Pressurized Water Reactor Steam Generator Lay-up: Corrosion Evaluation

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Pressurized Water Reactor Steam Generator Lay-up: Corrosion Evaluation

1011774

Interim Report, December 2005

EPRI Project Manager K. Fruzzetti

ELECTRIC POWER RESEARCH INSTITUTE 3420 Hillview Avenue, Palo Alto, California 94304-1395 PO Box 10412, Palo Alto, California 94303-0813 USA 800.313.3774 650.855.2121 [email protected] www.epri.com

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CITATIONS
This report was prepared by iSagacity, Inc. 625 Miramontes Street Suite 206 Half Moon Bay, CA 94019 Principal Investigators P. Millett J. Bates This report describes research sponsored by the Electric Power Research Institute (EPRI). The report is a corporate document that should be cited in the literature in the following manner: Pressurized Water Reactor Steam Generator Lay-up: Corrosion Evaluation. EPRI, Palo Alto, CA: 2005. 1011774.

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REPORT SUMMARY

This interim report summarizes work completed to date for a project to develop improved lay-up guidance for PWR Steam Generators (SG). Phase 1 of this project included a detailed literature review and a gap analysis of additional work needed to quantify the corrosion behavior of SG materials under wet lay-up conditions. As a result of the gap analysis, EPRI designed a corrosion test program (Phase 2) to measure general corrosion rates of steam generator materials under layup conditions. This report summarizes Phases 1 and 2 of the project. Phase 3 of this project (to be completed) will develop additional localized corrosion measurements, including galvanic corrosion for important SG material galvanic couples. Background Within the past 10 years, outage lengths have decreased dramatically. Many nuclear units routinely perform refueling outages in 25 days. Steam generator lay-up times have decreased accordingly. Some units have been able to take advantage of the EPRI guidance allowing lower concentrations of hydrazine and amine when the steam generators are in lay-up for less than 7 days. However, EPRI bases this guidance on industry practice and limited laboratory studies. Furthermore, there is no leeway in dealing with outages that are slightly longer than 7 days. There is little laboratory data to verify the effectiveness of lay-up solutions on critical steam generator metallurgies as a function of time. However, this guidance would be very beneficial to utilities both in refueling outages, as well as in forced outages where the outage length is not well known at the time when lay-up decisions need to be made. In order to maintain the integrity of the steam generator tubes during lay-up conditions, it would be prudent to develop the appropriate guidance for lay-up solutions based on time, steam generator critical metallurgy, deposit conditions, and existing steam generator corrosion conditions. Objectives To develop corrosion test data for steam generator materials under lay-up conditions. To provide the industry with improved guidance for laying up steam generators.

Approach The project team divided this work into four phases. Phase 1 included a detailed literature review and a gap analysis of additional work needed to quantify the corrosion behavior of SG materials under wet lay-up conditions. They designed Phase 2 to measure general corrosion rates of SG materials under lay-up conditions. This report summarizes Phases 1 and 2 of the project to date. Phase 3 of this project, to be completed, will analyze additional localized corrosion

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measurements, including galvanic corrosion for important SG material galvanic couples. Phase 4 will assess the results in full and provide improved guidance for SG wet lay-up. Results The experimental work performed in this study demonstrated that the corrosion resistant alloys I600, I690 and 405 SS experience low and acceptable general corrosion rates under all of the deaerated conditions tested. Although there were a few I600 measurements with higher than acceptable corrosion rates (probably as a result of experimental error), the majority of the data was at the limit of detection in this program. However, the project team determined that evaluation of galvanic and local corrosion is necessary before drawing any overall general conclusions with respect to these alloys. Under aerated conditions without pH control, both I600 and I690 experienced relatively high general corrosion rates for some specimens, but below LLD for other specimens. The remainder of the work focused on the carbon steel and weld materials, including an exploration of trends with respect to oxygen scavenger concentration and pH. In addition, the project team made comparisons to the literature data and discussed recommendations for future testing. EPRI Perspective Wet lay-up of steam generators during outages with chemically treated water (amine and oxygen scavenger) is desirable to minimize corrosion and oxidation during the lay-up period itself, and also minimize corrosion during subsequent startups and power operation. EPRI based the current lay-up guidance on industry experience with long outages and limited laboratory data. However, improved guidance is necessary to address current concerns with respect to shorter outage durations and discharge limits. EPRI will base the new guidance on a detailed review of existing field and laboratory data supplemented with an experimental program to fill critical voids in the corrosion database. This interim report addresses the literature review and gap analysis performed in the first phases of this project. Additional work is required before the development of improved guidance. Keywords Steam generator Corrosion Wet-layup

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ABSTRACT
This interim report summarizes work completed to date on a project to evaluate the current PWR steam generator lay-up guidance as described in sections 2.4.12 and 5.5.1 of the PWR Secondary Water chemistry Guidelines Revision 6 (EPRI TR-1008224, December 2004). Phase 1 of this project included an extensive literature review of the corrosion test data and basis for the current lay-up chemistry guidelines. A gap analysis was completed to determine what additional data would be needed to update the current guideline recommendations. Phase 2 is a corrosion test measurement program to evaluate the general corrosion rates of several SG materials under wet lay-up conditions. In the test program, weight loss measurements were made in varying concentrations of oxygen scavengers with solutions containing <20 ppb dissolved oxygen and the pH controlled to >9.0. Additional tests were performed in initially air saturated and nitrogen purged solutions with and without oxygen scavengers. The oxygen scavengers tested in this work include; hydrazine, carbohydrazide and di-ethyl hydroxylamine (DEHA). Phase 3, yet to be completed, will evaluate and measure localized and galvanic corrosion under steam generator lay-up chemistries.

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CONTENTS

1 INTRODUCTION....................................................................................................... 1-1 2 BACKGROUND ........................................................................................................ 2-1 Current Guidelines ................................................................................................... 2-2 3 LITERATURE REVIEW ............................................................................................ 3-1 Analysis of Literature Data ....................................................................................... 3-4 Bounding Materials .............................................................................................. 3-4 Acceptable Corrosion Rates ................................................................................ 3-4 Proposed Lay-up Corrosion Testing ........................................................................ 3-8 Initial Test Matrix.................................................................................................. 3-9 References............................................................................................................. 3-10 4 EXPERIMENTAL PROCEDURES ............................................................................ 4-1 Experimental Apparatus........................................................................................... 4-1 Experimental Procedures......................................................................................... 4-4 Pre Cleaning........................................................................................................ 4-4 Experimental Matrix ............................................................................................. 4-4 Post Cleaning ...................................................................................................... 4-6 5 EXPERIMENTAL RESULTS .................................................................................... 5-1 Effects of Oxygen Scavengers................................................................................. 5-5 Inconel 600 .......................................................................................................... 5-5 Inconel 690 .......................................................................................................... 5-7 405 Stainless Steel .............................................................................................. 5-8 1010 Carbon Steel............................................................................................. 5-10 A569 Carbon Steel ............................................................................................ 5-12

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A36 Carbon Steel .............................................................................................. 5-14 E 70-S Weld Metal............................................................................................ 5-15 E-7018 Weld Metal ............................................................................................ 5-17 Control Environments ............................................................................................ 5-18 Air Saturated Conditions.................................................................................... 5-18 I600.................................................................................................................... 5-18 I 690................................................................................................................... 5-19 405 SS............................................................................................................... 5-19 1010 Carbon Steel............................................................................................. 5-19 A569 Carbon Steel ............................................................................................ 5-20 A36 Carbon Steel .............................................................................................. 5-20 E-7018 Weld Metal ............................................................................................ 5-21 Controlled Conditions without Oxygen Scavengers ............................................... 5-21 I600.................................................................................................................... 5-21 1010 Carbon Steel............................................................................................. 5-22 A569 Carbon Steel ............................................................................................ 5-22 A36 Carbon Steel .............................................................................................. 5-23 E-7018 Weld Metal ............................................................................................ 5-24 E-70-S Weld Metal............................................................................................. 5-24 6 DISCUSSION OF RESULTS .................................................................................. 6-25 Effect of Solution pH on Corrosion Rates .............................................................. 6-26 Comparison to Literature Data ............................................................................... 6-28 Recommendations for Future Work ....................................................................... 6-31 A CHEMISTRY MEASUREMENT DATA.................................................................... A-1

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LIST OF FIGURES
Figure 2-1 RSG Full Wet Layup (RCS 200F) Steam Generator Sample................................2-2 Figure 2-2 OTSG Full Wet Layup (RCS 200F) (Technical Specification Modes 5 and 6) Steam Generator Sample ..................................................................................................2-3 Figure 3-1 Carbon Steel Corrosion Rates with Oxygen Scavengers under Aerated Conditions (Note: we will insert References for each data point in this graph) ..................3-5 Figure 3-2 Estimated Corrosion Rate of Carbon Steel in Aerated Hydrazine Solution ..............3-6 Figure 3-3 Corrosion Rate of Carbon Steel as a function of pH and Oxygen Scavenger (Note: we will insert references for each data point in this graph)......................................3-7 Figure 4-1 Metal Samples Corrosion Coupon............................................................................4-1 Figure 4-2 Metal Samples Coupon Rack ...................................................................................4-2 Figure 4-3 Assembled Test Apparatus ......................................................................................4-3 Figure 5-1 Corrosion Rate of Inconel 600 as a function of Oxygen Scavenger Concentration.....................................................................................................................5-6 Figure 5-2 Corrosion Rate of Inconel 690 as a function of Oxygen Scavenger Concentration.....................................................................................................................5-8 Figure 5-3 Corrosion Rate of 405 SS as a function of Oxygen Scavenger Concentration .......5-9 Figure 5-4 Corrosion Rate of 1010 CS as a function of Oxygen Scavenger Concentration...................................................................................................................5-11 Figure 5-5 Corrosion Rate of A569 CS as a function of Oxygen Scavenger Concentration...................................................................................................................5-13 Figure 5-6 Corrosion Rate of A36 CS as a function of Oxygen Scavenger Concentration...................................................................................................................5-15 Figure 5-7 Corrosion Rate of E-70-S as a function of Oxygen Scavenger Concentration .....5-16 Figure 5-8 Corrosion Rate of E-7018 as a function of Oxygen Scavenger Concentration.....5-18 Figure 6-1 Summary of all Carbon Steel data with Hydrazine additions................................6-26 Figure 6-2 1010 Corrosion Rate as a Function of Average Solution pH ................................6-27 Figure 6-3 A569 Corrosion Rate as a Function of Average Solution pH ...............................6-28 Figure 6-4 A36 Corrosion Rate as a Function of Average Solution pH .................................6-28 Figure 6-5 Comparison of Corrosion Data from This Study to Literature Data (Dearated Conditions) .......................................................................................................................6-30 Figure 6-6 Comparison of Corrosion Data from This Study to Literature Data (Aerated Conditions) .......................................................................................................................6-31 Figure 6-7 Future General Corrosion Test Recommendations ..............................................6-32

