Stress Corrosion Cracking in PWR and BWR Closed Cooling Water Systems

Stress Corrosion Cracking in
PWR and BWR Closed Cooling

Water Systems
1009721
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11924595
Stress Corrosion Cracking in PWR
and BWR Closed Cooling Water
Systems
1009721
Technical Update, October 2004
EPRI Project Manager
Andrew McGehee
EPRI • 3412 Hillview Avenue, Palo Alto, California 94304 • PO Box 10412, Palo Alto, California 94303 • USA
800.313.3774 • 650.855.2121 • askepri@epri.com • www.epri.com
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DISCLAIMER OF WARRANTIES AND LIMITATION OF LIABILITIES
THIS DOCUMENT WAS PREPARED BY THE ORGANIZATION(S) NAMED BELOW AS AN ACCOUNT OF
WORK SPONSORED OR COSPONSORED BY THE ELECTRIC POWER RESEARCH INSTITUTE, INC. (EPRI).
NEITHER EPRI, ANY MEMBER OF EPRI, ANY COSPONSOR, THE ORGANIZATION(S) BELOW, NOR ANY
PERSON ACTING ON BEHALF OF ANY OF THEM:
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DOCUMENT OR ANY INFORMATION, APPARATUS, METHOD, PROCESS, OR SIMILAR ITEM DISCLOSED IN
THIS DOCUMENT.
ORGANIZATION(S) THAT PREPARED THIS DOCUMENT
EPRI
Jonas, Inc.
This is an EPRI Technical Update report. A Technical Update report is intended as an informal report of
continuing research, a meeting, or a topical study. It is not a final EPRI technical report.
ORDERING INFORMATION
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Copyright © 2004 Electric Power Research Institute, Inc. All rights reserved.
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CITATIONS
This report was prepared by
Jonas, Inc.
1113 Faun Road
Wilmington, DE 19803
Principal Investigator
O. Jonas
EPRI Repair / Replacement Applications Center

1300 Harris Blvd
Charlotte, NC 28262
Principal Investigator
A. McGehee
This report describes research sponsored by EPRI.
The report is a corporate document that should be cited in the literature in the following manner:
Stress Corrosion Cracking in PWR and BWR Closed Cooling Water Systems, EPRI, Palo Alto,
CA: 2004. 1009721.
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ACKNOWLEDGEMENTS
The Principal Investigator (Otakar Jonas of Jonas, Inc.) and Project Manager (Andrew McGehee
of EPRI) would like to thank the following people for their help with this project:
Mr. Ron Bush Southern Nuclear Company
Ms. Kristin Carnahan Southern Nuclear Company
Mr. Mark Hickox Southern Nuclear Company
Mr. Marty Sims Southern Nuclear Company
Mr. Dave Meredith Wolf Creek Nuclear Operating Corporation
Mr. Steve McCracken AmerenUE
Ms. Vonda Sisson Tennessee Valley Authority
Mr. Kevin Braendle PSE&G Nuclear, LLC
Mr. Brad Tyers PSE&G Nuclear, LLC
Ms. Sarah Afarian PSE&G Nuclear, LLC
Mr. Lee Machemer Jonas, Inc.
The project coordination, technical assistance, and help in writing the report provided by Ms.
Joyce Mancini of Jonas, Inc. is also gratefully acknowledged.
The time and effort of the many people who responded to the survey is greatly appreciated.
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ABSTRACT
This report contains information surrounding Stress Corrosion Cracking (SCC) of carbon steel in
Closed Cooling Water Systems (CCW) that has been found in piping and heat exchanger shell
material in 13 PWR units and 1 BWR unit per the survey information which was conducted for
this report. The impetus for the research conducted herein was provided at the request of four
EPRI Repair Replacement Application Center (RRAC) members who were currently dealing
with this form of attack in their CCW systems. There were several goals for this project. The first
was to gather as much information about the specifics of the SCC in these systems including
documented cases and any technical information or forensic work associated with each case. The
second goal was to provide the reader with a general understanding of how SCC manifests itself
in these materials so that a non-metallurgist/ corrosion engineer could gain some fundamental
understanding of the SCC phenomenon and better understand the content of the report. The third
goal was to perform limited corrosion testing to provide data that would reveal obvious factors
associated with the SCC and supply foundational information relative to some of the chemical
environments in which the SCC is occurring. Metallurgical investigations of SCC were
performed for three of the EPRI Repair Replacement Application Center (RRAC) members who
were currently dealing with this problem to provide any recommendations or engineering
solutions, where applicable, for repair or replacement activities. Through this approach, the final
goal was to make utilities aware of the problem so that additional research could be done to
address the specific chemical aspect of the attack and attempt to develop a remedy to prevent a
widespread problem.
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CONTENTS
1 INTRODUCTION ....................................................................................................................1-1
Root Causes of the Cracking ................................................................................................1-4
NERC Statistics.....................................................................................................................1-4
Closed Cooling Water System Design ..................................................................................1-5
Materials ...........................................................................................................................1-7
Variations in Design..........................................................................................................1-9
Water Chemistry....................................................................................................................1-9
Control of Oxygen and Carbon Dioxide..........................................................................1-11
Control of Suspended Solids ..........................................................................................1-12
Water Treatment Chemicals...........................................................................................1-13
Corrosion Inhibitors....................................................................................................1-13
Biocides .....................................................................................................................1-13
Deposit Inhibitors .......................................................................................................1-14
pH Control..................................................................................................................1-14
Additives and Impurities in Water Treatment Chemicals ...........................................1-14
Handling and Discharge of Closed Cooling Water Treatment Chemicals ......................1-14
2 PLANT SURVEY ....................................................................................................................2-1

Salem and Hope Creek Nuclear Generating Stations...........................................................2-5
Corrosion Testing at Hope Creek .....................................................................................2-7
3 SCC INITIATION AND PROPAGATION ................................................................................3-1

Basics of Stress Corrosion Cracking.....................................................................................3-1
Industry Experience...............................................................................................................3-4
Crack Initiation and Propagation of Selected Welds in Units Experiencing Leaks................3-5
4 LABORATORY TESTING ......................................................................................................4-1

Cyclic Potentiodynamic Polarization Tests............................................................................4-2
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Test Procedure and Interpretation....................................................................................4-2
Results of Previous Work by Carolina Power and Light ...................................................4-5
Chromate .....................................................................................................................4-5
Molybdate and Tolyltriazole .........................................................................................4-6
Molybdate and Nitrite ...................................................................................................4-7
Molybdate, Nitrite, and Tolyltriazole.............................................................................4-8
Results of Current Work ...................................................................................................4-9
Test 1: Weld Metal in 1500 ppm Sodium Nitrate (as NO3) Solution...........................4-11
Test 2: A106 Grade B in 1500 ppm Sodium Nitrate (as NO3) Solution ......................4-12
Test 3: A106 Grade B in 1500 ppm Sodium Nitrite (as NO2) Solution .......................4-13
Test 4: A106 Grade B in 400 ppm Sodium Molybdate (as MoO4) + 50 ppm
Tolyltriazole Solution..................................................................................................4-14
Test 5: A106 Grade B in 250 ppm Trisodium Phosphate (as PO4) Solution ..............4-15
Conclusions ....................................................................................................................4-16
Galvanic Corrosion Test......................................................................................................4-17
Discussion of Results .....................................................................................................4-18
Conclusions ....................................................................................................................4-19
Slow Strain Rate (SSR) Tests .............................................................................................4-19
Conclusions ....................................................................................................................4-24
Nitrite Stability Test .............................................................................................................4-24
Conclusions ....................................................................................................................4-25
5 ROOT CAUSE ANALYSIS.....................................................................................................5-1

Root Causes .........................................................................................................................5-1
Materials................................................................................................................................5-2
Stresses ................................................................................................................................5-2
Socket Welds....................................................................................................................5-2
Environment ..........................................................................................................................5-4
Operating Temperature ....................................................................................................5-5
6 ENGINEERING RECOMMENDATIONS ................................................................................6-1

Materials................................................................................................................................6-1
Stress Reduction ...................................................................................................................6-1
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Post Weld Heat Treatment ...............................................................................................6-1
Changing Weld Geometry and Alignment ........................................................................6-2
Stress Redistribution by Hydrotesting ..............................................................................6-2
Water Chemistry and Temperature .......................................................................................6-2
Results of Limited Verification ...............................................................................................6-3
Additional Testing and Inspection .........................................................................................6-3
7 CRACK DETECTION THROUGH INSPECTION AND MAINTENANCE...............................7-1

Cracking Problem Detection..................................................................................................7-1
Inspection of CCW Systems..................................................................................................7-1
Hydrotest ..........................................................................................................................7-2
Field Test of SCC Specimens and Corrosion Potential....................................................7-2
Maintenance..........................................................................................................................7-2
8 CONCLUSIONS, RECOMMENDATIONS, AND MISSING KNOWLEDGE ...........................8-1

Root Causes and Mechanisms of SCC in CCW Systems.....................................................8-1
Results of Plant Survey .........................................................................................................8-3
Laboratory Testing and Sample Analyses.............................................................................8-3
SCC Problem Detection, Inspection, and Repairs ................................................................8-4
Cooling Water Chemistry ......................................................................................................8-5
Missing Knowledge ...............................................................................................................8-7
9 REFERENCES .......................................................................................................................9-1
Plant Specific ........................................................................................................................9-1
Wolf Creek........................................................................................................................9-1
Vogtle ...............................................................................................................................9-1
Callaway ...........................................................................................................................9-2
Sequoyah .........................................................................................................................9-2
Salem and Hope Creek ....................................................................................................9-2
Cooling Water Chemistry ......................................................................................................9-2
Corrosion Inhibitors ...............................................................................................................9-3
Microbiologically Influenced Corrosion..................................................................................9-5
General .................................................................................................................................9-5
Stress Corrosion Cracking ....................................................................................................9-6
Standards and Test Procedures............................................................................................9-7
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A CLOSED COOLING WATER SYSTEM CHEMISTRY AND EXPERIENCE
QUESTIONNAIRE .................................................................................................................... A-1
B ANALYSIS OF VOGTLE PIPE SAMPLES ........................................................................... B-1

Background .......................................................................................................................... B-1
Materials .......................................................................................................................... B-1
Water Chemistry.............................................................................................................. B-1
History of Leaks............................................................................................................... B-1
Visual Examination............................................................................................................... B-2
2-inch Pipe Section.......................................................................................................... B-2
In-situ pH of Surfaces........................................................................................................... B-6
Deposit Analysis................................................................................................................... B-7
White Residue on Flange Outside Surface................................................................. B-7
Oxide Flake from Pipe – Flange Crevice .................................................................... B-8
Dark Streak on Pipe ID (Flange Side)......................................................................... B-9
Elbow ID ..................................................................................................................... B-9
Paint Chip at Leak ...................................................................................................... B-9
Stain on Flange Outside Surface ................................................................................ B-9
Flange Side Pipe ID .................................................................................................... B-9
Shiny Deposits on Elbow ID ..................................................................................... B-10
Metallurgical Analysis......................................................................................................... B-12
2-inch Pipe Section........................................................................................................ B-12
1-inch Pipe Section........................................................................................................ B-14
Hardness ....................................................................................................................... B-15
Scanning Electron Microscopy (SEM)/Energy Dispersive X-ray Spectroscopy
(EDS)............................................................................................................................. B-16
SEM Fractographs......................................................................................................... B-16
Conclusions........................................................................................................................ B-17
C ANALYSIS OF WOLF CREEK PIPE SAMPLE .................................................................... C-1

Background .......................................................................................................................... C-1
Water Chemistry.............................................................................................................. C-2
Materials .......................................................................................................................... C-3
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History of Leaks............................................................................................................... C-3
Visual Examination............................................................................................................... C-3
Deposits ............................................................................................................................... C-5
Weld Neck Flange ID - Dry Scrape ................................................................................. C-5
Pipe ID – Dry Scrape....................................................................................................... C-6
Pipe ID - Dry Wipe Sample.............................................................................................. C-6
Energy Dispersive X-ray Spectroscopy (EDS) ..................................................................... C-6
D ANALYSIS OF CALLAWAY PIPE SAMPLE ....................................................................... D-1

Introduction .......................................................................................................................... D-1
Material............................................................................................................................ D-1
Water Chemistry.............................................................................................................. D-1
History of Leaks............................................................................................................... D-2
Visual Examination............................................................................................................... D-2
In-Situ pH of Surfaces .......................................................................................................... D-4
Deposit Analysis................................................................................................................... D-4
Shell ID ............................................................................................................................ D-5
Nozzle ID - Black Adherent Deposit ................................................................................ D-5
Nozzle ID - Loose Powdery Gray Deposit ....................................................................... D-5
Hardness Testing ................................................................................................................. D-6
Metallurgical Analysis........................................................................................................... D-6
(EDS)............................................................................................................................... D-8
SEM Fractographs........................................................................................................... D-9
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LIST OF FIGURES
Figure 1-1 Crack Locations – Horizontal Letdown Heat Exchangers; Compiled from
Several Units......................................................................................................................1-2
Figure 1-2 Letdown Heat Exchanger Leak in a Longitudinal Seam Weld; A Tube Support
Plate is Located Directly Behind the Weld on the Inside of the Shell.................................1-3
Figure 1-3 Examples of Letdown Heat Exchanger Outlet Piping Crack Locations at One
PWR Unit [2] ......................................................................................................................1-3
Figure 1-4 Typical Closed Cooling Water System [20] ..............................................................1-6
Figure 3-1 SCC Occurs When a Tensile Stress is Applied to a Susceptible Metal in a
Specific Corrosive Environment .........................................................................................3-1
Figure 3-2 Environmental Conditions (Electrochemical Potential and pH) Causing Stress
Corrosion Cracking of Carbon Steels [63] (Courtesy of ASM International) ......................3-2
Figure 3-3 Temperature and Concentration Limits for Stress Corrosion Cracking
Susceptibility for Carbon Steel in NaOH [76] (Courtesy of NACE International)................3-3
Figure 3-4 Stress Corrosion Crack Growth Rate as a Function of Applied Stress Intensity
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(KI) for Normalized Low-Carbon Steel in 208 F (98 C) 4N Ammonium Nitrate
Solution [84] (Courtesy of NACE International)..................................................................3-3
Figure 3-5 Effect of Carbon Content on Threshold Stress for SCC in Nitrate Solutions
[66] .....................................................................................................................................3-4
Figure 3-6 Estimated Crack Propagation Rate vs. Temperature for Units Experiencing
SCC as Compared to Typical Rates Experienced in Three Different Types of
Environments .....................................................................................................................3-7
Figure 4-1 Cyclic Potentiodynamic Polarization Test Setup ......................................................4-3
Figure 4-2 An Example of the Test Specimen Used for Both the Cyclic Potentiodynamic
Polarization Test and the Galvanic Corrosion Test (Left – Side View, Middle – Top
View, Right – Bottom View)................................................................................................4-3
Figure 4-3 Test Specimen Installed in Holder............................................................................4-3
Figure 4-4 Diagram Illustrating the Features of a Cyclic Potentiodynamic Polarization
Curve; the Active to Passive Transitions are the Regions of Susceptibility to SCC...........4-4
Figure 4-5 Potentiodynamic Polarization Curves for Carbon Steel Exposed to Deionized
Water with and Without Sodium Chromate Purged with Nitrogen [43] (Courtesy of
NACE International) ...........................................................................................................4-6
Water with and without Sodium Molybdate and Sodium Tolyltriazole [43] (Courtesy
of NACE International) .......................................................................................................4-7
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Water with and Without Sodium Molybdate and Sodium Tolyltriazole Purged with
Nitrogen [43] (Courtesy of NACE International) .................................................................4-8
Water with Chloride, Sulfate, Sodium Molybdate, Sodium Nitrite, and Sodium
Tolyltriazole Purged with Nitrogen [43] (Courtesy of NACE International) .........................4-9
Figure 4-9 Fast (Top) and Slow (Bottom) Potentiodynamic Polarization Scans of an
ER70S-2 Weld Metal Specimen in Aerated 1500 ppm Sodium Nitrate Solution at
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170 F (77 C) .....................................................................................................................4-12
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A106 Gr. B Specimen in Aerated 1500 ppm Sodium Nitrate Solution at 170 F (77 C) ....4-13
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A106 Gr. B Specimen in Aerated 1500 ppm Sodium Nitrite Solution at 170 F (77 C) .....4-14
Figure 4-12 Fast (Top) and Slow (Bottom) Potentiodynamic Polarization Scans of A106
Gr. B Specimen in Aerated 400 ppm Sodium Molybdate + 50 ppm Tolyltriazole
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Solution at 170 F (77 C) ...................................................................................................4-15
o
A106 Gr. B Specimen in Aerated 250 ppm Trisodium Phosphate Solution at 170 F
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(77 C) ...............................................................................................................................4-16
Figure 4-14 Galvanic Current and Coupled Potential for an A106 Gr. B and an ER70S-2
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Weld Metal Specimen in an Aerated 1500 ppm Sodium Nitrate Solution at 170 F
o
(77 C) ...............................................................................................................................4-18
Figure 4-15 Slow Strain Rate Test Specimen..........................................................................4-20
Figure 4-16 Slow Strain Rate Test Equipment.........................................................................4-21
Figure 4-17 Sample B Slow Strain Rate Test Specimen (No Service, No PWHT)
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Exposed to Aerated 300 ppm Molybdate + 7 ppm TTA at 145 F (63 C) [1] .....................4-23
Figure 5-1 Factors Considered in SCC in CCW Systems..........................................................5-1
Figure B-1 2-inch Pipe Section as Received from Vogtle 2 ...................................................... B-2
Figure B-2 2-inch Socket Weld Flange Face and Pipe ID with Black Adherent Scale
Flakes................................................................................................................................ B-3
Figure B-3 2-inch Socket Weld Flange with White Residue on the Outside Surface; The
Deposits (Indicated by Arrows) were Later Determined to be Mainly Comprised of
Sodium; NaOH is a Known SCC Agent ............................................................................ B-3
Figure B-4 2-inch Pipe-to-Flange Attachment Showing Pipe Misalignment; the Pipe is at
a 0.6 Degree Angle Away from the Centerline of the Flange ............................................ B-4
Figure B-5 Cross-section of 2” Flange Socket Weld; The Inside Diameter of the Socket is
0.06 in. (1.4 mm) Larger than the Diameter of the Pipe, which is Touching the
Socket Wall on One Side (Right) and Leaving a 0.06 in. (1.4 mm) Gap on the
Opposite Side (Left) as Indicated by the Arrows ............................................................... B-5
Figure B-6 1-inch Pipe Section as Received from Vogtle 2 ...................................................... B-5
Figure B-7 Inside Surface of Socket Weld Flange – Pipe is Not Centered Within Socket
(Indicated by Arrows) ........................................................................................................ B-6
Figure B-8 ID of Socket Weld Elbow – Shiny Orange Deposits Visible (Indicated by
Arrows).............................................................................................................................. B-6
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Figure B-9 White Residue on Outside Surface of 2-inch Flange (65X); Comprised Mainly
of Sodium .......................................................................................................................... B-8
Figure B-10 SEM of Oxide Flake Removed from 2-inch Flange Crevice (1000X);
Consists Mainly of Iron with some Carbon, Copper, and Traces of Manganese;
Copper can have a Synergistic Effect on Corrosion.......................................................... B-8
Figure B-11 Shiny Deposit Obtained from Dry Scraping 1-inch Pipe Elbow ID (65X) ............ B-10
Figure B-12 Photograph Showing the Fracture Path of the 2” Socket Weld; Cracking
Initiated from the Inherent Notch at the Root of the Weld and Propagated through
the Weld Metal to the Surface (10X) ............................................................................... B-13
Figure B-13 Branched Section of the Crack Propagation Near the OD of the 2” Socket
Weld (200X) .................................................................................................................... B-13
Figure B-14 Photograph of the 1” Socket Weld Failure Showing Initiation of the Through
Wall Leak at the Root; Another Crack Initiating from the Root can be seen
Propagating to a Lack of Fusion Defect Near the Root (10X) ......................................... B-14
Figure B-15 SEM Photograph of the Polished Metallographic Sample Showing
Branching and Oxidation Along the Fracture Surface of the 1” Socket Failure
(Location of the Photograph is Approximately Mid Length of the Crack) ........................ B-15
Figure B-16 SEM Image of the Polished Metallographic Sample Showing the Corrosion
Product Buildup on the 2-inch Socket Weld Fracture Surface Near the Initiation of
the Failure; the Box Highlights the Area in which the EDS Analysis (Dark Area) was
Performed on the Oxidation Deposit of the Fracture Surface ......................................... B-16
Figure B-17 SEM Fractograph of the 2” Fracture Surface in the Uncleaned Condition.
The EDS Spectra on the Right is Representative of the Fracture Surface Majority.
The EDS Spectra on the Left is Representative of the Fracture in the Root Area .......... B-16
Figure B-18 SEM Photograph of the Chemically Cleaned Fracture Surface of the 1”
Failure. The EDS Spectra from the Pipe O.D. to Socket I.D. Gap area is Given on
the Right and the EDS Spectra for the Fracture Surface of the Root Area is Given
on the Left. Both EDS Spectras were Taken Before Chemically Cleaning the
Fracture Surface. ............................................................................................................ B-17
Figure C-1 Flange Assembly As-Received from WCNOC ........................................................ C-1
Figure C-2 Flange Face As-Received from WCNOC ............................................................... C-4
Figure C-3 Flange Assembly ID Weld....................................................................................... C-4
Figure C-4 Surface of Deposit Particle that Faced Water Flow (Left) and Adhered to Pipe
Wall (Right) ....................................................................................................................... C-5
Figure C-5 EDS Spectra of White Deposit Taken from Pipe ID ............................................... C-6
Figure C-6 EDS Spectra of Deposit Removed from Weld Root................................................ C-7
Figure C-7 EDS Spectra of Deposit Removed from Weld Root................................................ C-7
Figure D-1 Outlet Nozzle and Shell as Received from Callaway .............................................. D-2
Figure D-2 Outlet Nozzle ID showing the Black Adherent Deposit and a Patch of Gray
Loose Deposit ................................................................................................................... D-3
Figure D-3 Shell ID Illustrating Where Two Specimens were Previously Removed for
Analysis by Callaway; Black Lines Indicate Locations of Additional Cracks ..................... D-3
Figure D-4 Loose Powdery Deposit Scraped from ID of Outlet Nozzle (65X)........................... D-5
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Figure D-5 Dye Penetrant Test Indications Showing Cracks Initiating in the Root Extra
Pass .................................................................................................................................. D-6
Figure D-6 Collage of Magnified Crack Through the Extra Root Pass of the Shell ID
(Each Photo 50X).............................................................................................................. D-7
Figure D-7 Photomicrograph Showing Intergranular Progression at the Tip of the Crack
Extending into the Shell Base Metal (250X)...................................................................... D-7
Figure D-8 SEM Photo Showing the Oxide Build-up at the Initiation of the Shell SCC and
the Corresponding EDS .................................................................................................... D-8
Figure D-9 SEM Photo of the Oxide Within the Shell ID Crack and the Corresponding
EDS................................................................................................................................... D-8
Figure D-10 SEM Photo of the Crack Through Porosity Found at the Interface of the
Shell ID and Extra Weld Pass and the Corresponding EDS ............................................. D-9
Figure D-11 Cross Sectioning on One of the Shell ID Cracks was Conducted to
Investigate the Crack Path. This Photograph Reveals the Sectioning Location
Employed to Prepare the Metallographic Samples. The Saw Cut Through the Crack
and Through a Plane of the Nozzle to Shell Fillet Weld on the Under Side of the
Sample. ........................................................................................................................... D-10
Figure D-12 Photograph of Crack Broken Open to Reveal Fracture Surface; the Dark
Area is the SCC and the Shiny Area is the Fresh Fracture Resultant from Forcing
the Crack Open ............................................................................................................... D-10
Figure D-13 Fracture Surface of the SCC Showing Signs of Intergranular Propagation;
Fracture Morphology Difficult to Characterize Due to Heavy Oxide Deposits on the
Surface............................................................................................................................ D-11
Figure D-14 SEM Photograph of Bi-pyramid Oxides Found on the Fracture Surface ............ D-11
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LIST OF TABLES
Table 1-1 Forced and Scheduled Outages and Deratings Caused by Closed Cooling
Water System Components in Nuclear Units for the Years 1991-2000; 126 Units
[75] .....................................................................................................................................1-5
Table 1-2 Forced and Scheduled Outages and Deratings Caused by Closed Cooling
Water System Components in Fossil Units for the Years 1991 – 2000; 1577 Units
[75] .....................................................................................................................................1-5
Table 1-3 Material Composition (%) of A106 Gr. B, A105, and ER70S-2 – as Shown in
the Material Specifications [98, 99] and Test Reports........................................................1-8
Table 1-4 Mechanical Properties of A106 Grade B, A105, and ER70S-2 – As Shown in
the Material Specifications [98, 99] and Material Test Reports ..........................................1-8
Table 1-5 EPRI: Corrosion Inhibitors – Typical Control Ranges for Systems with
Demineralized Water Makeup and Low Leakage [20, 21]................................................1-10
Table 1-6 Recommended Impurity Limits for Various Closed Cooling Water System
Water Treatments [21] .....................................................................................................1-11
Table 1-7 VGB Recommended Properties of Circulating Waters in Closed-Circuit
Cooling Systems [22] .......................................................................................................1-11
Table 1-8 Discharge Limits and Toxicity for Closed Cooling Water System Chemicals ..........1-15
Table 2-1 Summary of Data Compiled from Survey, Metallurgical Reports, and Literature
for Units Experiencing SCC Leaks; Shaded Cells Illustrate Similarities Among Units
Experiencing SCC; All Units are PWRs Except Cooper.....................................................2-2
Table 2-2 Summary of Data Compiled from Survey, Metallurgical Reports, and Literature
for Units Not Experiencing Leaks due to SCC ...................................................................2-3
Table 2-3 Characteristics of CCW Systems in Units Experiencing SCC ...................................2-5
Table 2-4 Diagnostic Parameters for Salem’s CCW System [19] ..............................................2-6
Table 2-5 CCW Corrosion Coupon Rate Guidelines [20] ..........................................................2-7
Table 3-1 Summary of Location of Leaks and Their Relationship to the Weld for Units
Experiencing SCC [1-18]....................................................................................................3-5
Table 3-2 Features of Crack Initiation and Propagation ............................................................3-6
Table 4-1 Summary of Results of Cyclic Potentiodynamic Polarization and Slow Strain
Rate Tests on A106 Grade B Test Specimens ..................................................................4-1
Table 4-2 Test Matrix for Cyclic Potentiodynamic Polarization Tests (All Solutions
Aerated, Made using Deionized Water) ...........................................................................4-10
Table 4-3 Summary of Results of the Cyclic Polarization Tests ..............................................4-10
Table 4-4 Results of Galvanic Test..........................................................................................4-18
Table 4-5 Environments Used for Slow Strain Rate Tests [1]..................................................4-19
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Table 4-6 Slow Strain Rate Tests in Air at 145 F (63 C) for the Three Sample Materials
[1] .....................................................................................................................................4-21
Table 4-7 Slow Strain Rate Tests in 1994 Chemistry (300 ppm Molybdate, 7 ppm TTA,
pH 8.5, Aerated) for Sample B (No Service, No PWHT) [1] .............................................4-22
Table 4-8 Slow Strain Rate Tests in 2001 Chemistry (500 ppm Molybdate, 17.5 ppm
1
TTA, pH 9.5, Aerated) for Sample A (Service + PWHT ) [1] ............................................4-22
Table 4-9 Slow Strain Rate Tests in 2001 Chemistry (500 ppm Molybdate, 17.5 ppm
TTA, pH 9.5, Aerated) and 2001 Chemistry without TTA for Sample C (No Service +
PWHT) [1] ........................................................................................................................4-23
Table 4-10 Concentration of Nitrite and Nitrate in Solution Before and After 10 Days
o o
Exposure to Air at to 170 F (77 C) ...................................................................................4-25
1
Table 5-1 Comparison of Units With and Without Leaks ; % Based on # of Units
Providing Data for Given Parameter ..................................................................................5-3
Table 5-2 Characteristics of CCW Systems in the 14 Units Experiencing SCC (13 PWRs,
1 BWR)...............................................................................................................................5-4
Table B-1 pH Measured at Various Locations on Pipe Samples .............................................. B-7
Table B-2 Magnetic Properties and Particle Size and Color of Deposits ................................ B-10
Table B-3 EDS Analysis of Selected Deposit Samples .......................................................... B-11
Table B-4 Average Hardness Measurements for Weld Metal, HAZ, and Base Metal............. B-15
Table C-1 Chronology of Changes in WCNOC CCW Chemistry [2] ......................................... C-2
Table C-2 Magnetic Properties and Particle Size and Color of Deposits.................................. C-5
Table D-1 Outlet Nozzle, Shell, and Weld Filler Material .......................................................... D-1
Table D-2 Cracks Identified Near Shell to Outlet Nozzle Weld ................................................. D-4
Table D-3 pH Measured at Various Locations on Pipe Samples .............................................. D-4
Table D-4 Magnetic Properties and Particle Size and Color of Deposits.................................. D-5
Table D-5 Average Hardness Measurements for Weld Metal, HAZ, and Base Metal .............. D-6
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1
INTRODUCTION
This report presents results of the EPRI project, “Stress Corrosion Cracking (SCC) in Closed
Cooling Water (CCW) Systems”*. The project was an investigation of the stress corrosion
cracking that has been found in component cooling water systems in carbon steel piping and
piping welds in 13 PWR units and 1 BWR unit.
There were several goals for this project. The first was to gather as much information about the
specifics of the SCC in these systems including documented cases and any technical information
or forensic work associated with each case. The second goal was to provide the reader with a
general understanding of how SCC manifests itself in these materials so that a non-metallurgist/
corrosion engineer could gain some fundamental understanding of the SCC phenomenon and
better understand the content of the report. The third goal was to perform limited corrosion
testing to provide data that might reveal any obvious factors associated with the SCC and also to
supply foundational information relative to some of the chemical environments in which the
SCC is occurring. Metallurgical investigations of SCC were performed for three Repair
Replacement Application Center (RRAC) members who were currently dealing with this
problem to provide any recommendations or engineering solutions, where applicable, for repair
or replacement activities. Through this approach, the final goal was to make utilities aware of the
problem so that additional research could be done to address the specific chemical aspect of the
attack and attempt to develop a remedy to prevent a widespread problem.
General information about CCW system design and operation and the water treatment chemicals
used can be found in Chapter 1. Chapter 2 summarizes the results of a survey conducted to
determine how widespread the SCC problem is. The mechanisms of SCC initiation and
propagation are discussed in Chapter 3. Chapter 4 presents the results of laboratory testing
performed specifically for this project and summarizes previous work. Chapter 5 presents results
of the root cause analyses conducted and Chapter 6 discusses engineering solutions. Methods for
detecting stress corrosion cracking, inspection methods, and maintenance issues are described in
Chapter 7. Chapter 8 summarizes the conclusions made during this project, provides
recommendations for further actions, and lists areas where more information is needed.
References are provided in Chapter 9 and are organized into the following categories: plant
specific [1-19], cooling water chemistry [20-32], corrosion inhibitors [33-55], microbiologically
influenced corrosion (MIC) [57-61], general [62-75], stress corrosion cracking [76-97], and
standards and test procedures [98-109].
The carbon steel piping and vessels used in Closed Cooling Water Systems are generally
resistant to stress corrosion cracking, however, leaks in 13 PWR and 1 BWR units (10% of the
* Closed Cooling Water (CCW) Systems include component cooling water systems, which were the primary focus
of this project.
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143 units surveyed) have been reported and analyzed [Chapter 2, 1-19]. In the previous
investigations, the root causes of the problem had not been determined. In particular, the specific
environmental conditions contributing to the problem were not identified. Besides the obvious
effect of high system stresses, it had been suggested that the SCC may be associated with nitrates
and biological activity, aerated systems, elevated temperature, low pH, insufficient molybdate
concentrations, the use of tolyltriazole, and the presence of crevices [2, 6, 19]. Most cases of
SCC have been found because of leaks. It is not known how many actual cases of SCC there are
because most of these systems are Class 3 and if a defect/leak is found it is cut out and
replaced/repaired during the next outage and no forensic examinations are conducted. Others are
not detected because of limited inspections for cracks that are not through-wall and therefore go
undetected until they cause a leak. Many of the leaks have been found in the letdown heat
exchanger shell and associated piping (Figure 1-1 to Figure 1-3) [1-18]. SCC was found in
welds, heat affected zone (HAZ), and in the base metal. After a leak was found in one unit, 88
welds were examined using ultrasonic testing. Of those, 34 (39%) showed reportable indications
and 41 welds were replaced (some welds were replaced to reduce radiation exposure) [7]. All of
the welds that showed reportable indications were located downstream of the letdown heat
exchanger.
Figure 1-1
Crack Locations – Horizontal Letdown Heat Exchangers; Compiled from Several Units
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Figure 1-2
Letdown Heat Exchanger Leak in a Longitudinal Seam Weld; A Tube Support Plate is
Located Directly Behind the Weld on the Inside of the Shell
Figure 1-3
Examples of Letdown Heat Exchanger Outlet Piping Crack Locations at One PWR Unit [2]
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Root Causes of the Cracking
Root cause analysis of the SCC problem had been attempted in several previous investigations
[1-18] and SCC of carbon steel is discussed in general corrosion literature [62-69, 76-96].
However, besides the obvious qualitative effects of material and stress, there are little data usable
in design, failure analysis, and the root cause analysis and there are no data on the effects of
corrosion inhibitors on low temperature SCC of carbon steel. Therefore, it was decided to derive
the environmental root causes from a worldwide survey (Chapter 2) and, wherever possible,
support them with experimental data.
Stress corrosion of carbon steel welds is one of the main industry-wide problems. Over 30% of
inspected deaerators [71, 72], wet steam and slightly superheated steam piping, blowdown flash
tanks, boiler drums [73], and PWR steam generator shells, all experienced SCC. This is contrary
to some of the statements by the investigators of CCW system cracking [6].
Several new effects and lack of basic knowledge were uncovered during this project, which
should be considered:
• There are little data on SCC of carbon steel vs. inhibitors and vs. MIC
• The statistics on SCC in CCW systems is based only on through wall cracks and leaks
• Socket welds can be prone to misalignment resulting in high system bending stresses
• Molybdate may not be an effective inhibitor at high temperatures [42, 48] and should not be
used without an oxidizing agent, such as oxygen or nitrite
• There are no data on NO2 to NO3 decomposition (except for bacterial) and the effects of
nitrite/nitrate mixtures on SCC
• Commercial corrosion inhibitors can have other additives and impurities (NaOH, H2SO4, etc.)
• Several azoles can cause mutations of microorganisms [55]
• CCW system scale can be comprised of numerous metal oxides, including copper oxide,
which, as in other cases, could significantly influence the SCC
• The effects of welds on SCC, including the use of a very low carbon weld rod, stress
concentration, the difference of yield strength between weld and base metal, and crevices
created by socket welds and backing ring, are not known
NERC Statistics
Data collected by the North American Electric Reliability Council (NERC) for 126 nuclear units
between 1991 and 2000 show that CCW components were responsible for 70 forced and
scheduled outages and deratings (Table 1-1) [75]. Fifty-six of these incidents occurred between
the years 1996 and 2000. CCW piping leaks would be included under “Other Problems”. Data
for CCW systems in fossil units are provided for comparison (Table 1-2).
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Table 1-1
Forced and Scheduled Outages and Deratings Caused by Closed Cooling Water System
Components in Nuclear Units for the Years 1991-2000; 126 Units [75]
Total Total MWh Losses

