replace the cement for typical application is limited is whether or not cement can be replaced by y ash above the lim-
to 1520% by mass of the total cementitious material [1]. As a iting quantity of 1520% by mass in the concrete. Indeed, the small
by-product of industrial process, the utilization of y ash has made percentage is benecial in optimizing the workability and low cost
some progress in addressing the challenges of sustainable con- but it may not improve the durability to any considerable extent
struction. In addition, y ash has pozzolanic activity which is [4]. On the other hand, due to slow pozzolanic properties of y
attributed to the presence of SiO2 and Al2O3. It reacts with calcium ash particles, low early age strength and durability properties are
hydroxide during cement hydration, to form additional Calcium observed [5,6]. Moreover, the optimization of high volume y ash
Silicate Hydrate (CSH) and Calcium Aluminate Hydrate (CAH) has raised many arguments and limitations regardless of the fact
that the variation of constituent in y ash such as alkalis, sulfates,
lime and organics may affect the crystallization and slow down the
Corresponding author. pozzolanic reaction [7]. In order to overcome this deciency, the
E-mail address: s.ahmed@curtin.edu.au (F.U.A. Shaikh). incorporation of very small size pozzolanic materials such as silica

http://dx.doi.org/10.1016/j.conbuildmat.2015.02.068
0950-0618/ 2015 Elsevier Ltd. All rights reserved.
F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205 193

fume in concrete containing y ash has also been studied [810]. both early age and long-term strength development, where
Finer and amorphous materials are expected to accelerate the poz- UFFA will compensate the low early strength and class F y ash
zolanic reaction to improve the early age strength characteristics of will contribute to the long-term strength development due to its
mortars and concretes. slow pozzolanic reaction. However, this hypothesis needs to
Among many micro size pozzolanic materials, ultrane y ash be conrmed experimentally before its use in the concrete
(UFFA) is recently developed. UFFA is produced by a proprietary industry.
separation system with a mean particle diameter of 15 microns The present paper, therefore, focused on investigating the
and contains 20% more amorphous silica than typical class F y development of compressive strength from very early age at 3 days
ash [11]. Generally, ultrane y ash (UFFA) is produced from pure to later age at 90 days of HVFA concretes containing ultrane y
class F y ash by grinding, and separating the ultrane particles ash. Various durability properties related to chloride induced cor-
through the air-classication process. The classication system is rosion are also evaluated at 28 and 90 days in above concretes to
performed for the removal of coarse particles by size and weight establish the benet of using UFFA in HVFA concrete. The
to retain the ner ash fraction. In some cases, this system is bene- microstructure of paste samples on each mix is also analysed by
cial not only in producing ner materials, but also in reducing the MIP and TGA/DTA results.
carbon content and minimizing the variability of constituents in
typical y ash [12]. The ner particle size improves the mor-
phology, mineralogy and chemical composition of materials. 2. Experimental details
Moreover, when compared to cement production, the UFFA pro-
2.1. Materials
duction does not require high energy-intensive process thus can
result in a cost saving [13]. The other benets include reducing The cement used in this study was ASTM type I cement in accordance with the
consumption of natural resources and reducing CO2 emission. On ASTM C150 [19] standard. The commercially available class F y ash (FA) and ultra-
the other hand, it has been reported that a reduction in the particle ne y ash (UFFA) were used as partial replacement of cement. The characteristics
of the raw materials based on XRD analysis are shown in Fig. 1. Previous analysis by
size of y ash increases the amorphous SiO2 content and tends to
the authors also showed that ultrane y ash is about 18% more amorphous class F
decrease the amount of SO3 which can prevent the hydration reac- y ash [20]. The chemical analysis and physical properties of all cementitious mate-
tion of harmful ions in concrete or mortar [14]. rials used in this study are listed on Table 1.
While the UFFA is used to replace cement in concrete, there is
strong indication that an enhancement of strength and higher
long-term durability can also be obtained in HVFA concretes due
to smaller particle size and higher surface area of UFFA.
Therefore, complete hydration reaction can be attained at earlier
ages compared to the ordinary class F y ash. In addition, the
smaller particles are effective to densify the pores structure and
increase the particle packing to increase the density of concrete
or mortar. However, the UFFA, when present at appreciably high
levels, it tends to increase the water demand as a consequence of
accelerated reaction under neness and high surface area.
Therefore, typical dosage of UFFA is suggested to be ranged from
8% to 12% of the total binder content [15].
Based on previous experimental research some benecial
effects have been reported that UFFA was able to enhance the com-
pressive strength when used as partial replacement of cement with
low w/c ratio. Obla et al. [11] reported about 25% and 30% higher
strength at 7 and 28 days, respectively than class F y ash and ten-
dency to minimize alkalisilica reaction expansion in concrete due Fig. 1. XRD analysis of ordinary Portland cement (PC), class F y ash (FA) and ultra-
to UFFA addition. Chindaprasirt et al. [16] reported denser matrix, ne y ash (UFFA) [20].
higher compressive strength and lower total porosity in blended
cement paste containing ner y ash particles. Hossain et al. [17]
also observed that the replacement of cement with 12% UFFA
Table 1
improved cracking resistance when compared to conventional Chemical composition and physical properties of materials.
Portland cement concrete and silica fume concrete. Subramaniam
et al. [18] observed slight reduction in 1 day compressive strength Chemical analysis Cement (%) Class F Ultrane
y ash (%) y ash (%)
of concrete containing 8% UFFA as partial replacement of cement
with no effect on long-term strength development. They also SiO2 20.2 51.80 73.4
Al2O3 4.9 26.40 17.7
observed higher shrinkage cracking resistance when UFFA contents
Fe2O3 2.8 13.20 4.4
increased from 8% to 12%. Choi et al. [6] also observed that the CaO 63.9 1.61 0.9
compressive strength of concrete increased with increasing ne- MgO 2.0 1.17 0.6
ness of y ash. The compressive strength was lower than control MnO 0.10 <0.1
K2O 0.68 1.03
mixes before 7 days and higher after 14 days. From above investi-
Na2O 0.31 0.11
gations, it was clear that the improvement of mechanical and dura- P2O5 1.39 0.2
bility properties was mainly caused by the neness of y ash and TiO2 1.44 0.7
became a main factor contributing to the compressive strength. SO3 2.4 0.21 0.2
However, although extensive research has been carried out on Physical properties
ultrane y ash blended cement, very few studies evaluated the Particle size 2540% 6 7 lm 40% of 10 lm Mean size 3.4 lm
effectiveness of ultrane y ash in compressive strength develop- Specic gravity 2.73.2 2.6 2.02.55
Surface area (m2/g) 2.51
ment and durability properties of high volume y ash concrete.
Loss on ignition (%) 2.4 0.5 0.6
The combination of UFFA and class F y ash is expected to improve
194 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205