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LIST OF TABLES
Table 3-1 Literature Review of Corrosion Data..........................................................................3-2 Table 3-2 Steam Generator Metallurgies...................................................................................3-3 Table 3-3 Millstone 2 SG Tubesheet Chemical Cleaning Corrosion Coupon Results ..............3-8 Table 3-4 Allowable Corrosion Rates for Susceptible Steam Generator Metallurgies...............3-8 Table 4-1 Materials Tested .......................................................................................................4-2 Table 4-2 Experimental Matrix of Metals Exposed to Oxygen Scavengers .............................4-5 Table 4-3 Experimental Matrix of Metals Exposed to No Oxygen Scavengers (Control).........4-6 Table 5-1 Summary of Experimental Runs ..............................................................................5-2 Table 5-2 Corrosion Rate of Inconel 600 as a function of Hydrazine Concentration .................5-5 Table 5-3 Corrosion Rate of Inconel 600 as a function of DEHA Concentration .......................5-6 Table 5-4 Corrosion Rate of Inconel 600 as a function of Carbohydrazide Concentration ........5-6 Table 5-5 Corrosion Rate of Inconel 690 as a function of Hydrazine Concentration .................5-7 Table 5-6 Corrosion Rate of Inconel 690 as a function of DEHA Concentration ......................5-7 Table 5-7 Corrosion Rate of Inconel 690 as a function of Carbohydrazide Concentration ......5-7 Table 5-8 Corrosion Rate of 405 SS as a function of Hydrazine Concentration ......................5-8 Table 5-9 Corrosion Rate of 405 SS as a function of DEHA Concentration ............................5-9 Table 5-10 Corrosion Rate of 405 SS as a function of Carbohydrazide Concentration...........5-9 Table 5-11 Corrosion Rate of 1010 CS as a function of Hydrazine Concentration.................5-10 Table 5-12 Corrosion Rate of 1010 CS as a function of DEHA Concentration ......................5-10 Table 5-13 Corrosion Rate of 1010 CS as a function of Carbohydrazide Concentration.......5-11 Table 5-14 Corrosion Rate of A569 CS as a function of Hydrazine Concentration ...............5-12 Table 5-15 Corrosion Rate of A569 CS as a function of DEHA Concentration......................5-12 Table 5-16 Corrosion Rate of A569 CS as a function of Carbohydrazide Concentration ......5-13 Table 5-17 Corrosion Rate of A36 CS as a function of Hydrazine Concentration .................5-14 Table 5-18 Corrosion Rate of A36 CS as a function of DEHA Concentration........................5-14 Table 5-19 Corrosion Rate of A36 CS as a function of Carbohydrazine Concentration ........5-14 Table 5-20 Corrosion Rate of E-70-S as a function o f Hydrazine Concentration..................5-15 Table 5-21 Corrosion Rate of E-70-S as a function of DEHA Concentration..........................5-16 Table 5-22 Corrosion Rate of E-7018 as a function of Carbohydrazide Concentration .........5-16 Table 5-23 Corrosion Rate of E-7018 as a function of Hydrazine Concentration ..................5-17 Table 5-24 Corrosion Rate of E-7018 as a function of DEHA Concentration ........................5-17 Table 5-25 Corrosion Rate of E-7018 as a function of Carbohydrazide Concentration .........5-17

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Table 5-26 Corrosion Rate of I600 in Air Saturated Demineralized Water ............................5-18 Table 5-27 Corrosion Rate of I600 in Vapor above Air Saturated Demineralized Water .........5-19 Table 5-28 Corrosion Rate of I690 in Air Saturated Demineralized Water ............................5-19 Table 5-29 Corrosion Rate of I690 in Vapor above Air Saturated Demineralized Water .......5-19 Table 5-30 Corrosion Rate of 405 SS in Air Saturated Demineralized Water.........................5-19 Table 5-31 Corrosion Rate of 1010 CS in Air Saturated Demineralized Water .....................5-19 Table 5-32 Corrosion Rate of 1010 CS in Vapor Above Air Saturated Demineralized Water................................................................................................................................5-20 Table 5-33 Corrosion Rate of A569 CS in Air Saturated Dimeralized Water .........................5-20 Table 5-34 Corrosion Rate of A569 CS in Vapor above Air Saturated Demineralized Water................................................................................................................................5-20 Table 5-35 Corrosion Rate of A36 CS in Air Saturated Demineralized Water .......................5-20 Table 5-36 Corrosion Rate of A36 CS in Vapor above Air Saturated Demineralized Water................................................................................................................................5-21 Table 5-37 Corrosion Rate of E-7018 in Air Saturated Demineralized Water........................5-21 Table 5-38 Corrosion Rate of I600 in pH Controlled Low Dissolved Oxygen Water..............5-21 Table 5-39 Corrosion Rate of I690 in pH Controlled Low Dissolved Oxygen Water..............5-22 Table 5-40 Corrosion Rate of 1010 CS in pH Controlled Low Dissolved Oxygen Water.......5-22 Table 5-41 Corrosion Rate of 1010 CS in Vapor above pH Controlled Low Dissolved Oxygen Water ..................................................................................................................5-22 Table 5-42 Corrosion Rate of A569 CS in pH Controlled Low Dissolved Oxygen Water ......5-22 Table 5-43 Corrosion Rate of A569 CS in Vapor above pH Controlled Low Dissolved Oxygen Water ..................................................................................................................5-23 Table 5-44 Corrosion Rate of A36 CS in pH Controlled Low Dissolved Oxygen Water ........5-23 Table 5-45 Corrosion Rate of A36 CS in Vapor above pH Controlled Low Dissolved Oxygen Water ..................................................................................................................5-24 Table 5-46 Corrosion Rate of E-7018 in pH Controlled Low Dissolved Oxygen Water .........5-24 Table 5-47 Corrosion Rate of E-70-S in pH Controlled Low Dissolved Oxygen Water..........5-24 Table A-1 Experiment No. 1 Chemistry Data ......................................................................... A-1 Table A-2 Experiment No. 2 Chemistry Data.......................................................................... A-2 Table A-3 Experiment No. 3 Chemistry Data.......................................................................... A-3 Table A-4 Experiment No. 4 Chemistry Data.......................................................................... A-4 Table A-5 Experiment No. 5 Chemistry Data.......................................................................... A-5 Table A-6 Experiment No. 6 Chemistry Data.......................................................................... A-6 Table A-7 Experiment No. 8 Chemistry Data.......................................................................... A-7 Table A-8 Experiment No. 9 Chemistry Data.......................................................................... A-8 Table A-9 Experiment No. 10 Chemistry Data........................................................................ A-9 Table A-10 Experiment No. 12 Chemistry Data.................................................................... A-10 Table A-11 Experiment No. 13 Chemistry Data.................................................................... A-11 Table A-12 Experiment No. 14 Chemistry Data.................................................................... A-12

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Table A-13 Experiment No. 15 Chemistry Data.................................................................... A-13 Table A-14 Experiment No. 16 Chemistry Data.................................................................... A-14 Table A-15 Experiment No. 17 Chemistry Data.................................................................... A-15

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1
INTRODUCTION
This interim report summarizes work completed to date for a project to develop improved lay-up guidance for PWR Steam Generators (SG). Phase 1 of this project included a detailed literature review and a gap analysis of additional work needed to quantify the corrosion behavior of SG materials under wet lay-up conditions. As a result of the gap analysis, a corrosion test program (Phase 2) was designed to measure general corrosion rates of steam generator materials under lay-up conditions. This report summarizes Phases 1 and 2 of the project. Phase 3 of this project (to be completed) will include additional localized corrosion measurements including galvanic corrosion for important SG material galvanic couples. The current lay-up guidance is based on industry experience with long outages and limited cost and or regulatory pressure on environmental discharge. Improved guidance is needed to address current concerns. The new guidance will be based on a detailed review of existing field and laboratory data supplemented with an experimental program to fill critical voids in the corrosion database. This interim report addresses the literature review and gap analysis that was performed in the first phase of the project. Additionally, this report summarizes general corrosion test data that was performed as a result of the gap analysis. Wet lay-up of steam generators during outages with chemically treated water is desirable to minimize corrosion and oxidation during the lay-up period itself and also corrosion during subsequent startups and power operation. Protection is provided by an amine for pH control and hydrazine (or other qualified oxygen scavenger) to maintain a protective oxide film and a reducing environment. Fossil fuel boiler experience and laboratory studies show that proper layup chemistry can provide corrosion protection for six months or longer. A positive nitrogen overpressure should be maintained during filling, draining, and cold shutdown to minimize oxygen ingress. Hydrazine in concentrations of >75 ppm is an effective oxygen scavenger at ambient temperatures. Nuclear units typically add hydrazine to the steam generators following a unit shutdown. Once the unit is cooled off, nitrogen sparging is used to mix the hydrazine and remove oxygen. Maintaining a reducing environment in the steam generators minimizes the corrosion potential on the tube surface. Removing oxygen from the lay-up solution also allows metal deposits, such as copper, to remain in the reduced state. Oxidation of deposited metals such as copper can contribute to an increase in the electrochemical potential in a localized area of the tube during start up. It is very important that during lay-up conditions, the steam generator tubes and deposits remain in a reducing environment. In more recent years, alternates to hydrazine have been introduced both in lay-up and in operating applications. Hydrazine is carcinogenic and its production of ammonia has contributed to hazardous working conditions in steam generators. Also, the discharge limitations on 1-1

EPRI Proprietary Licensed Material Introduction

hydrazine have caused further complications in its application. Alternate chemical treatments such as carbohydrazide and diethyl hydroxylamine (DEHA) have been used with varying success. Application guidance primarily has been supplied by chemical vendors with an emphasis on lower lay-up concentrations and higher reaction rate kinetics in scavenging oxygen. However, breakdown products such as carbonates, have caused many to return to dealing with the high concentrations and discharge limitation issues of hydrazine.

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2
BACKGROUND
Within the past 10 years, outage lengths have decreased dramatically. Many nuclear units routinely perform refueling outages in 25 days. Steam generator lay-up times have decreased accordingly. Some units have been able to take advantage of the EPRI guidance allowing lower concentrations of hydrazine and amine when the steam generators are in lay-up for less than 7 days. However, this guidance is based on industry practice and not on specific laboratory studies. Furthermore, there is no leeway in dealing with outages that are slightly longer than 7 days. Very few laboratory data have been taken to verify the effectiveness of lay-up solutions on critical steam generator metallurgies as a function of time. However, this guidance would be very beneficial to utilities both in refueling outages, as well as in forced outages where the outage length is not well known at the time when lay-up decisions need to be made. In order to maintain the integrity of the steam generator tubes during lay-up conditions, it would be prudent to develop the appropriate guidance for lay-up solutions based on time, steam generator critical metallurgy, deposit conditions, and existing steam generator corrosion conditions. The objectives of this project are as follows: To develop corrosion test data for steam generators materials under lay-up conditions. Provide the industry with improved guidance for laying up steam generators.

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EPRI Proprietary Licensed Material Background

Current Guidelines
The EPRI PWR Secondary Chemistry Guidelines, Revision 6 currently have the following specifications for lay-up chemistry:
CONTROL PARAMETERS FOR STEAM GENERATOR SAMPLE Monitor values until stable at a frequency of three times per week, then weekly once values are stable. Initiate Action <9.5
a

Parameter pH @ 25C Hydrazine, ppm Sodium, ppb Chloride, ppb Sulfate, ppb

Value Necessary Prior to Heatup (>200F) 100 100 100

<75 >1000 >1000 >1000

DIAGNOSTIC PARAMETERS FOR STEAM GENERATOR SAMPLE Parameter Boron Sludge analysis Consideration Applies only to plants using secondary side boric acid treatment. When sludge is available as a result of sludge lancing or other maintenance. CONTROL PARAMETERS FOR STEAM GENERATOR FILL SOURCE Parameter Dissolved O2, ppb
a. b. c.