Component/Problem MWh/Unit-Year* MWh/Outage
Occurrences for All Units
Pumps 2 17,936 15.2 8,945
Valves 1 590 0.5 574
Heat Exchangers 8 25,724 21.8 3,221

Other Problems 59 601,800 510.0 10,202
Total 70 646,050 547.5
* - Total Number of Unit-Years = 1180
Table 1-2
Forced and Scheduled Outages and Deratings Caused by Closed Cooling Water System
Components in Fossil Units for the Years 1991 – 2000; 1577 Units [75]
Total Total MWh Losses MWh/ MWh/

Component/Problem
Occurrences for All Units Unit-Year* Outage
Pumps 85 418,110 30.0 4,918

Piping 60 301,039 21.6 5,024
Valves 22 54,354 3.9 2,467
Heat Exchangers 218 636,921 45.7 2,919
System Fouling 19 139,370 10.0 7,344
Other Problems 185 918,448 65.9 4,967
Total 589 2,468,242 177.1
* - Total Number of Unit-Years = 13,937
Closed Cooling Water System Design
In nuclear plants, Closed Cooling Water Systems are designed to remove heat from heat
exchangers, pumps, and other systems. Figure 1-4 illustrates a typical CCW system. Cooling
water is pumped through these units in parallel flow circuits, removes heat from the various
components, and flows to the cooling heat exchanger, which is cooled by the service water.
Some CCW loops serve as an intermediate system between the reactor coolant system and the
service water system. This double barrier arrangement reduces the probability of leakage of high-
pressure, potentially radioactive coolant to the service water system.
There is usually a shared tank, called a surge tank, for the redundant sub-systems used as a
makeup supply if there is not enough water in the system and/or to handle a surge caused by
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fluctuations in water volume due to changes in temperature. Because of this, many of these
systems are not isolated from air ingress.
Figure 1-4
Typical Closed Cooling Water System [20]
Within a power plant, there are many closed water systems, including:
• Component Cooling Water System
• Turbine Building Closed Cooling Water System
• Emergency Diesel Generating Cooling Water System
• Safety Chilled Water System
• Non-Safety Chilled Water System
This project primarily focused on the component cooling water systems. In BWR plant designs,
the component cooling water system may be separate for each building: Turbine Building
Component Cooling Water and Reactor Building Component Cooling Water. In other plant
designs, such as the Westinghouse PWR, the component cooling water system may be
considered as one, regardless of where the cooling occurs.
PWR Component Cooling Water Systems cool a variety of equipment, including:

• Residual heat exchangers
• Reactor coolant pump motor bearings and thermal barriers
• Letdown heat exchanger
• Excess letdown heat exchanger
• Seal water heat exchangers
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• Spent fuel pit heat exchangers
• Sample heat exchangers
• Boric acid evaporator condenser
• Reactor vessel support cooling
• Residual heat removal pumps
• Safety injection pumps
• Charging pumps
• Waste gas compressors
• Boric acid evaporator vent condenser
• Boric acid evaporator distillate cooler
The BWR Turbine Building CCW Systems cool heat exchangers for:
• Feedwater Pump Seal Water
• Condensate Pump Seal Water
• Heater Drain Pump Seal Water
Materials
The materials used for the CCW system are a function of design parameters, water chemistry,
and cost. In most plant designs, the piping, heat exchangers tubesheets, channels, and channel
heads are carbon steel or stainless steel. Heat exchanger tube materials are typically a copper
alloy (i.e., admiralty brass or copper-nickel) or a stainless steel. The materials of concern in this
project are welded carbon steel pipes and fittings. Table 1-3 compares the material composition
of A106 Gr. B, A105, and ER70S-2 weld material in a CCW system where SCC occurred and
Table 1-4 compares the mechanical properties of the materials. It should be noted that the weld
metal carbon content is 0.05% and the weld yield strength is significantly higher than the yield
strength of the base metal.
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Table 1-3
Material Composition (%) of A106 Gr. B, A105, and ER70S-2 – as Shown in the Material
Specifications [98, 99] and Test Reports
Material C Mn P S Si Al Ti Zr Cu Ni Cr Mo V Co
ASTM 0.30 0.29- 0.035 0.035 0.10 --- --- --- 0.40 0.40 0.40 0.15 0.08 ---
Standard for max 1.06 max max min max max max max max
A106 Gr. B
A106 B 0.20 0.87 0.006 0.018 0.21 --- --- --- 0.18 0.07 0.04 0.01 0.001 ---
Heat #217554
ASTM 0.35 0.60- 0.040 0.050 0.35 --- --- --- 0.40 0.40 0.30 0.12 0.03 ---
Standard for max 1.051 max max max max max max max max
A105
A105 0.21 1.10 0.008 0.019 0.20 --- --- --- 0.05 0.03 0.06 0.01 0.001 0.01
Heat #8861721
ER70S-2 0.07 0.90- 0.025 0.035 0.40- 0.05- 0.05- 0.02- 0.50 --- --- --- --- ---
Standard max 1.40 max max 0.70 0.15 0.15 0.12 max
ER70S-2 0.05 1.14 0.022 0.014 0.42 0.08 0.08 0.05 0.19 0.02 0.02 <0.01 <0.01 ---
Heat #065627
1 – For each reduction of 0.01 below the specified carbon maximum, an increase of 0.06% manganese
above the specified maximum will be permitted, up to a maximum of 1.35%
Table 1-4
Mechanical Properties of A106 Grade B, A105, and ER70S-2 – As Shown in the Material
Specifications [98, 99] and Material Test Reports
Material Yield Strength Ultimate Tensile Strength

ksi (MPa) ksi (MPa)
Specification Actual Specification Actual
A106 B 35.0 (240) 51.5 (354.8) 60.0 (415) 78.2 (539.2)

Heat #217554 minimum minimum
A105 36.0 (250) 46.9 (323.4) 70.0 (485) 81.0 (558.5)

ER70S-2 60.0 (413) 72.6 (500.6) 72.0 (496) 88.3 (608.8)

(As-Welded)
ER70S-2 60.0 (413) 75.6 (521.3) 72.0 (496) 86.8 (598.5)

(Stress-Relieved*)
* Weldment Stress Relieved at 1125oF (607oC) for 8 hours. Cooling rate 100oF/hr (38oC/hr) to 600oF
(316oC), then air cooled
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Variations in Design
Although most CCW systems share the same basic design, there can be variations including:
• Open to air vs. nitrogen blanketed system
• System materials (copper alloy tubing, titanium, stainless steel)
• Operating temperature
• Flow rates
• Idle (stagnant) heat exchangers
• Low-flow heat exchangers
• Thermal load
• Makeup water purity, source, and deaeration
• Radiation
• Shared heat exchangers
In addition to water-cooled systems, there are some air-cooled CCW systems. There is also at
least one nuclear plant with a “hybrid” design that only operates as a closed loop during normal
operation [20]. Under emergency or shutdown conditions, the flow is diverted through an open
recirculating cooling tower.
Water Chemistry
There are several, very different, guidelines in existence for cooling water systems [20-22, 32].
The water in CCW systems can be either fresh water that is chemically treated to inhibit
corrosion and biological growth, or is high purity demineralized water, to which an oxygen
scavenger may be added. In the 143 units surveyed, high purity demineralized water has been
used.
Historically, carbon steel corrosion control in CCW systems was achieved by adding chromate-
based inhibitors. In addition to being a corrosion inhibitor, chromate had the added advantage of
being toxic to microbiological organisms. Environmental issues led to the decline in the use of
chromate inhibitors in the mid 1980’s. This resulted in the replacement of chromates with other
corrosion inhibitors in many plants. Some plants still successfully use chromate, handling
discharges by purifying them by ion exchange. Other inhibitors (nitrites, molybdates, silicates,
etc.) can achieve comparable inhibition of general corrosion, but also introduce more variables
and they do not inhibit the growth of microbiological organisms. To control MIC and slime
formation, biocides are added.
In 1985, Westinghouse issued chemistry Guidelines [32] and in 1991, they formed a group to
qualify PWR water chemistry, including closed cooling water, by corrosion testing. The group
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eventually disintegrated and utilities assumed their own responsibilities for whatever water
chemistry they wanted to use. It is not clear whether the original Guidelines are still valid.
The EPRI guidelines [20, 21] for various types of CCW water chemistries are summarized in
Table 1-5 and are based on current plant practices and the recommendations of equipment
manufacturers. It should be noted that Revision 1 of the Guidelines [21] supersedes the original
Guidelines [20]. Table 1-6 provides EPRI recommended impurity limits for several different
water treatments. Other impurity limits may need to be added on a site-specific basis.
The properties of circulating waters in closed-circuit cooling systems recommended by VGB

*
PowerTech are given in Table 1-7 [22]. The VGB Guidelines state that chemical additions are
not necessary if the conductivity and pH value are in line with the recommended limits.
However, in large cooling systems with various material combinations, the circulating water
must be treated to prevent corrosion. It is common practice to use alkaline conditioning agents to
establish pH values between 9.0 and 9.5. Commonly used conditioning agents are ammonia and
sodium hydroxide.
In contrast to the EPRI and VGB recommendations, Electricite de France (EdF) has used
trisodium phosphate and a pH between 11.0 and 11.5 in the CCW systems in a total of 58 units at
18 different plants, without any reported problems with SCC in the carbon steel pipes or welds.
Table 1-5
EPRI: Corrosion Inhibitors – Typical Control Ranges for Systems with Demineralized
Water Makeup and Low Leakage [20, 21]
Provides Typical Control pH Control

Inhibitor Comments2
Protection of1 Range (ppm) Range
CrO4 Fe, Cu, Zn, Al, Sol 150 – 300 8.0 – 11.0
NO2 Fe 500 – 1500 8.5 – 11.0
D.O. conditions need to
MoO4 Fe, Al 200 – 1000 9.0 – 11.0
be considered
50 - 1500 NO2
NO2/MoO4 Fe, Al 8.5 – 11.0
160 - 1000 MoO4
8.5 – 9.6 with Cu Dissolved oxygen
Hydrazine Fe, Cu 5 – 50
8.5 – 10.5 if no Cu • 100 ppb
8.5 – 9.5 with Cu Ultra-low D.O. is critical
Carbohydrazide Fe, Cu 5 – 50
8.5 – 10.5 if no Cu for Cu control
TTA/BZT3 Cu 5 – 100 8.5 – 11.0
MBT3 Cu, Sol 5 – 100 8.5 – 11.0
Not for use if pH<7;
20 – 60 above
Silicate Fe, Cu, Al 9.0 – 11.0 forms a fragile film –
background
weak inhibitor
Dissolved oxygen
Pure Water Fe, Cu N/A 5.5 – 8.0
• 200 ppb
1. Fe = ferrous alloys, Cu = copper alloys, Zn = zinc, Al = aluminum, Sol = soft solder (containing Pb, Sn)
2. D.O. = dissolved oxygen
3. TTA = tolyltriazole, BZT = benzotriazole, MBT = mercaptobenzothiazole
* VGB PowerTech is a voluntary association of power (as well as heat generating) utilities in Germany. Its main
objective is joint support and improvement of operational safety, availability, efficiency and environmental
compatibility of power plants both in operation and under construction.
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Table 1-6
Recommended Impurity Limits for Various Closed Cooling Water System Water
Treatments [21]
Limit
Impurity
Chromate Nitrite Molybdate Nitrite/Molybdate Hydrazine Pure Water
Chloride • 10 ppm • 10 ppm • 10 ppm • 10 ppm • 150 ppb • 50 ppb

Fluoride • 10 ppm • 10 ppm • 10 ppm • 10 ppm • 150 ppb • 50 ppb
Sulfate --- --- --- --- • 150 ppb • 50 ppb
Cation --- --- --- --- < 1 µS/cm ---
Conductivity
Conductivity --- Consistent --- --- --- < 2 µS/cm
with nitrite
level
Ammonia --- --- --- --- < 500 ppb ---
Dissolved --- --- --- --- • 100 ppb • 200 ppb
Oxygen
Table 1-7
VGB Recommended Properties of Circulating Waters in Closed-Circuit Cooling Systems
[22]
Parameter Recommendation
Conductivity at 77oF (25oC) (µS/cm) <30
Cation Conductivity at 77oF (25oC) (µS/cm) <5
pH value at 77oF (25oC) >7
Oxygen (ppb) <20
Oil (ppm) <1
Control of Oxygen and Carbon Dioxide
Control of air ingress (O2 + CO2) is achieved by nitrogen blanketing or other protection of
storage and surge tanks in the CCW systems. Additional control of oxygen is achieved with the
use of an oxygen scavenger (hydrazine). According to the survey (Chapter 2), 72% of nuclear
o
units report that they do not control air ingress. At an average operating temperature of 150 F
o
(66 C) (in the units with leaks), the oxygen saturation concentration in the cooling water is 4.1
ppm. However, oxidation of the CCW system materials reduces this concentration to a few
hundred ppb within the piping system.
EPRI [21] only recommends dissolved oxygen levels for CCW systems using hydrazine or pure
water treatments (Table 1-6), VGB [22] recommends that oxygen concentration be less than 20
ppb, and EdF reports that their cooling water is aerated. In order to meet the dissolved oxygen
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limits recommended by VGB, surge tanks must be sealed against ingress of air by means of a
diaphragm or nitrogen blanketing and must be adequately protected against overpressure and
excessive vacuum by means of suitable safety features (vent facility, safety valve, rupture disc,
etc.).
For molybdate treatments, an oxidizing agent, such as oxygen or nitrite, must be present for
effective corrosion inhibition [20].
Control of Suspended Solids
Suspended solids are a cause of fouling in CCW systems. These solids settle on the cooling
system surfaces often being “glued” by microbiological slimes [20, 21]. Foulants originate from
three sources:
• Water-borne foulants from outside the system
• Foulants generated within the system
• Airborne impurities and microorganisms
Both chemical and mechanical methods are used to control fouling. If raw water is used for
makeup, there is a potential for formation of mineral scale that cannot be handled effectively in
the recirculating water with chemical treatment. For mineral scale and other foulants, the
application of chemicals such as dispersants, sludge fluidizers, and surfactants, will not deliver
acceptable results unless side-stream or full-flow filtration is used.
Storage and surge tanks that are not nitrogen blanketed are vented to air, often without filters
attached to the vents. This results in ingestion of airborne dust and microbial, which can
contaminate the system. Airborne chloride is of particular concern in seaside installations.
Corrosion of system materials, particularly carbon steel components, can result in the
introduction of significant quantities of suspended material to the system. Although copper and
copper alloy corrosion may not produce significant levels of suspended solids, the corrosion
products, combined with other impurities, can cause pitting of carbon steel.
There are two types of chemicals that are used for suspended solids control in CCW systems:
dispersants and surfactants. In many CCW systems, one of these could be part of the water
treatment program. Supplementary doses of dispersants or surfactants are usually applied only in
response to an identified or perceived problem. Often more than one technique can be used. It is
important that the foulant first be identified before a dispersant or surfactant is selected [20].
Further R&D is needed to address appropriate limits for suspended solids for incorporation in
EPRI [20, 21].
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Water Treatment Chemicals
In CCW systems, water treatment chemicals are used for:

• Minimizing corrosion
• Controlling microbiological growth
• Controlling the deposition of suspended solids
• Preventing Scale
Corrosion Inhibitors
Corrosion control requires knowledge of the metallurgy of the system, an understanding of the
susceptibility of the metals to corrode under the operating conditions, and an understanding of
the limitations and environmental effects of the specific corrosion inhibitors being applied. In
order for the corrosion inhibitors to be effective, the metal surfaces must be free of deposits.
Corrosion inhibitors act by reducing the flow of electrons on the metal surface. Cathodic
inhibitors reduce the flow of electrons at the cathodic areas; anodic inhibitors reduce the flow of
electrons at the anodic areas. Underfeeding an anodic inhibitor can lead to pitting. Table 1-5
summarizes the commonly used inhibitors and their typical control ranges for systems with
demineralized water makeup and low leakage.
While corrosion inhibitors control general corrosion, their effects on SCC and crevice corrosion
in aerated and deaerated cooling water are not clear. Additional research needs to be conducted
in this area to fully understand how these treatments affect SCC and other forms of corrosion.
Biocides
Hundreds of species of bacteria and algae have been identified in cooling water systems [57-61].
Some of these can cause MIC, such as the sulfur reducing bacteria, and others metabolize water
treatment chemicals such as nitrite, converting it into nitrate. While nitrate is known to promote
SCC in carbon steels, the exact concentration needed is unknown. Increased knowledge into
microbiologically induced conversion of nitrite to nitrate and its affect leading to SCC of carbon
steel is needed so that limits on nitrate can be put in place. In cooling water systems where MIC
or slime formation becomes a problem, biocides must be used. Some azoles and other biocides
can cause mutations of algae and other organisms [55].
Biocides used to control microbiological growth fall into two broad categories: non-oxidizing
and oxidizing. Oxidizing biocides are chemicals whose effectiveness depends upon their ability
to oxidize, and therefore destroy organic material. Oxidizing biocides are not frequently used in
CCW systems. A chemical that is not an oxidizing agent but is toxic to one or more classes of
microorganisms (and in some cases macroogranisms) is classified as a non-oxidizing biocide.
There are many different types used, each with certain limitations. Non-oxidizing biocides are
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chemicals that kill organisms via a metabolic mechanism, cell transpiration or
ingestion/digestion disruption, suffocation, starvation, poisoning, or trauma.
In many cases, it is necessary to use more than one non-oxidizing biocide in a CCW system. This
is because a specific biocide may be more effective for one type of organism than another. The
more resistant organism might continue to grow in spite of biocide application. The use of a
second biocide on an alternating basis helps prevent the establishment of resistant organisms.
Non-oxidizing biocides must be used with care. After a biocide is added, the active portion
eventually degrades and loses effectiveness. An organic molecule remains that can then become
a nutrient for bacteria or can add to CO2 loading in the CCW system.
Deposit Inhibitors
Deposit inhibitors are low molecular weight polymers that help keep particulate material in
suspension. They also prevent suspended solids from settling on heat transfer surfaces or in low-
flow areas. Although used more often in open recirculating systems, they are used in CCW when
the accumulation of suspended solids is a potential problem. Scale formation is not usually a
problem in CCW systems unless there is excessive system leakage and raw water is used for
makeup.
pH Control
The purpose of pH control is to keep pH in a range where corrosion is minimized and where
treatment chemicals are most effective. These chemicals may include: sodium (or potassium)
hydroxide, sodium bicarbonate, and sodium carbonate.
Additives and Impurities in Water Treatment Chemicals
CCW System water treatment chemicals and biocides are being supplied with additives and
impurities that may be contributing to the stress corrosion cracking problem. For example,
tolyltriazole (TTA) can contain up to 0.5% NaOH and 100 ppm chloride [47] and the
benzotriazole (BZT) supplied by at least one manufacturer contains sulfuric acid. BZT also
contains NaOH [48]. Isothiazolene contains magnesium chloride and nitrate as a stabilizer and
may contain 0.05 to 0.25 ppm of copper. The addition of 1.5 ppm of active isothiazolene will
contribute up to 1.3 ppm chloride and up to 1 ppm sulfate to the water [21]. Methylene
bis(thiocyanate) will contribute 0.75 ppm of sulfate to the cooling water for every 1 ppm of the
biocide added [21]. Adding 1 ppm of 2,2-Dibromo-3-nitrilopropionamide can contribute up to
0.7 ppm of bromide to the water [21].
Handling and Discharge of Closed Cooling Water Treatment Chemicals
During refueling outages, some sections of the CCW system are not needed, and are
subsequently drained for the duration of the outage. Due to the chemicals used to prevent
corrosion and biofouling, the water that is removed from the system cannot be discharged
without treatment (Table 1-8) [54]. Depending upon the chemicals being used, this could vary
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from a simple pH adjustment, to the need to remove large quantities of hazardous chemicals
before discharging.
In systems using chromate, the water must go through dechromation, where the concentration of
chromate is reduced from 15 to 1000 ppm to less than 100 ppb through ion exchange. This
reduces the amount of hazardous waste from thousands of gallons of water to a few cubic feet of
ion exchange resins.
Because of the hazardous nature of many of the cooling water treatment chemicals, special
precautions, such as safety goggles, gloves, boots, and protective clothing, must be taken by
plant personnel responsible for handling these materials.
Table 1-8
Discharge Limits and Toxicity for Closed Cooling Water System Chemicals
Toxicity
Chemical Discharge Limits
(mg/kg - rat LD50)
Chromate Y, 100 ppb* 136, Carcinogen
Phosphate N 5950
Molybdate N 520
Nitrite Y 180
Azoles N 560
Borate N 2660
2,2-Dibromo-3-nitrilopropionamide Y 118
Glutaraldehyde N 2.4
Methylene bis(thiocyanate) Y 81
Isothiazolene Y N
Chlorine Y, 1000 ppb FCR* 90
* - Limit Set by EPA

Y – Discharge is limited, N - Not listed, FCR - Free Chlorine Residual
1-15
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2
PLANT SURVEY
The first step in the project was to conduct an international survey of plants with and without
stress corrosion cracking in order to determine what factors are influencing, causing, or
preventing the SCC in CCW systems. A “Water Chemistry and Stress Corrosion Cracking
Experience” Questionnaire (Appendix A) was sent to all of the U.S. nuclear plants, as well as
plants in Sweden, Japan, Korea, Germany, the United Kingdom, the Czech Republic, and France.
The Questionnaire was also sent to Alstom, GE, Siemens, VGB, and the Moscow Energy
Institute. Data received from the survey responses have been added to the data found in various
reports supplied by the plants [1-19] and is summarized in the tables below. There is full or
partial information for 143 units with 14 units (13 PWRs and 1 BWR) reporting the SCC
problem.
Table 2-1 summarizes all of the data obtained from the survey and reports for units experiencing
stress corrosion cracking. Table 2-2 summarizes the data for the units that have not experienced
any leaks due to SCC. Table 2-3 summarizes the characteristics of the CCW systems in plants
experiencing SCC.
It is clear from the data that there are several, very different, water treatment regimes used
throughout the nuclear industry including chromate (13%), nitrite (17%), molybdate (8%),
phosphate (41%), and just pure water (21%) with and without hydrazine; all with and without
o o
access of air. The average maximum temperature in units with leaks was 150 F (66 C) as
o o
compared to only 122 F (50 C) in units without leaks. Only three units reported that they stress
relieved their carbon steel welds while 14 units reported using backing rings. All of the units use
demineralized water for makeup. Additional statistics based on the results of the survey can be
found in Chapter 5.
In addition to the written survey, Vogtle, Wolf Creek, and Callaway also sent specimens for
further examination by Jonas, Inc. and EPRI. Details of these analyses are provided in Appendix
B for Vogtle, Appendix C for Wolf Creek, and Appendix D for Callaway.
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Table 2-1
Summary of Data Compiled from Survey, Metallurgical Reports, and Literature for Units Experiencing SCC Leaks; Shaded Cells
Illustrate Similarities Among Units Experiencing SCC; All Units are PWRs Except Cooper
Backing Rings
Maximum pH
Minimum pH
Max. Temp.
Hydroxide6
Phosphate
Molybdate
Biological
Hydrazine
Chromate
Max D.O.
Relieved
Activity
Borate
Stress
Azole5
Nitrite
(ppb)
Unit
Relationship
(oF)8
Plant System, Location of Leaks
to Weld
LHX thermal relief line, LHX outlet

Callaway --- 139 N Y N Y N T N T N N 10.0 9.5 Sat7 N At welds
piping, LHX outlet nozzle
1
Catawba 1, 2 140 Y Y N Y B N B N N 11.0 9.0 Sat Y Under deposits, at socket welds Weld material
Weld material, HAZ,
Cook 1, 2 175 Y Y N2 Y B N B N N 10.4 8.7 Sat Y Under backing rings of butt welds
adjacent to HAZ
Weld material, HAZ,
Cooper4 --- Y Y N N N N Sat N Under backing rings of butt welds
adjacent to HAZ
4
Cooper Y N N N N N N N N Sat N
Clinton N Y N N N
Pipe downstream of recycle
evaporator package distillate coolers, Weld material, HAZ,
McGuire 1, 2 150 Y Y N Y B N B N N 9.0 Sat Y
pipe to surge tank, LHX drain line, adjacent to HAZ
LHX shell, pipe from XLHX
T, Pipe nipple off of reactor coolant Appears to be
Sequoyah 1, 2 200 N N N Y N T N N N 9.0 7.0 Sat Y
K pump discharge line outside HAZ
Vogtle 1 137 N Y N3 Y B N B N N 10.0 8.5 Sat Y Turbine building CCW system At or near welds
3 ACCW LHX shell (several leaks),
Vogtle 2 180 N Y Y N Y B N B N N 10.0 8.5 Sat Y Weld material
return line from LHX
Weld material, HAZ,
Wolf Creek 1 175 N N N Y N T N Na N N 11.0 8.0 Sat Y LHX shell, return line from LHX
adjacent to HAZ
1) Catawba changed from using Nitrite to Molybdate in February 2003
2) Cook changed from using Nitrite to Molybdate in 2003; Unit 1 in November 2003 and Unit 2 in June 2003
3) Vogtle changed from using Nitrite to Molybdate in 2003 in the Turbine Building CCW System; Unit 2 in March 2003, Unit 1 in July 2003
4) Changed to pure water treatment in 1980 after observing cracks – new cracks discovered in 1994
5) T - tolyltriazole, B – benzotriazole, N – none
6) T – present in tolyltriazole, B – present in benzotriazole, Na – sodium hydroxide added, K – potassium hydroxide added, N – none
7) Surge tank vented to atmosphere
8) oC = (oF-32)*(5/9)
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Table 2-2
Summary of Data Compiled from Survey, Metallurgical Reports, and Literature for Units Not Experiencing Leaks due to SCC
Max D.O. (ppb)3

Max Temp. (oF)4
Backing Rings
Nitrite (NaNO2)
(TTA or BZT)
Welds Stress
Maximum pH
Minimum pH
Hydroxide2
Phosphate
Potassium
Sodium or
Molybdate
Biological
Hydrazine
(Na2MoO4)
Chromate
(Na2B4O7)
Relieved
Sodium
Activity
(KCrO4)
Borate
Used?
Azole1
(N2H4)
Plant
Unit
Almaraz (Spain) 2 plants N N Y N N N Na N 10.2 10.0 Sat

Byron 1, 2 Y N N T N T N N 10.5 8.5 Sat
Calvert Cliffs 1, 2 N N N N N N N Y 5
Diablo Canyon 130 N N Y Y N T N T N 9.0 8.0 10
E. Fermi 1 Y U N N N N N N N 10.5 8.0 ppb
EdF (18 plants) 58 units 116 N N N N N N Y N 11.5 11.0 Sat
Germany 14 units N N N N N N N Y 10.0 9.0 <50
Hope Creek 1 N N N N N N N N N N 7.0 5.5 Sat
Kansai (Japan) 4 plants N N N N N Y N N 9.7 8.0
Kansai (Japan) 7 plants N N N N N N N N N Y 9.7 8.0 <100
Kori (Korea) 1, 2 N N N N N Y N N 9.5 8.0 N
Kori (Korea) 1, 2 N N N N N N N N Y 9.5 8.0 N
Kori (Korea) 3, 4 Y N N N N Y N N Y 9.5 8.0
Kori (Korea) 3, 4 Y N N N N N N N Y 9.5 8.0
LaSalle 130 N Y Y N N T N T N 10.5 8.5
Millstone 2, 3 Y N N N N N N Y
Nine Mile Pt. 1,2 100 N N N N N N N N N N 6.0 6.0 3000
North Anna 1, 2 120 N N N N N N Y N N N 9.5 8.0
Point Beach 1, 2 N N N N Y N N
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Max D.O. (ppb)3
Max Temp. (oF)4
Backing Rings
Nitrite (NaNO2)
(TTA or BZT)
Welds Stress
Maximum pH
Minimum pH
Hydroxide2
Phosphate
Potassium
Molybdate
Sodium or
Biological
Hydrazine
(Na2MoO4)
Chromate
(Na2B4O7)
Relieved
Sodium
Activity
(KCrO4)
Borate
Used?
Azole1
(N2H4)
Plant
Unit
Palo Verde 1, 2, 3 105 Y N Y T N T N 10.0 8.5 50
Quad Cities 1, 2 100 Y Y N N T N T N N Sat
Ringhals
(Sweden) 2 N N N N N Y N N 10.5 8.5
Ringhals
(Sweden) 3 N N Y N T N T N N 10.5 8.5 Sat
Ringhals
(Sweden) 4 N N Y N T N T N N 10.5 8.5 Sat
Robinson 2 N N N N Y N N
Salem 1, 2 125 N N N N N N Y Y N N 9.0 8.0 Sat
San Onofre 2, 3 113 N N Y N Y T N T N N 9.5 8.9 N2
Surry 1, 2 N N N N Y N N N
Susquehanah 1 190 N Y Y N Y T N T N 10.5 8.5 ppb
Susquehanah 2 190 N Y Y N Y T N T N 10.5 10.5 ppb
Three Mile Island 1 Y Y N N N T N
Vandellos (Spain) N N N N N N N Y N 12.0 11.5 Sat
VGB (Germany) N N N N N Y N N 7 20
1) T - tolyltriazole, B – benzotriazole, N – none
2) T – present in tolyltriazole, B – present in benzotriazole, Na – sodium hydroxide added, K – potassium hydroxide added, N –
none
3) Sat = Surge tank vented to atmosphere
4) oC = (oF-32)*(5/9)oC = (oF-32)*(5/9)
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Table 2-3
Characteristics of CCW Systems in Units Experiencing SCC
# of Units Not # of Units

Parameter # of Units Reporting
Reporting Unknown
Temperature above 130oF (54oC) 12 0 2
Use of Aerated Water 13 0 2
Use of Sodium Nitrite1 9 6 0
Use of an Azole (TTA or BZT)1 12 1 2
Use of Borate1 8 5 2
Evidence of Biological Activity 11 2 1
Use of Backing Rings 9 3 2
PWR 13 1 0
1 - Cooper changed water chemistry in 1980 and is therefore counted twice (once with and once without).
Cooper experienced cracking under both water chemistries.
Salem and Hope Creek Nuclear Generating Stations
On February 24, 2004, Jonas, Inc. had the opportunity to meet with system engineers and
metallurgists from the Salem (PWR) and Hope Creek (BWR) Nuclear Generating Stations in
Hancock’s Bridge, NJ. The CCW System design, chemistry, and operation at both plants were
discussed and drawings reviewed.
In 1993, a 3” pipe for Salem’s reactor coolant pump cooling water began leaking inside the
containment area. Thirty feet of the straight pipe was removed and examined. Long grooves and
1/8” to 1/4” diameter holes were found in the 6 o’clock position along the entire length of the
pipe section. No root cause was determined for the failure but it does not appear to be related to
the SCC found at other plants. The section of pipe was replaced with the same material and has
remained leak free. Neither Salem nor Hope Creek report ever having any other leaks except at
valves and gaskets.
Although neither plant has had any SCC problems, the two plants have different approaches to
CCW system water chemistry control. Salem uses demineralized water with chromate as a
corrosion inhibitor and potassium hydroxide to adjust the system pH, while Hope Creek only
uses demineralized water with no further chemical additions. The chemistry limits for Salem are
shown in Table 2-4.
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Table 2-4
Diagnostic Parameters for Salem’s CCW System [19]
Sample Spec. Control

Parameter1 Remarks
Frequency2 Limit3 Limit3
175 - 2254
Chromate (ppm) W N/A None
• 11005
8.0 – 9.04
pH @ 25oC W N/A None
8.0 – 9.55
Specific Conductivity/Chromate Ratio M N/A N/A None
Chloride (ppb) M <1000 N/A Diagnostic
Fluoride (ppb) M <1000 N/A Diagnostic
Specific Conductivity @ 25oC (µS/cm) W N/A >3504 None
Diagnostic confirmation
Sodium (ppb) W <750 N/A
of river water inleakage
Diagnostic confirmation
Gamma Isotopic (µCi/ml) W N/A N/A of RCS inleakage.
80-10 Requirement
Iron (ppb) M •1000 N/A None
Copper (ppb) M •1000 N/A None
Only performed during

Nickel (ppb) W N/A N/A
dechromated periods
1) All samples are grab samples

2) W – weekly, M – monthly
3) N/A – not applicable
4) For normal operation except when dechromated
5) For passivation activities
Because of the safety concerns with chromate and EPA regulations that do not allow chromate to
be used on any new systems, the elimination of chromate from the CCW treatment regime was
considered. However, it was recommended by the utility's metallurgists that plant systems
already using chromate water chemistry not switch to another type of water chemistry. This was
recommended because chromate forms a passivating oxide layer on the carbon steel, which
needs to be preserved. If this layer is damaged, galvanic corrosion will occur at the point where
the layer was compromised if chromate is not present in the water to reestablish the oxide layer.
Neither plant uses any type of layup in the CCW system during short plant outages (less than 90
days). During refueling outages at Salem (every 18 months), some sections of the CCW system
are drained and all of the water is dechromated using ion exchange resin and then recirculated to
rinse the system. The water is then rechromated and added back to the system.
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Makeup water for the CCW system is fed from the demineralized water tanks. At Salem, these
tanks have floating roofs to limit the amount of contact air has with the water. However, the
demineralized water tanks at Hope Creek and the surge tanks at both plants are open to the
atmosphere.
During operation, system operators walk-down the CCW system every day to check for leaks
and other problems. Radiation monitors and sump pump run times are the only other leak
indicators used. There are no weld inspections because of the potential for many false
indications, all of which would have to be investigated.
Salem does not utilize a corrosion coupon system. The Salem corrosion-monitoring program
involves the trending of the system chemistry data and making recommendations on necessary
courses of action.
Corrosion Testing at Hope Creek
Hope Creek has been monitoring CCW system material corrosion rates with corrosion coupons
since 1987. Corrosion test data from 1987 indicated that the carbon steel corrosion rate for the
CCW systems was 0.85 mil/yr (21.6 µm/yr) before the installation of demineralizers. The latest
corrosion coupon data report for the Safety and Turbine Auxiliaries Cooling (STACS) system for
the first quarter of 2003 indicated that the carbon steel corrosion rate was 0.03 mil/yr (0.76
µm/yr) and corrosion rate for copper was 0.25 mil/yr (6.35 µm/yr) [19].
According to EPRI’s Cooling Water Guideline [20], it should be possible to achieve the
corrosion rates on corrosion coupons shown in Table 2-5 when adequate inhibitor levels, pH
levels, and microbiological control are maintained in the system. Hope Creek has been able to
achieve an “excellent” carbon steel corrosion rate and a “fair” copper alloy corrosion rate,
without needing to add any chemicals to the CCW system.
Table 2-5
CCW Corrosion Coupon Rate Guidelines [20]
Condition Carbon Steel Copper Alloy Stainless Steel

mil/yr (µm/yr) mil/yr (µm/yr) mil/yr (µm/yr)
Excellent <0.2 (<5.1) --- ---
Good 0.2 – 0.5 (5.1 – 12.7) <0.1 (<2.5) <0.1 (<2.5)
Fair 0.5 – 1.0 (12.7 – 25.4) 0.1 – 0.3 (2.5 – 7.6) ---
Poor >1.0 (>25.4) >0.3 (>7.6) >0.1 (>2.5)
2-7
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3
SCC INITIATION AND PROPAGATION
Basics of Stress Corrosion Cracking
Stress corrosion cracking (SCC) is defined as cracking of a metal produced by the combined
action of corrosion and tensile stress (residual or applied) [64]. SCC is a form of slow crack
growth that occurs when a susceptible metal is stressed in tension in a specific corrosive
environment (Figure 3-1). All alloys are susceptible to SCC in at least one environment but SCC
does not occur in all environments, nor does an environment that induces SCC in one alloy
necessarily induce it in another alloy. SCC may be initiated if the anodic reaction is stimulated
by the tensile stress (residual or applied) at specific sites on the metal surface. For instance, the
application of stress may be accompanied by the emergence of a slip band at the metal surface
that ruptures the protective oxide film and exposes the underlying metal. Repeated metal
dissolution, film repair, and film rupture in this region can lead to the slow propagation of a
stress corrosion crack. This mechanism is called stress induced pitting [95] and may be the SCC
initiation mechanism.
Figure 3-1
SCC Occurs When a Tensile Stress is Applied to a Susceptible Metal in a Specific
Corrosive Environment
Cracks may propagate across grains or along the grain boundaries of a metal, thus giving rise to
two broad classes of SCC: transgranular stress corrosion cracking (TGSCC) and intergranular
stress corrosion cracking (IGSCC). Cracks may prefer to propagate along grain boundaries
because of differences in chemical composition at, or immediately adjacent to, the grain
boundary. Whether cracks are intergranular or transgranular, they always tend to propagate
roughly perpendicular to the applied or residual tensile stress. On a microscopic scale, the path is
controlled to some extent by the local microstructure. Cracks may be either branched or not
branched, but branched SCC is more common.
3-1
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Carbon steels and carbon steel welds are susceptible to SCC in a number of environments [63,
67, 68, 76-96]. The shaded areas shown in Figure 3-2 represent the combinations of corrosion
potential and pH that give rise to SCC in the type of environment indicated. All of these
environments can exist in CCW systems. At high tensile stresses, such as residual weld stresses,
SCC can occur even in pure, low-oxygen water. It is believed that SCC can initiate at stresses
higher than ~0.5 times yield strength. Cracks may initiate by stress induced pitting where there is
a competition between a fracture of the protective oxide film due to local plasticity (emergence
of slip bands) and repassivation [95]. Stress corrosion crack propagation rate is constant over a
range of stress intensity factors (during so-called Stage II cracking) for carbon steels with similar
yield strength and specific environments and temperatures. The propagation rate increases
-5 o -4
exponentially with temperature (for pure low oxygen water: 2x10 mm/hr at 100 C and 10
o
mm/hr at 150 C). The crack growth rate during the steady Stage II follows the equation:
o
Log R (mm/hr) = A + B/T( K)
According to the Nuclear Regulatory Commission, for low yield strength carbon steels, the
constants are: A = 1.447 and B = -2.115. The crack growth rate is about three times higher for
mildly corrosive environments and several orders of magnitude higher in aggressive
environments, such as concentrated NaOH.
Figure 3-2
Environmental Conditions (Electrochemical Potential and pH) Causing Stress Corrosion
Cracking of Carbon Steels [63] (Courtesy of ASM International)
The temperature and concentration limits for SCC susceptibility are fairly well defined based on
field experience [76]. Figure 3-3 indicates that with even for small concentrations of NaOH,
o o
carbon steel welds in the temperature range of 175 to 212 F (80-100 C) should receive post weld
3-2
11924595
heat treatment. Figure 3-4 shows the dependence crack velocity has on stress intensity (KI) for
carbon steel.
Figure 3-3
Temperature and Concentration Limits for Stress Corrosion Cracking Susceptibility for
Carbon Steel in NaOH [76] (Courtesy of NACE International)
Figure 3-4
Stress Corrosion Crack Growth Rate as a Function of Applied Stress Intensity (KI) for
Normalized Low-Carbon Steel in 208oF (98oC) 4N Ammonium Nitrate Solution [84]
(Courtesy of NACE International)
3-3
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Industry Experience
Stress corrosion of carbon steel welds is an industry wide generic problem occurring in about
30% of deaerators, in low temperature steam piping, in various pressure vessels, boiler drums,
PWR steam generator shells, and elsewhere [64, 70-73]. It occurs in a variety of environments,
such as those shown in Figure 3-2, and in amine solutions, pure water, and wet steam. Carbon
steel welds are also susceptible to high- and low-cycle corrosion fatigue. In both pure water and
in NaOH solutions, an increase in temperature and/or an increase in yield strength cause the SCC
crack initiation time to be shorter and the crack propagation rate to increase.
In low-carbon steels, carbon content has a strong effect on susceptibility to nitrate-induced

cracking. Initiation of SCC is minimized when carbon content is lower than 0.001% (extremely
low) or higher than about 0.18% [63]. The threshold stress for cracking is low for carbon
contents of ~0.05%, but increases at carbon contents above ~0.10% (Figure 3-5). Accordingly,
decarburization of steel surfaces can lead to cracking in nitrate solutions. This effect of carbon
content applies primarily to crack initiation. A stress-corrosion crack that starts in a decarburized
surface layer will continue to propagate into the higher-carbon interior region of the metal. Tests
performed on notched specimens have shown that pre-existing cracks will propagate in steels of
high carbon content [63].
Figure 3-5
Effect of Carbon Content on Threshold Stress for SCC in Nitrate Solutions [66]
3-4
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Crack Initiation and Propagation of Selected Welds in Units Experiencing
Leaks
Table 3-1 summarizes the locations of leaks and their relationship to a weld and Table 3-2
summarizes the features of the crack initiation and propagation identified as part of the survey
(Chapter 2) and review of metallurgical reports [1-18].
Table 3-1
Summary of Location of Leaks and Their Relationship to the Weld for Units Experiencing
SCC [1-18]
Plant Location of Leaks Relationship to Weld
LHX thermal relief line, LHX outlet piping, LHX