2.2. Mixture proportions Q 900I0 2I30 2I60 2I120 . . . . . . . . . I360 1

where, Q = charge passed (coulombs), I0 = current (amperes) immediately after volt-


The experimental program is divided into two parts, the rst part investigated
age is applied, and It = current (amperes) at t min after voltage is applied.
the effects of 8% and 12% (by wt.) replacement of cement by UFFA on the compres-
sive strength of ordinary concrete and HVFA concretes containing 40% and 60% class
F y ash. The above UFFA contents are selected based on authors earlier study 2.3.5. Mercury intrusion porosimetry (MIP) analysis
where among various UFFA contents of 5%, 8%, 10%, 12% and 15%, above two select- This measurement was performed with a PoreMaster series Quantachrome
ed UFFA contents exhibited the best performance in compressive strength of instruments, with a pressure ranged between 0.0083 and 207 MPa, and the pore
cement mortar [20]. Among 8% and 12% UFFA contents, the UFFA content that diameter and intrusion mercury volume were recorded at each pressure point.
exhibited the highest compressive strength in present study is used to evaluate The pressures were converted to equivalent pore diameter using the Washburn
the corrosion and related durability properties of HVFA concretes containing 40% equation [25], as expressed in Eq. (2):
and 60% class F y ash. Detail mixture proportions are described in Table 2.
2c cos h
d 2
P
2.3. Methods
where d is the pore diameter (lm), c is the surface tension (mN/m), h is the contact
All concretes were mixed in a pan mixer using water to binder ratio of 0.4. The angle between mercury and the pore wall (), and P is the net pressure across the
concrete samples of size 100  200 mm cylinder are cast and demoulded after 24 h. mercury meniscus at the time of the cumulative intrusion measurement (MPa).
The concrete specimens were cured in water at room temperature until the testing
days. The mineralogical and microstructural characteristics of the materials were 2.3.6. Chloride diffusion
studied by means of TGA/DTG and MIP. In order to evaluate the chloride content and chloride diffusion coefcient of
various concretes, 100  200 mm cylinder specimens were cast and cured. After
2.3.1. Compressive strength 28 days of water curing, two specimens of 50 mm thick were sliced from each cylin-
The compressive strength of concretes was determined at 3, 7, 28, 56 and der and placed in the exposure container containing NaCl solution prepared with a
90 days according to ASTM C39 [21] using a loading rate of 0.33 MPa/s. For each concentration of 165 1 g NaCl per L of solution. In this study, the specimens were
age, three specimens were tested and the mean value of these measurements is remained in the NaCl solution for 60 days. Prole grinding was applied to collect
reported. concrete powder samples at depth increments ranging between 1 mm and
16 mm, according to ASTM C1556 standard [26]. Chloride contents of the powder
samples were measured using CL-2000, Chloride Test System, James instruments.
2.3.2. Water sorptivity
An accurately weighed 3 g sample is dissolved in 20 ml extraction liquid consisting
The rate of water absorption (sorptivity) of concrete samples with 50 mm thick
of a precisely measured concentration of acid. The chloride ions reacted with the
disk was determined at 28 and 90 days according to ASTM C1585 [22]. The principle
acid of the liquid in an electrochemical reaction. An electrode, with an integral tem-
of the method is that a specimen has one surface in free contact with water (no
perature sensor, is inserted into the liquid. The percentage of chlorides is displayed
more than 5 mm above the base of the specimen) while the other sides are sealed.
directly on LCD readout of the apparatus. Chloride diffusion coefcient of each sam-
This test determines the rate of absorption of water by hydraulic cement concrete
ple is determined by tting the data obtained from the chloride prole analysis
by measuring the increase in the mass of specimen resulting from absorption of
according to Ficks second law of diffusion equation [27].
water as a function of time. The mass of the concrete specimen is regularly mea-
Ficks second law of diffusion is a differential equation that describes how the
sured to determine the initial absorption from 1 min to the rst 6 h. The absorption
concentration of a diffusing species varies with time. For one-dimensional diffusion,
(I) is the change in mass divided by the product of the cross-sectional area of the
the differential equation is as follows:
test specimen and the density of water. The initial rate of water absorption value
(mm/s1/2) is calculated as the slope of the line that is the best t to I plotted against @cx; t @ 2 Cx; t
the square root of time (s1/2). Da 3
@t @x2
From a dimensional analysis, it can be shown that the diffusion coefcient, Da,
2.3.3. Volume of permeable voids (VPV)
has unit of length2/time. The chloride penetration distance is measured in mm and
This test was conducted to estimate the percentage of voids present in the con-
the exposure time is in terms of years.
crete specimens after curing at 28 and 90 days based on ASTM C642 [23] standard.
If it is assumed that there is one-dimension diffusion and that the chloride ion
Volume of permeable voids (VPV) is determined by boiling the 50 mm cut concrete content at the surface is constant, a solution to Ficks second law is as follows:
specimens for at least 5 h in a water tank at 105 C, weighing the samples in water,
 