Frequency (b)

Initiate Action >100c

Alternatives to hydrazine may be used if qualified by the utility. Appropriate limits for any hydrazine alternative should be substituted. Required prior to and/or during fill for plants with oxygen control of their fill water source. For plants without control of oxygen in their fill source, appropriate compensatory actions shall be taken to minimize steam generator exposure to oxygen, e.g., nitrogen sparging or addition of a reducing agent to the fill source or directly to the steam generators. Figure 2-1 RSG Full Wet Layup (RCS 200F) Steam Generator Sample

The Guidelines provides the following instructions; During outages, when the time period between cold shutdown and draining or partial draining of the SGs for maintenance or startup is expected to be less than seven days or the time period between completion of the maintenance and startup is expected to be less than seven days, it is not necessary to place the steam generators in full wet layup. However, to the extent practicable considering personnel safety and environmental issues, the critical elements of full wet layup, i.e., elevated pH, hydrazine (or alternative oxygen scavenger) at greater than 75 ppm, nitrogen overpressure, low dissolved 2-2

EPRI Proprietary Licensed Material Background

oxygen, and low impurities should be maintained. If one or more of these conditions cannot be maintained, the remaining conditions should still be applied. When filling the steam generators from a drained or partially drained condition, the hydrazine concentration in the steam generator should be >5 ppm and a nitrogen overpressure should be established. If condenser vacuum is broken, steps should be taken to ensure that oxygenated feedwater is not introduced into the steam generators via feedwater. Water used to fill the steam generators should contain less than 100 ppb dissolved oxygen.
CONTROL PARAMETERS Monitor all values every other day until stable, then weekly or after significant water additions a Parameter pH @ 25C Hydrazine, ppmb Sodium, ppb Chloride, ppb Sulfate, ppb Oxygen, ppb
c

Initiate Action 9.5 <75 or >500 >1000 >1000 >1000

Value Necessary Prior to Heatup Above >200F 100 100 100 100

DIAGNOSTIC PARAMETERS Parameter Nitrogen Overpressure,d psig Hideout Return Databasee (Na, Cl, SO4, SiO2, K, Mg, Ca, Al)
a. b. c. d. e.

Justification Minimization of oxygen ingress to the steam generators during wet layup. Assessment of OTSG crevice and superheat region solution chemistry during operation; impurity source term assessment.

Chemical addition and OTSG recirculation should be initiated as soon as possible after entering Mode 5. Alternatives to hydrazine may be used if qualified by the utility. Appropriate limits for any hydrazine alternative should be substituted. Routine monitoring not required prior to initial heatup if hydrazine concentration is within normal range. A nitrogen overpressure should be maintained on the steam generators when personnel safety will not be compromised. Hideout return assessments generally should be based on data collected during fill/drain operations immediately subsequent to shutdown.

Figure 2-2 OTSG Full Wet Layup (RCS 200F) (Technical Specification Modes 5 and 6) Steam Generator Sample

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LITERATURE REVIEW
The purpose of the literature review was to gather all relevant corrosion data that has served as the basis for the current lay-up chemistry guidelines. A listing and brief summary of the pertinent data for the literature review is given at the end of this Chapter. The main requirement of wet lay-up is to reduce or eliminate oxygen from the gas space of the steam generators. An oxygen scavenger is added to the water to remove any oxygen that enters the SG during lay-up. Finally, an elevated pH is maintained to reduce the solubility principally of iron in SG steels. Rabeau et. al. [19] showed that a hydrazine concentration of 50 ppm to 100 ppm was necessary to minimize the corrosion rate for carbon steel in an aerated, pH 10.0 environment. This is in agreement with the current EPRI guidelines. However, deoxygenating the lay-up solution with nitrogen removed the dependency of the corrosion rate on hydrazine. Thus, the driving force for corrosion is available oxygen in the lay-up solution. The reaction of oxygen with metal surfaces is much preferred over the reaction of oxygen with hydrazine in solution, particularly at lay-up temperatures. The following is an overview of the data from the literature reviewed that contain corrosion rate information for carbon steel. The data were taken from referenced sources and are sorted by the reported corrosion rate, CR.

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EPRI Proprietary Licensed Material Literature Review

Table 3-1 Literature Review of Corrosion Data Iso ascorbic Acid, ppm Carbon Steel CR, mpy < LLD < LLD <LLD 0.0048 0.089 0.137 0.167 0.57 0.66 1.755 290 315 400 800 200 0.020 0.030 0.004 0.016 0.003 0.010 1 40 100 40 200 170 460 50 1.755 2.457 2.5 2.691 2.964 20.67 30

pH(25) 9.6 9.6 9.9 9.3 8.7 9.3 9.9 10.6 10.6

O2, ppm 1 1 < LLD 0.003

N2H4, ppm 200 145 0.003 0.03 145

CH, ppm 100

HQ, ppm

DEHA

MEK ppm

360 36 0.025 0.040 0.075 0.090 0.020 0.030 45 - 100

10.1

9.6

MEK- methyl ethyl ketone, CH-Carbohydrazide, HQ-hydroquinone, DEHA-Diethyl hydroxylamine

The majority of the literature focused testing on carbon steel, however the SG contains a number of potentially susceptible materials. A combined listing of materials from two different steam generators (replacement B&W and Westinghouse D5) is given below: [24]

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Table 3-2 Steam Generator Metallurgies Component 6"/8" Handhole Diaphragms AFW Nozzle AFW Permanent Cap AFW Safe End AFW Thermal Sleeve Anti Vibration Bars Aux Nozzle Cap Plug Back-up Rings Baffle Plate Retaining Blocks Channel Head Diaphragm Screws Drum Internals FW Header Pipe FW Inlet Nozzle FW Safe End Handhole Covers Inspection Port cover Inspection Port Diaphragms J tube Pipe Lattice Support Rings Lower Shell Barrels Main FW Nozzle Main FW Nozzle Limiter/Insert Main FW Thermal Sleeve Main FW Thermal Slv Transition Manway/HH Gaskets Misc Internal Non-Pressure Parts Misc Internal Non-Pressure Parts Misc Internal Non-Pressure Parts Misc Internal Non-Pressure Parts Misc Internal Non-Pressure Parts Misc Internal Non-Pressure Parts Misc Internal Non-Pressure Parts Misc Internal Non-Pressure Parts NR Level Tap NR Upper/Lower Level Taps Pre-heater Partition Plate Recirc Nozzle Sample Tap Material SB-168 SA-508 SA-234 SB-166 SB-167 Inconel 600 SA-350 SA-285 SA-285 SA-216 SA-193 Carbon Steel SA-335 SA-508 SA-508 SA-516 SA-105 SB-168 SB-167 SA-516 SA-533 SA-508 SB-166 SA-106 Gr B SA-516 Flexitallic ASTM A-285 Gr C Inconel SA-106 Gr B SA-240 Type 405 SA-36 SA-508 SA-516 Gr 70 SA-696 Gr C SA-508 SA-350 ASTM A-285 Gr C E7018-A1 SA-508 Component SD Nozzles Sec. Shell Drain Secondary Manway Secondary MW Diaphragm Secondary Shell Shell Cone Shroud Stayrod Stayrod Bolting Steam Drum Head Steam Drum Shell Steam Drum Support ring Steam Outlet Nozzle Steam Outlet Safe End Stub Barrel Transition Cone TSP AntiRotation blocks TSP back-up bars TSP Shims TSP Spacer Pipes TSP Wedges Tube Support Plates Tube Supports Tubes Tubesheet Upper Head Upper Shell Barrels Weld Filler Material - Typical SMAW Wet Lay-up Tap Wide Range Level Tap WR Upper/Lower Level Taps Wrapper Antirotation Block Wrapper AntiRotation Key Wrapper Barrel Wrapper Jacking Blocks Wrapper Jacking Studs Wrapper Key Restraint Wrapper Position Blocks Material E7018-A1 SA-508 SA-508 SB-168 SA-533 SA-508 SA-516 SA-696 Gr C SA-193 SA-508 SA-533 SA-516 SA-508 SA-350 SA-533 SA-533 ASTM A-576 ASTM A-576 SB-168 SA-106 ASTM A-576 A-240 SA-240-410S SB-163 SA-508 SA-533 SA-533 SFA 5.1 Class E7018 SA-508 SA-508 SA-350 SA-516 SA-516 ASTM A285 SA-516 SA-36 SA-516 SA-516

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EPRI Proprietary Licensed Material Literature Review

The material analysis performed by B&W for the qualification of a polymer dispersant in the ANO steam generators helped to identify specific materials whose susceptibility bounded the corrosion susceptibility in the steam generators. These included steam generator tubing material, support plate material, high susceptible carbon steels, and high susceptible welding material. Similar considerations are applicable to this programs test matrix.

Analysis of Literature Data

Bounding Materials The literature survey supplied a short list of steam generator materials that were used as bounding conditions in the approval for a steam generator polymer dispersant [15].
Materials LTMA Inconel 600 405 SS SA-335 Gr P11 ER70S-6 GMAW E7018-A1SMAW SA-569 SA-36

Acceptable Corrosion Rates An acceptable corrosion rate for carbon steel in a high pH aerated environment can be determined from the literature survey data [1, 6, 7, 17, and 19].

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EPRI Proprietary Licensed Material Literature Review

8 7 Carbon Steel Corrosion Rate, mpy 6 5 4 3 2 1 0 9.6 9.7 9.8 9.9 10 10.1 pH N2H4 CH 10.2 10.3 10.4 10.5 10.6 10.7 360 ppm [1] 36 ppm [1]

30 ppm [17]

80 ppm [17]

Figure 3-1 Carbon Steel Corrosion Rates with Oxygen Scavengers under Aerated Conditions

This is compared with the recommendations of Marks [1] where to prevent corrosion, the following correlation was presented: [N2H4] > -210pH + 2200 ppm and [CH] > 125 ppm. The hydrazine data in Figure 3-1 shows that a lay-up solution with hydrazine at 30 ppm and pH of 9.7 yields a corrosion rate for carbon steel of 5 mpy in an aerated solution. At an increased pH of 9.9 and hydrazine of 80 ppm, the carbon steel corrosion rate is 2.5 mpy.

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EPRI Proprietary Licensed Material Literature Review

9 8 7 Corrosion Rate, mpy 6 5 4 3 2 1 0 9.4 9.5 9.6 9.7 pH 9.8 9.9 10 10.1 Estimated Hydrazine Corrosion Rate

Figure 3-2 Estimated Corrosion Rate of Carbon Steel in Aerated Hydrazine Solution

Assuming that the corrosion rate is a function of pH within the hydrazine concentration range of 30 ppm to 145 ppm, the corrosion rate at the EPRI lay-up limit of pH 9.5 is estimated to be 9 mpy. It is inferred that the corrosion rate of carbon steel in the EPRI guideline values of pH 9.5 and hydrazine at 75 ppm would be less than or equal to 9 mpy in an aerated solution. The testing performed in low oxygen environments are shown in Figure 3-3.