Callaway At welds
outlet nozzle
Catawba Under deposits, at socket welds Weld material
Cook Under backing rings of butt welds Weld material, HAZ, adjacent to HAZ
Cooper Under backing rings of butt welds Weld material, HAZ, adjacent to HAZ
Pipe downstream of recycle evaporator package

McGuire distillate coolers, pipe to surge tank, LHX drain Weld material, HAZ, adjacent to HAZ
line, LHX shell, pipe from XLHX
Pipe nipple in recirculation line off of reactor

Sequoyah Appears to be outside HAZ
coolant pump discharge line
Vogtle 1 Turbine building CCW system At or near welds
Vogtle 2 LHX shell (several leaks), return line from LHX Weld material
Wolf Creek LHX shell, return line from LHX Weld material, HAZ, adjacent to HAZ
LHX – Letdown Heat Exchanger

XLHX – Excess Letdown Heat Exchanger
HAZ – Heat Affected Zone
3-5
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Table 3-2
Features of Crack Initiation and Propagation
Crack Pipe and Weld

Plant Crack Initiation Crack Surface Reference
Propagation Surface
Extra weld pass Intergranular, Deposits, a few Oxides, Appendix D

around the nozzle interdendritic small pits deposits
Callaway section fillet weld
root on the ID of
the shell
Deposits at socket [6]

Catawba weld crevices,
biological activity
Cracks generally Intergranular Under backing [6]

Cook associated with rings or in socket
pitting welds
Pits formed under Intergranular Possible biological [6]

Cooper
backing rings activity
Deposits Intergranular Deposits and [6]

McGuire
biological activity
Intergranular attack Intergranular Deposits Oxides, [17]

deposits, high
Sequoyah concentration
of molybdate at
crack tip
Lack of penetration Intergranular, Deposits Oxides, Appendix B

of the root pass of interdendritic deposits
Vogtle 2 the socket weld,
lack of fusion Some
transgranular
Intergranular Intergranular Some pits, some Significant [2],

attack, some deposits amount of Appendix C
Wolf Creek
cracks initiating molybdenum
from pits
Figure 3-6 compares the estimated crack growth rates for several plants experiencing stress
corrosion cracking to an earlier compilation of data for carbon steel in three different types of
environments. The crack growth rates were estimated by dividing the thickness of the failed
component by the estimated average number of operating hours from the time the component
was installed until the time the leak was discovered.
The time to through-wall cracking ranges from 4 years to 19 years. In the case of Sequoyah,
crack initiation was found in the replacement piping in just three years. The average crack
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propagation rates (not considering the crack initiation time) range from 1.2x10-7 in/hr (3.0x10-6
mm/hr) to 7.1x10-6 in/hr (1.8x10-4 mm/hr).
The figure shows that the units with SCC either have a corrosive environment or the weld and
heat affected zone are having a strong influence on the cracking. The differences in the crack
propagation rates may be due to differences in water treatment, weld size, or weld geometry.
Figure 3-6
Estimated Crack Propagation Rate vs. Temperature for Units Experiencing SCC as
Compared to Typical Rates Experienced in Three Different Types of Environments
3-7
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4
LABORATORY TESTING
Presented in this Chapter are the results of cyclic potentiodynamic polarization tests, a galvanic
corrosion test, and a nitrite stability test. These tests were used to determine the effects of various
CCW system chemical environments on carbon steel. In addition, Wolf Creek Nuclear Operating
Corporation provided results of several slow strain rate tests. Results of all these tests are
summarized in Table 4-1, where an indication of possible stress corrosion cracking is also given.
Table 4-1
Summary of Results of Cyclic Potentiodynamic Polarization and Slow Strain Rate Tests on
A106 Grade B Test Specimens
Added Oxygen Temp Type of

Inhibitor pH6 Possible SCC
Impurities1 Conc.2 o
F (oC) Test3
CrO4 (100 to 600 ppm) NA Low 77 (25) CPP No
CrO4 (200 ppm) 150 ppb Cl- NA Low 77 (25) CPP No
CrO4 (200 ppm) 1.5 ppm Cl- NA Low 77 (25) CPP Yes
CrO4 (200 ppm) 1.5 ppm Cl- NA Low 77 (25) CPP Inconclusive - high
1.5 ppm SO42- general corrosion
MoO4 (50 - 500 ppm) NA Sat 77 (25) CPP Yes
MoO4 (500 ppm) 9.5 Sat 145 (63) SSR Yes
MoO4 (200 ppm) NA Low 77 (25) CPP Inconclusive
MoO4 (100 ppm) + TTA (5 - 10 ppm) NA Sat 77 (25) CCP Inconclusive
MoO4 (300 ppm) + TTA (7 ppm) 8.5 Sat 145 (63) SSR Yes
MoO4 (400 ppm) + TTA (50 ppm) 6.0 Sat 170 (77) CCP Inconclusive
MoO4 (500 ppm) + TTA (17.5 ppm) 9.5 Sat 145 (63) SSR Yes
MoO4 (100 ppm) + TTA (10 ppm) NA Low 77 (25) CPP Yes
MoO4 (300 ppm) + NO2 (300 ppm) + 150 ppb Cl- NA Low 77 (25) CPP Yes
TTA (10 ppm)
MoO4 (300 ppm) + NO2 (300 ppm) + 1.5 ppm Cl- NA Low 77 (25) CPP Yes
TTA (10 ppm)
MoO4 (300 ppm) + NO2 (300 ppm) + 1.5 ppm Cl- NA Low 77 (25) CPP Yes
TTA (10 ppm) 1.5 ppm SO42-
MoO4 (100 - 415 ppm) + NA Low 77 (25) CPP Yes
NO2 (100 - 300 ppm)
NO2 (1500 ppm) 6.35 Sat 170 (77) CPP Inconclusive
NO3 (1500 ppm)4, 5 6.37 Sat 170 (77) CPP Inconclusive - high
general corrosion
PO4 (250 ppm) 9.03 Sat 170 (77) CPP No
1. All test solutions were made with deionized water. Several tests had impurities added
2. Sat – Saturated
3. CPP - Cyclic Potentiodynamic Polarization Test, SSR - Slow Strain Rate Test
4. Known stress corrosion cracking promoter
5. An ER70S-2 weld metal specimen also tested in this environment with similar results
6. NA – Not Available
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Cyclic Potentiodynamic Polarization Tests
Electrochemical polarization tests are utilized to determine general corrosion rates as well as
assess the susceptibility of materials to localized corrosion-pitting and stress corrosion cracking,
in different environments.
Test Procedure and Interpretation
The technique used for potentiodynamic polarization tests is described in ASTM G5, “Standard
Reference Test Method for Making Potentiostatic and Potentiodynamic Anodic Polarization
Measurements” and ASTM G61, “Standard Test Method for Conducting Cycle Potentiodynamic
Polarization Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-
Based Alloys”. The test involves the use of a potentiostat to apply voltage to an electrode made
from the material under consideration. The voltage is increased at a continuous rate relative to a
reference electrode while the current between the two electrodes is monitored. Initially, the
voltage is increased in the anodic (noble) direction (forward scan) and once a pre-selected
current or voltage is reached, the voltage scan direction is reversed and progresses in the cathodic
or active direction (reverse scan). The corrosion behavior of the test material is predicted from
the structure of the polarization scan, which is a graph of the potential versus the current density.
The polarization cell that was used in the testing performed as a part of this project is shown in
Figure 4-1. A calomel reference electrode was inserted into a temperature controlled salt bridge,
with the tip of the salt bridge placed approximately 0.08 in. (2 mm) from the surface of the
working electrode (test specimen). The counter electrode was a coil of platinum wire that was
cleaned before each scan. A Gamry Instruments DC105B basic DC corrosion measurement
system, which consisted of a computer based potentiostat, Model PCI4-300, was used for
conducting the measurements. The cylindrical test specimens measured 0.5 inches (12.7 mm)
long and 0.375 inches (9.5 mm) in diameter (Figure 4-2) and were polished using 600 grit paper.
Before exposure, each test specimen was cleaned, degreased, and mounted in an ASTM G5 type
o o
electrode holder (Figure 4-3). The specimen was exposed to the 170 F (77 C) test solution for
two hours followed by a measurement of pH, conductivity, and dissolved oxygen before the
initiation of the scan. Air was sparged through each test solution up to the point where the scan
began and discontinued for the duration of the scan. For each test, a fast scan (17 mV/s) and a
slow scan (0.17 mV/s) was conducted using a fresh test specimen for each scan.
The results of each polarization test were analyzed for corrosion rate using a Tafel analysis of the
data and for corrosion behavior by analyzing the graphical presentation of the data. There are
several features on the potentiodynamic polarization curves that have significance, including the
corrosion potential (Ecorr), regions of active corrosion, regions of passive behavior, hysteresis, and
active to passive transitions.
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Figure 4-1
Cyclic Potentiodynamic Polarization Test Setup
Figure 4-2
An Example of the Test Specimen Used for Both the Cyclic Potentiodynamic Polarization
Test and the Galvanic Corrosion Test (Left – Side View, Middle – Top View, Right – Bottom
View)
Figure 4-3
Test Specimen Installed in Holder
The corrosion potential is the voltage on the forward scan at which the specimen changes from
cathodic to anodic. It is indicated by a large sharp reduction of the current density (several orders
of magnitude). The current density is related to the general corrosion rate for the material. A
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region of passive behavior is where the current density is low and remains constant with
increasing potential. High current density indicates active corrosion. The active to passive
transition is a region of the forward scan above the corrosion potential, where the current density
is reduced and the chemistry of the specimen surface changes from active corrosion to passivity.
Surfaces must undergo an active to passive transition and the metal-environment combination
must display such transitions if the system is to be susceptible to stress corrosion cracking [91-
95]. Each of these regions is illustrated in Figure 4-4.
Figure 4-4
Diagram Illustrating the Features of a Cyclic Potentiodynamic Polarization Curve; the
Active to Passive Transitions are the Regions of Susceptibility to SCC
The hysteresis refers to a feature of the slow scan rate cyclic polarization curve in which the
forward and reverse portions of the scan do not overlay each other. It is created when the current
density during the reverse scan is greater than during the forward scan at the same potential. The
difference is a result of the disruption of the passivation chemistry of the surface by the increase
in potential. The magnitude of the difference between the forward and reverse scans reflects the
ease with which passivation is restored as the potential is decreased back toward the corrosion
potential. The larger the hysteresis, the greater the disruption of surface passivity, the greater the
difficulty in restoring passivity, and therefore, a higher risk of localized corrosion.
A convenient way of anticipating the range of potentials in which stress corrosion cracking
(SCC) may occur is through potentiodynamic polarization curves determined at different sweep
rates. The rationale of this test procedure is that if the potential of an initially film-free surface is
rapidly changed (~1000 mV/min), then the currents passed at the surface will indicate ranges of
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potential at which relatively high anodic activity is likely. The rapid sweep of the potential range
is an effort to minimize film formation.
If the experiment is repeated at a slow rate of potential change (~20 mV/min), allowing filming
to occur, a comparison of the two curves will indicate ranges of potential within which high
anodic activity in the film-free condition reduces to insignificant activity at the slow sweep rate,
thereby identifying the range of potentials in which SCC is likely.
The nominal conditions that delineate the critical potential range for SCC are a combination of a
current density of greater than 6.5 mA/in2 (1 mA/cm2) during the fast scan and an order of
magnitude difference in current density between the fast and slow scans.
Results of Previous Work by Carolina Power and Light
Carolina Power and Light performed cyclic potentiodynamic polarization tests as a part of an
evaluation of alternatives to chromate as a corrosion inhibitor in CCW systems [43]. The tests
were performed using a method similar to that described above, however the test specimens were
2.0 in. x 1.0 in. x 0.04 in. (5 cm x 2.5 cm x 0.1 cm) plates instead of cylinders. The data from this
work was originally only evaluated in relation to the potential for general corrosion, pitting, and
crevice corrosion. As a part of this project, this data was reevaluated with consideration for stress
corrosion cracking.
The tests were performed using A106 Gr. B carbon steel specimens and included the inhibitors
chromate, molybdate, nitrite, and tolyltriazole in deionized water and water containing chloride
and sulfate, with and without a nitrogen purge. Before measurement of the polarization curves,
the samples were stripped cathodically at a constant potential of -500 mVSCE for 2 minutes to
remove any air formed film. The samples were then allowed to attain a stable open-circuit
potential (OCP) before starting the polarization scan. All tests were performed at room
temperature at a scan rate of 0.1 mV/s and electrode potential measurements were made with
reference to a saturated calomel electrode (SCE).
Chromate
As shown in Figure 4-5, the addition of chromate results in a passive region above the corrosion
potential that increases with the concentration of chromate. The low current density in this
passive region indicates negligible corrosion rates and the lack of an active to passive transition
makes stress corrosion cracking unlikely.
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Figure 4-5
Potentiodynamic Polarization Curves for Carbon Steel Exposed to Deionized Water with
and Without Sodium Chromate Purged with Nitrogen [43] (Courtesy of NACE International)
Molybdate and Tolyltriazole
The use of molybdate in aerated water results in corrosion rates similar to chromate (Figure 4-6),
however, there is an active to passive transition that could indicate susceptibility to stress
corrosion cracking. In many plants where copper alloys are present in the cycle, tolyltriazole is
added to inhibit copper corrosion. The addition of tolyltriazole reduces the active to passive
transition at 100 mVSCE for carbon steel, while maintaining the low corrosion rate. However,
when the water is purged with nitrogen to reduce the concentration of oxygen, the corrosion rate
is increased and the active to passive transition reappears. This occurs because molybdate
requires the presence of oxygen or a strong oxidizer in order to passivate the metal surface
effectively.
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Figure 4-6
and without Sodium Molybdate and Sodium Tolyltriazole [43] (Courtesy of NACE
International)
Molybdate and Nitrite
The use of molybdenum in CCW systems requires the presence of another oxidizing agent, such
as oxygen or nitrite. A comparison of deionized water with no inhibitor (Figure 4-7, Curve 1)
and deionized water containing 200 ppm of molybdate (Figure 4-7, Curve 2) shows that in a low
oxygen environment, the corrosion rate with molybdate is higher than without an inhibitor. The
addition of an oxidizer (nitrite) reduced the current density by an order of magnitude, however an
active to passive transition is now present (around 100 mVSCE), indicating the possibility of stress
corrosion cracking.
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Figure 4-7
and Without Sodium Molybdate and Sodium Tolyltriazole Purged with Nitrogen [43]
(Courtesy of NACE International)
Molybdate, Nitrite, and Tolyltriazole
In systems where low oxygen concentrations are maintained and copper alloys are present, a
combination of molybdate, nitrite, and tolyltriazole is sometimes used to inhibit corrosion on
both carbon steel and copper alloys. The effectiveness of this combination of inhibitors in a low
oxygen environment in the presence of chloride and sulfate is shown in Figure 4-8. The
inhibitors maintain lower corrosion rates than deionized water even with higher concentrations of
impurities, however as the impurity concentration increases, the active to passive transition is
increased, indicating an increasing susceptibility to stress corrosion cracking.
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Figure 4-8
Chloride, Sulfate, Sodium Molybdate, Sodium Nitrite, and Sodium Tolyltriazole Purged with
Nitrogen [43] (Courtesy of NACE International)
Results of Current Work
As a part of this project, five sets of cyclic potentiodynamic polarization tests were performed.
Four of the tests used A106 Grade B material and one test used ER70S-2 weld material that was
welded and machined to the proper specimen shape. A summary of the test environments is
given in Table 4-2. The results of these tests are summarized in Table 4-3. Graphs of potential
versus current density for both the fast and slow scans for each test and a discussion of each test
are provided below
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Table 4-2
Test Matrix for Cyclic Potentiodynamic Polarization Tests (All Solutions Aerated, Made
using Deionized Water)
Dissolved
Conductivity
pH Oxygen
Test (µS/cm)
Test Environment (ppm)
Specimen
No. (T = 170oF, 77oC)
Material
Fast Slow Fast Slow Fast Slow
Scan Scan Scan Scan Scan Scan
1 1500 ppm sodium nitrate (as NO3) ER70S-2 6.20 6.25 2100 2100 4.3 4.2
(Weld Metal)
2 1500 ppm sodium nitrate (as NO3) A106 Gr. B 6.40 6.37 2100 2100 4.2 4.3
3 1500 ppm sodium nitrite (as NO2) A106 Gr. B 6.23 6.35 3100 3100 4.25 4.3
4 400 ppm sodium molybdate (as MoO4) A106 Gr. B 5.97 6.00 630 630 4.3 4.3
+ 50 ppm tolyltriazole
5 250 ppm trisodium phosphate (as PO4) A106 Gr. B 9.03 8.97 900 900 4.3 4.2
Table 4-3
Summary of Results of the Cyclic Polarization Tests
Test
Test Environment Appearance of
Specimen Test Result
No. (T = 170oF, 77oC) Specimen after Test
Material
1 1500 ppm sodium nitrate (as NO3) ER70S-2 Active corrosion, Coated with gray
(Weld Metal) inconclusive on SCC oxide, 0.6 mil deep pits
2 1500 ppm sodium nitrate (as NO3) A106 Gr. B Active corrosion, Coated with gray
inconclusive on SCC oxide, 0.4 mil deep pits
3 1500 ppm sodium nitrite (as NO2) A106 Gr. B Unstable passive Bright metal, scattered
behavior, inconclusive oxide particles, no pits
on SCC
4 400 ppm sodium molybdate (as A106 Gr. B Unstable passive Areas of iridescent
MoO4) + 50 ppm tolyltriazole behavior, possible staining, heavy coating
SCC of oxide particles, 0.2
mil deep pits
5 250 ppm trisodium phosphate (as A106 Gr. B Passive behavior, no Bright metal, no pits
PO4) SCC
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Test 1: Weld Metal in 1500 ppm Sodium Nitrate (as NO3) Solution
At the conclusion of both the fast and slow scans, the test specimens were covered with a dark
gray oxide. The test solutions also became discolored. Optical microscopy shows that both
specimens are pitted with the larger pits (up to 0.4 mils (10 µm) deep) being found on the fast
scan specimen. One area of the fast scan specimen is heavily corroded (up to 0.6 mils (15 µm)
deep). Both specimens have 0.5 to 1 µm orange particles and 1 to 5 µm white crystals on the
surface.
The potentiodynamic polarization curves for this test show that there is active corrosion at all
potentials above the corrosion potential (-365 mVSCE) with a corrosion rate of 32 mils (0.8 mm)
per year. There is no indication of a susceptibility to stress corrosion cracking, however the
general corrosion rate may be too high for localized corrosion to be detected.
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Figure 4-9
Fast (Top) and Slow (Bottom) Potentiodynamic Polarization Scans of an ER70S-2 Weld
Metal Specimen in Aerated 1500 ppm Sodium Nitrate Solution at 170oF (77oC)
Test 2: A106 Grade B in 1500 ppm Sodium Nitrate (as NO3) Solution
At the conclusion of both the fast and slow scans, the test specimens were covered with a dark
gray oxide. The test solutions also became discolored. Optical microscopy revealed a few pits up
to 0.2 mils (5 µm) deep on the fast scan specimen and up to 0.4 mils (10 µm) deep on the slow
scan specimen. Both specimens have 0.5 to 1 µm orange particles lightly covering the surface
and a few scattered 1 to 40 µm white crystals.
The potentiodynamic polarization curves for this test show that there is active corrosion at most
potentials above the corrosion potential (-372 mVSCE) with a corrosion rate of 33 mils (0.8 mm)
per year. There is no indication of a susceptibility to stress corrosion cracking, however the
general corrosion rate may be too high for localized corrosion to be detected.
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Figure 4-10
Fast (Top) and Slow (Bottom) Potentiodynamic Polarization Scans of an A106 Gr. B
Specimen in Aerated 1500 ppm Sodium Nitrate Solution at 170oF (77oC)
Test 3: A106 Grade B in 1500 ppm Sodium Nitrite (as NO2) Solution
At the conclusion of both the fast and slow scans, the surface of the test specimens remained
bright metal. Optical microscopy revealed that there are 0.5 to 1 µm white crystals lightly
scattered on the surface of the fast scan specimen. The slow scan specimen has more particles on
the surface than the fast scan. These include 1 to 25 µm white crystals and 0.5 to 1 µm orange
particles. A portion of the flat end of the slow scan specimen has round areas that are coated with
0.5 to 1 µm orange particles. No pits were observed on either specimen.
The potentiodynamic polarization curves for this test show that there is an unstable passive
region between the corrosion potential (-34.8 mVSCE) and the start of active corrosion (300
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mVSCE). This unstable passivation region could indicate susceptibility to stress corrosion
cracking, however, it is inconclusive. The general corrosion rate is negligible.
Figure 4-11
Specimen in Aerated 1500 ppm Sodium Nitrite Solution at 170oF (77oC)
Test 4: A106 Grade B in 400 ppm Sodium Molybdate (as MoO4) + 50 ppm Tolyltriazole
Solution
At the conclusion of both the fast and slow scans, the test specimens were coated with an
iridescent film. Optical microscopy revealed that there was staining on both specimens, with the
slow scan having more. A few areas of the fast scan specimen are heavily coated with 0.5 to 1
µm orange particles and there are small mounds of 0.5 to 2 µm gray particles scattered on the
surface. Several of these are broken, revealing pits up to 0.2 mils (5 µm) deep underneath the
mound. The slow scan specimen has a heavy coating of 0.5 to 2 µm gray particles over the entire
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surface with several areas being coated with 1 to 10 µm gray particles. The slow scan also has
small mounds of oxide scattered on the surface.
The potentiodynamic polarization curves for this test show behavior intermittent between
passivity and active dissolution, as indicated by the presence of a cathodic loop in the potential
range of -100 to 200 mVSCE on the slow scan rate curve. The oxidizing strength of the solution is
inadequate to polarize the steel fully into the passive region, resulting in an oscillation between
active dissolution and passivity. This represents an unstable condition that could indicate
susceptibility to stress corrosion cracking.
Figure 4-12
Fast (Top) and Slow (Bottom) Potentiodynamic Polarization Scans of A106 Gr. B Specimen
in Aerated 400 ppm Sodium Molybdate + 50 ppm Tolyltriazole Solution at 170oF (77oC)
Test 5: A106 Grade B in 250 ppm Trisodium Phosphate (as PO4) Solution
At the conclusion of both the fast and slow scans, the surface of the test specimens remained
bright metal. Both specimens have 0.5 to 1 µm white crystals scattered on the surface. The slow
scan specimen has one small area with a higher concentration of 0.5 to 2 µm white crystals. No
pits were observed on either specimen.
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The potentiodynamic polarization curves for this test show passive behavior corrosion at
potentials above the corrosion potential (-110 mVSCE) with a negligible corrosion rate. The large
reduction of the current density during the backward scan indicates that the surface passivation
was increased at the higher potential, resulting in less corrosion upon returning to the lower
potential.
Figure 4-13
Specimen in Aerated 250 ppm Trisodium Phosphate Solution at 170oF (77oC)
Conclusions
The results of the cyclic potentiodynamic polarization tests show:
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• The following solutions could result in SCC of carbon steels: CrO4 + Cl (impurity), MoO4,
MoO4 + TTA, MoO4 + NO2 + TTA + Cl (impurity), MoO4 + NO2 + TTA + Cl (impurity) +
SO4 (impurity), MoO4 + NO2 (see Table 4-1)
• Chromate is a good inhibitor of general, as well as localized, corrosion of carbon steel.
• Molybdate in water containing high concentrations of oxygen is a good inhibitor for general
corrosion of carbon steel; however, it may not prevent stress corrosion cracking.
• The addition of tolyltriazole to water containing molybdate and high concentrations of
oxygen may reduce the susceptibility of carbon steel to stress corrosion cracking.
• Molybdate and molybdate + tolyltriazole in water containing low concentrations of oxygen
are poor inhibitors for carbon steel with corrosion rates that can be greater than in water
without any inhibitor. When using molybdate, the presence of oxygen or an oxidizing agent
is necessary for protection from general corrosion.
• The addition of nitrite to water containing molybdate and low concentrations of oxygen
reduces the rate of general corrosion of carbon steel, however, it increases the susceptibility
to stress corrosion cracking. The susceptibility is further increased in the presence of
corrosive compounds, such as chloride and sulfate.
• Nitrate is a strong corrodent that can be produced by the conversion of nitrite by
microorganisms. Nitrate is known to result in stress corrosion cracking of carbon steel [63].
Biofouling in systems using nitrite should be avoided.
• Phosphate is a good inhibitor of general corrosion of carbon steel and does not result in stress
corrosion cracking.
Galvanic Corrosion Test
When two dissimilar metals in electrical contact are exposed to a common electrolyte, one of the
metals can undergo increased corrosion while the other can show decreased corrosion. This type
of accelerated corrosion is referred to as galvanic corrosion. The more active (electronegative)
metal will have a tendency to undergo increased corrosion while the more noble (electropositive)
metal will have reduced corrosion. In general terms, the greater the potential difference between
the two metals, the greater the driving force for galvanic corrosion.
Galvanic corrosion behavior is affected by many factors besides corrosion potentials. These
factors must also be considered in judging the behavior of a galvanic couple. They include:
• Anode-to-cathode area ratio
• Electrolyte conductivity
• Distance between coupled metals
• Shielding of metal surfaces by marine growth, sediments, etc.
• Localized electrolyte concentration changes in shielded areas
• Polarization characteristics of the metals involved
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Based on the results of the cyclic potentiodynamic polarization tests, the environment used in
Tests 1 and 2 (1500 ppm NO3) was selected for use in a galvanic corrosion test. A galvanic
couple was created between the test specimen (Figure 4-2) fabricated from A106 Grade B and
one from ER70S-2 weld material that was welded and machined to the proper specimen shape.
o o
The test specimens were inserted into the 170 F (77 C) aerated solution and allowed to stabilize
for 2 hours. A setup similar to the one described above in the Cyclic Potentiodynamic
Polarization Test was used for this test [103]. The weld metal specimen was connected as
Electrode #1 (working electrode) and the A106 Gr. B specimen was connected as Electrode #2
(counter electrode). The galvanic current and the coupled potential were then measured for 72
hours.
Figure 4-14
Galvanic Current and Coupled Potential for an A106 Gr. B and an ER70S-2 Weld Metal
Specimen in an Aerated 1500 ppm Sodium Nitrate Solution at 170oF (77oC)
Discussion of Results
The galvanic test data was analyzed for current polarity and magnitude based on the working
electrode. The weld metal had an open circuit potential that was 56 mV more negative than the
A106 Gr. B specimen. When the A106 Gr. B specimen and the weld metal specimen were
coupled, the galvanic current polarity remained positive throughout the test, which indicated that
the weld metal remained anodic to the A106 Gr. B. It is estimated that under these conditions,
the weld metal will corrode at a rate of 5 mils per year due to galvanic corrosion. The results of
the galvanic test are summarized in Table 4-4.
Table 4-4
Results of Galvanic Test
Solution pH 6.32
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Conductivity (µS/cm) 2100
Dissolved Oxygen (ppm) 4.2
Open Circuit Potential (mV) Weld Metal: -476

