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Film Forming Metal Passivation Technology

TH Wharton Generation Texas


Cost of corrosion in the Power Industry



Corrosion of water/steam touched components cost USA fossil-fueled steam
plants in excess of $3.5 Billion/year by James Mathews Program Manager, EPRI, 2013 Metrohm
Conference

Thermoelectric Plant corrosion damage is attributable to poor chemistry and
impurities in the steam/water cycle by James Mathews Program Manager, EPRI, 2013 Metrohm
Conference

Eight of the fifteen highest corrosion costs are associated with the water/steam
cycle and water cooled generator by James Mathews Program Manager, EPRI, 2013 Metrohm
Conference

The water/steam purity demands of the thermoelectric industry is the 3rd
greatest after the microchip technology and pharmaceutical industries by James
Mathews Program Manager, EPRI, 2013 Metrohm Conference

The world production of thermoelectric generation exceeds 16.6 TWh (10
12

watt hrs), requiring more than 2 billion Mg/hr of high purity steam at
conditions of up to 25 MPa and 600C by James Mathews Program Manager, EPRI, 2013
Metrohm Conference


corrosion increases the cost of electricity more than it increases the cost of
any other product, adding over 10 % to its price. Neil B. Caris (PPChem Volume 8
(2006), No. 3)

The total cost of corrosion to U.S. industry is in excess of $276 billion annually,
half of the forced outages are caused by corrosion failures. More than 30 % of
the cost of corrosion failures could be prevented through the use of optimum
corrosion management practices. Neil B. Caris (PPChem Volume 8 (2006), No. 3)

Corrosion failures are the fifth highest cause of forced outages

23% of turbine outage hours are due to corrosion failures

Efficiency Losses due to corrosion per Year

Turbine blade deposits U$ 500,000

Feedwater heater fouling U$ 80,000

Boiler blowdowns U$ 1,000,000



Impact of Corrosion
Component Cost Outage
Duration
Partial economizer U$ 6 - 7 million 25 40 weeks
Row of LP turbine blades U$ 6 - 21 million 15 30 weeks
HP heater U$ 150 200,000 4 8 weeks
O
2
Depleted
Metal
**Trapped contaminants can promote corrosion of base metal
Limitations
Conventional Filming Amines
Isolation & trapping of contaminants creates a hydrophobic surface but also a very dangerous
under deposit corrosion mechanism. The oxide contaminants (typically always inorganic in
nature) would attack the under side of the film architecture & result in release of the
protective film, its subsequent degradation, loss of base metal protection and the formation
of waxy, slimy degradation products, a commonly reported problem with filming amines
Trapped and isolated inorganic contaminants would be allowed to concentrate below the film
and result in an aggressive attach on the base metal.

Water

Experiences Using A
Full Standards Compliant
Organic Film Forming Technology in High Pressure Boilers.

Presentation by:-


Paul R Hattingh President Anodamine Inc

Green Organic Cycle Chemistry For High Pressure
Boilers
U.S.A.
South Africa Columbia Thailand Indonesia Chile Panama
Over 10 years of experience in the USA
(25 years internationally).
Currently treating 27 power stations in the US.
with 3 more power groups soon to be online.
Distributors currently in 7 countries.

Protect & Ensure Safety Of All Staff & Site Personnel.
Avoid Exposure of People & Environment to Toxic Chemistries.
Prevention Of Corrosion In All Steam / Water Sections.
Preventing Scale and/or Deposits Efficiency Of Heat Transfer.
Eliminating Boiler Cleaning.
Protecting Utilities Exposed To Operational Peculiarities
Ease Of Application.
Economics Of Treatment.
Technical Support & Service
Innovation in Cycle Chemistry Creating Real Solutions To Complex Utility Metal Protection Problems.
Anodamine Corporation
All formulations are exclusively manufactured in the United States using locally sourced US Raw materials.
Protection of all ferrous and mixed metallurgies.
Protection against FAC in single and 2 phase areas.
Protection of Mixed & All Ferrous Metallurgies irrespective of
oxygen and residual ammonia concentrations.
Full standards compliant cycle chemistry.
Volatile liquid ratio approx. 60/40 protection throughout the
entire steam water cycle.
No negative effects to online instrumentation
Can be easily quantified spectrophotometrically
Has been scientifically proven to slow/eliminate SCC **