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EPRI Proprietary Licensed Material Literature Review

3.5 40 - 200 DEHA 4 - 16 ppb O2 [7] 40 - 100 ppm CH 20 - 30 ppb O2 [7] 45 - 100 ppm N2H4 25 - 40 ppb O2 [7]

3 Carbon Steel Corrosion Rate, mpy

2.5

1.5

20 - 150 ppm CH < 10 ppb O2 [7]

30 ppm N2H4 < 10 ppb O2 [17] 80 ppm N2H4 100 ppb O2 [17]

1 0.003 ppm N2H4 < 10 ppb O2 [1] 9.2 9.3 9.4 9.5

0.5

80 ppm N2H4 < 10 ppb O2 [17] 30 ppm N2H4 100 ppb O2 [17] 9.6 pH N2H4 CH DEHA 9.7

20 - 150 ppm CH < 10 ppb O2 [7] 100 - 500 ppm DEHA < 10 ppb O2 [7] 9.8 9.9

10

10.1

Figure 3-3 Corrosion Rate of Carbon Steel as a function of pH and Oxygen Scavenger

Corrosion rates were dramatically lower in this environment for hydrazine, and slightly elevated for the one set of data for DEHA and two sets of data for carbohydrazide. It is important to note that the concentration of DEHA and carbohydrazide were typically lower as compared with the tests run in fully aerated environments. Further data were reviewed from two steam generator chemical cleaning qualifications [22, 23]. These provided the allowable amount of corrosion over a 40 year operating life. These results are summarized from Table 5-8 of the report [22] in the first 3 columns of Table 33. A fourth column was added to give a calculated corrosion rate (Utility limit/40 years). It is assumed, for simplicity, that the average corrosion rate is the same in all modes of operations.

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EPRI Proprietary Licensed Material Literature Review

Table 3-3 Millstone 2 SG Tubesheet Chemical Cleaning Corrosion Coupon Results Material Category Utility Limits (40 Year Allowance), mils Calculated Ave. Corrosion Rate, mpy (Utility Limits/40 yrs.) SB 163 SA 570 Gr 40 SA 516 Gr 70 Tubing Eggcrate Secondary Shell Welds SA 508 Cl2 Tubesheet 7.0 11.0 91.2 270 550 0.175 0.275 2.28 6.75 13.75

The resulting corrosion rates for carbon steel in steam generators are summarized: In aerated lay-up solutions using the EPRI guideline pH and hydrazine amounts, 9 mpy In low oxygen environments using elevated concentrations of oxygen scavengers, < 3 mpy, and Performing a simple calculation using chemical cleaning criteria, 2.3 mpy.

As a point of conservatism, the allowable carbon steel corrosion rate of < 2.3 mpy will be used for this evaluation. Following this simple calculation of average corrosion rate, the corrosion rates for the other metallurgies listed as boundary conditions from the polymer dispersant application [15] will also be used as corrosion criteria for this evaluation. Table 3-4 lists the acceptable corrosion rates for all metallurgies to be tested based on the chemical cleaning allowable corrosion divided by a 40 year operating life.
Table 3-4 Allowable Corrosion Rates for Susceptible Steam Generator Metallurgies Materials LTMA Inconel 600 405 SS SA-335 Gr P11 ER70S-6 GMAW E7018-A1SMAW SA-569 SA-36 Allowable Corrosion Rate, mpy 0.175 0.175 2.28 6.75 6.75 2.28 2.28

Proposed Lay-up Corrosion Testing

Data for aerated corrosion testing of carbon steel in high pH water has supported the current guidelines values of 75 ppm hydrazine and pH > 9.5 [2, 17, 19]. Data for acceptable alternates to hydrazine (carbohydrazide, DEHA) along with unacceptable alternatives (hydroquinone, methyl ethyl ketoxime, and isoascorbic acid) were found in the literature search [6, 7]. Additional testing is needed to determine the concentrations of hydrazine, carbohydrazide, and DEHA that yield corrosion rates that are compatible with the allowable corrosion rates summarized in Table 3-4. 3-8

EPRI Proprietary Licensed Material Literature Review

To support this, corrosion data are needed over a wider range of SG pHs and oxygen scavenger concentrations. A standard test program using ASTM G-31-72, Standard Practice for Laboratory Immersion Corrosion Testing of Metals was used for measuring weight loss of coupons in this project. In the test program, oxygen concentrations were maintained at < 20 ppb with continuous nitrogen sparging and initial oxygen scavenger concentrations in the test solutions were varied. Additional control test runs were performed without oxygen scavengers and using different nitrogen sparging procedures to simulate different plant operating procedures. The corrosion rates were calculated based on measured weight loss using the procedures provided in ASTM G-31-72. There are concerns about the effects of steam generator sludge and deposits, particularly in regards to copper. Copper can catalyze the breakdown of oxygen scavengers and in some cases, affect the system pH. The instability of carbohydrazide in the presence of simulated steam generator sludge led Ontario Hydro to choose DEHA as the preferred oxygen scavenger over hydrazine [7]. However, the effects of the sludge pile will not be included in the scope of this work, but may be included in testing proposed for Phase 3 of this program. The test program defined here is not designed to identify either local corrosion (e.g. pitting, crevice corrosion) or galvanic corrosion. Although visual observations were made on all corrosion test coupons for localized corrosion, a more detailed program will be carried out in Phase 3. Initial Test Matrix The following Test Matrix was proposed for this project. As will be discussed in Section 5, the experimental matrix was varied based on results obtained during the test program. Fixed Parameters: pH >9.0 using ammonia Initial Oxygen < 20 ppb by nitrogen sparging Temperature = 25 C Time 500 hours

The metallurgies tested are listed in Table 3-4 above. Control Testing was also performed with no oxygen scavenger and the above conditions.

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EPRI Proprietary Licensed Material Literature Review

Varied Parameters: Oxygen Scavenger Hydrazine Carbohydrazide DEHA Concentrations, ppm 50 100 150 25 50 100 10 25 50 1 1 1

Measurements made in the test program were as follows: pH (3x/week) Dissolved oxygen (3x/week) Conductivity (3x/week) Calculated Corrosion Rate (end of experiment) Pit Depths (if any, at the end of experiment)

The purpose of this testing is to provide support for conditions where the steam generator oxygen concentration remains low (i.e. system integrity is not broken) or for lay-up where deoxygenation of the lay-up solution is possible. Although not all situations would be covered under this testing, issues 1, 2, and to some extent 3 listed below would be addressed. Issues that cause utility personnel to not establish full wet lay-up typically include: 1. Short lay-up time (< 7 days) 2. Discharge limitations for chemicals such as hydrazine 3. Steam generator support system isolation cannot add or properly mix chemicals 4. Steam generator drained or partially drained for maintenance activities

References
1. Marks, C.R., Evaluation of Hydrazine and Carbohydrazide Levels during Lay-up as a Function of pH, EPRI Secondary Water Chemistry Guidelines Review, February, 2000. Data were reviewed based on pH and oxygen scavenger concentrations on carbon steel. Corrosion prevention was described by the author for hydrazine (ppm) as: [N2H4] > -210*pH + 2200 and for carbohydrazide (ppm) as: [Cz] > 125 3-10

EPRI Proprietary Licensed Material Literature Review

Oxygen concentrations and the amount of copper and iron deposits were not considered in this data set. This resource cited 23 pertinent references. Additional data that was referenced in this report and is not cited elsewhere in this literature search are as follows:
Test Solution 200 ppm N2H4, 10 ppm NH3 360 ppm CH, 200 ppm NH3 36 ppm CH, 200 ppm NH3 pH 8.7, 3 ppb O2 pH 9.3, 3 ppb N2H4, < LLD O2 pH 9.3, 30 ppb N2H4 pH 9.9, N2H4 145 ppm pH 9.9, N2H4 145 ppm, lube oil Corrosion Rate, mpy 2.5 0.57 0.66 0.089 0.0048 0.137 < LLD 0.167

2. Armentano, J.A., V.P. Murphy, Stand-By Protection of High Pressure Boilers, th 25 Annual International Water Conference, Pittsburgh, September, 1964.
Test Solution 100 ppm N2H4, pH 9.2 200 ppm N2H4, pH 9.5 300 ppm N2H4, pH 9.9 200 ppm N2H4, pH 10.0 200 ppm, pH 10.2 to 11.0 Corrosion Information Some Discoloration after 24 hours Some Discoloration after 24 hours No Discoloration after 24 hours No Discoloration after 5 days No corrosion detected after 6 months

3. Bohnsack, G. Chemistry of Corrosion Inhibition and Surface Passivation of Mild Steel by Hydrazine in Power Plant Circuits, Corrosion 89, April, 1989, New Orleans, LA. Paper looks at the Shikorr reaction and the hydrazine influences on iron oxide formation. Oxide layers that prevent corrosion are formed at T< 105 C. 4. Romaine, S., Cotton, I. J., Effectiveness of a New Volatile Oxygen Scavenger, American Power Conference, Illinois Institute of Technology, Chicago, IL April, 1986. A case study is provided to show the effectiveness of hydroquinone over hydrazine at the Virginia Power, Chesterfield Station. Laboratory corrosion data were reported. Metal coupons were sealed in bottles containing deionized, deaerated, pH 9.5 water for 2 years. The corrosion rate of the coupon in hydrazine was 0.675 mil/yr. and the corrosion rate for the coupon in hydroquinone was 0.085 mil/yr. The concentrations of hydrazine and hydroquinone in the lab data were not given in the paper. 5. Ellis, D. M., Cuisia, D. G., Thompson, H. W., The Oxidation and Degradation Products of Volatile Oxygen Scavengers and their Relevance in Plant Applications, Corrosion 87, Paper Number 432, Moscone Center San Francisco, CA March, 1987. The paper reported principal breakdown products of DEHA to be acetaldehyde, dialkylamines, acetate, and acetaldoxime. No corrosion data was presented in the paper. 3-11

EPRI Proprietary Licensed Material Literature Review

6. Miller, A.D., Survey of Alternate Reducing Agents for Secondary Chemistry Control, EPRI TR-107949, March 1997. The report summarizes industry experience with hydrazine and alternate reducing agents. Sandra Pagans work at Ontario Hydro listed the following corrosion rates:
Test Solution 45 - 100 ppm N2H4, 25 - 40 ppb O2 40 - 200 ppm DEHA, 4 - 16 ppb O2 170 - 460 ppm HQ, 3 - 10 ppb O2 290 - 315 ppm MEK, 75 - 90 ppb O2 40 - 100 ppm CH, 20 - 30 ppb O2 400 - 800 ppm IsoAsc, 20 - 30 ppb O2 Corrosion Rates 45 um/yr 76 um/yr 530 um/yr 45 um/yr 69 um/yr 63 um/yr

7. Pagan, S., Evaluation and Application of an Alternative Reducing Agent for Steam Generator Lay-Up at Pickering A NGS, EPRI Amine Workshop, New Orleans, LA, September, 1993. Two alternates to hydrazine were tested based on initial screening for stability and corrosion rates; DEHA and Carbohydrazide. These were tested for 3 weeks in aqueous, static and stirred, 2% O2 and N2 cover, with and without sludge, 10, 25, and 50 C, and pH ranges of 5 - 5.3, 9.5 10, and 10.8 11. The materials tested were carbon steel, Monel 400, and 90/10 Cu Ni. Testing results:
Metallurgy Temp pH Cover Gas CR (DEHA 100 500 ppm), um/y None None 13 164, occasional pits 180, occasional pits CR (Carbo 20 150 ppm), um/y None None 15 26, minor pits 220

Monel 400 90/10 Cu/Ni Carbon Steel Carbon Steel Carbon Steel

25 50 25

9.5 10.0 9.5 10.0 5.0 5.3

2% O2/N2 2% O2/N2 2% O2/N2

DEHA was chosen as the preferred alternative to hydrazine because carbohydrazide displayed stability problems, and there was a concern about degradation to ammonia in the steam generator. A DEHA specification was developed for lay-up at 100 ppm 300 ppm, typical value of 250 ppm, and a pH of 9.5 11.0, typical value of 10.2 and dissolved oxygen typical value of 30 ppb 8. Rohani-Rad, A., Mofidi, J., Modaress-Tehrani, Z., Anticorrosive behaviour of octadecylamine for protection of boiler surfaces, Technical note, Corrosion Engineering, Science and Technology 2003, Vol 38. No. 1. Weight loss and electrochemical tests were used to determine the anticorrosive behavior of octadecylamine (ODA) on carbon steel, brass, and austenitic stainless steel. The corrosive solution was soft water with 1 ppm Fe, 240 ppm Cl, 445 ppm Na, 4 ppm K, 0.5 ppm PO4, 5.75 ppm O2, 730 ppm SO4, 1270 ppm TOC, 280 ppm HCO3, 2 ppm Ca, and 2 ppm Mg. The pH was 8.27 and ODA concentration of about 10 ppm. Coupon testing 3-12

EPRI Proprietary Licensed Material Literature Review

was performed on steel 20, brass and 18/10 steel over 1100 hours with average rates determined ever 100 hours.