A106B: -420
Final Galvanic Current Density (A/cm2) 10.5x10-6
Final Galvanic Corrosion Rate (mpy) 4.8 (Weld Metal)
Weld Metal Specimen Appearance after Testing Dark Gray Oxide with Reddish Orange Oxide
A106B Specimen Appearance after Testing Thin Dark Gray Oxide Film
1 inch = 2.54 cm, 1 mil = 25.4 µm
Conclusions
In the aerated environment used for the galvanic corrosion test, the weld material was anodic and
the base metal cathodic. This indicates that in this environment, the weld material would be
preferentially attacked. The actual corrosion rate of a pipe weld could be higher due to the larger
ratio of base metal (cathode) to weld (anode).
Slow Strain Rate (SSR) Tests
Slow strain rate (SSR) tests were conducted by InterCorr International for Wolf Creek Nuclear
Operating Corporation (WCNOC) [1] in order to determine the susceptibility to stress corrosion
cracking of welded A106 Grade B carbon steel in three different environments (Table 4-5). The
environments represented WCNOC’s CCW chemistry in 1994, 2001, and 2001 without the
o o
copper inhibitor. All tests were conducted at 145 F (63 C) and the solutions were aerated.
Table 4-5
Environments Used for Slow Strain Rate Tests [1]
Sodium Molybdate Tolyltriazole

No. Environment pH1
(ppm) (ppm)
1 1994 Water Chemistry 300 7 8.5
2 2001 Water Chemistry 500 17.5 9.5
3 2001 Water Chemistry 500 0 9.5
without Copper Inhibitor
1 - sodium hydroxide used to adjust the pH of the solutions
Three different samples of welded A106 Grade B were provided for testing:
• Sample A – This sample was previously in service in the WCNOC CCW system and
subsequently received post weld heat treatment (PWHT). This particular sample was selected
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because WCNOC was interested in understanding the effect of PWHT on a weld that had
been in service under the molybdate and tolyltriazole (TTA) chemistry. The original ID pipe
scale was preserved on the specimens. Furthermore, the specimens were inspected at high
magnification to verify that no indications of SCC or intergranular attack were present before
testing.
• Sample B – This sample had not been in service and the specimens prepared from this
sample received a pre-treatment with the corresponding CCW chemistry. No PWHT was
performed.
• Sample C - This sample had not been in service and the specimens prepared from this
sample received a pre-treatment with the corresponding CCW chemistry. PWHT was
performed.
The test specimens (Figure 4-15) had the circumferential weld and specifically the heat affected
zone centered in the gage length. The specimens had nominal dimensions of 1.0 inch (25.4 mm)
gage length, 0.100 inch (2.5 mm) width, and 0.125 inch (3.2 mm) thickness. All specimens were
-7 -1
subjected to the same strain rate (2x10 s ), temperature, and aerated conditions. Figure 4-16
shows the test equipment setup.
Figure 4-15
Slow Strain Rate Test Specimen
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Figure 4-16
Slow Strain Rate Test Equipment
All results were compared to baseline tests conducted in air at the same strain rate and
temperature as the environmental tests. At the conclusion of each SSR test, the gage section and
fracture surface of the specimens were examined for indications of environmental cracking.
Table 4-6 summarizes the results of the tests in air and compares the differences due only to the
material conditions. Table 4-7 to Table 4-9 summarize the results for three chemical
environments of the testing in the specific chemical environments. It should be noted that only
one type of specimen (Sample A, B, or C) was tested in each chemical environment.
Table 4-6
Slow Strain Rate Tests in Air at 145oF (63oC) for the Three Sample Materials [1]
Sample A Sample B Sample C

Parameter
(In-Service + PWHT2) (No Service, No PWHT) (No Service + PWHT)
Maximum Load (lb) 786 940 845
Ultimate Tensile Strength (ksi) 59.7 73.6 66.3
Fracture Load (lb) 125 677 475
Time to Failure (hrs) 104.8 173.1 236.0
1
Elongation (%) 6.1 10.9 15.3
Reduction in Area (%) 16.6 46.0 63.3
1) Elongation corresponds only to the plastic component
2) Received PWHT after being in service
1 lb = 0.45 kg
1 ksi = 6.89 MPa
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Table 4-7
Slow Strain Rate Tests in 1994 Chemistry (300 ppm Molybdate, 7 ppm TTA, pH 8.5,
Aerated) for Sample B (No Service, No PWHT) [1]
Parameter Specimen 1 Specimen 2 Average

Initial pH 8.5 8.5 8.5
Final pH 7.6 7.9 7.8
Maximum Load (lb) 832 929 880.5
Time to Failure (TTF) (hrs) 113.1 120.3 116.7
TTF/TTF in air (hours) 0.65 0.69 0.67
Elongation* (%) 6.8 7.2 7.0
Elongation/Elongation in Air 0.63 0.66 0.65
Reduction in Area (RA) (%) 13.5 17.2 15.4
RA/RA in Air 0.29 0.37 0.33
* Elongation corresponds only to the plastic component
1 lb = 0.45 kg
1 ksi = 6.89 MPa
Table 4-8
Slow Strain Rate Tests in 2001 Chemistry (500 ppm Molybdate, 17.5 ppm TTA, pH 9.5,
Aerated) for Sample A (Service + PWHT1) [1]
Parameter Specimen 1 Specimen 2 Average

Initial pH 9.5 9.5 9.5
Final pH 8.3 7.8 8.1
Maximum Load (lb) 866 685 776
Time to Failure (TTF) (hrs) 147.4 77.9 112.7
TTF/TTF in air (hours) 1.41 0.74 1.08
2
Elongation (%) 9.2 4.7 7.0
Elongation/Elongation in Air 1.51 0.77 1.14
Reduction in Area (RA) (%) 29.9 5.5 17.7
RA/RA in Air 1.80 0.33 1.07
1) Received PWHT after being in service
2) Elongation corresponds only to the plastic component
1 lb = 0.45 kg
1 ksi = 6.89 MPa
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Table 4-9
Slow Strain Rate Tests in 2001 Chemistry (500 ppm Molybdate, 17.5 ppm TTA, pH 9.5,
Aerated) and 2001 Chemistry without TTA for Sample C (No Service + PWHT) [1]
2001 Chemistry 2001 Chemistry without TTA

Parameter
Specimen 1 Specimen 2 Average Specimen 1
Initial pH 9.5 9.5 9.5 9.5
Final pH 9.0 8.8 8.9 8.8
Maximum Load (lb) 768 799 784 756
Ultimate Tensile Strength (ksi) 60.8 64.0 62.4 59.9
Fracture Load (lb) 475 464 470 361
Time to Failure (TTF) (hrs) 191.0 198.4 194.7 200.6
TTF/TTF in air (hours) 0.81 0.84 0.83 0.85
*
Elongation (%) 12.4 13.2 12.8 13.2
Elongation/Elongation in Air 0.81 0.86 0.84 0.86
Reduction in Area (RA) (%) 28.6 30.6 29.6 38.2
RA/RA in Air 0.45 0.48 0.47 0.60
* Elongation corresponds only to the plastic component
1 lb = 0.45 kg
1 ksi = 6.89 MPa
Severe fissuring around the necked region of the specimen and corrosion was observed in the
Sample B (No Service, No PWHT) specimens that were exposed to the 1994 chemistry (Figure
4-17). In addition, these specimens showed an extremely low reduction in area ratios (0.29 and
0.37) vs. tests in air. The primary purpose of the test in this environment was to reproduce the
cracking problems previously observed in the CCW system. The results indicate that the material
was clearly susceptible to stress corrosion cracking. The fracture surfaces were severely corroded
and did not provide useful information other than the verification of the embrittled nature of the
fracture.
Figure 4-17
Sample B Slow Strain Rate Test Specimen (No Service, No PWHT) Exposed to Aerated 300
ppm Molybdate + 7 ppm TTA at 145oF (63oC) [1]
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Sample A specimens were fabricated from material that had previously been in service and
subsequently received PWHT. As shown in Table 4-8, when exposed to the 2001 chemistry, one
of the specimens tested presented unusually high ratios, while the second specimen showed
ratios that were similar to those observed on Sample B. The high ratios resulting from the first
test of the material are questionable since the material also demonstrated fissuring indications
around the necked region of the specimen.
Sample C (No Service + PWHT) specimens, which were also exposed to the 2001 chemistry,
showed severe corrosion and fissuring around the necked region of the specimen, but the
reduction in area ratios (0.45 and 0.48) were higher than those observed in the Sample B
specimens exposed to the 1994 chemistry. However, these ratios are still considered low. In most
applications, the ratios should at least be 0.80 [1]. The elimination of TTA in one test showed
some improvement in the reduction of area ratio (0.60), but even this value is still low.
Conclusions
Evidence of environmental cracking, in the form of fissuring, was observed on all of the
specimens tested. In general, the time to failure and elongation and reduction in area ratios were
better for the specimens in the 2001 chemistry than for those tested in the 1994 chemistry. In
addition, the Sample C, which received post weld heat treatment, showed some improvement
over Sample B.
Nitrite Stability Test
Several plants use sodium nitrite as a corrosion inhibitor; however, it can oxidize to become
sodium nitrate, a known promoter of SCC. To determine the possibility of nitrate formation
leading to SCC in CCW systems, a nitrite stability test was conducted.
A 1500 ppm nitrite solution was prepared and the nitrite and nitrate concentrations were
measured using ion chromatography. The air saturated solution was then heated to a temperature
o o
of 170 F (77 C) and held at temperature for a period of 10 days with continuous exposure to air.
At the end of the 10 days, the concentrations of nitrite and nitrate were measured.
The concentrations of nitrite and nitrate before and after testing are given in Table 4-10. There
was approximately 2 ppm of nitrite that was converted to nitrate during the 10-day test. After six
months, this would correspond to conversion of approximate 40 ppm of nitrite to nitrate if the
conversion rate was linear over that range.
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Table 4-10
Concentration of Nitrite and Nitrate in Solution Before and After 10 Days Exposure to Air at
to 170oF (77oC)
Concentration of NO2 (ppm) Concentration of NO3 (ppm)
Before Exposure 1492 21
After Exposure 1490 23
Conclusions
This short time test may indicate a slow conversion of nitrite to nitrate. It is known that
significant conversion occurs only after months of exposure to temperature and air and that
bacteria can accelerate this conversion. The concentration and NO2/NO3 ratio at which nitrate
would start promoting SCC is not known.
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5
ROOT CAUSE ANALYSIS
Root Causes
The root cause of SCC of carbon steel piping welds and base metal in CCW systems is a
combination of a susceptible material, high residual welding and/or system stresses, and cooling
water chemistry. The chemistries from the survey which have some correlation with SCC
include: nitrite + benzotriazole (BZT) (100% of users with this combination had SCC) and
molybdate + tolyltriazole (TTA) + aerated water (67% of users with this combination
experienced SCC). Molybdate + TTA was also shown to induce SCC in a series of Slow Strain
Rate Tests. Contributing factors are: water exposed to air, high temperature, biofouling, and
possibly the presence of crevices at socket welds and backing rings and the presence of copper.
As in any investigation of SCC, the three main factors, material – stress – environment, were
investigated. In the approach to the root cause analysis, the items shown in Figure 5-1 were
considered.
Figure 5-1
Factors Considered in SCC in CCW Systems
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A summary of the information compiled from the Questionnaires (Chapter 2) and other reports is
given in Table 5-1 and the characteristics of the CCW systems in the 14 units experiencing leaks
caused by SCC in Table 5-2. Table 5-1 compares the data supplied by the units with leaks to
those that reported having no leaks. It should be realized that all of the statistics in this chapter
and in Chapter 2 are based on detection of SCC by leaks. There may be many units listed as
having no leaks/SCC that actually have undetected SCC cracks.
For this root cause analysis, correlations of the parameters listed in Table 5-1 with leaks/SCC
were derived from the percentages listed in the Column “% Leaking of Total Units Using”. A
correlation is considered valid when it is higher than 65% (arbitrarily selected).
Materials
The base metal and weld materials in the units with and without leaks are all similar. Based on
the plant survey, it has been determined that for piping and fittings, A105, A106 Grades A and
B, A516-70, A53, SC1140, St35 and St37 (German specifications) carbon steels have been used.
For welds, the use of ER70S-2 and E7018 has been reported. Most of the welds are not stress
relieved. There is ample experience with SCC in the weld areas of these steels in a variety of
environments, including boiler feedwater.
Stresses
None of the welds in the CCW systems experiencing SCC were stress relieved and only 3 units
(2%) not experiencing leaks reported stress relieving welds. Residual welding stresses have been
measured in other applications, and without stress relief, they can be as high as the material yield
strength. With the component geometries, such as socket welds, there are stress concentrations
that can further increase the stresses into the plasticity region and flange and fitting misalignment
increase the stresses even further. At these high stresses, the crack initiation mechanism is likely
to be stress induced pitting [95]. The presence of high tensile stresses and strains is indicated by
crack openings seen during metallographic investigations (see Appendix B and D).
Socket Welds
Socket welds are a convenient way to join piping components together, however, within the
current standard geometry, it is easy to misalign the two joined components, which can generate
very high local bending stresses. The misalignment is combined with the weld geometry
producing a local stress concentration, particularly at the weld root. This situation is illustrated in
Appendix B, Figure B-4.
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Table 5-1
Comparison of Units With and Without Leaks1; % Based on # of Units Providing Data for
Given Parameter
% Leaking Correlation
Parameter2 Units with Leaks3 Units with no Leaks3 of Total for Units
Units Using with Leaks5
Number of Units 14 129 10
4
130 – 200, Avg. = 150.4 100 – 190 , Avg. = 122.4
Max. Temperature oF (oC) Yes
(54 – 93, Avg. = 65.8) (38 – 88, Avg. = 50.2)
Maximum pH 9.0 – 11.0, Avg. = 10.0 6.0 – 12.0, Avg. = 9.9 No
Biofouling Reported 11 (85%) 0 (0%) 100 Yes
Aerated Water 14 (100%) 72 (69%) 16 No
Chromate 0 (0%) 18 (14%) 0 No
Molybdate 5 (36%) 6 (5%) 45 No
Nitrite 9 (64%) 16 (12%) 36 No
Tolyltriazole (TTA) 4 (33%) 15 (12%) 21 No
Benzotriazole (BZT) 8 (67%) 0 (0%) 100 Yes
TTA or BZT 12 (92%) 15 (12%) 44 No
Molybdate + TTA 4 (33%) 4 (3%) 50 No
Molybdate + TTA +
4 (33%) 2 (2%) 67 Yes
Aerated Water
Molybdate + BZT 0 (0%) 0 (0%) 0 No
Molybdate + Hydroxide 3 (21%) 2 (2%) 60 ?
Nitrite + TTA 0 (0%) 13 (10%) 0 No
Nitrite + BZT 8 (67%) 0 (0%) 100 Yes
Nitrite + Borate 8 (67%) 7 (5%) 53 No
Nitrite + Aerated H2O 9 (64%) 4 (4%) 69 Yes
Molybdate + Aerated H2O 5 (36%) 4 (4%) 56 No
Stress Relief 0 (0%) 3 (2%) 0 No
Backing Rings 9 (90%) 5 (22%) 64 ?
1 – Because of the limited inspection, there are no statistics on cracking
2 – Data for some conditions not available for some plants
3 – % based on number of units providing data, not total units
4 – Only 1 Plant (2 units) reported a maximum temperature this high. By eliminating this Unit, the range
becomes 100 - 130oF (38 – 54oC) with an average maximum temperature of 110.1oF (43.4oC)
5 – ? = Possible correlation
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Table 5-2
Characteristics of CCW Systems in the 14 Units Experiencing SCC (13 PWRs, 1 BWR)
# of Units # of Units Not # of Units

Parameter
Reporting Reporting Unknown
Temperature above 130oF (54oC) 12 0 2
Use of Aerated Water 13 0 1
Use of Sodium Nitrite 9 6* 0
Use of an Azole (TTA or BZT) 12 1* 2
Evidence of Biological Activity 11 1 2
Use of Backing Rings 9 3 2
* - Cooper changed water chemistry in 1980 and had SCC under both conditions. It is therefore counted
twice.
While the materials and stresses described above are a prerequisite for SCC, there is no
correlation between the problem in units with and without leaks because they are all the same.
Literature data indicate that the susceptibility of carbon steel to SCC increases as the carbon
content decreases (see Chapter 3) [63, 66]. This may be the case for the welds in the CCW
systems where carbon concentration is as low as 0.05%, while the typical base metal carbon
concentration is 0.2%. The reasons for this effect of carbon are not understood and it is not clear
whether the low carbon plays a role in the CCW systems.
Environment
Environmental effects on corrosion include chemical composition of the cooling water, possible
concentration mechanisms (evaporation, concentration in scale and on crack surfaces),
temperature, and flow characteristics. Environment during operation and layup needs to be
considered.
After a review of the survey results (Chapter 2) and design and operation of the CCW systems,
the main items found to correlate with the SCC include: corrosion inhibitors, systems open vs.
closed to air, presence of biofouling, and temperature. The main input for the determination of
the environmental root causes is derived from Table 5-1. There are strong correlations with SCC
for the units using nitrite + BZT, aerated nitrite solutions, and aerated molybdate + TTA cooling
water. Biofouling is reported in 84% of the problem units. All of the problem units have copper
alloy tubing heat exchangers and up to 25% copper has been found in scale of the piping that has
been investigated. While there is no statistical information on the presence of copper, it is known
that copper oxides can increase the propensity of the environment to SCC. All of the units use
demineralized water for makeup.
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Operating Temperature
Stress corrosion crack initiation and propagation in carbon and low alloy steels is strongly
influenced by the operating temperature. The affect of temperature on crack propagation is
illustrated in Figure 3-6, which shows a compilation of crack growth rates for carbon steel vs.
operating temperature for three different environments (corrosive, aggressive, and good quality
low oxygen water).
A comparison of the operating temperatures of the units with and without leaks due to SCC
shows that all of the units with cracking operate above 130oF (54oC) and that the average
o o
operating temperature of these units is 150 F (66 C) as compared to units without leaks where it
o o
is 122 F (50 C) (Table 5-1). Two units, which have not experienced SCC, operate at high
temperature; however, they use low oxygen water.
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6
ENGINEERING RECOMMENDATIONS
Based on the previous Chapters and considering that the piping and heat exchanger shell
materials (carbon steels) will stay the same, the engineering recommendations to reduce the
occurrence of SCC in CCW systems include:
• Reduction of stresses
• Changing the weld geometry
• Further research into the environmental (cooling water chemistry and temperature) aspects
related to SCC to make sound recommendations on alternative water treatments
Materials
It is not recommended to change the piping and heat exchanger shell materials, however, there is
a possibility that using weld metal with higher carbon [63, 66] and lower yield strength could be
beneficial. This would require substantial research followed by the changing of the current
welding practices since higher carbon filler materials are not common practice.
Stress Reduction
Stress reduction in the weld area can be achieved by:

• Post weld heat treatment
• Changing the weld geometry – reducing stress concentration and crevice effects
• Improving piping component alignment procedures, particularly at socket welds, which will
lead to a reduction of system bending stresses
• Redistributing stress by over pressure hydrotesting
Post Weld Heat Treatment
Thermal stress relief may be an effective measure for preventing, or at least, prolonging, the time
to SCC. For stress relief, the temperature is a more important factor than time at temperature. It
o o
is believed that stress-relieving temperatures below 1100 F (595 C), regardless of the hold time,
are not effective for preventing SCC [63].
The ASME Code for Pressure Piping, Section B31.1 “Power Piping”, requires a postweld heat
treatment temperature of 1100 to 1200oF (600 to 650oC) for carbon steel welds when the nominal
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thickness exceeds 0.75 inch (19 mm). It is recommended that the post weld heat treatment in the
upper portion of this range be used for all CCW system carbon steel welds, regardless of
thickness. In addition, many socket welds are exempt from PWHT based on current rules set
forth by the ASME codes. It is recommended that the PWHT exemption not be taken in areas of
known SCC activity. For new carbon steel piping, special precautions must be observed during
PWHT, such as adequate support to avoid distortion and the removal of dirt, grease, and other
foreign material that might react with the steel at elevated temperatures.
It should be noted that additional stress corrosion cracking has been found in vessels that were
stress relieved after SCC was found in the original as-welded vessels and were repaired by
grinding and welding. It is believed that the stress relieving propagated tiny cracks that were not
o
detected during repairs [63]. Stress relief within the temper-embrittlement range (650 to 1000 F,
o
345 to 540 C) can also adversely affect SCC resistance as well as toughness if the steel
composition contains certain impurities such as phosphorus, antimony, arsenic and / or tin.
Changing Weld Geometry and Alignment
At many SCC locations, such as at socket welds, the stress concentration factor, kt, is very high
(up to ~10). This means that the maximum surface stresses, even at moderate pressure and the
alignment stresses, are beyond the yield strength. These effects would be significantly reduced if
butt-welding was used.
The misalignment of socket welds is illustrated in Figure B-4 of Appendix B. When a misaligned
flange is tightened to the matching flange, the local stresses at the weld root can again be beyond
the yield strength.
Stress Redistribution by Hydrotesting
A hydrotest at 1.5 times the operating pressure produces plastic deformation in the areas of high
stress concentration. When the pressure is reduced to normal, these areas are under a residual
compressive stress, which protects them against SCC initiation. Even with preexisting cracks, a
short time increase of the stress intensity usually results in a delay of crack propagation [97].
In older systems with large, non-through-wall, cracks, the hydrotest could break the remaining
ligament, producing a leak that can be repaired during the outage. This is a much better situation
than a forced outage from an unexpected leak and may be a suitable option to UT inspection in
this case.
Water Chemistry and Temperature
Based on the survey results (Chapter 2) and the results of the limited testing (Chapter 4)
conducted for this project the SCC of carbon steel CCW system components appear to have a
correlation with the following: use of aerated nitrite with benzotriazole (BZT), aerated
molybdate with tolyltriazole (TTA) solutions, presence of microbial activity, and higher
o o
temperatures (above 130 F, 54 C). This leads to the following preliminary engineering
recommendations:
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• Further the R&D into the chemistry effects associated with the above mentioned water
treatments and their influence on SCC. After that, a more definitive engineering
recommendation can be made on the efficiency of certain chemistries to provide adequate
protection to all forms of corrosion in these systems.
• Investigate the effects/consequences on the overall performance of the system by
discontinuing the use of the above mentioned cooling water chemistries and switching to
alternative water treatments (i.e., chromate, phosphate, or pure water – all deaerated) that
have had no history of SCC.
• Stringently control microbiological activity, especially in systems using nitrite
•
o o
Reduce the maximum CCW operating temperature to below 130 F (54 C)
Results of Limited Verification
A verification of the applicability of the above recommended water chemistries is provided in the
survey (Chapter 2) and by the good experience EdF has had using phosphate and other European
nuclear power plants have had using the VGB Guidelines [22]. Additional verification is
provided through the electrochemical testing described in Chapter 4 (Table 4-1), for chromate
and phosphate. To protect the system, impurities, such as chloride, must also be controlled.
Additional Testing and Inspection
The survey results, corrosion testing and metallurgical evaluations have indicated areas of focus
related to the chemical sources involved with the SCC problem in these systems. In order to
better understand the various chemical interactions that are responsible for the SCC initiation and
growth, additional testing, inspection and data accumulation is needed to make sound judgments
as to which water treatment combination(s) could be promoting the SCC in the affected units.
Inspections and NDE procedures should be performed for those sites which are experiencing
SCC and also for those that meet the criteria for increased probability of cracking that are
discussed in the next chapter. Field testing of stress corrosion specimens (welded U-bends and
pre-cracked specimens) is an excellent method for early detection of SCC through the periodic
inspections of these specimens.
Missing Knowledge – In relation to cooling water chemistry, there is a significant lack of

knowledge on the effects of corrosion inhibitors and MIC on stress corrosion cracking of carbon
steel. Filling this knowledge gap is best accomplished via a collaborative research effort. A
Tailored Collaboration (TC) project (17.3F) has been developed that is intended to attract
individual utilities to participate in this effort. The TC project not only provides site specific
technical information related to this problem but also reinforces the knowledge gained in this
report, by maintaining a consistent methodology in the evaluation process.
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7
CRACK DETECTION THROUGH INSPECTION AND
MAINTENANCE
Cracking Problem Detection
According to the survey (Chapter 2) and personal communications with individual power plants,
the only inspection typically done on the CCW system is a visual inspection for leaks. As a
result, SCC is only detected once a leak occurs. It is anticipated that there is more cracking in
both PWR and BWR units than has been reported.
To prevent unexpected leaks, it is recommended to evaluate all CCW systems for the likelihood
of SCC and to increase NDE examinations (ultrasonic or radiography), based on this evaluation.
Based on the correlations of this report, the probability of cracking increases with:
• Operating temperature (above 130oF)
• Use of aerated water with NO2 + BZT or MoO4 + TTA
• Use of azoles (TTA or BZT)
• Misalignment of piping, particularly at socket welds
• Use of backing rings
• Presence of biological activity (past or present)
• Unit age (although leaks have occurred in as little as 4 years, see Appendix B)
It is also recommended, that for early leak detection, leak detectors be installed on drains and
locally under susceptible weld connections.
Inspection of CCW Systems
It is recommended to inspect the letdown heat exchanger welds in all units, particularly the
nozzle outlet to shell weld, and other locations that are classified as susceptible based on the
evaluation described above. Any welded components that are replaced because of cracking
should be saved for metallurgical failure analysis. The detection of cracking should be reported
to EPRI for tracking purposes and guidance on sample removal for the failure analysis.
Inspection methods should include visual inspection for misalignment and leaks, ultrasonic
inspection, and radiography. The inspection methods should be verified using plant samples from
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this project and other samples. Achievable NDT crack size detection limits should be
determined.
Hydrotest
Hydrotesting the CCW system at 1.5 times the operating pressure can be useful in preventing
unexpected leaks from large cracks by forcing the leaks to occur during the outage. If leaking
does not occur as a result of the hydro testing, the procedure may still temporarily slow any
appreciable crack growth by favorably rearranging high residual welding and misalignment
stresses [97]. This in turn may extend the service life of the component to a point in which a
larger crack could be detected by NDE and Repair and Replacement (R&R) activities could be
conducted to repair the affected areas.
Field Test of SCC Specimens and Corrosion Potential
It is recommended to install stress corrosion specimens in the circuits that experienced cracking,
such as at the letdown heat exchanger outlet or in any other important sections of the CCW
system, particularly where the temperature is high. This will aid in root cause analysis and
provide early warning.
Recommended specimens include single and double U-bend and fracture mechanic specimens –
all with a weld. The specimens can be installed in an autoclave on a small side-stream.
For faster information on the propensity to SCC, corrosion potential probe should be used. The
corrosion potential in the known SCC region (transient) will indicate possible SCC.
Maintenance
The maintenance items important for reducing the probability of SCC in CCW systems include:
• Maintaining water treatment related equipment, including chemical addition, sampling and
analysis, filters for suspended solids, and nitrogen blanketing systems
• Maintaining system cleanliness and avoiding accumulation of suspended materials
Accumulated iron and copper oxides, particularly in crevices and at root welds in socket welds
and backing rings, can promote local concentration of chemicals and microbial growth, which in
turn can result in localized corrosion. Such accumulation has been observed during some failure
analyses (Table 2-1).
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8
CONCLUSIONS, RECOMMENDATIONS, AND MISSING
KNOWLEDGE
The following conclusions and recommendations are based on the data compiled from the latest
and previous surveys covering a total of 143 units, a review of metallurgical reports from units
experiencing stress corrosion cracking, new metallurgical failure analyses of pipe samples from
3 units, laboratory testing of carbon steel and weld samples in various environments, and a
review of EPRI, VGB, and other guidelines, and corrosion and water chemistry literature. The
work conducted within this project represents preliminary research directed toward addressing
this phenomenon as a potential generic issue which as of late has been documented and
evaluated on an individual basis. The following sections state discoveries that were made during
the course of this project and also reveal areas in which more knowledge needs to be gained so
that accurate corrective actions are undertaken to reduce the likelihood of SCC reoccurrence.
Root Causes and Mechanisms of SCC in CCW Systems
1. The root cause of SCC of carbon steel piping welds and base metal in CCW systems is a
combination of a susceptible material, high residual welding and/or system stresses, and
cooling water chemistry. The chemistries which have some correlation with SCC include:
nitrite + benzotriazole (BZT) (100% of users with this combination had SCC) and molybdate
+ tolyltriazole (TTA) + aerated water (67% of users with this combination experienced
SCC). Molybdate + TTA was also shown to induce SCC in a series of Slow Strain Rate
Tests. Contributing factors are: water exposed to air, high temperature, biofouling, and
possibly the presence of crevices at socket welds and backing rings and the presence of
copper.
The estimated stress corrosion crack propagation rates (Figure 3-6) show that the units with
SCC have an environment promoting SCC. The crack propagation rates seen in the units with
cracking are higher than those for pure low oxygen water, such as boiler feedwater.
It is recommended to:
•
o
Inspect CCW systems for cracking in units that have high temperatures (above 130 F,
54oC) aerated systems using NO2 + BZT or MoO4 + TTA and equip these units with SCC
specimens on a side stream
• Visually inspect all CCW systems for misalignment of pipes and flanges, which could
cause high system stresses
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• Investigate the effects/consequences of changing water chemistry to one of those not
producing stress corrosion cracking: chromate, phosphate, or pure water – all deaerated
(mechanically and/or chemically) with microbiological control
• Conduct additional testing (R&D) on existing CCW water treatments so that they can be
experimentally verified to protect against general corrosion, microbiological activity and
SCC
• Stress relieve all new (replacement) sections in CCW systems that have been found to
contain SCC
2. The base metal and weld materials in the units with and without SCC are all similar. Based
on the plant survey, it has been determined that for piping and fittings, A105, A106 Grades A
and B, A516-70, A53, SC1140, St35 and St37 carbon steels have been used. For welds, the
use of ER70S-2 and E7018 has been reported. Most of the welds are not stress relieved.
There is ample experience with SCC in the weld areas of these steels in a variety of
environments, including boiler feedwater. Most of the SCC cracks are intergranular.
None of the units experiencing stress corrosion cracking stress relieved the welds. Residual
welding stresses have been measured in other applications, and without stress relief, they can
be as high as the material yield strength. With component geometries, such as socket welds,
there are stress concentrations that can increase the stresses into the plasticity region of the
material. Flange and other fitting misalignment can increase the stresses even further. At
these high stresses, the crack initiation mechanism is likely to be stress induced pitting. The
presence of high tensile stresses and strains is indicated by crack openings seen during
metallographic investigations (see Appendix B and D).
The materials and stresses described above relate to the material and stress factors that must
be present for SCC to occur. Additional work is necessary related to the CCW chemistry in
order to arrive at specific root causes associated with the environmental aspect of the SCC.
Literature data indicate that the propensity to SCC of carbon steel increases with low carbon
content (see Chapter 3). This is the case of the welds in CCW systems where carbon
concentration is ~0.05%, while the typical base metal carbon concentration is ~0.2%. Further
research is needed to determine whether low carbon plays a role in the CCW systems.
3. Stress corrosion crack propagation in carbon and low alloy steels is strongly influenced by
the operating temperature. A comparison of the operating temperatures of the units with and
o o
without SCC shows that all of the units with cracking operate above 130 F (54 C) and that
o o
the average operating temperature of these units is 150 F (66 C) as compared to units without
o o
cracking where it is 122 F (50 C) (Table 5-1). Two units, which have not experienced SCC,
operate at high temperature; however, both use low oxygen water.
4. The time to through-wall cracking ranges from 4 years to 19 years. In the case of Sequoyah,
crack initiation was found in the replacement piping in just three years. The average crack
-7
propagation rates (not considering the crack initiation time) range from 1.2x10 in/hr
-6 -6 -4
(3.0x10 mm/hr) to 7.1x10 in/hr (1.8x10 mm/hr).
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EPRI Licensed Material
Conclusions, Recommendations, and Missing Knowledge
It is recommended that, in the plants with cracking, SCC specimens (U-bends, KISCC) be
installed on a side stream of a high temperature subsystem. This is to monitor SCC crack
initiation and propagation under the actual plant conditions and to give each plant an early
warning about the problem.
5. The mechanism of cracking is mostly intergranular stress corrosion with crack initiation from
both pits and smooth surfaces. Some transgranular cracking was also observed (Appendix B).
The cracking is mostly in the weld heat affected zone but in some cases at the smooth pipe
surfaces. There is no pronounced general corrosion on the pipe and weld surfaces, but there
is some scale accumulation.
The crack surfaces are corroded, indicating old age. Many cracks initiated at crevices formed
by socket welds and backing rings.
6. While the survey reveals a correlation to cracking with some cooling water chemistries the
SCC initiation mechanism as a result of the chemical interactions of the nitrite, nitrate,
molybdate, azoles, oxygen, and temperature are not clearly understood or defined.
Results of Plant Survey
7. Most of the stress corrosion cracks have occurred at or near the outlet side of the letdown
heat exchanger. SCC has also occurred downstream of the recycle evaporator package
distillate coolers, in the pipe to the surge tank, in the pipe leading from the excess letdown
heat exchanger, and in a pipe nipple in a recirculation line off of the reactor coolant pump
discharge line (Table 3-1).
8. The identified cases of SCC are based on detection of leaks caused by through wall cracks.
There has been only limited inspection which, together with the slow crack growth rate at the
CCW system operating temperatures, most likely leads to a significant under-estimation of
the frequency of cracking. Most of these type failures are routine repairs done during outages
and therefore a failure / root cause analysis is rarely performed.
It is recommended that all nuclear units consider inspection of the highest temperature
component welds. It is also recommended that samples be retained for analysis if damage is
found.
Laboratory Testing and Sample Analyses
9. The cyclic potentiodynamic test confirmed that carbon steel is susceptible to SCC in the
o o
aerated 1500 ppm nitrate (NO3) solution at 170 F (77 C). In addition, it was found that
although carbon steel is passive in nitrite (NO2), the unstable current density could indicate
the possibility of SCC. The molybdate (400 ppm) + TTA (50 ppm) test was inconclusive.
10. When the A106 Gr. B specimen and the weld metal specimen were coupled in a 1500 ppm
o o
nitrate solution at 170 F (77 C), the galvanic current polarity remained positive throughout
the test. This indicates that the weld metal remained anodic to the A106 Gr. B. The weld
metal had an open circuit potential that was 56 mV more negative than the A106 Gr. B
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specimen. It is estimated that the weld metal will corrode at a rate of 5 mils per year due to
galvanic corrosion for the base metal to weld (cathode to anode) ratio of 1:1. At higher ratios
in a piping system, the corrosion rate will be higher.
11. Slow Strain Rate Tests - Evidence of environmental cracking, in the form of fissuring, was
o o
observed on all of the specimens tested in aerated, 145 F (63 C) MoO4 solutions. In general,
the time to failure and elongation and reduction in area ratios were better for the solution
containing higher molybdate and TTA concentrations and having a higher pH (500 ppm
MoO4, 17.5 ppm TTA, and pH = 9.5 vs. 300 ppm MoO4, 7 ppm TTA, and pH = 8.5). In
addition, the specimens that received post weld heat treatment showed a small improvement
over the specimens that did not.
12. Potentiodynamic polarization and pitting scan testing of carbon steel by Carolina Power and
Light revealed that the scans in molybdate + TTA, molybdate + nitrite, and molybdate +
nitrite + TTA have pronounced transition potentials typical for SCC. It was also found that
the sodium molybdate corrosion inhibitor needs to be combined with an oxidizing agent or
aeration to provide adequate protection against general corrosion for carbon steel.
13. Four cracked pipe samples from three units (Calloway, Vogtle, Wolf Creek) were analyzed
by Jonas, Inc. and EPRI. The results of the analysis shows mostly intergranular/interdendritic
attack (some transgranular was seen) and cracks initiating in the weld metal and propagating
into the underlying base metal. Molybdenum, zinc, and copper were found on the fracture
surface of the Callaway sample.
There was evidence of Na, C, Zr, Al, Cl, Cu, Ca, Mn, S, and Ti on the fracture surface of the
1” Vogtle sample. Several Vogtle sample surfaces had high carbon (4.2 to 10.4%), probably
from a dried out organic inhibitor. The white residue on the outside surface produced by a
leak, had 50% Na. All of these samples were analyzed by EDS and had high concentration of
iron in the matrix.
Destructive testing was not allowed to be performed on the WCNOC specimen; however,
some scale was removed from the weld root. Traces of Zn, Zr, Cu, Ti, and Mo were
identified in the scale.
The surface chemistry at the crack and other surfaces is evidence that impurities can
concentrate to appreciable percent levels and that the impurities, such as Cu, which are SCC
promoters, can be transported through the CCW system. Copper concentration on some of
the surfaces was as high as 25%.
SCC Problem Detection, Inspection, and Repairs
14. Since there is an industry wide generic problem of SCC and corrosion fatigue of carbon steel
welds in numerous environments with thousands of cases world-wide and because there are
limited inspections in CCW systems, there is a strong possibility that the SCC exists in more
systems which has not yet been detected. Ultrasonic inspection should be conducted on
critical (related to safety and operation) and highest temperature components. Priority should
be given to units using nitrite plus BZT or molybdate plus TTA, welds with backing rings,
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socket welds, and other welds with the roots at crevices, and systems operating at
temperatures over 130oF (54oC).
The inspection methods should be verified using plant samples from this project and other
samples. Achievable NDT crack size detection limits should be determined.
15. Stress relieve PWHT should be performed when repair welding known SCC damaged areas.
Do not use backing rings and try to avoid socket welds and other crevices. Pipe alignment
before welding, particularly for flanges with socket welds, is very important.
According to literature data, increasing the concentration of carbon can reduce susceptibility
of carbon steel to SCC. It should be experimentally verified whether this would benefit the
SCC in CCW problem and whether higher carbon weld metals should be used.
16. It is not necessary to repair all small cracks. However, stress corrosion crack growth rates
should be estimated and the safe inspection interval determined using fracture mechanics and
leak before break methodology.
17. Because of the limited range of weld inspections and low sensitivity of the NDT methods
(ultrasonic and radiography) to small ID cracks, it is recommended to perform hydrotests of
important CCW systems at 1.5 times the operating pressure. This will cause deep cracks to
leak and may delay further propagation of smaller cracks by stretching the crack front and
resulting in residual compressive stresses during operation.
Cooling Water Chemistry
18. The plant survey identified many different cooling water chemistries used in component
cooling water systems in nuclear units. These include: chromate (aerated), nitrite (both
aerated and deaerated), molybdate (aerated and deaerated with nitrite), demineralized water
(both aerated and deaerated), and phosphate (aerated). In addition, units using copper alloys
for heat exchanger tubing use tolyltriazole or benzotriazole. Other plants have also used
sodium tetraborate. Both sodium and potassium hydroxides have been used in some plants to
adjust the pH. Chromate is still successfully used by 13% of the surveyed units.
SCC resulting in through wall cracks and leaks has been identified in 14 units using nitrite or
molybdate corrosion inhibitors with aerated water, with 12 of the 14 using either TTA or
BZT. In addition, 11 of the units experiencing SCC reported having problems with
biofouling. Systems using chromate, demineralized water, or phosphate have not reported
experiencing leaks due to SCC. None of the units using deaerated nitrite reported
experiencing SCC (leaks).
Considering the results of this project, it is recommended that:

• Further research be conducted into the use of aerated nitrite with BZT and nitrite and
molybdate treatments to evaluate their potential for SCC.
• Further research be conducted into the effects of switching from those water chemistries
identified in this project that have a possible correlation with SCC to those identified that
have no reports of having SCC. Testing should also be implemented to show that the
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proposed new water chemistries and biocide combinations fulfill acceptable general
corrosion rates while not to promoting SCC.
• Units using molybdate for general corrosion protection should be inspected at high
temperature locations (>130oF) due to testing results that indicate molybdate looses its
effectiveness to provide adequate general corrosion protection at higher temperatures.
• There should be a strict control of biofouling for all water treatments, especially nitrite.
• Storage, expansion, and surge tanks should be nitrogen sparged and blanketed to achieve
operation with low (<100 ppb) oxygen
• Where nitrogen blanketing cannot be done, storage and expansion tank vents should be
equipped with air filters to prevent contamination with microorganisms and dust
19. There is some evidence that CCW system water treatment chemicals and biocides are being
supplied with additives and impurities that may be contributing to the stress corrosion
cracking problem. For example, tolyltriazole (TTA) can contain up to 0.5% NaOH and 100
ppm chloride and the benzotriazole (BZT) supplied by at least one manufacturer contains
sulfuric acid. BZT also contains NaOH. Isothiazolene contains magnesium chloride and
nitrate as a stabilizer and may also contain 0.05 to 0.25 ppm of copper. The addition of 1.5
ppm of active isothiazolene will contribute up to 1.3 ppm chloride and up to 1 ppm sulfate to
the water. Methylene bis(thiocyanate) will contribute 0.75 ppm of sulfate to the cooling
water for every 1 ppm of the biocide added. Adding 1 ppm of 2,2-Dibromo-3-
nitrilopropionamide can contribute up to 0.7 ppm of bromide to the water. Further research
into the concentration of these impurities and additives should be conducted to reveal their
affect on SCC initiation in the CCW system.
In selecting water treatment chemicals, consideration should be given to the impurities that
would also be added to the system.
20. It is recommended that low oxygen levels be maintained in these systems. Consideration of
other successful water treatments, such as the simple trisodium phosphate treatment used by
EdF or conditioning with only NaOH or ammonia as recommended by VGB should be
investigated and experimentally verified to fulfill general corrosion protection and not
promote SCC. Minimizing chemical discharges should also be considered.
21. No data could be found to show that the various CCW chemical treatments protect crevices
or inhibit SCC. Further testing of the treatment chemicals, particularly the organics, should
be conducted to show they are stable and exhibit low volatility under the service conditions
of elevated temperature and presence of air (oxygen and CO2).
22. It is recommended to install stress corrosion specimens in the circuits that experienced
cracking, such as at the letdown heat exchanger outlet or in any other important sections of
o o
the CCW system, particularly where the temperature is high (above 130 F, 54 C). This will
aid in root cause analysis and provide early warning.
Recommended specimens include single and double U-bend and fracture mechanic
specimens – all with a weld. The specimens can be installed in an autoclave on a small side-
stream.
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For faster information on the propensity to SCC, corrosion potential probe should be used.
The corrosion potential in the known SCC region (transient) will indicate possible SCC.
Missing Knowledge
The following information, which could lead to more accurate root cause analysis, is not
available:
• Presence of SCC in units not yet experiencing leaks
• Effects of corrosion inhibitors in aerated and deaerated cooling water on SCC of carbon steel
welds for typical base metal and weld geometries and presence of impurities, such as
chloride, sulfate, and copper, iron, and other oxides
• Comprehensive chemical analysis of cooling water constituents and impurities including
concentrations of dissolved and suspended iron and copper oxides, sulfate, hydroxide, nitrate,
and carbonate
• Chemical composition of azoles (TTA and BZT) used in various power plants, including
concentrations of sulfate, chloride, bromide, and hydroxide
• Stability of sodium nitrite in aerated and deaerated cooling water, formation of nitrate, and
particularly the concentration percentage and its effect on SCC initiation of carbon steel
• Effect of low carbon weld metal on SCC in CCW systems
• Effect environment has on SCC during both operation and layup
• Basic knowledge on the mechanism of SCC and stress induced pitting or cracking including
stress and strain distribution between the lower yield strength base metal and higher yield
strength welds and the effects of lowering the carbon content on increasing of propensity to
SCC
• The effect(s) / consequence(s) changing water chemistry has on the overall system
performance in relation to provide general corrosion protection and resistance to SCC
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9
REFERENCES
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12. C. Myer. Metallurgical Evaluation of Damaged TPCCW 4” Section of Pipe (Unit 1). File
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Callaway
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41. B. Cavano. “Clearer Vision for Azoles Users.” The Analyst. Vol. III, No. 4, 1996.
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42. C.M. Mustafa, A.K.M. Obaydur Rahman and D.A. Begum. “Effects of Time and
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43. D.B. Alexander and A.A. Moccari. “Evaluation of Corrosion Inhibitors for Component
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Solution.” Chinese Journal of Materials Science, Vol. 25, No. 1. 1993.
45. P. Burda. “Molybates as Chromate Replacement for Closed Cooling Water Systems in
Nuclear Industry.” Paper No. 118, Corrosion/92. NACE, 1992.
46. K. Fivizzani, S. Shim. “Effects of Molybdate in Cooling Water Treatment Programs.” 1990
Cooling Tower Institute Annual Meeting. Houston, TX. February 5-7, 1990. Paper TP90-13.
47. Preventol CI 7 – A Corrosion Inhibitor for Industrial Applications. Bayer Corporation

Product Literature.
48. Preventol BZT – Corrosion Inhibitor for Copper, Brass, Bronze, and Multi-Metal Systems.
Bayer Corporation Product Literature.
49. Preventol CI 7, Preventol CI 8 – Corrosion Inhibitors for Copper, Copper Alloys and Other
Metals. Bayer Corporation Product Literature.
50. T. Weber, M. Stranick, and M. Vukasovich. “Molybdate Corrosion Inhibition in Deaerated

and Low-Oxygen Waters.” Corrosion, September 1986.
51. D. Robitaille. Sodium Molybdate Corrosion Inhibitor - An Update. Climax Molybdenum

Company. 1980.
52. G. Hatch. “Inhibition of Cooling Water.” Corrosion Inhibitors. NACE. Houston, TX. 1973.
53. M. Vukasovich and J. Farr. “Molybdate in Corrosion Inhibition – A Review.” Climax

Molybdenum Publication C-140. March 1986.
54. A. Mercer, et al. “Comparative Study of Factors Influencing the Action of Corrosion
Inhibitors for Mild Steel in Neutral Solution, III. Sodium Nitrite.” Br. Corrosion J., Vol. 3.
May 1968.
55. Administrative Manual: Part III – Water Quality Regulations. Delaware River Basin
Commission, West Trenton, NJ. October 23, 1996.
56. J. Ambrozova and J. Macak. “Influence of Several Corrosion Inhibitors on Growth of the
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Algae (Scenedesmus Quadricauda).” Chemistry of Energy Cycles 3. Proceedings of the 3
International Power Cycle Chemistry Conference, June 2000, College of Chemical
Engineering – Prague, 2000.
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57. G. Kobrin, “Reflection on Microbiologically Influenced Corrosion.” Materials Performance.