then measuring the percentage of boiled specimen with dried mass and mass in the x
Cx; t C s  C s  C i erf p 4
water. 2 Da t

where, C(x,t) = the chloride ion concentration at a depth x in mm from the exposed
2.3.4. Rapid chloride permeability test
surface for an elapsed time t in years since the start of chloride exposure, Cs = the
In order to determine the resistance of concrete to the penetration of chloride
chloride concentration at the surface, expressed as percentage (%) of concrete mass,
ion, the rapid chloride permeability test (RCPT) was conducted according to
Ci = the initial (or background) chloride concentration of the concrete, expressed as a
ASTM C1202 [24]. The specimens from each series were tested after 28 and 90 days
% of concrete mass, erf = the error function (a special function related to the integral
curing. After curing, the specimens of 100 mm in diameter and 50 mm in thickness
of a normal probability function), Da = the chloride diffusion coefcient in mm2/year.
which had been conditioned according to the standard were placed in the cells and
subjected to a 60-V potential for 6-h. One of the cells was lled with 0.3 N NaOH
solution while the other lled with 3% NaCl solution. The amount of electrical cur- 2.3.7. Accelerated corrosion test
rent passed through the specimen is measured and the total charge passed (in cou- Accelerated corrosion test was employed to simulate the corrosion of steel rein-
lombs) is used as an indicator of the resistance of the concrete to chloride ion forcement in concrete. The corrosion process was accelerated by impressing an
penetration. The total charge passed through the concrete specimens was calculat- anodic potential between rebar (anode) and steel plate (cathode) to record the var-
ed using the following formula in Eq. (1) [24]: iation of current with time. Concrete specimens of 100  200 mm cylinder were
used after curing in water for 28 days. Deformed steel bars of 16 mm diameter
and 250 mm in length are used and xed in the center of the specimens after being
cleaned and accurately weighed. The steel bar has an effective cover of 50 mm at
the bottom. The reinforced concrete specimens were immersed in a 3.5% sodium
Table 2 chloride solution in a 3 days wet and 4 days dry cyclic regime to accelerate
Mixture proportions of binary and ternary blended concretes. the corrosion. Readings for each type of mixes were taken from two specimens
and recorded every hour using an automatic data taker. The average was calculated
Mix Cement Class F y Ultrane Sand Coarse Water
to compute the time of corrosion for the reinforced steel bar.
designation (kg/m3) ash (kg/ y ash (kg/ (kg/ aggregate (kg/
The schematic of the accelerated corrosion test setup is presented in Fig. 2. The
m3) m3) m3) (kg/m3) m3)
steel bar (anode) of the sample is connected to a 10-V DC power supply. The nega-
PC 400 1100 1184 160 tive terminal of the DC power source is connected to the stainless steel plate (cath-
FA40 240 160 1100 1184 160 ode). The impressed current ow is measured regularly and test is stopped when
FA60 160 240 1100 1184 160 the initiation of corrosion is detected. A rapid increase in current ow indicates
UFFA8 368 32 1100 1184 160 the formation of cracks in concrete samples. In order to measure the weight loss
UFFA12 352 48 1100 1184 160 measurement, the corroded steel is retrieved from the broken samples and weight
FA32.UFFA8 240 128 32 1100 1184 160 to be compared with the initial weight after accelerated corrosion test.
FA52.UFFA8 160 208 32 1100 1184 160 After applying the current for a given time, the degree of induced corrosion can
be theoretically calculated according to Faradays law as follows:
F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205 195

Fig. 2. The accelerated corrosion test set up.