Potentiostatic measurements were made for the steel 20. Corrosion rates were determined at constant potentials for exposure periods of 5 hours.

9. Marks, C., Varrin, R., D., Oxidation and Reduction of PWR Steam Generator Secondary Side Deposits: Experimental Data and Predictive Models, EPRI 1003591, July 2002. Report models the decomposition of hydrazine and carbohydrazide in steam generator scale, crevice, and sludge pile environments. Participation in the crevices is predicted to be minimal. 10. Syrett, B. C., Low Temperature Corrosion Problems in Fossil Power Plants State of Knowledge Report, EPRI 1004924, December 2003. This report is an extensive overview of corrosion problems in the fossil industry. Report contains no boiler lay-up data or oxygen scavenger corrosion rate information. 11. Dooley, R.B., Interim Cycle Chemistry Guidelines for Combined Cycle Heat Recovery Steam Generators (HRSGs), EPRI TR-110051, Final Report, November 1998.

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EPRI Proprietary Licensed Material Literature Review

Successful extended boiler wet lay-ups contain a pH of 10.0 and up to 200 ppm hydrazine. Nitrogen blanketing is recommended for short-term outages with no additional pH or hydrazine concentrations given. 12. Allen, G. C., Sourcebook for Plant Lay-up and Equipment Preservation (Revision 1), EPRI NP-5106 Revision 1, May 1992. Report overviews the PWR and BWR lay-up experiences and reflects the guidance given in the PWR and BWR Guidelines. 13. Millett, P., PWR Secondary Water Chemistry Guidelines Revision 5, EPRI TR102134-R5, Final Report May 2000. Report specifies lay-up for RSGs with > 9.5 pH and > 75 ppm hydrazine for outages of 7 days or greater. For lay-up of less than 7 days hydrazine should be > 5 ppm and oxygen should be < 100 ppb. For OTSGs, the lay-up chemistry specifies pH > 9.8 and hydrazine to be between 75 ppm and 500 ppm. 14. Marks, C., Varrin, R., D., Oxidation and Reduction of Copper in Steam Generator Deposits: Experimental Data and Predictive Models, EPRI 1001204, September 2001. The report applies the work of Bowers et. al. to the reduction of copper deposit in thin films using hydrazine. The reaction follows an Arrhenius model with a pre-exponential factor of 32 + 4 s-1 and an activation energy of 32 + 2 kJ/mol. 15. Robbins, P., Frattini, P., Dispersants for Tube Fouling Control Volume 1: Qualification for a Short-Term Trial at ANO-2, EPRI 1001422, Final Report March 2001. The report identifies a short list of steam generator metallurgies that bound the testing concerns for application of a new polymer in nuclear steam generators. The final recommendations for material and testing were:
Material TT Inconel 690 405SS SA-335 Gr P11 ER70S-6 GMAW E7018-A1SMAW SA-569 SA-36 Test(s) CERT, LPR, PDS CERT (optional), LPR, PDS LPR, PDS LPR, PDS LPR, PDS LPR, PDS, Weight Loss Weight Loss

16. Whyte, D. D., Laboratory Program to Examine Effects of Lay-up Conditions on Pitting of Inconel 600, EPRI NP-3012, Final Report, April 1983. Pitting of Inconel 600 tubing for steam generators was studied at 40 C. Pitting solutions included copper chloride or sea water, plus sludge containing copper, copper oxide, and magnetite. In less than 3 weeks, pitting of A600 occurred in (700 ppm Cl) copper chloride solution. Similar results occurred in sea water (6000 ppm Cl). Pitting was reduced by decreasing oxygen, decreasing copper, or increasing the pH. 17. Long, A., Organista, M., Brun, C., Combrade, P, Optimization of Wet Lay-Up Conditions for Steam Generators Hydrazine Chemical Treatment, Presented at the 3-14

EPRI Proprietary Licensed Material Literature Review

International Conference: Water Chemistry of Nuclear Reactor Systems, Avignon, France, April 2002. The paper outlines a test program to reduce the amount of hydrazine used during lay-up. The study showed the importance of nitrogen blanketing or performing dry lay-up. Testing was performed on two types of samples; free unalloyed A42, coupled with A600, fully immersed in water, and unalloyed A42, positioned at the water line. Corrosion was monitored by sample weight loss. The air interaction with the lay-up solution greatly increased corrosion rates as shown below:

18. Foucault, M.. Long, A., Combrade, P., Rodet, I., Bouchacourt, M., Secondary Chemistry of Steam Generator. Influence of Hydrazine on Corrosion Potential. Optimization of Shutdown Conditions and Return to Nominal Conditions, Presented at the International Conference: Water Chemistry of Nuclear Reactor Systems, Avignon, France, April 2002. Autoclave testing was performed to determine the effects of increased oxygen in systems with high, and low hydrazine concentrations. Corrosion potential measurements were taken at 280 C. The results showed that increased oxygen with low hydrazine resulted in increased corrosion potential in carbon steel at 280 C. No data at lay-up temperatures were taken. 19. Rabeau, A.M., et. al., Steam Generators Lay-Up Optimization and Derived Wastes Reduction, Presented at the International Conference: Water Chemistry of Nuclear Reactor Systems, Avignon, France, April 2002 Corrosion testing of carbon steel (NF A 35-501) was performed in aerated and deaerated solutions with ammonia (pH(25) = 10.0), and hydrazine (0 ppm 400 ppm). Under aerated conditions, the corrosion testing supported the current PWR guidelines for pH > 9.5 and hydrazine > 75 ppm.

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EPRI Proprietary Licensed Material Literature Review

With nitrogen blanketing, the corrosion rates were lower than 3 um/yr, which is 10 to 30 times less than the aerated conditions in the absence of hydrazine. 20. Casar, D.J., San Onofre Generating Station Control of Oxidants in the Secondary System during Shutdown, Lay-up and Startup, Revision 0, December 2001. Document describes utilities compliance to the EPRI guidelines, but does not contain any new corrosion data for lay-up. 21. McIlree, A., R., Proceedings: 1999 EPRI Workshop on Startup Oxidant Control, TR-112815, Final Report June 1999. Document describes utilities implementation of lay-up and start-up oxidant control, but does not contain any new corrosion data for lay-up. 22. Pearl, W. L., Chemical Cleaning of Millstone Unit 2, EPRI NP-4597, Final Report, May, 1986. This report was used to determine allowable corrosion rates for various steam generator components. These results are summarized from Table 5-8 of the report listed below in the first 3 columns. A forth column was added to give a calculated corrosion rate:
Material SB 163 SA 570 Gr 40 SA 516 Gr 70 SA 508 Cl2 Category Tubing Eggcrate Secondary Shell Welds Tubesheet Utility Limits (40 Year Allowance), mils 7.0 11.0 91.2 270 550 Calculated Ave. Corrosion Rate, mpy 0.175 0.275 2.28 6.75 13.75

23. Prestegiacomo, J. B., et al, Qualification of PWR Steam Generator Chemical Cleaning For Indian Point-2, Volume 1 Summary Report, EPRI NP-6356-SL, Final Report, May 1989. This report was used to determine corrosion limits for various steam generator components. A selection of the results is included to show allowable corrosion amounts and a calculated rate based on a 40 year life is added to the table. The corrosion results listed are from Table 4-8 in the report:
Material Category Limit that includes design corrosion allowance, mils Calculated Ave. Corrosion Rate, mpy

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EPRI Proprietary Licensed Material Literature Review SA508 SA533 SA285 SA106 SA105 A234 SAE 1020 A36 Tubesheet Stub Barrel Wrapper Blowdown Pipe Boss Blowdown Elbow End Plate Channel 125 125 37 70 48 64 70 70 37 3.125 3.125 0.925 1.75 1.2 1.6 1.75 1.75 0.925

24. Personal communication with Jay Smith, Byron Station.

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4
EXPERIMENTAL PROCEDURES
The effect of varying the concentrations of oxygen scavengers on different metals was investigated using the ASTM G-31-72, Standard Practice for Laboratory Immersion Corrosion Testing of Metals Procedure. The metals examined were Inconel 600, Inconel 690, 405SS, 1010, ER70S-GMAW, E7018-A1SMAW, SA-569, and SA-36.

Experimental Apparatus
Corrosion coupons from Metal Samples, Inc. (www.metalsamples.com) were used for the experiments. All of the coupons with the exception of 405SS had the following dimensions: 2 x 3/4 by 1/8. The 405SS coupons were 1/16 thick. Figure 4-1 shows a typical corrosion coupon. The hole in the coupon was used to attach the coupons to the coupon test rack (see Figure 4-2). All coupons were exposed in the as- received mill finished condition.

Figure 4-1 Metal Samples Corrosion Coupon

The calculated wetted area of the coupons and the allowable corrosion rate in mils per year based on the analysis in Section 3 is shown in Table 4-1.

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EPRI Proprietary Licensed Material Experimental Procedures

Table 4-1 Materials Tested Material Inconel 600 Inconel 690 405 SS 1010 ER70S-6 GMAW E7018-A1SMAW SA-569 SA-36 Density (g/cm2) 8.47 8.19 7.80 7.87 7.87 7.87 7.87 7.60 A (cm2) 22.387 22.387 27.484 27.484 22.387 22.387 27.484 27.484 Allowable Corrosion Rate mpy 0.175 0.175 0.175 2.28 6.75 6.75 2.28 2.28

Each experiment consisted of exposing a number of test coupons to a test solution. The coupons were attached to a coupon test rack that was supplied by Metal Samples, Inc. A test rack similar to that shown in Figure 4-2 was used. In this test program, only flat (e.g. no U-bend) coupons were used. The flat bar rack, hex bolts and hex nuts were made of HASTELLOY C-276. The insulating washers and shoulder washers were Teflon.

Figure 4-2 Metal Samples Coupon Rack

4-2

EPRI Proprietary Licensed Material Experimental Procedures

The coupon racks were constructed as shown in Figure 4-2. In most experiments, twelve or more coupons were attached to the coupon rack. Typically, three coupons were attached to each side of the flat bar rack at two elevations. In most experiments, the coupons were exposed to the test solution, however in some cases the upper coupons were exposed to the gas or vapor space above the test solution. Test solutions were prepared using reagent grade chemicals and each coupon rack was inserted into a 1 liter high density polyethylene bottle. The bottle top was modified to pass through the flat bar rack. Tygon tubing was used to deliver nitrogen to the test solution and three probes were inserted through the vessel top to monitor the chemical environment in the test solution. Figure 4-3 is a photograph of the experimental apparatus completely assembled and inserted in the isothermal bath. Typically up to three tests were run simultaneously in an isothermal bath controlled to 25C. The apparatus is shown with a single probe in Figure 4-3. During most experiments, three probes; dissolved oxygen, conductivity and pH were used. Any unused openings in the bottle top were plugged with a glass or rubber stopper during the experiments. Otherwise there was no attempt to seal the vessels from oxygen ingress. The continuous nitrogen purge was used to maintain the solution oxygen free.