April 1994.
58. K. Selby and P. Puckorius. “Microorganisms in Cooling Water Systems – Case Histories:
Detrimental and Beneficial Effects.” Corrosion/93. NACE, 1993.
59. Detection and Control of Microbiologically Influenced Corrosion. EPRI. Palo Alto, CA:
1990. NP-6815.
60. D. Pope. “Mechanisms of Microbiologically Influenced Corrosion of Carbon Steels.”

Presented at the IGT Gas, Oil, Coal and Environmental Biotechnology Conference, New
Orleans, LA, 3-5 December 1990.
61. D. Pope and T. Zintel. “Methods for Investigating Underdeposit Microbiologically

Influenced Corrosion.” Materials Performance. November 1989.
General
62. Materials Handbook for Nuclear Plant Pressure Boundary Applications. EPRI, Palo Alto,
CA: December 2002. 1002792.
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63. Metals Handbook, 9 Edition, Volume 13: Corrosion. ASM International. Metals Park, OH.
1987.
64. Low Temperature Corrosion Problems in Fossil Power Plants – State of Knowledge Report.
EPRI, Palo Alto, CA: 2003. 1004924.
65. R. Revie, ed. Uhlig’s Corrosion Handbook. John Wiley & Sons, Inc. New York. 2000.
66. C. Briant. Metallurgical Aspects of Environmental Failures. Elsevier Science Publishers,

Amsterdam, 1985.
67. H. Logan. The Stress Corrosion of Metals. John Wiley and Sons, Inc. New York. 1966.
68. W. Robertson, ed. Stress Corrosion Cracking and Embrittlement. John Wiley and Sons, Inc.
New York. 1956.
69. Methods and Controls to Prevent In-Service Environmental Cracking of Carbon Steel
Weldments in Corrosive Petroleum Refining Environments. NACE, 2000.
70. O. Jonas. “Design Against Localized Corrosion.” Second Int’l Symp. on Env. Degradation of
Materials in Nuclear Power Systems – Water Reactors. Monterey, CA. Sept. 9-12, 1985.
71. O. Jonas. “Deaerators, An Overview of Design, Operation, Experience, and R & D.”
Proceedings of the American Power Conference, Vol. 49, A. 979. Illinois Institute of
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72. O. Jonas “Deaerator, Design and Operation, Effects on Water Chemistry, Corrosion
Problems.” EPRI Symposium on Fossil Utility Water Chemistry, Atlanta, June 11-13, 1985.
73. L. Arthur and C. Morgan. “Norway Inquiry Yields Big Clue to Blast.” The Miami Herald,
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74. Boiler Pressure Vessel Code Section III – Rules: Construction of Nuclear Power Plant
Components. ASME International, 2001.
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76. D. Graver. Corrosion Data Survey-Metals Section, Sixth Edition. NACE, 1985.
77. R. Trescder and R. Badrak. “Effect of Cold Working on SCC Resistance of Carbon and Low
Alloy Steels – A Review.” Corrosion/97. NACE 1997.
78. J. Mickalonis. “Slow Strain Rate Testing of Carbon Steel in Solutions with High Nitrate
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High-Level Waste Repository Environments. NTIS. February 1987. NUREG/CR-3861.
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A
CLOSED COOLING WATER SYSTEM CHEMISTRY AND
EXPERIENCE QUESTIONNAIRE
Completion of this survey will take ~1 hour and may require input from both the plant chemist and
metallurgist/maintenance department
Please complete the survey by typing next to the questions and returning by email as an attachment to
jonasinc@steamcycle.com or by hand and faxing to (302) 478-8173 or mailing to Jonas, Inc., 1113 Faun Road,
Wilmington, DE 19803 USA.
Name: _____________________________________________ Title: ____________________________________
Phone:________________________________ Email: ________________________________________________
Plant:_____________________________________________ Unit: ________ In Service Date________________
Location: _________________________________________________ Type of Unit: BWR PWR
1. Temperature and Pressure:
1.1 What are typical operating temperatures for the warmest portions of system?
Maximum operating temperature:________________
Average operating temperature:_________________
% of time system operated near the maximum temperature: ____%
1.2 What are the typical operating pressures for the system?
2. Materials:
2.1 What are the CCW system piping materials?
2.2 What other materials are included in the system (e.g., heat exchanger tube materials)? Any copper alloys?
2.3 To what Codes/Standards is the piping designed and maintained?
2.4 What pipe sizes and thicknesses (schedule) are used in your CCW system?
3. Welding:
3.1 What type of welding process is used on the CCW System piping and components?
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3.2 Are backing rings used?
3.3 Were the welds stress relieved after welding?
3.4 What is the weld filler material used? Please provide % carbon of filler material.
4. Cooling Water Chemistry:
4.1 What is the source of the cooling water? Please provide analysis.
4.2 What water treatment chemicals and corrosion inhibitors are used and at what concentrations? Please
provide example of analysis.
4.3 pH range for the system?
4.4 Dissolved oxygen concentration range?
4.5 Organics and biofouling (describe)
4.6 What chemical parameters are monitored, how (meter, grab sample, ASTM standard,…), and how
frequently?
4.7 Is the water chemistry handled by an outside company (Name) or by plant people?
4.8 Have there been any problems (e.g. cracking, corrosion, pitting, organic growth) associated with the
chemistry? Is so, please describe.
4.9 Describe the short- and long-term layup practices used for the CCW system.
5. For systems using molybdate chemistry, please answer the following:
5.1 When did operation with molybdates start?
5.2 If you converted from another chemistry, what was used before molybdates?
5.3 Did you clean and flush the system of all previous chemicals?
5.4 What molybdate concentrations are used? (If the control range for molybdate concentration has changed
over time, provide historical information.)
5.5 What other treatment chemicals are used with the molybdate (e.g., nitrite, azole, pH control, biocide)?
Concentrations?
5.6 Have the molybdate additive chemicals been analyzed for chemical impurities? If so, please provide
results.
6. Cracking Experience:
6.1 Have you inspected the piping and heat exchanger welds in the CCW system? If so, what were the results?
What NDE method was used? When was the last inspection?
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6.2 Have you ever had leaks from cracks or pits in the CCW piping or heat exchanger components at welds or
otherwise? If so, please describe.
6.3 If you had cracks, how were they repaired?
6.4 If you had any cracks, was the failure mechanism and/or root cause determined? If so, please describe.
Please provide copies of the failure analysis and metallurgical reports, if possible.
6.5 If you had cracks, how long before they occurred and how extensive were they?
6.6 Describe the surfaces at the crack(s): any scale, deposits, pitting, erosion, general corrosion?
6.7 Plans to inspect: how, what, and when
6.8 Samples: If you have any pipe samples with or without cracks, please send them to Jonas, Inc., 1113 Faun
Road, Wilmington, DE 19803 USA.
7. Your opinion as to why you do or don’t have stress corrosion cracking problems in your CCW system and what
are the root causes:
A-3
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B
ANALYSIS OF VOGTLE PIPE SAMPLES
On October 29, 2003, leaks were discovered in two pipe sections in the Vogtle Unit 2 ACCW
System. One leak was at a pipe to flange socket weld on a 2-inch dead leg that was no longer
used. The second leak was at a pipe to flange socket weld on a new 1-inch pipe used to cool the
motor for the normal charging pump. These sections (each with one leaking weld) were removed
during the next outage (~1 month later) and retained for analysis. The results of the analysis,
which included visual, optical, and scanning electron microscopic (SEM) examination, energy
dispersive x-ray spectroscopy (EDS), and metallurgical analysis, are described in this Appendix.
Background
The 2-inch piping sample is from the original return line from the Positive Displacement Pump
(PDP) Oil Cooler. The 2-inch line was in service from 1989 until 1999, when, because of a
design change, the PDP was replaced with a small centrifugal pump, which is used for normal
charging - Normal Charging Pump (NCP). During the 1999 modification, the 2-inch line was cut
and capped and has been in a dead stagnant leg for the last 4 years. The leaking 1-inch pipe
section was installed in 1999 and is a section of piping to the motor cooler for the NCP.
Materials
All of the piping/fittings were procured to the following specifications:

• Pipe: ASME SA-106 Gr. B. Seamless, Schedule 80
• Fittings: ASME SA-105, 3000 lb., Socket Weld
• Flanges: ASME SA-105, 150 lb., Raised Face Socket Weld
Water Chemistry
The Vogtle unit 2 auxiliary component cooling water system has surge tanks that are open to the
atmosphere and is treated with a blend of sodium nitrite, sodium borate, and benzotriazole.
History of Leaks
In addition to the two samples submitted for analysis, Vogtle 2 has experienced several other
leaks in the ACCW system including:
B-1
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• July 24, 2003 – A small leak was found on the longitudinal shell weld ~ 6 to 7 feet (1.8 to 2.1
meters) from the end (hotter end) of the ACCW heat exchanger shell. This location
corresponds to a baffle plate on the interior of the heat exchanger.
• June 1, 2003 – A pinhole leak was found under the reinforcing saddle where the return pipe
of the ACCW connects to the letdown heat exchanger shell. Water was also found coming
out of two weep holes, which served as an indication that water had found its way beneath
the saddle.
• December 24, 2002 – Several pinhole leaks were discovered on the longitudinal shell weld
~3 to 4 feet (0.9 to 1.2 meters) from the auxiliary component cooling water end of the heat
exchanger. The leaks formed a line approximately 0.5 inch (12.7 mm) in length,
perpendicular to the direction of the longitudinal seam weld of the shell. The location
corresponded to a baffle plate attached to the tubes inside the heat exchanger.
• Fall 2002 – A leak was discovered in the pipe which returns the auxiliary component cooling
water from the letdown heat exchanger to the auxiliary component cooling water heat
exchanger.
• 2001 – A through wall leak on the shell side of the letdown heat exchanger was discovered.
Circumferential and axial indications were identified near the joint between the shell and
shell head.
Visual Examination
2-inch Pipe Section
The 2-inch pipe section, which leaked at the flange socket weld, is shown in Figure B-1. The
pipe is approximately 20 inches (50.8 cm) long and has a Class 150 socket weld raised face
flange on one end and a forged elbow on the other. The pipe ID seems to be well passivated and
coated with a dark gray oxide. At the 6 o'clock position, there is an approximately 0.3 inch (0.7
cm) wide band of black adherent scale flakes along the entire pipe section (Figure B-2). The
same 6 o'clock area of the pipe-flange drop is filled with hard solid oxide that has been partially
removed where there is an orange rusted spot. The elbow at the other end of the 2-inch pipe
seems to be less oxidized. All internal surfaces are covered with orange spots, similar to flash
rusting. There are traces of white residue (Figure B-3) on the flange and the pipe to flange weld.
Figure B-1
2-inch Pipe Section as Received from Vogtle 2
B-2
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Figure B-2
2-inch Socket Weld Flange Face and Pipe ID with Black Adherent Scale Flakes
Figure B-3
2-inch Socket Weld Flange with White Residue on the Outside Surface; The Deposits
(Indicated by Arrows) were Later Determined to be Mainly Comprised of Sodium; NaOH is
a Known SCC Agent
The 2-inch pipe is not attached perpendicular to the raised face of the flange (Figure B-4). It is at
a 0.6 degree angle away from the centerline of the flange (i.e., 0.08 in. (2 mm) from centerline at
7.5 in. (190 mm) from the flange). When installed in the system, the force required to seal the
flange may have resulted in stress at the weld connecting the pipe and the flange.
B-3
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Figure B-4
2-inch Pipe-to-Flange Attachment Showing Pipe Misalignment; the Pipe is at a 0.6 Degree
Angle Away from the Centerline of the Flange
The inside diameter of the socket is 0.06 in. (1.4 mm) larger than the diameter of the pipe which
is touching the socket wall on one side, leaving the 0.06 in. (1.4 mm) gap on the opposite side
(Figure B-5). The pipe is 0.17 in. (4.25 mm) from the bottom of the socket. The area of the
flange raised face that appears to have been in contact with the gasket has an outside diameter of
2.75 in. (70 mm). The outside diameter of the entire raised face is 3.6 in. (92 mm).
B-4
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Figure B-5
Cross-section of 2” Flange Socket Weld; The Inside Diameter of the Socket is 0.06 in. (1.4
mm) Larger than the Diameter of the Pipe, which is Touching the Socket Wall on One Side
(Right) and Leaving a 0.06 in. (1.4 mm) Gap on the Opposite Side (Left) as Indicated by the
Arrows
1-inch Pipe Section
The 1-inch pipe section is shown in Figure B-6. A socket welded flange (Figure B-7) is located
at the inlet end of the section and a socket welded forged elbow is at the other end. The pipe ID
is covered by a thin mill scale with numerous small spots of orange rust along with several large
patches of shiny residue (Figure B-8). A small hole, which could have been a weld defect and
through which this weld leaked, was detected at one location on the OD of the pipe-to-flange
weld where the paint was chipped off. There is a brown residue on the weld and flange, possibly
indicating that there was a leak nearby.
The pipe section is off-center within the flange socket (Figure B-7). In addition, the flange and
pipe components were not perpendicular when installed. This may have introduced high
assembly stresses, in addition to the residual welding stresses, and caused the crack to form.
Figure B-6
1-inch Pipe Section as Received from Vogtle 2
B-5
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Figure B-7
Inside Surface of Socket Weld Flange – Pipe is Not Centered Within Socket (Indicated by
Arrows)
Figure B-8
ID of Socket Weld Elbow – Shiny Orange Deposits Visible (Indicated by Arrows)
In-situ pH of Surfaces
The in-situ pH of the deposits on various surfaces of the piping samples was measured using fine
division pH paper, wetted with deionized water. The results are summarized in Table B-1.
B-6
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Table B-1
pH Measured at Various Locations on Pipe Samples
Location pH
2-inch Pipe Section
Flange ID 8.5
Pipe ID 8.5
Elbow ID ND*
White Residue on Flange Outside Surface 8.5
White Residue on Pipe OD Near Elbow 8.5
1-inch Pipe Section
Flange Outside Surface 8.5
Pipe OD 7.0
Pipe ID 8.5
Elbow ID 7.0
Elbow ID Stains ND*
* - Not Detected
Deposit Analysis
Several deposits from the two pipe sections were examined visually and using optical and
scanning electron microscopy (SEM) (Figure B-9 and Figure B-10) and analyzed using energy
dispersive x-ray spectroscopy (EDS). The deposits are described below and the results are
summarized in Table B-2 and Table B-3.
2-inch Pipe Section
White Residue on Flange Outside Surface
The white and tan sample (Figure B-9) was obtained by scraping off the dry deposit from the
outside surface of the 2-inch flange outside surface. The deposit consists of white crystals with
sporadic round orange and red particles and a larger area of black particles. The white crystals
are 0.5 - 35 µm, the orange particles are 10 - 30 µm, and the black particles are more elongated
20 - 100 µm. Red particles are 25 - 35 µm. The deposit consists mainly of sodium and oxygen
with traces of iron and chromium. NaOH is a known SCC agent.
B-7
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Figure B-9
White Residue on Outside Surface of 2-inch Flange (65X); Comprised Mainly of Sodium
Oxide Flake from Pipe – Flange Crevice
A large oxide flake (Figure B-10) was removed from the crevice between the pipe and flange
socket with a pair of tweezers. Orange particles cover most of the surface of the flake, which is
an agglomeration of black particles. The orange and black particles are approximately 1 µm in
diameter. A gray/black area on the flake contains 0.5 µm yellow and orange round particles, and
0.5 µm oblong white particles. Several 20 µm red particles are scattered throughout the deposit.
The deposit consists mainly of iron with some copper, oxygen, carbon, and traces of manganese.
It should be noted that copper can have a synergistic effect on corrosion.
Figure B-10
SEM of Oxide Flake Removed from 2-inch Flange Crevice (1000X); Consists Mainly of Iron
with some Carbon, Copper, and Traces of Manganese; Copper can have a Synergistic
Effect on Corrosion
B-8
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Dark Streak on Pipe ID (Flange Side)
This fine powdery black sample was obtained by scraping off the dry deposit from a dark streak
on the ID of the pipe near the flange. The appearance of this deposit is similar to the oxide flake
taken from the pipe – flange crevice (see above). The deposit consists mainly of iron, copper,
and carbon with some oxygen and traces of silicon, manganese, and nickel.
A wet wipe sample was taken after the dry scrape sample and appears as black residue on the
filter paper. This wipe sample consists of 0.5 µm gray and black particles clumped together on
the fibers of the filter paper. The residue consists mainly of iron and oxygen with some carbon
and traces of manganese.
Elbow ID
The sample was obtained by scraping off the dry deposit and is in the form of small black
particles. This deposit consists of 0.5 µm round orange and yellow particles, and a few oblong 15
µm red particles.
1-inch Pipe Section
Paint Chip at Leak
A chip of paint was removed from the area around the leak. One side of the chip is blue due to
the blue paint coating on the pipe, and the other side is gray. The gray side of the chip that was
against the pipe OD surface consists of 0.5 to 15 µm black and gray particles, 50 µm diameter
red areas with 0.5 µm red particles, and two 25 µm diameter white areas that have an unclear
structure (possibly some of the paint).
Stain on Flange Outside Surface
The dry wipe sample take from the outside surface of the flange appears as a light yellow residue
on the filter paper. This wipe sample contains 10 - 20 µm black clumps consisting of smaller 0.5
µm black particles. The residue consists mainly of iron, oxygen, and carbon with traces of
sodium, silicon, sulfur, chloride, potassium, calcium, titanium, and manganese.
A wet wipe sample was taken after the dry scrape sample and appears as a yellow/green residue
on the filter paper. The wipe sample consists of 50 - 70 µm orange particles with 0.5 - 20 µm
white particles on their surfaces.
Flange Side Pipe ID
The sample was obtained by scraping off the dry deposit from the ID of the pipe near the flange
and is in the form of a fine black powder. This deposit is similar to the 2-inch pipe flange crevice
flake. However, in one area, there are several flat translucent orange pieces.
B-9
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Shiny Deposits on Elbow ID
The sample was obtained by scraping off the dry deposit from a shiny area on the ID of
the elbow (Figure B-11). The deposit is made up of black and dark red particles with
areas that are shiny metallic. The deposit consists of 10 - 50 µm red and black particles
with scattered 0.5 - 20 µm metallic areas. The red particles are translucent. All of the
particles have 0.5 µm orange particles scattered on the surface, however, the orange
particles are more sporadic on the metallic areas. The deposit consists mainly of iron
and oxygen with traces of silicon, chromium, copper, and zinc.
Figure B-11
Shiny Deposit Obtained from Dry Scraping 1-inch Pipe Elbow ID (65X)
A wet wipe sample was taken after the dry scrape sample. Traces of orange residue can
be seen on the filter paper. The pieces of deposit that are present in this wipe sample have
the same consistency as those in the 1-inch pipe elbow ID shiny deposit scraping. The
residue mainly consists of iron and oxygen with some carbon and traces of silicon,
phosphorous, manganese, copper, and zinc.
11924595 B-10
Table B-2
Magnetic Properties and Particle Size and Color of Deposits
Sample Sample Quantity Magnetic Particle Size (µm)/Color1, 2
2-inch Pipe Section
White Residue on
0.5 - 35/w; 10 - 30/o; 25 -
Flange Outside Few flakes on filter paper No
35/r; 20 - 100/b
Surface
Oxide Flake from

Large Flake Yes 0.5/b, y, w; 0.5 - 1/o; 20/r
Pipe-Flange Crevice
Dark Streak on Pipe

Few flakes on filter paper Yes 0.5/b, y, w; 0.5 - 1/o; 20/r
ID (Flange Side)
Dark Streak on Pipe

Wet Wipe --- 0.5/g, b
ID (Flange Side)
Elbow ID Few flakes on filter paper Yes 0.5/o, y; 15/r
1-inch Pipe Section
Paint Chip at Leak Chip No 0.5/r, 0.5 - 15/b, g
Stain on Flange
Dry wipe --- 10 - 20/b; 0.5/b
Outside Surface
Stain on Flange
Wet Wipe after Dry Wipe --- 50 - 70/o; 0.5 - 20/w
Outside Surface
Flange Side Pipe ID Few flakes on filter paper Yes 0.5/b, y, w; 0.5 - 1/o; 20/r
Shiny Deposits on
Few flakes on filter paper Yes 0.5/o; 0.5 - 20/m; 10 - 50 r, b
Elbow ID
Shiny Deposits on Wet Wipe after Dry

--- 0.5/o; 0.5 - 20/m; 10 - 50 r, b
Elbow ID Scrape
1) 1 µm = 0.04 mils
2) o - orange, w - white, g - gray, y - yellow, b - black, r - red, m – metallic
11924595 B-11
Table B-3
EDS Analysis of Selected Deposit Samples
Elemental Composition by Weight (%)

Deposit Sample
C O Na Si P S Cl K Ca Ti Cr Mn Fe Ni Cu Zn
2-inch Pipe Section
White Residue on
Flange Outside --- 46.8 50.2 --- --- --- --- --- --- --- 0.3 --- 2.7 --- --- ---
Surface
Oxide Flake from
9.0 8.0 --- --- --- --- --- --- --- --- --- 1.7 71.5 --- 9.9 ---
Pipe-Flange Crevice
Dark Streak on Pipe
ID (Flange Side) – 10.4 8.3 --- 0.5 --- --- --- --- --- --- --- 0.3 54.7 0.9 25.0 ---
Dry Scrape
Dark Streak on Pipe
ID (Flange Side) – 4.2 22.9 --- --- --- --- --- --- --- --- --- 1.2 71.7 --- --- ---
Wet Wipe
1-inch Pipe Section
Stain on Flange
Outside Surface – 24.2 28.5 1.4 0.5 --- 0.5 0.4 0.3 0.3 0.3 --- 0.4 43.3 --- --- ---
Dry Wipe
Shiny Deposits on
Elbow ID – Dry --- 25.9 --- 0.8 --- --- --- --- --- --- --- 1.1 69.4 --- 0.6 2.3
Scrape
Shiny Deposits on
Elbow ID – Wet 4.2 16.0 --- 0.5 0.3 --- --- --- --- --- --- 0.5 74.8 --- 0.9 3.0
Wipe
--- Not Detected (less than 0.1% by weight)
Metallurgical Analysis
2-inch Pipe Section

Two areas that were suspected to have been leaks were identified on the flange to pipe
weld. To investigate both areas, the excess pipe was cut away just above the weld and the
flange was cut at both locations. At each cut, the weld and surrounding material were
lightly ground and then polished with 600 grit sandpaper to remove machining marks. At
one of the locations, optical microscopic examination of the weld area revealed a 0.2 in.
(0.5 mm) branched crack extending part way into the weld. The location of this crack
corresponds to the area that would have been under stress due to the misalignment of the
pipe and flange.
Metallographic sections were removed and prepared for microstructural characterization
(Figure B-12 and Figure B-13). Etched samples were prepared using a 3% Nital etchant.
The 2-inch pipe section showed evidence of lack of penetration of the root pass of the socket weld.
11924595 B-12
Figure B-12
Photograph Showing the Fracture Path of the 2” Socket Weld; Cracking Initiated from the
Inherent Notch at the Root of the Weld and Propagated through the Weld Metal to the
Surface (10X)
Figure B-13
Branched Section of the Crack Propagation Near the OD of the 2” Socket Weld (200X)
B-13
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1-inch Pipe Section
One area that was suspected to have been a leak was identified on the flange to pipe weld where
a section of paint had been chipped off. To investigate this area, the excess pipe was cut away
just above the weld and the flange was split in half at the suspected location. The weld and
surrounding material on both sides of the cut were lightly ground to remove machining marks.
Optical microscopic examination of the weld area revealed a through-wall crack extending
completely across the weld. The location of this crack corresponds to the area that would have
been under stress due to the misalignment of the pipe and flange.
Further analysis revealed a large lack of fusion (LOF) defect that does not appear to propagate to
the through wall crack (Figure B-14). Branching and oxidation along the fracture surface was
also noted (Figure B-15).
Figure B-14
Photograph of the 1” Socket Weld Failure Showing Initiation of the Through Wall Leak at
the Root; Another Crack Initiating from the Root can be seen Propagating to a Lack of
Fusion Defect Near the Root (10X)
B-14
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Figure B-15
SEM Photograph of the Polished Metallographic Sample Showing Branching and
Oxidation Along the Fracture Surface of the 1” Socket Failure (Location of the Photograph
is Approximately Mid Length of the Crack)
Hardness
Hardness traverses were conducted to measure socket base metal – heat affected zone (HAZ) –
weld metal and the pipe base metal – HAZ – weld metal for both the 1-inch and 2-inch pipe
samples. All hardness measurements were made using the Vickers indenter with a 500 gram
force load. The measurements were taken at the toes of the weld (pipe side and flange side), mid
wall, and root of the weld for comparison (Table B-4).
Table B-4
Average Hardness Measurements for Weld Metal, HAZ, and Base Metal
Location Average Weld Average HAZ Average Base