WIapp T
M th 5
F
Mth = theoretical mass of rust per unit surface area of the bar (g/cm2), W = equivalent
weight of steel which is taken as the ration of atomic weight of iron to the valency of
iron (27.925 g), Iapp = applied current density (Amp/cm2), T = duration of induced
corrosion (s), F = Faradays constant (96,487 Amp-s).
The actual mass of corroded products per unit surface area is measured accord-
ing to Eq. (6) by gravimetric method in accordance with ASTM G1 [28] on rebars
extracted from the concrete by breaking the specimens after the accelerated corro-
sion test

Wi  Wf
M ac 6
pDL
where Mac = actual mass of rust per unit surface area of the bar (g/cm2), Wi = initial
weight of the bar before corrosion (g), Wf = weight after corrosion (g) for a given
duration of induced corrosion (T), D = diameter of the rebar (cm), L = length of the
rebar sample (cm).

2.3.8. Differential thermal analysis and thermogravimetric analysis (DTA/TGA)


DTA/TGA analysis measures both heat ow and weight changes in a material as
a function of temperature in a controlled atmosphere. DTA gures the thermal
decompositions of different phases in the paste, while TGA simultaneously mea-
sures the weight loss due to the decomposition of phases. About 50 mg of well-
Fig. 3. Measured slump values of HVFA concretes, concretes containing UFFA and
powdered sample in a 110 lL platinum crucible was heated from ambient to
HVFA concretes containing UFFA.
1000 C at 20 C per minute in a nitrogen atmosphere owing at 100 ml per minute.
Mass and differential temperature data were acquired with respect to furnace
temperature.

compressive strength at all ages compared to that of control con-


3. Results and discussion crete and concretes containing HVFA. Among different UFFA con-
tents, the highest compressive strength was achieved when
3.1. Workability cement was replaced by 8% UFFA. The results show that the
UFFA8 concrete had a compressive strength of 45 MPa, whereas
The effect of ultrane y ash on the workability of ordinary con- the compressive strength of control concrete was 29 MPa at
crete and concretes containing HVFA is shown in Fig. 3. The work- 28 days. It was also evident that the UFFA content of 8% signicant-
ability of concrete is measured in terms of slump value according ly improved the early age compressive strength at 3 and 7 days of
to ASTM C1437 [29]. It can be seen in Fig. 3 that the addition of ordinary concrete by about 50% and 100%, respectively. The long-
UFFA decreased the workability and the reduction in slump term compressive strength at 90 days of UFFA8 concrete is also
increases with increase in UFFA content from 8% to 12% in ordinary increased by more than 50% compared to control concrete. The rea-
concrete. Similar phenomenon is also observed in HVFA concretes son behind this improvement is due to the small particle and high
containing 40% and 60% y ash. The lower workability of ordinary amorphous content of UFFA which accelerates the pozzolanic reac-
concrete and HVFA concretes containing UFFA is due to smaller tion and lls the pores resulting in improved compressive strength.
particle size and higher surface area of UFFA. Similar behavior is One of the main purposes of this study was to evaluate the
also observed in the case of HVFA mortar [21]. effectiveness of UFFA on the development of compressive strength
of HVFA concretes both at early age as well as later ages (e.g.
3.2. Compressive strength 90 days). The effect of ultrane y ash on the compressive strength
development of high volume y ash (HVFA) concretes can also be
The effect of UFFA on the development of compressive strength seen in Fig. 4. The ultrane y ash content of 8% was selected since
of ordinary concrete and HVFA concretes is shown Fig. 4. It can be it exhibited the highest compressive strength in binary blended
seen that the concretes containing UFFA exhibited higher cement concrete. Results show that the addition of 8% UFFA
196 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205

Fig. 4. Compressive strengths of HVFA concretes, concretes containing UFFA and HVFA concretes containing UFFA.