Figure 4-3 Assembled Test Apparatus

For some of the air saturated control experiments and for those without continuous nitrogen sparging, a standard 2-3 L pyrex glass beaker was used in place of the HDPE bottles. Solutions were prepared with reagent grade chemicals. The initial oxygen scavenger concentrations were prepared and added directly to the HDPE (or glass) test vessel. The air space above the test solution was initially evacuated using high purity nitrogen. The nitrogen was introduced through tygon tubing which was inserted into each test vessel below the solution level. In most experiments, continuous nitrogen sparging was maintained by slowly bubbling 4-3

EPRI Proprietary Licensed Material Experimental Procedures

nitrogen into the vessel. As the tops of the vessels were not air tight, atmospheric or slightly above atmospheric pressure was maintained with the nitrogen purge throughout the experiments.

Experimental Procedures
The oxygen scavengers studied were hydrazine, carbohydrazide, and DEHA. The metal coupons were submerged in solutions of various concentrations of oxygen scavengers. While in solution, pH, dissolved oxygen, conductivity, and temperature were monitored. The amount of corrosion is determined by comparing the weights of metal coupons before and after exposure to the solutions. For each experimental run, the coupons were left in solution for 20 days. Pre Cleaning ASTM G-31-72 was used for preparing the coupons for the test. The procedures for the pre cleaning are as follows: Brush coupon and rinse in deionized water Soak coupon in methanol for 5 minutes Air dry coupon for 10 minutes weigh coupon and record

Experimental Matrix The coupons were submerged in different concentration of oxygen scavengers for 20 days and corrosion rates of the metals were calculated based on the weight difference of the test materials. Each experiment with an oxygen scavenger consisted of preparing approximately 750 mls of the desired concentration of scavenger and adding it to the test vessel. Nitrogen sparging was then initiated and the oxygen concentration in the vessel was continuously monitored until the concentration was reduced to < 20 ppb. This normally took less than 5 minutes, and the dissolved oxygen was less than detectable shortly thereafter. The initial pH and conductivity was then measured and recorded. If necessary, a pH adjustment was made to each test solution by adding reagent grade ammonia. During the subsequent 20+ days, readings of the dissolved oxygen, conductivity, pH and test temperature were recorded at a frequency of at least 3x/week. Adjustments to maintain the pH above 9.0 were made as needed using reagent grade ammonia. The experimental matrix consisted of using different concentrations of oxygen scavengers as shown in Table 4-2. Nitrogen was sparged into these solutions to assure that the oxygen concentrations were less than 20 ppb. The temperature of the solution was kept constant at or near 25 C using an isothermal water bath and the pH of the solutions was maintained >9.0 using ammonia. The set up of the apparatus was described in experimental apparatus section. Other sets of experiments were performed containing no oxygen scavenger. The experiments were performed to determine the effect of pH and/or the use of nitrogen sparging on the test materials. The experimental matrix for these experiments is shown in Table 4-3. 4-4

EPRI Proprietary Licensed Material Experimental Procedures Table 4-2 Experimental Matrix of Metals Exposed to Oxygen Scavengers

Metal Type

N2H4 (ppm) 1, 25, 50, 1000,10000, 25000 1, 25, 50, 1000,10000,25000 1, 25, 50, 1000,10000,25000 1, 25, 50, 1000,10000,25000 1, 25, 50, 1000,10000,25000 1, 25, 50, 1000,10000,25000 1, 25, 50, 1000,10000,25000 1, 25, 50, 1000,10000,25000

DEHA (ppm)

CHZ (ppm)

Inconel 600 Inconel 690 405 SS 1010 CS ER70S-GMAW E7018-A1SMAW SA-569 SA-36

1, 150 1, 150 1, 150 1, 150 1, 150 1, 150 1, 150 1, 150

1, 100 1, 100 1, 100 1, 100 1, 100 1, 100 1, 100 1, 100

4-5

EPRI Proprietary Licensed Material Experimental Procedures

Table 4-3 Experimental Matrix of Metals Exposed to No Oxygen Scavengers (Control) O2 Scavengers (ppm) 0 0 0 0 0 0 0 0

Metal Type Inconel 600 Inconel 690 405 SS 1010 CS ER70S-GMAW E7018-A1SMAW SA-569 SA-36

Control Conditions a,b,d a,b,d a,d a,b,c,d c,d a,c a,b,c,d a,b,c,d

a- indicates that the test coupons were placed above DI water. The dissolved oxygen is at airsaturated level and the pH is about 5.5 b- indicates that no nitrogen has been purged into the DI water in which the test coupons have been submerged, so the liquid is at air-saturated level. The pH is maintained >9.0. c- indicate that nitrogen has been purged into the DI water only at the beginning of the experiment. Typcially dissolved oxygen reached air-saturated level within 10 minutes of securing the nitrogen purge. The pH is maintained >9.0. d- indicates that nitrogen has been purged continuously into the DI water through out the experiment

Post Cleaning After exposing the coupons for at least 20 days, each experiment was terminated by removing the test racks from the test vessels. Prior to re-weighing the coupons, ASTM G1-03, Standard Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens was used for cleaning and preparing the coupons for the weight measurements. For chemical cleaning the 1010 CS, SA 36, SA 569, ER 70S-GMAW, and E7018-A1SMAW coupons, the procedure was as follows: 1. Prepare a 1000 ml hydrochloric acid (HCl), 20 g antimony trioxide (Sb2O3) and 50g of stannous chloride (SnCl2) solution 2. Maintain the temperature between 20 to 25C 3. Stir the solution 4. Soak the test coupons in the solution for 4 minutes 5. Take the coupons out from solution and brush to remove loose corrosion products 6. Rinse with DI water 4-6

EPRI Proprietary Licensed Material Experimental Procedures

7. Air dry 8. Weigh and record For chemical cleaning the Inconel 600 and Inconel 690 coupons, the following procedure was used: 1. Prepare a solution with 150 ml hydrochloric acid (HCl) and 1000 ml DI water 2. Maintain the temperature between 20 to 25C 3. Soak the test metals for 2 minutes 4. Take the coupons out from solution and brush to remove loose corrosion products 5. Rinse with DI water 6. Air dry 7. Weigh and record For chemical cleaning the 405 SS coupons, the following procedure was used: 1. Prepare a solution with 100 ml nitric acid (HNO3) and 1000 ml DI water 2. Maintain the temperature at 60C 3. Soak the test metals for 20 minutes 4. Take the coupons out from solution and brush to remove loose corrosion products 5. Rinse with DI water 6. Air dry 7. Weigh and record

4-7

EPRI Proprietary Licensed Material

5
EXPERIMENTAL RESULTS
The results for the first seventeen experiments are reported here. A brief summary of the conditions for each experiment is provided in Table 5-1. As described in Section 4, Experimental Procedures, continuous nitrogen sparging was used in most of the experimental runs. The sparging rate was not directly measured, but was sufficient to maintain the dissolved oxygen levels to <20 ppb when employed. In some experiments, no sparging was used. The solutions for these experiments were air saturated. In experiment 16, the test vessel was initially purged with nitrogen for less than 5 minutes at the beginning of the experiment to reduce the dissolved oxygen to <20 ppb. During the course of experiment 16, three subsequent 5 minute nitrogen sparges were used to bring the dissolved oxygen levels to <20 ppb. As shown in the Appendix, the dissolved oxygen level in experiment 16 typically re-saturated within 1 day. It should also be noted that all coupons were exposed directly in the test solution except where noted in Table 5-1. In some cases the coupons were above the solution level in the air space of the test vessel. The coupons were exposed to the vapor in equilibrium with the test solution. Many of the tests employed pH control by NH3 addition. In some cases, the initial scavenger concentration was sufficient to maintain the pH above the target of 9.0 for the entire test period. The average pH for each test is presented in Table 5-1, however, it should be noted that in many cases the pH varied by 0.5 units or more during the test period. Appendix A includes trend plots of the pH for each test.

5-1

EPRI Proprietary Licensed Material Experimental Results

Table 5-1 Summary of Experimental Runs Experiment No. 1 Materials (No. of coupons) 1010 (2)* I600 (2) I690 (1) SA36 (2)* 405 (2) SA569 (2) 1010 (2) I600 (1) I690 (2) SA36 (2) 405 (3) SA569 (2) 1010 (1) I600 (1) 405 (3) SA569 (1) 1010 (2) I600 (2) I690 (1) SA36 (1) 405 (2) SA569 (2) E70S (2) E7018 (1) 1010 (2) I600 (2) I690 (2) SA36 (1) 405 (2) SA569 (1) E70S (1) E7018 (2) 1010 (3) I600 (2) I690 (2) SA36 (2) 405 (2) SA569 (2) 1010 (3) I600 (3) I690 (3) SA36 (3) 405 (1) SA569 (2) Oxygen Scavenger N2H4 Conc.ppm 50,000 pH Range in Experiment 10.3-10.8 Ave. pH 10.5 Nitrogen Sparging Continuous Notes No NH3 added

DEHA

150

9.0-10.4

9.4

Continuous

No NH3 added

3 4

CHZ N2H4

100 25,000

8.1-9.3 10.1-11.0

9.0 10.6

Continuous Continuous

NH3 used to adjust pH No NH3 added

N2H4

10,000

9.4-10.7

10.0

Continuous

No NH3 added

N2H4

1,000

8.8-10.2

9.2

Continuous

No NH3 added

None

N/A

N/A

~5.5

None

Air Saturated Control, No Scavenger or NH3 added

5-2

EPRI Proprietary Licensed Material Experimental Results Experiment No. 8 Materials (No. of coupons) 1010 (2) I600 (1) I690 (1) SA36 (2) SA569 (2) E70S (1) E7018 (1) 1010 (2) I600 (1) I690 (1) SA36 (2) SA569 (3) E70S (1) E7018 (1) 1010 (2) I600 (1) I690 (1) SA36 (2) SA 569 (2) E70S (1) E7018 (1) 1010 (2) I600 (2) I690 (2) SA36 (3) SA569 (3) Oxygen Scavenger DEHA Conc.ppm 1 pH Range in Experiment 9.8-10.3 Ave. pH 10.0 Nitrogen Sparging Continuous Notes NH3 used to adjust pH

CHZ

8.7-9.9

9.4

Continuous

NH3 used to adjust pH

10

None

N/A

9.0-10.3

9.4

Continuous

NH3 used to adjust pH

11

None

N/A

N/A

~5.5

None

Air Saturated, Coupons exposed above a pool of stagnant water. Coupons sprayed with DI water at beginning of run NH3 used to adjust pH

12

1010 (2) I600 (2) I690 (1) SA36 (1) 405 (2) SA569 (2) E70S (2) E7018 (1) 1010 (1) I600 (2) I690 (2) SA36 (1) 405 (2) SA569 (1) E70S (1) E7018 (2) 1010 (3) I600 (2) I690 (2) SA36 (2) 405 (1) SA569 (2) 1010 (2) SA36 (2)

N2H4

50

9.1-10.0

9.4

Continuous

13

N2H4

25

9.1-10.0

9.4

Continuous

NH3 used to adjust pH

14

N2H4

9.2-10.1

9.4

Continuous

NH3 used to adjust pH

15

DEHA

9.0-9.9

9.3

Continuous

NH3 used to adjust pH

5-3

EPRI Proprietary Licensed Material Experimental Results

Experiment No.