Corrosion Fatigue & Stress Corrosion
Cracking on LP Turbine Blades
pitting
Cost of corrosion in the Power Industry
Presentation at Metrohm Analytical Conference, March 2013 by James Mathews Program Manager, EPRI
Cycle Chemistry Challenges
Utility
Reliability
&
Availability
Operational
Compliance
Cycle Chemistry


Compliance



Non Compliance
How Is Success Measured
Misconceptions (FALSE ASSUMPTIONS)
I have added an oxygen scavenger, I have removed
oxygen, I cant have corrosion, my plant must be well
protected. FALSE
I always measure adequate treatment chemical
residuals, my treatment performance is optimum. FALSE
Cathode
Example O
2
+ 2e
-
+ 2H
2
O 2OH
-
Water
Moisture
Corrosion Monster
Fe
2
O
3 Hematite
(Iron 111 oxide)

O
2
x
Fe
3
O
4 Magnetite
FeO.Fe
2
O
3
(Iron 11 & 111 oxide)

Oxygen
remova
l
14
Anode Fe Fe
2+
+ 2e
-
Magnetite Metal Protection
15
2H
2
O + 2 e
-
H
2
+2OH
-
(cathodic reaction)

reduction of water in an OXYGEN FREE environment

Fe(OH)
2
Fe
3
O
4
+ 2H
2
O + H
2 **
(Magnetite)
FeO.Fe
2
O
3 promotes HYDROGEN embrittlement

2+ 3+


Hydrogen Damage in Boiler Tubing
Cost of corrosion in the Power Industry
Presentation at Metrohm Analytical Conference, March 2013 by James Mathews Program Manager, EPRI
Existing Treatment Protocols
AVT (R) All Volatile Treatment Reducing (ideal involving complete oxygen removal)

AVT (O) All volatile Treatment (oxidizing) Maintaining oxygen at approx 20 ppb

OT Oxygenated Treatment Addition of oxygen to maintain residual 150 300 ppb
FAC
Flow Assisted Corrosion
Single & 2 Phase Flow
AVT (R)
Chemical Protocol FAC Limitations
O
2
Depleted
Reducing Environment
in Aqueous Phase
O
2
Depleted
Single Phase FAC
When Physical & Chemical Conditions Are Correct,
Destabilization & Release of Magnetite,
Corrosion of Base Metal & Tube Wall Thinning


Fe
3
O
4
+ 4H
+
+ 2e
-
3Fe
2+
+ 4OH
-
Fe
2+
Fe
2+
Fe
2+
Fe
2+
Fe
2+
Fe
0
Fe
2+
+ 2 e
-
AVT (O) & OT
Chemical Protocol 2 Phase FAC Limitations
Oxidizing Environment
in Vapor Phase
Reducing Environment
in Aqueous Phase
Potential FAC zone
Destabilization & Release of Magnetite,
Corrosion of Base Metal & Tube Wall Thinning
Due to Poor Solubility of Oxygen at High Temperature
Oxygen will Partition in Vapor Creating Oxidizing Environment
Leaving Aqueous Layer in a Reducing Environment
O
2
O
2
Depleted
Fe
2
O
3
+ 3H
+
+ 2e
-
- 2Fe
2+
+ 3OH
-

Fe
3
O
4
+ 4H
+
+ 2e
-
- 3Fe
2+
+ 4OH
-
Oxygen Free Water, Low pH Conditions & Changes in Flow
Promote Destabilization, Dissolution
& Loss of Magnetite
Fe
2+
Fe
2+
Fe
0
Fe
2+
+ 2 e
-
Copper Oxides, Corrosion and Amines
O
2
Depleted
3 N
2
H
4
4NH
3
+ N
2

(ammonia is added or produced and/or
addition of neutralizing or filming amines)