improved the compressive strengths of HVFA concrete containing concrete. Based on the sorptivity values in Fig. 6, the water sorp-
40% y ash at all ages. Similar behavior is also observed in HVFA tivity of FA32UFFA8 concrete at 28 and 90 days is about 40% and
concrete containing 60% y ash, however, the compressive 60%, respectively lower than that of FA40 concrete. However, the
strength at 28 days and beyond deviated from this trend. The reduction in sorptivity of this concrete was not as great as of
XRD analysis results, shown in [21], also support this observation FA32UFFA8 concrete. In addition, in both HVFA concretes the inu-
where the drop of calcium hydroxide (CH) peaks at 2theta angels ence of UFFA addition on reduction of water absorption due to cap-
of 18.04 and 34 can be seen due to addition of 8% UFFA in illary pores suction after 90 days of water curing was more than
HVFA concrete containing 32% y ash. The change in CSH peak 28 days curing, since mature concrete has a more discontinuous
can also be seen in the XRD plot indicating the formation of CSH pore system.
due to reaction of UFFA with CH in the pozzolanic reaction. On The above results show that by combining UFFA in HVFA con-
the other hand, no signicant difference in the CH and CSH peaks crete, the capillary absorption of water can be reduced. The reduc-
are observed in above concrete at 28 days. The above result is also tion in water sorptivity can be explained as the rapid reaction of
consistent with the calculated CH content from the TGA analysis UFFA with CH, thus accelerating the hydration products and
discussed in following section. improving the bonding effect between cement paste and aggre-
gate. This process, therefore, improves the density of concrete
due to reduction of pore volume, which is also observed in mercury
3.3. Water sorptivity
intrusion porosity tests discussed in following section.
Water sorptivity describes the water ingress into pores of
unsaturated concrete due to capillary suction. It is a function of 3.4. Volume of permeable voids (VPV)
porosity including pore volumes and continuity of pores within
the concrete matrix and can be related to permeability. The rate Fig. 7 presents the volume of permeable voids of different con-
of absorption (mm) of all type of concrete mixtures at 28 and crete mixes at 28 and 90 days. The VPV is recognized as an impor-
90 days are presented in Fig. 5ad. The best-t lines in above g- tant property of concrete since it affects the transport mechanism
ures are based on r2 values of greater than 0.98 for all mixes. It of aggressive uids through concrete. As expected, the VPV of
can be seen that the cumulative volume of water absorbed in the UFFA8 concrete shows a decreasing trend with increase in curing
concrete specimens increased with the square root of time. The time. The VPV of UFFA8 concrete at 28 and 90 days is reduced by
slope of the obtained line denes the sorptivity of different con- nearly between 15% and 20% compared to ordinary concrete. The
cretes during the initial 6 h of testing. It can be clearly seen that effect of UFFA on the VPV of HVFA concretes is also shown in
the rate of water absorption of ordinary concrete is reduced at Fig. 7. It can be seen that the VPV is reduced by about 1520% in
28 and 90 days due to addition of 8% UFFA as partial replacement HVFA concrete containing 40% y ash and by about 1314% in
of cement (see Fig. 5a and c). It is due to neness, high pozzolanic HVFA concrete containing 60% y ash due to addition of 8% UFFA.
activity and the formation of secondary CSH due to reaction of
UFFA particles with CH. According to the summarized sorptivity 3.5. Rapid chloride permeability
values in Fig. 6, the minimum water sorptivity at 28 and 90 days
were 32 and 19 (104 mm/s1/2), respectively for UFFA8 concrete. Rapid chloride permeability test (RCPT) was conducted to
The values are about half of the ordinary concrete. investigate the performance of concrete against chloride ingress.
Fig. 5b and d shows that the sorptivity of HVFA concretes is The penetration of chloride ions can reach reinforcing steel bars
higher than those containing 8% UFFA with similar w/b ratio and corrode them rapidly. The lower the total charge passed
because of high y ash content. In HVFA concretes containing through the concrete matrix, the higher the resistance to chloride
UFFA, it can be seen that the FA32UFFA8 concrete exhibits higher penetration. ASTM C1202 [24] species the rating of chloride per-
resistance to water absorption by capillary suction than FA40 meability of concrete based on the charge passed through the
F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205 197

Fig. 5. Rate of water absorption of different concretes after 28 days (a and b) and 90 days (c and d) moist curing.

Fig. 6. Effect of UFFA on sorptivity of concrete and HVFA concretes.

specimen during 6 h of testing period. RCPT value of less than 2000 Fig. 8 illustrates the effect of UFFA as a partial cement replace-
coulombs is characterized as low chloride permeability, 2000 ment on the resistance to chloride ion penetration in ordinary con-
4000 coulombs is medium level while higher than 4000 coulombs crete at 28 and 90 days. It can be seen that by combining 8% UFFA
is dened as high chloride permeability [24]. in ordinary concrete a decrease in chloride penetration in terms of
198 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205

Fig. 7. Effect of UFFA on volume of permeable voids of concrete and HVFA concretes.

Fig. 8. Effect of UFFA on volume of chloride ion penetration of concrete and HVFA concretes.