Materials (No. of coupons) 405 (3) SA569 (2)

Oxygen Scavenger

Conc.ppm

pH Range in Experiment

Ave. pH

Nitrogen Sparging

Notes

16

Above Waterline 1010 (3) SA36 (2) SA569 (2) Below Waterline 1010 (3) SA36 (4) SA569 (4) E70S (3)

None

N/A

8.9-10.3

9.85

Initial to reduce DO <20 ppb, 3x for 5 minutes during remainder of the experiment

NH3 used to adjust pH. Coupons exposed above and below waterline

17

Above Waterline SA569 (3) I690 (2) I600 (1) Below Waterline 1010 (2) SA36 (3) E7018 (3) I690 (3) I600(3)

None

N/A

N/A

~5.5

None

Air Saturated Control, No Scavenger or NH3 added. Coupons exposed above and below waterline. Coupons above waterline sprayed with DI water at beginning of run.

5-4

EPRI Proprietary Licensed Material Experimental Results

Effects of Oxygen Scavengers

The weight loss measurements are presented in the following tables for each of the oxygen scavengers and for each material. The results for the control and air saturated tests without an oxygen scavenger are presented later in this section. In the tables below, W1 represents the weight of the coupon before exposure to the test solution. W2 represents the weight of the coupon after exposure and chemical cleaning of the corrosion products. The concentration column is for the oxygen scavenger, and represents the initial concentration of oxygen scavenger. No measurements were made of the oxygen scavenger concentration either during or at the end of each test. There were no additions of oxygen scavenger made after each test was initiated. However in two of the tests, some additional test solution (at the initial concentration) was added to the test vessels during the course of the experiment. T is the total mils of corrosion during the experiment and R is the calculated corrosion rate in mils per year. The lower limit reported for corrosion of the I600 and I690 corrosion coupons is 0.013 mpy, for all other materials the lower limit is 0.014 mpy. It should be noted that in some cases, W2 the weight after the test and cleaning was slightly greater than W1, the weight before exposure. In these cases, the corrosion rate was reported as less than the lower limit of 0.013 or 0.014 mpy, since the positive weight gain must represent experimental error. The pH was not held constant in any tests but was maintained above 9.0 as indicated in Table 5-1. Inconel 600
Table 5-2 Corrosion Rate of Inconel 600 as a function of Hydrazine Concentration Coupon Number I 600-4 I 600-5 I 600-3 I 600-7 I 600-1 I 600-2 I 600-4 I 600-6 I 600-3 I 600-7 I 600-1 I 600-2 I 600-1 I 600-2 W1 (g) 23.799 23.834 23.771 23.769 23.835 23.633 23.799 23.682 23.770 23.771 23.834 23.633 23.834 23.633 W2 (g) 23.798 23.833 23.770 23.769 23.835 23.632 23.804 23.681 23.768 23.769 23.842 23.623 23.834 23.633 Hydrazine Concentration (ppm) 1 1 25 25 50 50 1000 1000 10000 10000 25000 25000 50000 50000 T (mils) 0.001 <0.001 0.001 <0.001 <0.001 <0.001 <0.001 0.002 0.003 0.005 <0.001 0.020 <0.001 <0.001 R (mils per year) 0.020 <0.013 0.020 <0.013 <0.013 <0.013 <0.013 0.023 0.048 0.065 <0.013 0.289 <0.013 <0.013

5-5

EPRI Proprietary Licensed Material Experimental Results Table 5-3 Corrosion Rate of Inconel 600 as a function of DEHA Concentration Coupon Number I 600-1 I 600-3 23.842 23.770 23.835 23.770 W1 (g) W2 (g) DEHA Concentration (ppm) 1 150 0.016 <0.001 T (mils) R (mils per year) 0.182 <0.013

Table 5-4 Corrosion Rate of Inconel 600 as a function of Carbohydrazide Concentration Coupon Number I 600-3 I 600-4 23.768 23.799 23.771 23.799 W1 (g) W2 (g) Carbohydrazide Concentration (ppm) 1 100 <0.001 <0.001 T (mils) R (mils per year) <0.013 <0.013

The Inconel 600 results for the three oxygen scavengers are summarized in Figure 5-1. Note, with the exception of two points all of results were at or near the lower limit of detection (0.013 mpy) and well below the allowable corrosion rate of 0.175 mpy. The two extreme points may well have been due to experimental error. The number in parentheses indicates the number of test results at the specified point.

I600 Corrosion Rates

Corrosion Rate, mpy 0.3 0.25 0.2 0.15 0.1 0.05 0 0.01 1

Hydrazine DEHA Carbohydrazide

(2) (2)

100

10000 1000000

Concentration, ppm
Figure 5-1 Corrosion Rate of Inconel 600 as a function of Oxygen Scavenger Concentration

5-6

EPRI Proprietary Licensed Material Experimental Results

Inconel 690
Table 5-5 Corrosion Rate of Inconel 690 as a function of Hydrazine Concentration Coupon Number I 690-4 I 690-5 I 690-2 I 690-3 I 690-1 I 690-4 I 690-5 I 690-2 I 690-3 I 690-1 I 690-2 W1 (g) 26.665 27.912 26.468 28.175 28.611 26.664 27.912 26.468 28.175 28.612 26.469 W2 (g) 26.665 27.911 26.468 28.175 28.611 26.665 27.910 26.469 28.173 28.611 26.468 Hydrazine Concentration (ppm) 1 1 25 25 50 1000 1000 10000 10000 25000 50000 T (mils) <0.001 0.002 <0.001 <0.001 <0.001 <0.001 0.004 <0.001 0.003 0.001 <0.001 R (mils per year) 0.014 0.026 <0.013 <0.013 <0.013 <0.013 0.056 <0.013 0.052 0.020 <0.013

Table 5-6 Corrosion Rate of Inconel 690 as a function of DEHA Concentration Coupon Number I 690-1 I 690-3 I 690-4 28.611 28.175 26.664 28.6114 28.17501 26.66383 W1 (g) W2 (g) DEHA Concentration (ppm) 1 150 150 <0.001 <0.001 <0.001 T (mils) R (mils per year) <0.013 <0.013 <0.013

Table 5-7 Corrosion Rate of Inconel 690 as a function of Carbohydrazide Concentration Coupon Number I 690-10 28.287 28.290 W1 (g) W2 (g) Carbohydrazide Concentration (ppm) 1 <0.001 T (mils) R (mils per year) <0.013

The results for Inconel 690 are summarized in Figure 5-2. All of the measured corrosion rates are well below the corrosion allowance of 0.175 mpy. Most of the results are below the lower limit of detection of 0.013 mpy.

5-7

EPRI Proprietary Licensed Material Experimental Results

I690 Corrosion Rates

Corrosion Rate, mpy 0.3 0.25 0.2 0.15 0.1 0.05 0 0.01 1 100 10000 1000000
(2) Hydrazine (2)

Hydrazine DEHA Carbohydrazide

Concentration, ppm
Figure 5-2 Corrosion Rate of Inconel 690 as a function of Oxygen Scavenger Concentration

405 Stainless Steel

Table 5-8 Corrosion Rate of 405 SS as a function of Hydrazine Concentration Coupon Number 405-6 405-2 405-3 405-1 405-4 405-6 405-7 405-3 405-2 405-4 405-1 405-1 405-2 W1 (g) 6.819 6.840 6.709 6.709 6.618 6.825 6.776 6.716 6.8465 6.625 6.7146 6.715 6.847 W2 (g) 6.819 6.840 6.709 6.709 6.617 6.825 6.779 6.715 6.8648 6.624 6.7748 6.715 6.847 Hydrazine Concentration (ppm) 1 25 25 50 50 1000 1000 10000 10000 25000 25000 50000 50000 T (mils) <0.001 0.001 0.001 <0.001 0.002 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 R (mils per year) <0.014 0.020 0.021 <0.014 0.025 <0.014 <0.014 <0.014 <0.014 <0.014 <0.014 <0.014 0.021

5-8

EPRI Proprietary Licensed Material Experimental Results Table 5-9 Corrosion Rate of 405 SS as a function of DEHA Concentration Coupon Number 405-5 405-8 405-9 405-4 405-3 405-4 405-5 6.339 6.733 6.985 6.624 6.716 6.625 6.347 6.339 6.733 6.984 6.618 6.716 6.625 6.347 W1 (g) W2 (g) DEHA Concentration (ppm) 1 1 1 1 150 150 150 <0.001 0.001 0.002 0.015 <0.001 <0.001 <0.001 T (mils) R (mils per year) <0.014 0.018 0.025 0.190 <0.014 <0.014 <0.014

Table 5-10 Corrosion Rate of 405 SS as a function of Carbohydrazide Concentration Coupon Number 405-6 405-7 405-8 6.825 6.776 6.743 6.825 6.776 6.743 W1 (g) W2 (g) Carbohydrazide Concentration (ppm) 100 100 100 <0.001 <0.001 0.002 T (mils) R (mils per year) <0.014 <0.014 0.019

The results for 405 SS are shown in Figure 5-3. All of the corrosion rates are well below the corrosion allowance and most are at or below the lower limit of detection of 0.014 mpy.

405 SS Corrosion Rates

Corrosion Rate, mpy 0.3 0.25 0.2 0.15 0.1 0.05 0 0.01 1
(2) (3) (2) (2) (2) (2)

Hydrazine DEHA Carbohydrazide

100

10000

1000000

Concentration, ppm
Figure 5-3 Corrosion Rate of 405 SS as a function of Oxygen Scavenger Concentration

5-9

EPRI Proprietary Licensed Material Experimental Results

1010 Carbon Steel

Table 5-11 Corrosion Rate of 1010 CS as a function of Hydrazine Concentration Coupon Number 1010-4 1010-5 1010-7 1010-6 1010-1 1010-2 1010-4 1010-5 1010-7 1010-3 1010-6 1010-1 1010-2 1010-1 W1 (g) 21.355 21.168 21.003 21.200 21.082 23.314 21.398 21.208 21.043 21.216 21.215 21.168 23.360 21.174 W2 (g) 21.313 21.111 20.969 21.192 21.033 23.278 21.380 21.195 21.036 21.216 21.215 21.150 23.339 21.168 Hydrazine Concentration (ppm) 1 1 1 25 50 50 1000 1000 1000 10000 10000 25000 25000 50000 T (mils) 0.094 0.129 0.076 0.019 0.109 0.080 0.041 0.029 0.017 <0.001 <0.001 0.039 0.048 0.011 R (mils per year) 1.149 2.039 1.206 0.298 1.734 1.273 0.594 0.424 0.248 <0.014 <0.014 0.571 0.694 0.140

Table 5-12 Corrosion Rate of 1010 CS as a function of DEHA Concentration Coupon Number 1010-8 1010-9 1010-1 1010-2 1010-3 1010-4 20.092 20.987 21.150 23.339 21.216 21.398 20.036 20.918 21.082 23.314 21.216 21.398 W1 (g) W2 (g) DEHA Concentration (ppm) 1 1 1 1 150 150 0.125 0.156 0.153 0.056 <0.001 <0.001 T (mils) R (mils per year) 1.986 2.470 1.741 0.642 <0.014 <0.014

5-10

EPRI Proprietary Licensed Material Experimental Results

Table 5-13 Corrosion Rate of 1010 CS as a function of Carbohydrazide Concentration Coupon Number 1010-6 1010-10 1010-5 21.215 21.278 21.210 21.200 21.268 21.208 W1 (g) W2 (g) Carbohydrazide Concentration (ppm) 1 1 100 0.034 0.022 0.003 T (mils) R (mils per year) 0.385 0.355 0.037

The results for 1010 carbon steel are summarized in Figure 5-4. There is a correlation of corrosion rate with concentration for all three oxygen scavengers. The use of carbohydrazide appeared to produce lower corrosion rates than hydrazine and DEHA. At the 1ppm oxygen scavenger level, some of the corrosion rates were at or near the corrosion limit for hydrazine and DEHA, but well below the corrosion limit for carbohydrazide.