Cu + O
2
+ H
2
O Cu
II
(OH)
2

Cu
II
(OH)
2
+ 4NH
3
(amines)
Cu(NH
3
)
4
(OH)
2

flow of liquid washes away the protective
patina. More copper will corrode to replace
that lost.
2-Phase Flow Accelerated Corrosion Damage
in HP Feedwater Heater w/ Ancillary
Damage
Cost of corrosion in the Power Industry
Presentation at Metrohm Analytical Conference, March 2013 by James Mathews Program Manager, EPRI
Electrochemical Reaction
FAC
Flow Accelerated Corrosion in unit feedwater system






FAC
Flow Accelerated Corrosion - in unit feedwater system






FAC
Flow Accelerated Corrosion - in unit feedwater system






Black/shiny

Tiger-Striping

Orange Peel

Anodamine Preferred Oxide
Yang merah anodamine filming
Metal
Comparative
Advanced Filming Amine Protection
A slow, progressive molecular permeation through oxide layer resulting in proportional release
of trapped inorganic contaminants (cycle clearance), and a temporary manageable increase in
cycle cation conductivities, followed by absorption on the metal/oxide topotactic layer and a
decline in cation conductivities to < 0.2 uS/cm.
Inspection of exposed oxide at this stage may reveal only water bleeding, with little or no
signs of water beading/hydrophobicity
Surface loose non-adherent oxide can be brushed away to reveal base metal hydrophobicity

Step 1 (real site images illustrating this stage next)
**FFA film protection at base metal topotactic layer
Slow and controlled progressive release of inorganic oxide contaminants
Water
Example Step 1
When water is placed on a high temperature produced oxide surface and the protective film
exists only at the metal topotactic layer, the water will be seen to bleed through the oxide. This
is often in error confused as a sign of no protection.
The high pressure oxide produced surface is manually brushed or wiped off to
remove any loose non adherent oxide and debri. The surface is once again
checked by carefully placing a drop on to the metal surface. Now
hydrophobicity is clearly evident thus demonstrating the permeation of the
proprietary FFA through the oxide to the base metal surface.
Molecular absorption on the metal/oxide topotactic layer. This stage of molecular orientation
and absorption is rapid. With sufficient dosage creating a driving force toward the metal,
excellent metal protection is achieved within 24 hours. Progress from this stage is simply based
upon volume chemical added vs. available surface area.
Surface loose non-adherent oxide can be brushed away to reveal base metal hydrophobicity
Step 2 (real site images illustrating this stage next)
Comparative
Advanced Filming Amine Protection
Metal
** FFA film protection at base metal topotactic layer
Water
Example of Step 2
Low Pressure Drum from HRSG inspection showing
varying levels of hydrophobicity with some oxide water bleed through the
remaining loose surface oxide. Base metal topotactic layer is hydrophobic
Example Step 3
Complete hydrophobicity achieved across all available oxide surface. Oxide is
however very fine and competent. Image from LP drum feed water manifold.
The same is found in feed water sections, LP Heaters, boiler drums, ACC ducts and
saturated steam lines etc in both single and 2 phase areas
Excellent proprietary FFA hydrophobicity with no oxide water bleeding
To achieve this stage requires an ongoing routine chemical treatment approach with chemical
residuals maintained at 800 1000 ppb. This continual treatment results in a tenacious,
competent, dense and very stable oxide to metal surface with an increased 3+ oxide content.
Either the oxide is very thin and/or the base metal is protected and exposed oxides are all found
hydrophobic. The extent/magnitude of oxides and time of treatment exposure will determine
completion of this stage and final level of (water beading) hydrophobicity.
Step 3 (real site images illustrating this stage next)
Comparative
Advanced Filming Amine Protection
Metal
FFA film protection at base metal topotactic layer &
throughout the fine dense, competent oxide layer
Example Step 3
Complete hydrophobicity achieved across all available oxide surface. Oxide is
however very fine and competent.
The same can be found in feed water sections, LP Heaters, boiler drums, ACC
ducts and saturated steam lines etc in both single and 2 phase areas
Excellent proprietary FFA hydrophobicity with no oxide water bleeding
Hydrazine addition (complete oxygen removal +
phosphonate chelant)
Start Of Accelerated Corrosion Test