total charged passed from 3443 to 2775 coulombs and from 2916 shown. The results indicated that when 8% UFFA was added in con-
to 887 coulombs can be achieved at 28 and 90 days, respectively. crete containing 32% y ash the charge passed decreased sig-
At 90 days, the effect of UFFA on chloride ion resistance of concrete nicantly from 4996 to 2459 coulombs at 28 days, a drop of
was even more favorable with about 70% reduction in chloride ion about 50% when compared to the reference FA40 concrete without
penetration. This clearly indicates that at later ages the chloride UFFA. The lower values of charge passed obtained in RCPT test can
penetration resistance of concrete containing UFFA is signicantly be attributed to the change of concrete microstructure and rene-
improved. Based on the above classication, the concretes contain- ment in the pore system due to the use of UFFA in HVFA concretes.
ing UFFA can be classied as low chloride permeability category However, based on the coulomb value, the concrete containing 52%
indicating the high corrosion resistance. y ash and 8% UFFA exhibits higher chloride permeability than
In HVFA concretes, the results show that the chloride ion FA32UFFA8 concrete indicates connected pore structure. It is also
penetration is increased at both ages compared to ordinary con- interesting to see that due to addition of 8% UFFA in HVFA concrete
crete. The total charge passed of concrete containing 40% y ash containing 32% y ash the chloride ion penetration can be reduced
(FA40) was 4996 and 3559 coulombs and for concrete containing below the ordinary concrete level at both ages. Furthermore, when
60% y ash (FA60) was 6076 and 4937 coulombs at 28 and 90 days, concrete mixes are properly designed in terms of the amount of
respectively (see Fig. 8). In the same gure, the effect of 8% UFFA on UFFA as cement replacement in HVFA concretes, it is possible to
the chloride ion penetration resistance of HVFA concrete is also achieve medium chloride ion penetration level as standardized in
F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205 199

ASTM C1202 and at later ages this chloride ion resistance is expect- chloride concentration (Cs) and the effective diffusion coefcient
ed to increase. (Da) are calculated for each concrete. The procedure used a least-
square best-t analysis for Cranks solution to Ficks law as men-
3.6. Chloride diffusion tioned earlier. The chloride diffusion coefcient of concrete mixes
is presented in Fig. 10. For the ordinary concrete, the calculated
The chloride content prole of different mixes of 28 days cured chloride diffusion coefcient is 4.1  1012 m2/s while for concrete
concretes subjected to 60 days exposure to NaCl solution is pre- containing 8% UFFA (UFFA8), the diffusion coefcient is 1.28 
sented in Fig. 9. The gure shows the measured chloride concentra- 1012 m2/s, which is about 70% reduction from the ordinary con-
tion at different depths, where the chloride concentration inside crete. The chloride diffusion coefcient of HVFA concretes is also
the concrete is measured by percent of binders weight. In the chlo- reduced by about 25% to 50% when 8% UFFA is added (see
ride content prole, the rate of chloride diffusion can be deter- Fig. 10). It indicates that the UFFA is very effective in reducing
mined from the steepness of the curve. A less steep curve the pore space and its connectivity inside the concrete and there-
indicates small difference in chloride concentration between inside fore the chloride diffusion.
and external surface. On the other hand, the steep curve indicates
slow chloride ion diffusion inside the concrete due to very slow 3.7. Porosity
chloride penetration from the concretes surface.
In Fig. 9, it is clearly seen than the steepness of the curves is Mercury intrusion porosimetry (MIP) analysis is widely used to
high up to about 8 mm from the external surface in both ordinary evaluate total porosity and size distributions of pores in cement
concrete and HVFA concretes containing 8% UFFA indicating the pastes and concretes. The MIP results of paste samples after
inuence of UFFA on the reduction of chloride diffusivity. In order 28 days of curing are shown in Fig. 11. It shows the relationship
to quantify the durability performance of the concretes, the surface between the cumulative pore volume and pore diameter in the

Fig. 9. Chloride penetration prole of concrete containing UFFA, HVFA concretes and those containing UFFA at 28 days.

Fig. 10. Effect of UFFA on chloride ion diffusion of concrete and HVFA concretes at 28 days.
200 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205

Fig. 11. Effect of UFFA on porosity of cement paste (a) and HVFA pastes (b) after 28 days of moist curing.

range of 0.01 to 100 lm. Zhang and Islam [30] classied the pores capillary pore volume and gel pores (Fig. 11a). It can also be seen
from 10 to 0.05 lm as large capillary pores, from 0.05 to 0.01 lm that the addition of UFFA signicantly reduced the large capillary
as medium capillary pores and <0.01 lm as gel pores. Gel pores pores of cement paste. The effect of UFFA on porosity of HVFA
form as part of CSH and are considered as micro pores. They are pastes is shown in Fig. 12b. It can be seen that by adding 8%
not active in water permeability and do not inuence the strength. UFFA in paste containing 40% and 60% y ash the total cumulative
However, they inuence shrinkage and creep of the concrete. The pore volume is reduced by about 36% and 33%, respectively.
capillary pores are partially and completely lled with water and Fig. 12a and b show the differential pore size distribution curves
reduce as hydration continues. Capillary pores affect the strength of binary and ternary blended cement pastes obtained by differen-
and durability of concrete. tiating the cumulative curves in Fig. 11. The region under the curve
Fig. 11a shows the cumulative pore volume of cement paste, represents the concentration of the pores. The value of critical dia-
HVFA pastes and pastes containing UFFA cured at 28 days. It can meter of pore corresponds to the peak point of differential curve.
be clearly seen that the total pore volume particularly capillary Fig. 12a shows that the maximum concentration of pores in UFFA
pores of HVFA pastes is higher than pure cement paste and the paste is approximately at 0.06 lm and the curves peak shifted
pastes containing UFFA. Higher capillary pores of HVFA pastes towards smaller pore sizes as compared to HVFA pastes and
can be attributed to the less cement and hence less CSH formed cement paste. The critical pore diameter of UFFA paste is also con-
during hydration reaction and slow pozzolanic reaction of y ash centrated between 0.04 and 0.1 lm. The above results also show
in concrete. On the other hand, due to larger surface area and high- that the UFFA paste exhibits not only a lower porosity but also a
er neness of UFFA than y ash, more CSH gel are formed in the ner pore structure than the cement paste. The UFFA paste con-
paste containing UFFA, which contributed to the reduction in tains mainly pores with diameter <0.1 lm which restricts the ow
F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205 201