1-inch Pipe Sample
Pipe Side Toe 196.1 173.4 164.3
Flange Side Toe 202.2 186.9 150.4
Midwall Pipe 216.8 183.1 169.6
Midwall Flange 190.0 181.3 154.9
Root Pipe 188.7 172.0 161.5
Root Flange 194.5 188.2 161.6
2-inch Pipe Sample
Pipe Side Toe 219.3 181.9 147.3
Flange Side Toe 227.6 219.8 176.7
Midwall Pipe 220.0 168.7 149.7
Midwall Flange 221.5 226.5 179.3
Root Pipe 206.7 171.7 137.1
Root Flange 212.8 251.8 185.4
B-15
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(EDS)
The 1-inch pipe sample was cleaned in methanol in an ultrasonic cleaner before entering the
SEM chamber. The 2-inch section was not cleaned. EDS analysis was conducted on the
uncleaned fracture surface (Figure B-16).
Figure B-16
SEM Image of the Polished Metallographic Sample Showing the Corrosion Product
Buildup on the 2-inch Socket Weld Fracture Surface Near the Initiation of the Failure; the
Box Highlights the Area in which the EDS Analysis (Dark Area) was Performed on the
Oxidation Deposit of the Fracture Surface
SEM Fractographs
SEM fractographs were taken for each sample (Figure B-17 and Figure B-18). Following EDS
analysis of the fracture surface, the samples were chemically cleaned to remove the oxidized
coating on the fracture surface in an attempt to more clearly show the fracture path morphology.
Metallographic and fractographic inspection both show mostly intergranular/interdendritic crack
propagation in the weld metal only. Some transgranular cracking was also observed. The
initiation of the crack was from the inherent defect of the socket weld at the root.
Figure B-17
SEM Fractograph of the 2” Fracture Surface in the Uncleaned Condition. The EDS Spectra
on the Right is Representative of the Fracture Surface Majority. The EDS Spectra on the
Left is Representative of the Fracture in the Root Area
B-16
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Figure B-18
SEM Photograph of the Chemically Cleaned Fracture Surface of the 1” Failure. The EDS
Spectra from the Pipe O.D. to Socket I.D. Gap area is Given on the Right and the EDS
Spectra for the Fracture Surface of the Root Area is Given on the Left. Both EDS Spectras
were Taken Before Chemically Cleaning the Fracture Surface.
Conclusions
1. The 1” pipe section experienced stress corrosion cracking through the weld initiated at the
pipe weld juncture in the crevice of the socket weld. The average crack growth rate was
approximately 1.5x10-4 mm/hr (1.4 mm/year) falling within the corrosive environment area of
the crack propagation diagram shown in Figure 3-6.
2. After sectioning the 2” flange, a 0.5 mm crack was visible. The average crack growth rate for
this visible crack was approximately 4.5x10-6 mm/hr (4.0x10-2 mm/yr). The crack growth rate
-5
for a through-wall crack would be approximately 5.0x10 mm/hr (0.4 mm/yr). In both cases,
the crack growth rate would fall within the corrosive environment area of the crack
propagation diagram shown in Figure 3-6.
3. Impurities (such as NaOH, organics, and copper) that could contribute to SCC of carbon steel
welds were found to be concentrated to high percent levels. NaOH found as a white residue
on the 2” pipe section OD is a known SCC agent and copper found in the 2” pipe section ID
can have a synergistic effect.
4. The flange – pipe assembly of both pipe sections have been welded out of alignment (not a
right angle), which, upon tightening of the flange, may have introduced very high assembly
stresses, in addition to the residual welding stresses.
B-17
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C
ANALYSIS OF WOLF CREEK PIPE SAMPLE
During an ultrasonic inspection of the Wolf Creek Nuclear Operating Corporation (WCNOC)
component cooling water system, a crack, located at a pipe to flange weld, was detected in the
discharge piping downstream of the letdown heat exchanger. No through-wall leak was reported.
The cracked section was replaced in October 2003. The sample is comprised of a 6-inch 150 lb
A105 raised face weld-neck flange and an 8.9 inch (22.6 cm) long section of A106 Grade B pipe
(Figure C-1). WCNOC requested that the sample remain intact and returned upon completion of
the examination. Therefore, only a visual examination was performed, the results of which are
described in this Appendix.
Figure C-1
Flange Assembly As-Received from WCNOC
Background
The WCNOC plant is a 1235 MW PWR unit that started commercial operation in 1985. SCC in
the CCW system was first detected in 1994 and again in 2000 in piping operating at ~150oF
C-1
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(66oC). Detection of through-wall leakage through the letdown heat exchanger shell in October
2000 prompted an expanded scope of ultrasonic testing (UT) inspections of the CCW piping
welds. A total of 88 welds were inspected using UT, of which 34 were identified as having a
crack indication. The sample sent to Jonas, Inc. for analysis was one of these 34 welds.
Water Chemistry
The CCW system uses demineralized water and has an open to air surge tank. Over the life of the
unit, there have been several changes in the CCW corrosion control program. A chronology of
WCNOC chemistry for the CCW system is shown in Table C-1 [2]. The molybdate
concentration started low, peaked in 1995, and then decreased again until mid-2001 when a
decision was made to increase the concentration to 800 ppm. The tolyltriazole concentration
slowly increased with time until mid-2001, when it was increased significantly to 20 ppm. The
pH decreased with time until January 2002, when NaOH was added to increase the pH to 9.4.
After the initial operation of the plant, the concentration of chloride in the system has been low.
Table C-1
Chronology of Changes in WCNOC CCW Chemistry [2]
Molybdate (ppm) Tolyltriazole (ppm) Chloride (ppb) pH

Year
Average Range Average Range Average Range Average Range
1984 50 2-83 0 800 50-1700 11 8-11.5
1985 80 5-150 0 60 7-120 9.5 9-10
1986 225 90-350 5 3-7 40 10-95 9.3 8.7-10.5
1987 250 180-400 5 2.5-6.5 45 3-105 9.4 9-10
1988 250 170-505 5 2-7.5 25 5-65 9.1 8.6-9.3
1989 300 250-345 5 4-6 27 13-40 9.1 8.8-9.9
1990 300 190-440 5 1.9-7 20 4-39 9 8.8-9.2
1991 280 210-450 5.3 3-7 30 6-45 8.8 8.5-9
1992 350 280-415 6 4-7 25 13-48 8.9 8.6-9
1993 340 270-450 6.5 4-9.9 15 6-38 8.6 7.9-9.1
1994 360 290-540 8 5-9.3 17 8-40 8.6 8-8.8
1995 510 440-550 7 5.8-8.2 20 9-33 8.6 8.4-9.5
1996 360 230-500 8.8 4.2-11 15 10-28 8.5 8.3-9.6
1997 340 200-380 8 5-10.6 18 10-34 8.5 8.3-8.6
1998 275 250-350 8 7.2-9.1 18 10-25 8.4 8-8.7
1999 240 210-260 8.5 6-10 14 10-27 8.4 8-8.7
2000 220 200-380 8 3.1-11 13 10-15 8.6 7.6-8.8
2001-2002 8001 201 9.42
1 – Levels of molybdate and tolyltriazole increased in mid-2001
2 – NaOH added to increase pH to 9.4 in January 2002
C-2
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Materials
All of the pipe materials involved conformed to ASTM A106 Grade B. The fittings conformed to
A105.
History of Leaks
The first through wall leak was discovered in 1994, after approximately 9 years of service. The
leak was located at a weld approximately 12 - 15 feet (3.7 – 4.5 meters) downstream of the
letdown heat exchanger discharge nozzle. The next through wall leak was found in 1996 in the
same section of piping (different weld) as the first leak. In May 2000, a through-wall leak was
discovered in a weld in the CCW return line from the letdown heat exchanger.
Detection of through-wall leakage through the letdown heat exchanger shell in October 2000
prompted an expanded scope of UT inspections of the CCW piping welds. A total of 88 welds
were inspected using ultrasonic testing (UT). Of those, 34 (39%) showed reportable indications
and 41 welds were replaced [7]. In some instances, sections of piping were replaced in order to
reduce radiation exposure. All of the welds that showed reportable indications were located
downstream of the letdown heat exchanger Cracking also was detected in two welds on the CCW
return piping from the upper bearing cooler on a reactor coolant pump [4]. An additional leak on
the letdown heat exchanger was found at the base of the shell at the lifting lug closest to the
discharge nozzle.
In 2002, ultrasonic testing identified SCC in 3” Schedule 160 and 4” Schedule 120 piping
o o
operating at a much lower temperature – 90 F (32 C).
Visual Examination
The OD surface of the pipe, weld, and part of the weld-neck flange are coated with a green paint.
There are several locations where the paint has chipped on the weld and pipe OD, however, there
are no indications of any leaks. The surfaces on the outside diameter that are not coated show
signs of light rusting. The flange face has some red and white deposits and mild corrosion
(Figure C-2).
The weld root appears to be slightly protruding from the ID surface and there are a few features
on the weld that may be weld defects (Figure C-3). Overall, the weld appears to be of good
quality. The in-situ pH was measured on the flange assembly ID, but no pH was detected.
C-3
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Figure C-2
Flange Face As-Received from WCNOC
Figure C-3
Flange Assembly ID Weld
C-4
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Deposits
Samples of deposits were removed from the flange assembly ID on both the “pipe side” and
“flange side” of the assembly. The deposits were examined visually and using optical
microscopy and the results are summarized in Table C-2.
Table C-2
Sample Magnetic Particle Size (µm)/Color1, 2
Weld Neck Flange ID - Dry Scrape Yes 1-10/o, <1/b
Pipe ID – Dry Scrape Yes 0.5-5/w, o, r, g
Pipe ID – Dry Wipe Sample N/A 0.5-5/w, o, r, g
1) 1 µm = 0.04 mils
2) o – orange, b – black, w – white, r – red, g - gray
Weld Neck Flange ID - Dry Scrape
The powdery scraping consists of oxide pieces with some 1 to 10 µm orange particles scattered
on the surface. The outside surface (side which faced the water flow) of a large piece of deposit
is completely covered with submicron black particles with some scattered 1 to 10 µm orange
particles on the surface (Figure C-4). The surface of the deposit that was adhered to the pipe wall
is white (Figure C-4). Both the powdery deposits and large particle are magnetic.
Figure C-4
Surface of Deposit Particle that Faced Water Flow (Left) and Adhered to Pipe Wall (Right)
C-5
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Pipe ID – Dry Scrape
This powdery scraping consists of oxide pieces with 0.5 to 5 µm white, orange, red and gray
particles scattered on the surface. The oxide pieces are magnetic, indicating the presence of
magnetite.
Pipe ID - Dry Wipe Sample
This brown-gray wipe sample consists of 0.5 to 5 µm white, orange, red and gray particles,
similar to those on the dry scrape sample above.
Energy Dispersive X-ray Spectroscopy (EDS)
An EDS analysis was conducted on some deposits removed from the pipe ID (Figure C-5) as
well as from the weld root (Figure C-6 and Figure C-7). The pipe ID deposit consists mainly of
iron with trace amounts of manganese, molybdenum, copper, and zinc. The weld root deposit is
similar to the pipe ID deposit, however, it also contains silica and trace amounts of titanium and
zirconium.
Figure C-5
EDS Spectra of White Deposit Taken from Pipe ID
C-6
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Figure C-6
EDS Spectra of Deposit Removed from Weld Root
Figure C-7
EDS Spectra of Deposit Removed from Weld Root
C-7
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D
ANALYSIS OF CALLAWAY PIPE SAMPLE
During Refuel Outage 12 (October and November 2002), ultrasonic inspection revealed cracks in
the Callaway Nuclear Plant letdown heat exchanger shell near the outlet nozzle. The cracked
section of the exchanger was sent to Ameren UE for examination and a metallurgical report was
issued in June 2003 [16]. The pipe section was shipped to Jonas, Inc. for additional analysis in
March 2004. The results of the analysis, which included visual, optical, and scanning electron
microscopic (SEM) examination, energy dispersive x-ray spectroscopy (EDS), and metallurgical
analysis, are described in this Appendix.
Introduction
During an ultrasonic inspection, Callaway identified two ID cracks on the shell side of the
nozzle-to-shell weld, radiating out from the ID of the nozzle. The outlet nozzle is located on the
top rear of the letdown heat exchanger on the northeast side.
Material
The chemical composition of the shell, nozzle, and weld was tested and it was confirmed that the
composition conformed to the standards shown in Table D-1 [16].
Table D-1
Outlet Nozzle, Shell, and Weld Filler Material
Component Size Material
Nozzle 8” Schedule 40 A106 Grade B
Shell 22” Schedule 20 A106 Grade B
Weld Filler Material N/A Conformed to E7018 and ER70S-2
Water Chemistry
The Callaway CCW system uses a combination of molybdate and tolyltriazole to inhibit
corrosion of the carbon steel and copper alloy materials. The surge tank is open to the
atmosphere and the source of the makeup water is the demineralized water storage tank, which is
supplied from a deep well.
D-1
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History of Leaks
After approximately 16 years of operation, a through wall leak occurred in a socket weld joint in
the CCW system. This attributed to an overstress condition at installation when a pipe off a relief
valve was forced into place during installation and welded because the pipe was too short.
Most recently, leaks were discovered in the letdown heat exchanger outlet nozzle to shell weld
(sent to Jonas, Inc. for analysis) and in a welded tee downstream of the letdown heat exchanger.
Visual Examination
The ID surfaces of the shell and nozzle are covered with black oxides with adherent small
particles, which could have been weld splatter. There are groups of small pits, some of which are
near the cracks. The weld has some porosity, however, it is not associated with any of the cracks.
Figure D-1 shows the sample in the “as-received” condition. Figure D-2 shows the black
adherent oxide scale and a patch of the loose powdery gray deposit. Figure D-3 shows the shell
ID and the locations where the two samples were removed previously.
Figure D-1
Outlet Nozzle and Shell as Received from Callaway
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Figure D-2
Outlet Nozzle ID showing the Black Adherent Deposit and a Patch of Gray Loose Deposit
Figure D-3
Shell ID Illustrating Where Two Specimens were Previously Removed for Analysis by
Callaway; Black Lines Indicate Locations of Additional Cracks
D-3
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The ID of the shell was lightly ground using 600 grit paper to reveal the extent of the cracking. A
total of eight cracks were found. All of the cracks radiated out from the nozzle starting about
0.25 inches (6.4 mm) from the ID. The crack lengths are listed in Table D-2.
Table D-2
Cracks Identified Near Shell to Outlet Nozzle Weld
Length
Crack No.* Description
inches (mm)
1 0.91 (23) Non-branching, located on shell, perpendicular to weld, occurring in HAZ
8 0.06 (1.5) Non-branching, located on shell, perpendicular to weld, occurring in HAZ
Notes:
1) Two pieces of the weld were removed by Callaway prior to examination by Jonas, Inc. and EPRI
2) Crack Nos. 2, 3, and 4 are partially aligned following one after the other
3) Crack Nos. 7 and 8 are partially aligned following one after the other
In-Situ pH of Surfaces
The in-situ pH of the deposits on various surfaces of the piping samples was measured using fine
division pH paper, wetted with deionized water. The results are summarized in Table D-3.
Table D-3
pH Measured at Various Locations on Pipe Samples
Location pH
Shell ID 6.5
Nozzle ID – Black Adherent Deposit 6.5
Nozzle ID – Gray Loose Deposit 6.5
Deposit Analysis
Three deposits were examined visually and using optical microscopy. The results are
summarized in Table D-4 below.
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Table D-4
Sample Magnetic Particle Size (µm)/Color1, 2
Shell ID Yes 5-10/w
Nozzle ID – Black Adherent Deposit Yes 5-10/o
Nozzle ID – Gray Loose Deposit Yes 0.5-1/br, 5-20/r, 5-20/o, blue stains
1) 1 µm = 0.04 mils
2) w – white, br – brown, r – red, o - orange
Shell ID
This powdery scraping consists of oxide pieces. A few of the pieces have 5 to 10 µm white
crystals on the surface.
Nozzle ID - Black Adherent Deposit
The powdery scraping consists of oxide pieces with some 5 to 10 µm orange particles scattered
on the surface.
Nozzle ID - Loose Powdery Gray Deposit
This green scraping consists gray oxide pieces coated with 0.5 to 1 µm brown particles (Figure
D-4). There are 5 to 20 µm red and orange particles scattered on the oxide surfaces and a few
areas of blue staining.
Figure D-4
Loose Powdery Deposit Scraped from ID of Outlet Nozzle (65X)
D-5
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Hardness Testing
Hardness traverses were conducted to measure the base metal, heat affected zone and weld metal
on both the nozzle and the shell for both the fillet and extra pass weld metal. All hardness tests
were performed using the Vickers indenter with a 500 gram force load.
Table D-5
Average Hardness Measurements for Weld Metal, HAZ, and Base Metal
Average Average Average

Location
Weld Metal Heat Affected Zone Base Metal
Nozzle Side Face 170.1 185.7 169.8
Shell Side Face 175.5 186.7 157.2
Nozzle Side Mid 148.9 168.6 169.8
Shell Side Mid 148.4 164.7 152.8
Nozzle Side Root 146.8 158.7 169.8
Shell Side Root 143.4 149.1 151.7
Metallurgical Analysis
Numerous cracks (Figure D-5) were detected around the nozzle to shell weld joint predominantly
where the convex portions of the nozzle contour mated with the shell on the ID of the shell. The
cracks appear to be initiating in an extra weld pass around the circumference of the nozzle
section fillet weld root on the ID of the shell. The cracks were all transverse to the welding
direction of this extra weld pass. The crack morphology was branched and indicative of SCC
(Figure D-6). The surface roughness of the extra pass was greater than the surface roughness of
the root pass of the fillet weld. Metallographic sections were prepared for microstructural
characterization. Etched samples were prepared using a 3% Nital etchant (Figure D-7).
Figure D-5
Dye Penetrant Test Indications Showing Cracks Initiating in the Root Extra Pass
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Figure D-6
Collage of Magnified Crack Through the Extra Root Pass of the Shell ID (Each Photo 50X)
Figure D-7
Photomicrograph Showing Intergranular Progression at the Tip of the Crack Extending
into the Shell Base Metal (250X)
D-7
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(EDS)
The crack is partially filled with oxide, indicating corrosion continued as the crack propagated.
The EDS analysis (Figure D-8 to Figure D-10) conducted on these oxides showed the presence
of molybdenum, consistent with the molybdate water treatment used by Callaway. There were
also traces of zinc and copper found in the oxide.
Figure D-8
SEM Photo Showing the Oxide Build-up at the Initiation of the Shell SCC and the
Corresponding EDS
Figure D-9
SEM Photo of the Oxide Within the Shell ID Crack and the Corresponding EDS
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Figure D-10
SEM Photo of the Crack Through Porosity Found at the Interface of the Shell ID and Extra
Weld Pass and the Corresponding EDS
SEM Fractographs
To study the Fractography of the crack, a cross section of the crack was removed (Figure D-11)
and was split open by fracturing the remaining shell material. Metallographic and fractographic
inspection of the fracture surface both show intergranular/interdendritic attack and crack
propagation initiating in the weld metal and propagating into the underlying base metal (Figure
D-12 and Figure D-13). There was some evidence of the crack arresting in the shell material. The
initiation of the cracks appeared to be in the extra weld pass on the shell ID. The crack did
exhibit branching, which was visible at low magnifications and also intergranular faceted crack
path morphology. One area of the fracture contained 10 micron bipyramid oxides (Figure D-14).
D-9
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Figure D-11
Cross Sectioning on One of the Shell ID Cracks was Conducted to Investigate the Crack
Path. This Photograph Reveals the Sectioning Location Employed to Prepare the
Metallographic Samples. The Saw Cut Through the Crack and Through a Plane of the
Nozzle to Shell Fillet Weld on the Under Side of the Sample.
Figure D-12
Photograph of Crack Broken Open to Reveal Fracture Surface; the Dark Area is the SCC
and the Shiny Area is the Fresh Fracture Resultant from Forcing the Crack Open
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Figure D-13
Fracture Surface of the SCC Showing Signs of Intergranular Propagation; Fracture
Morphology Difficult to Characterize Due to Heavy Oxide Deposits on the Surface
Figure D-14
SEM Photograph of Bi-pyramid Oxides Found on the Fracture Surface
D-11
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Stress Corrosion Cracking in PWR and BWR Closed Cooling Water Systems

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Stress Corrosion Cracking in PWR and BWR Closed Cooling Water Systems

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Stress Corrosion Cracking in

PWR and BWR Closed Cooling

Technical Update, October 2004

EPRI Project Manager

ORGANIZATION(S) THAT PREPARED THIS DOCUMENT

This report was prepared by

EPRI Repair / Replacement Applications Center

This report describes research sponsored by EPRI.

2 PLANT SURVEY ....................................................................................................................2-1

3 SCC INITIATION AND PROPAGATION ................................................................................3-1

4 LABORATORY TESTING ......................................................................................................4-1

5 ROOT CAUSE ANALYSIS.....................................................................................................5-1

6 ENGINEERING RECOMMENDATIONS ................................................................................6-1

7 CRACK DETECTION THROUGH INSPECTION AND MAINTENANCE...............................7-1

8 CONCLUSIONS, RECOMMENDATIONS, AND MISSING KNOWLEDGE ...........................8-1

B ANALYSIS OF VOGTLE PIPE SAMPLES ........................................................................... B-1

C ANALYSIS OF WOLF CREEK PIPE SAMPLE .................................................................... C-1

D ANALYSIS OF CALLAWAY PIPE SAMPLE ....................................................................... D-1

Total Total MWh Losses

Pumps 2 17,936 15.2 8,945

Valves 1 590 0.5 574

Heat Exchangers 8 25,724 21.8 3,221

Total 70 646,050 547.5

* - Total Number of Unit-Years = 1180

Total Total MWh Losses MWh/ MWh/

Pumps 85 418,110 30.0 4,918

Valves 22 54,354 3.9 2,467

Heat Exchangers 218 636,921 45.7 2,919

System Fouling 19 139,370 10.0 7,344

Other Problems 185 918,448 65.9 4,967

Total 589 2,468,242 177.1

* - Total Number of Unit-Years = 13,937

Closed Cooling Water System Design

PWR Component Cooling Water Systems cool a variety of equipment, including:

Material Yield Strength Ultimate Tensile Strength

Specification Actual Specification Actual

A106 B 35.0 (240) 51.5 (354.8) 60.0 (415) 78.2 (539.2)

A105 36.0 (250) 46.9 (323.4) 70.0 (485) 81.0 (558.5)

ER70S-2 60.0 (413) 72.6 (500.6) 72.0 (496) 88.3 (608.8)

ER70S-2 60.0 (413) 75.6 (521.3) 72.0 (496) 86.8 (598.5)

The properties of circulating waters in closed-circuit cooling systems recommended by VGB

Provides Typical Control pH Control

Chloride • 10 ppm • 10 ppm • 10 ppm • 10 ppm • 150 ppb • 50 ppb

Conductivity at 77oF (25oC) (µS/cm) <30

Cation Conductivity at 77oF (25oC) (µS/cm) <5

pH value at 77oF (25oC) >7

Oxygen (ppb) <20

Oil (ppm) <1

Control of Oxygen and Carbon Dioxide

Control of Suspended Solids

In CCW systems, water treatment chemicals are used for:

Additives and Impurities in Water Treatment Chemicals

Handling and Discharge of Closed Cooling Water Treatment Chemicals

Chromate Y, 100 ppb* 136, Carcinogen

Chlorine Y, 1000 ppb FCR* 90

* - Limit Set by EPA

LHX thermal relief line, LHX outlet

Max D.O. (ppb)3

Almaraz (Spain) 2 plants N N Y N N N Na N 10.2 10.0 Sat

# of Units Not # of Units

Temperature above 130oF (54oC) 12 0 2

Use of Aerated Water 13 0 2

Use of Sodium Nitrite1 9 6 0