After
10
minutes
After
4 hours
Start of Corrosion Test using anodamine
ZERO oxygen scavenging
Reaction after 24 hours
A Perfect Partnership Between Metal & Water
Introducing Performance
Boiler & Cooling Water
Metal Passivation Technologies
The LPR (Linear Polarization Resistance) Corrator instrument configuration was used having a
dedicated Anode + Cathode + Reference electrode, Product Code: LP327EH0311000 Serial No.
Y791.
The instrument was set to give a duty cycle (activation of anode with a
generated potential between the anode and cathode) of 15 minutes
on and 1 minute off this ON / OFF sequence was continued
for approx 24 36 hours.
Experimental Procedure
The water used for all experimental tests was raw water (untreated) and softened water (after
sodium ion exchange softening) in both cases with zero oxygen scavenging (oxygen saturated
> 5 ppm).

The LPR (Linear Polarization Resistance) Corrator instrument configuration was used having a
dedicated Anode + Cathode + Reference electrode and a Product Code:
LP327EH0311000 Serial No. Y791. The instrument was set to give a duty cycle (activation of
anode with a generated potential between the anode and cathode) of 15 minutes on and 1
minute off this ON / OFF sequence was continued for approx
24 36 hours.
A Perfect Partnership Between Metal & Water
Interpretation of Results

Untreated Raw water gave a corrosion rate of 11 mpy
Softened water gave a corrosion rate of 14 mpy

The corrosion rate on both waters treated with Anodamine were reduced to 0.01 0.03 mpy.
This rate of corrosion is equivalent to a max 0.0003 per annum; or equivalent to 0.00762 mm
per annum. Assuming a pipe wall thickness of 8mm
this would give an approx.
50 % service life expectancy of 5,250 years
A Perfect Partnership Between Metal & Water


BASIC CHEMICAL PHILOSOPHY


ISOLATION OF THE ANODE.
METAL PROTECTION INDEPENDENT OF OXYGEN.
NO OXYGEN CONTACT.
NO CORROSION.
THERMAL STABILITY.
FULL COMPLIANCE WITH 0.2uS/cm.
ENVIRONMENTALLY COMPATIBLE.
SINGLE PACK, MULTI-COMPONENT DOSING.
PROGRAM SIMPLICITY & MONITORING.
ANODIC SURFACE ACTIVE
BARRIER PROTECTION
A Perfect Partnership Between Metal & Water
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p
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Time (minutes)
CWA Raw Water Analysis

pH = 10.2
Conductivity = 254 us/cm
Hardness = 69 ppm
Silica = 2.52 ppm
Iron = 0.020 ppm
Chloride = 25 ppm
Maximum = 10.08 mpy

Minimum = 0.46 mpy

STD Deviation = 2.67 mpy
Some fouling of the corrosion probes leads to a temporary
reduction in corrosion but under deposit pitting corrosion increases
0
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Time (minutes)
Softened Water Analysis

pH = 10.22
Hardness = 0
Conductivity = 301 us/cm
Silica = 2.63 ppm
Iron = 0.030 ppm
Chloride = 36 ppm
Maximum = 11.77 mpy
Minimum = 0.06 mpy
STD Deviation = 3.60 mpy
Corrosion rate increases
due to presence of residual
brine in softened water
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
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p
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Time (minutes)
Maximum = 0.14 mpy
Minimum = 0.01 mpy
STD Deviation = 0.03 mpy
Best Industry Standard
0.01 0.02 mpy within 8 hours
Anodamine LP boiler formulation employs a larger more branched
thermally stable molecule that takes time to orientate to metal
passivation is immediately better than industry standard and
improves to optimum within 8 hours
Carbon Steel
0
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Admiralty
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Time (minutes)
Raw Water
Softened Water
Softened Water + anodamine LP
A Perfect Partnership Between Metal & Water
Typical Case Studies
Advanced Proprietary
Filming Amine Protection
Averages from > 10 Power Plants (natural and forced circulation) operational pressures ranging
from 1,800 psig 2,500 psig (124 to 172 bar), reheat 1050
o
F 566
o
C MIXED METALLURGY
All circuits were previous treated under strict AVT (R) reducing treatment protocol.
Treatment changed to proprietary FFA and now operational under AVT(O)
Averages from > 10 Power Plants (natural and forced circulation) operational pressures ranging
from 1,800 psig 2,500 psig (124 to 172 bar), reheat 1050
o
F 566
o
C MIXED METALLURGY
0
10
20
30
40
50
60
70
80
90
100
Fe (soluble) Fe (particulate) Fe (total) Cu
%