Fig. 12. Effect of UFFA on pore size distribution of cement paste (a) and HVFA pastes (b) after 28 days of moist curing.

of harmful ions into the paste. Since the permeability and penetra- 3.8. Accelerated corrosion test
tion of harmful ions into concrete are affected mainly by the large
and medium capillary pores [30], the incorporation of 8% UFFA is Fig. 13 illustrates the corrosion currenttime relationship of dif-
expected to improve the durability properties of concrete. ferent types of concretes. The current variation with time was
In the case of HVFA pastes with 8% UFFA addition, there is a recorded by using a data taker until the corrosion cracks appear
notable reduction in pore concentration indicating the presence on the surface of concrete specimens. The gure shows that the
of UFFA is advantageous for the pores modication. With regard concretes containing UFFA perform better in terms of lower mea-
to FA40 paste sample, the result shows that the cumulative pore sured corrosion currents than ordinary concrete. In this study,
volume is reduced signicantly after addition of 8% UFFA. the UFFA8 concrete took more than 1000 h to crack. Once the
Fig. 12b shows that the porosity of FA32.UFFA8 is concentrated cracks appeared, oxygen and chloride ions penetrated rapidly
around 0.030.05 lm which is lower than the concentration of through the specimens and accelerated the corrosion that is evi-
the pores in FA40 paste. The addition of 8% UFFA shifted the con- dent in the high currents reading. In HVFA concretes, it can be seen
centration of critical pores diameters of HVFA paste containing in Fig. 13b that the time to crack in FA40 and FA60 concretes are
32% y ash from large to medium capillary pores. Similar trend is around 350 h, which is much shorter when compared to the crack
also observed in FA52.UFFA8 paste. It is noted that UFFA has a sig- initiation time of HVFA concrete containing 32% y ash and 8%
nicant inuence in decreasing the total capillary pores and pore UFFA (see Fig. 13b). However, the corrosion induced crack
diameter of HVFA pastes. This suggests that the presence of highly appeared much earlier in HVFA concrete containing 52% y ash
amorphous UFFA can overcome the negative effect of high volume and 8% UFFA. The longer time of FA32UFFA8 concrete to crack than
y ash by increasing the reaction degree, lling spaces between FA52UFFA8 concrete is probably due to the higher resistance of the
cement and y ash particles, and increasing the density of former concrete to chloride penetration and reduced porosity then
microstructure. later as discussed in previous sections.
202 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205

Table 3
Corrosion mass-loss measurement of rebar from different types of concretes
containing UFFA.

Mix Initial Final Actual mass Theoretical Percentage of


designation mass mass loss (g/cm2) mass loss (g/ mass loss (%)
(g) (g) cm2)
PC 536 377 2.11 2.80 29.67
UFFA8 532 428 1.37 1.35 19.53
FA40 539 485 0.71 0.84 9.99
FA60 532 467 0.87 0.93 12.31
FA32.UF8 530 492 0.50 0.74 7.16
FA52.UF8 534 469 0.85 0.44 12.09

HVFA concretes. In contrast, the rebars taken from HVFA concretes


containing UFFA are almost free from corrosion as indicated by a
reduction in the weight loss of rebar.
The cumulative theoretical mass loss and the actual mass loss of
rebar of each sample are also tabulated in Table 3. The mass loss
measurement is known as the most reliable method to investigate
the degree of corrosion. Based on the results obtained, the mass
loss of rebar in ordinary concrete was higher than that of UFFA8
concrete. It is also shown that the ordinary concrete lost an esti-
mated 29.67% of its steel reinforcement while the UFFA concrete
lost about 19.53%. The better corrosion resistance of HVFA concrete
specimens containing 8% UFFA is also conrmed from the actual
mass loss where the FA32.UFF8 and FA52.UFFA8 concretes reached
about 7.16% and 12.09% steel loss (approx. 13% and 9% lower than
FA40 and FA60 concretes, respectively). It indicates that the pres-
ence of UFFA reduced the corrosion of rebar in HVFA concretes.

3.9. Differential thermal analysis (DTA) and thermogravimetric


analysis (TGA)
Fig. 13. Effect of UFFA on chloride induced corrosion of concrete (a) and HVFA
concretes (b).
The results of DTA/TGA analysis of HVFA cement paste contain-
ing 40% y ash and that containing 8% UFFA after 3 and 28 days of
curing are shown in Fig. 15. From DTA analysis, the V-shape of the
Fig. 14 shows the actual corrosion of steel in HVFA concretes DTA curve refers to rapid loss of weight followed by rapid gain in
and those containing 8% UFFA after the accelerated corrosion test. weight under endothermic process. Endothermic process is a pro-
Signicant corrosion can be seen on the surface of the rebars in cess or reaction in which the system absorbs energy from the

Fig. 14. Corrosion status of HVFA concrete containing 40% and 60% y ash and that containing UFFA (areas with signicant corrosion are shown in circles).
F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205 203

Fig. 15. TGA/DTG values of concrete containing UFFA and HVFA concretes containing UFFA measured at (a) 3 days and (b) at 28 days.

surroundings in the form of heat [31]. Several peaks can be detect- system. TGA is dened as the technique whereby the mass of a
ed in the DTA curves. The peak between 105 and 420 C represents substance in a heated environment is recorded at a controlled rate
the mass loss of combined water due to dehydration of calcium as a function of time or temperature [33]. In this study, TGA curves
silicate hydrate, aluminate hydrate and ferroaluminate hydrate, indicate the changes in mass of pastes due to heating from room
between 420 and 540 C corresponds to the dehydration of calcium temperature to about 1000 C. This analysis allows the estimation
hydroxide [32]. of CH from the weight losses in paste samples. Based on the gures,
In Fig. 15, the DTA curves showed two major endothermic peaks the weight loss due to the dehydroxylation of CH can be observed
at 103 C and 462 C, corresponding to the dehydration of calcium at temperature range between 400 and 500 C. The calcium
silicate hydrate (CSH)/ettringite (AFt) and calcium hydroxide (CH), hydroxide (CH) content thus can be calculated according to
respectively. In addition, the AFt/CSH phases can also be identied Taylors formula as follows [34]:
by observing the decomposition of hydration products within the
MWCH
temperature range of about 62157 C. In Fig. 15a, when CH % WLCH %  7
FA32UFFA8 paste is compared with FA40 paste, it can be seen less MWH2 O
weight loss of CH in FA32UFFA8 paste compared to FA40 paste at where, WLCH is the weight loss during the dehydration of CH as per-
470 C indicating the CH consumption turns into CSH. However, centage of the ignited weight (%), MWCH is the molecular weight of
since the weight loss from unbound water is lost between CH, MWHO is the molecular weight of H2O.
50200 C overlapped with the weight loss from CSH gel thus it From Fig. 16, the calculated CH content of HVFA paste contain-
is impossible to accurately determine the amount of CSH formed ing 8% UFFA is approximately 7.52% and 6.62% at 3 and 28 days,
between them. The TGA curves also show similar pattern to respectively which is much lower than the CH content of FA40
explain that UFFA participates in the hydration process of the paste. It also can be seen that the amount of CH decreased in
204 F.U.A. Shaikh, S.W.M. Supit / Construction and Building Materials 82 (2015) 192205

7. The mercury intrusion porosimetry (MIP) analysis results


showed that the addition of 8 wt.% UFFA in ordinary con-
crete and HVFA concretes decreased the total capillary
porosities and shifted the pore distribution towards smaller
pore sizes.
8. The concrete containing UFFA also exhibited better corro-
sion resistance in terms of smaller measured corrosion cur-
rents with respect to time when compared to cement
concrete. The UFFA8 concrete took more than 1000 h for
the corrosion cracks to appear. Similar results are also
observed in the case of concrete containing 32% y ash and
8% UFFA.
9. The mass loss of rebar due to corrosion in cement concrete is
about 29.67% while in UFFA8 concrete loss is about 19.53%.
The addition of 8% UFFA also showed better corrosion resis-
tance in terms of about 29% and 8% reduction in mass loss in
Fig. 16. Calculated calcium hydroxide (CH) contents of HVFA concrete and that
HVFA concretes containing 40% and 60%, respectively.
containing UFFA at 3 and 28 days.
10. From the microstructure and phase identication point of
view, the MIP and DTA/TGA analysis conrms that the incor-
poration of 8% UFFA reduced the CH content and decreases
HVFA pastes due to the addition of UFFA. This could be due to the the total capillary porosities and pores diameter which can
reactivity of UFFA in HVFA paste and the consumption of CH by the prevent the harmful chloride ions transport leading to corro-
pozzolanic reaction. sion of rebar and deterioration to the ordinary and HVFA
concretes.
4. Conclusions

The following conclusion can be drawn from the obtained Acknowledgement


experimental results:
Authors acknowledge y ash Australia for donating class F y
1. The concrete containing 8 wt.% UFFA yielded the highest ash and ultrane y ash used in this study.
compressive strength at all ages. The early age compressive
strength of HVFA concretes is also improved due to addition
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