C
o
m
p
l
i
a
n
c
e

t
o

<

1
0
p
p
b

I
r
o
n

AVT(R) vs FFA operational AVT(O)
Overall Cycle Chemistry Compliance
(incl. transient and base load operation)
AVT(R) Economizer Inlet FFA Economizer Inlet
Ferrozine

Method TOTAL Iron Adapted from Stookey, L.L., Anal. Chem., 42(7), 779 (1970)
Information & Data
Courtesy George Verib FirstEnergy Corp USA., Published
PPChem June 2012, page 338
0
100
200
300
400
500
600
Fe (soluble) Fe (particulate) Fe (total) Cu
p
p
b

Cold Start / Transient Operation
Comparison Iron & Copper Transport
AVT(R) Economizer Inlet FFA Economizer Inlet
Averages from > 5 Power Plants (natural and forced circulation) operational pressures ranging
from 1,800 psig 2,500 psig (124 to 172 bar), reheat 1050
o
F (566
o
C) MIXED METALLURGY
Ferrozine

Method TOTAL Iron Adapted from Stookey, L.L., Anal. Chem., 42(7), 779 (1970)
Typical Case Studies
1,980 MW Cyclic Operational Once Through Units using OT Chemistry + Proprietary FFA
All Ferrous Supercritical Once Through Pressure 4,500psi / 310 bar.
Full Compliance FFA Cycle Chemistry.
Steam Reheat 1,000
o
F / 538
o
C Cation Conductivity <0.09 uS/cm
In-service full flow POWDEX negligible FFA impact/removal.
Advanced Proprietary
Filming Amine Protection
1,980 MW Cyclic Operational Once Through Units using OT Treatment + FFA
All Ferrous Supercritical Once Through Pressure 4,500psi / 310 bar.
Full Compliance FFA Cycle Chemistry.
Steam Reheat 1,000
o
F / 538
o
C Cation Conductivity <0.09 uS/cm
In-service full flow POWDEX no/limited FFA removal.
Ultra Low Ferrozine

Method TOTAL Iron Adapted from Stookey, L.L., Anal. Chem., 42(7), 779 (1970)
released March 2013
0
2
4
6
8
10
12
Fe (soluble) Fe (particulate) Fe (total)
p
p
b

(OT) Base Load Operation
Corrosion Product Transport Comparison
OT Economizer Inlet FFA Economizer Inlet
1,980 MW Cyclic Operational Once Through Units using OT Chemistry + FFA
All Ferrous Supercritical Once Through Pressure 4,500psi / 310 bar.
Full Compliance FFA Cycle Chemistry.
Steam Reheat 1,000
o
F / 538
o
C Cation Conductivity <0.09 uS/cm
In-service full flow POWDEX no/limited FFA removal.
Ultra Low Ferrozine

Method TOTAL Iron Adapted from Stookey, L.L., Anal.


Chem., 42(7), 779 (1970) released March 2013
0
2
4
6
8
10
12
Fe (soluble) Fe (particulate) Fe (total)
p
p
b

(OT) Transient Load Operation
Comparison Corrosion Product Transport
OT Economizer Inlet FFA Economizer Inlet
Typical Case Studies
Advanced Proprietary
Filming Amine Protection
Total MW for the 2X1 (at max load) 600 MW
Design Drum pressure HP 2781 psig (190 bar), IP 721 psig (50 bar), LP 129 psig (9 bar)
Design Superheat Steam Temp 1055
o
F ( 568
o
C)
Design Steam Flow 1,022,366 lbs/HR (465 ton/hr)
HRSGs & ACCs Protection Single &
2 Phase FAC Using A Proprietary FFA
HRSGs and ACCs
Protection Against Single and 2 Phase FAC Using A Proprietary FFA
HRSGs and ACCs
Single and 2 phase Passivation
Saturated exhaust turbine steam streets and A frame Air Cooled Condensers supplied with
low pressure, low temperature steam with approx 5 6 % moisture.
Typical operational pH steam/condensate 9.8 and operational on AVT(o) chemistry protocol with
proprietary FFA chemistry
LP turbine exhaust lower distribution duct. The operational environment is supplied with steam
having approx 5 6 % moisture, image taken after the LP section of the turbine just prior to
steam distribution vanes.
The entire lower pipe sections were found wet with lots of water pooling.
The unit had been offline for 3 months with no external form of preservation.
Air-cooled Condenser Saturated Steam Ducting. Unit had been offline for 3 months with water
pooling and no additional form of preservation.
The internal environment was found very warm and extremely humid during the inspection.
Entry to A Frames of ACC tubes.
No visible signs of FAC in any of the steam flow path areas.
It was reported by site inspections that old areas noted as being previously
affected by FAC damage had now been terminated.
Excellent metal protection and hydrophobicity was evident on all metal surfaces and
right down in to the high velocity steam flow path
Entry to A Frames of ACC tubes.
Excellent metal protection and hydrophobicity was evident on all metal surfaces and
right down in to the high velocity steam flow path
Excellent metal protection and hydrophobicity was evident on all metal
surfaces and right down in to the high velocity steam flow path
Thank You.
The chemistry and properties of organic boiler feed water additives based on film-forming amines, and their use in steam
generators
W. Hater , D. Olivet BKG Water Solutions, Dusseldorf, Germany BKG Water Solutions, Barcelona, Spain
Acknowledgments
Impact of Film Forming Amines on the Reliability of Online Analytical Instruments
Marco Lendi and Peter Wuhrmann Power Plant Chemistry 2012, 14(8)
Organics: A Retrospective Look at Fossil Plant Cycle Chemistry and the Possible Requirements for the Future
A. Bursik, PowerPlant Chemistry GmbH (Germany); B. Dooley, EPRI (U.S.A.)
International Conference on the Interaction of Organics and Organic Cycle Treatment Chemicals with Water,
Steam, and Materials. October 46, 2005
Formation of Polyamine Films on Iron Surfaces Under Power Plant Conditions Laboratory Investigations
Dietrich Frahne, Thomas Blum
International Conference on the Interaction of Organics and Organic Cycle Treatment Chemicals with Water,
Steam, and Materials October 46, 2005 (pg 215)
The Nalco Water Handbook (Chapter 39.55)
Three Years of Experience with Polyamines in the High Pressure Steam System of a Naphta Cracker
Roy van Lier
Interaction of Organics and Organic Cycle Treatment Chemicals with Water, Steam, and Materials Lucerne,
Switzerland, November 4-6, 2008
Operational Experience with Organics in Industrial Steam Generation
Jo Savelkoul Roy van Lier (PPChem July 2005)
Effect of Polyamines on Corrosion of Carbon Steel and Brass in Water
Tamara I. Petrova and Anna V. Furunzhieva Moscow Power Institute, Russia
International Conference on the Interaction of Organics and Organic Cycle Treatment Chemicals with Water,
Steam, and Materials October 46, 2005
The behavior of certain conditioning agents in a boiler at high temperature
R. Roodthooft, G. Bohnsack, R De Caluwe
Fifth International EPRI Conference (4-13)
Assessing and Controlling Corrosion in Air-Cooled Condensers
R. Barry Dooley, J. Denis Aspden, Andrew G. Howell, and Francois du Preez
PowerPlant Chemistry 2009, 11(5)
Flow Accelerated Corrosion in Fossil and Combined Cycle/HRSG Plants
R. Barry Dooley,
PowerPlant Chemistry 2008, 10(2)
ACC Corrosion / FAC. A Perspective on Chemistry and Corrosion
Barry Dooley & Andy Howell
10
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International Cycle Chemistry Conference, Seattle Washington
Determining the Coupling Current as a Means of Detecting Crevice Activation and Inhibition
SangKwon Lee1, Wenjun Kuang1, James B. Mathews2, and Digby D. Macdonald1,3
Center for Electrochemical Science and Technology ,Department of Materials Science and Engineering
Pennsylvania State University, University Park, PA 16802, USA
2013 Southwest Utilitys HRSG/ACC Water/Steam Side Inspection, United States Of America