1010 Corrosion Rates

Corrosion Rates, mpy 3.5 3 2.5 2 1.5 1 0.5 0 0.01 1

Hydrazine DEHA Carbohydrazide

(2) (2)

100

10000

1000000

Concentration, ppm

Figure 5-4 Corrosion Rate of 1010 CS as a function of Oxygen Scavenger Concentration

5-11

EPRI Proprietary Licensed Material Experimental Results

A569 Carbon Steel

Table 5-14 Corrosion Rate of A569 CS as a function of Hydrazine Concentration Coupon Number A 569-4 A 569-5 A 569-3 A 569-1 A 569-2 A 569-4 A 569-5 A 569-3 A 569-1 A 569-2 A 569-1 A 569-2 20.272 20.280 20.192 20.278 20.450 20.294 20.347 20.287 20.367 20.546 20.375 20.551 20.222 20.230 20.178 20.238 20.412 20.285 20.331 20.286 20.352 20.529 20.367 20.546 W1 (g) W2 (g) Hydrazine Concentration (ppm) 1 1 25 50 50 1000 1000 10000 25000 25000 50000 50000 0.112 0.112 0.031 0.089 0.083 0.020 0.034 0.004 0.034 0.039 0.014 0.008 T (mils) R (mils per year) 1.777 1.773 0.496 1.408 1.323 0.293 0.501 0.051 0.489 0.563 0.175 0.102

Table 5-15 Corrosion Rate of A569 CS as a function of DEHA Concentration Coupon Number A 569-6 A 569-7 A 569-1 A 569-2 A 569-3 A 569-4 20.108 20.481 20.352 20.529 20.288 20.295 20.060 20.405 20.278 20.450 20.287 20.294 W1 (g) W2 (g) DEHA Concentration (ppm) 1 1 1 1 150 150 0.108 0.171 0.166 0.178 0.001 0.002 T (mils) R (mils per year) 1.720 2.706 1.891 2.029 0.010 0.019

5-12

EPRI Proprietary Licensed Material Experimental Results

Table 5-16 Corrosion Rate of A569 CS as a function of Carbohydrazide Concentration Coupon Number A 569-3 A 569-4 A 569-5 A 569-5 20.286 20.285 20.331 20.349 20.192 20.272 20.280 20.347 W1 (g) W2 (g) Carbohydrazide Concentration (ppm) 1 1 1 100 0.211 0.030 0.114 0.003 T (mils) R (mils per year) 2.406 0.336 1.300 0.043

The results for A569 are summarized in Figure 5-5 The results are similar to 1010. There is a correlation of corrosion rate with oxygen scavenger concentration. On average, it also appears that carbohydrazide performed better with respect to corrosion rate, however, there is more scatter than with 1010 carbon steel.

A569 Corrosion Rates

Corrosion Rate, mpy

3.5 3 2.5 2 1.5 1 0.5 0 0.01

+(2) Hydrazine

Hydrazine DEHA Carbohydrazide

(2)

100

10000

1000000

Concentration, ppm

Figure 5-5 Corrosion Rate of A569 CS as a function of Oxygen Scavenger Concentration

5-13

EPRI Proprietary Licensed Material Experimental Results

A36 Carbon Steel

Table 5-17 Corrosion Rate of A36 CS as a function of Hydrazine Concentration Coupon Number A 36-3 A 36-4 A 36-2 A 36-1 A 36-3 A 36-4 A 36-2 A 36-1 A 36-2 23.091 23.251 23.055 21.122 23.125 23.291 23.093 21.219 23.096 23.054 23.208 23.042 21.083 23.109 23.280 23.089 21.200 23.093 W1 (g) W2 (g) Hydrazine Concentration (ppm) 1 1 25 50 1000 1000 10000 25000 50000 0.085 0.100 0.029 0.090 0.035 0.026 0.010 0.042 0.006 T (mils) R (mils per year) 1.351 1.594 0.459 1.432 0.514 0.375 0.142 0.611 0.071

Table 5-18 Corrosion Rate of A36 CS as a function of DEHA Concentration Coupon Number A 36-5 A 36-6 A 36-1 A 36-2 A 36-3 A 36-4 23.260 23.304 21.200 23.089 23.126 23.292 23.188 23.237 21.122 23.055 23.125 23.291 W1 (g) W2 (g) DEHA Concentration (ppm) 1 1 1 1 150 150 0.167 0.155 0.182 0.079 0.003 0.002 T (mils) R (mils per year) 2.648 2.460 2.077 0.897 0.038 0.021

Table 5-19 Corrosion Rate of A36 CS as a function of Carbohydrazine Concentration Coupon Number A 36-4 A 36-7 23.280 23.261 23.251 23.208 W1 (g) W2 (g) Carbohydrazide Concentration (ppm) 1 1 0.066 0.123 T (mils) R (mils per year) 0.755 1.399

5-14

EPRI Proprietary Licensed Material Experimental Results

The results for A36 are summarized in Figure 5-6. The results are similar to both 1010 and A569.
A36 Corrosion Rates

3.5 3 2.5 2 1.5 1 0.5 0 0.01 1

Corrosion Rate,mpy

Hydrazine DEHA Carbohydrazide

(2)

100

10000

1000000

Concentration, ppm
Figure 5-6 Corrosion Rate of A36 CS as a function of Oxygen Scavenger Concentration

E 70-S Weld Metal

Table 5-20 Corrosion Rate of E-70-S as a function o f Hydrazine Concentration Coupon Number E 70S-3 E 70S-1 E 70S-2 E 70S-3 E 70S-1 E 70S-2 21.722 21.439 21.624 21.744 21.532 21.710 21.667 21.360 21.563 21.743 21.526 21.698 W1 (g) W2 (g) Hydrazine Concentration (ppm) 25 50 50 10000 25000 25000 0.124 0.176 0.136 0.002 0.012 0.028 T (mils) R (mils per year) 1.961 2.798 2.153 0.033 0.181 0.402

5-15

EPRI Proprietary Licensed Material Experimental Results

Table 5-21 Corrosion Rate of E-70-S as a function of DEHA Concentration Coupon Number E 70s-1 21.526 21.439 W1 (g) W2 (g) DEHA Concentration (ppm) 1 0.195 T (mils) R (mils per year) 2.226

Table 5-22 Corrosion Rate of E-7018 as a function of Carbohydrazide Concentration Coupon Number E 70s-2 21.698 21.624 W1 (g) W2 (g) Carbohydrazide Concentration (ppm) 1 0.165 T (mils) R (mils per year) 1.885

The data for E-70-S is summarized in Figure 5-7. The correlation of corrosion rate with oxygen scavenger concentration was less pronounced with E-70-S, although there was less experimental data for E-70-S. It is also noted that all corrosion rates were well below the corrosion allowance which is much higher than for the carbon steels previously shown.

E 70s Corrosion Rates

Corrosion Rate, mpy 7 6 5 4 3 2 1 0 0 1 100 Concentration, ppm 10000 1000000

Hydrazine DEHA Carbohydrazide

Figure 5-7 Corrosion Rate of E-70-S as a function of Oxygen Scavenger Concentration

5-16

EPRI Proprietary Licensed Material Experimental Results

E-7018 Weld Metal

Table 5-23 Corrosion Rate of E-7018 as a function of Hydrazine Concentration Coupon Number E 7018-2 E 7018-3 E 7018-1 E 7018-2 E 7018-3 E 7018-1 21.807 21.450 21.749 21.856 21.477 21.900 21.780 21.402 21.698 21.859 21.475 21.862 W1 (g) W2 (g) Hydrazine Concentration (ppm) 25 25 50 10000 10000 25000 0.060 0.106 0.113 <0.001 0.004 0.083 T (mils) R (mils per year) 0.954 1.681 1.794 <0.014 0.054 1.210

Table 5-24 Corrosion Rate of E-7018 as a function of DEHA Concentration Coupon Number E 7018-1 21.862 21.749 W1 (g) W2 (g) DEHA Concentration (ppm) 1 0.255 T (mils) R (mils per year) 2.903

Table 5-25 Corrosion Rate of E-7018 as a function of Carbohydrazide Concentration Coupon Number E 7018-2 21.859 21.807 W1 (g) W2 (g) Carbohydrazide Concentration (ppm) 1 0.116 T (mils) R (mils per year) 1.322

The results for E-7018 are summarized in Figure 5-8. The results are similar to E-7018.

5-17

EPRI Proprietary Licensed Material Experimental Results

E 7018 Corrosion Rates

Corrosion Rate, mpy

7 6 5 4 3 2 1 0 0 1 100

Hydrazine DEHA Carbohydrazide

(2)

10000 1000000

Concentration, ppm

Figure 5-8 Corrosion Rate of E-7018 as a Function of Oxygen Scavenger Concentration

Control Environments
Air Saturated Conditions Three sets of experiments were completed under air saturated conditions with no chemical additives as described in Table 5-1. The main difference in these sets of experiments was whether the coupons were exposed within the demineralized water test solution or above the pool of demineralized water in the vapor space. The latter case is meant to simulate conditions where the SGs have been partially drained and some portions of the SG would be exposed above the waterline. The experimental results are presented in the following sets of tables. I600
Table 5-26 Corrosion Rate of I600 in Air Saturated Demineralized Water Coupon I 600-5 I 600-9 I 600-10 I 600-2 I 600-3 I 600-4 W1 (g) 23.835 23.672 23.762 23.632 23.770 23.798 W3 (g) 23.824 23.661 23.765 23.631 23.771 23.801 Experiment No. 7 7 7 17b 17b 17b T (mils) 0.023 0.022 <0.001 <0.001 <0.001 <0.001 R (mils per year) 0.336 0.327 <0.013 <0.013 <0.013 <0.013

5-18

EPRI Proprietary Licensed Material Experimental Results Table 5-27 Corrosion Rate of I600 in Vapor above Air Saturated Demineralized Water Coupon I 600-4 I 600-9 I 600-8 W1 (g) 23.804 23.661 23.734 W3 (g) 23.799 23.667 23.740 Experiment No. 11 11 17a T (mils) 0.011 <0.001 <0.001 R (mils per year) 0.128 <0.013 <0.013

I 690
Table 5-28 Corrosion Rate of I690 in Air Saturated Demineralized Water Coupon I 690-8 I 690-9 I 690-10 I 690-2 I 690-3 I 690-4 W1 (g) 28.058 26.561 28.290 26.468 28.175 26.665 W3 (g) 28.024 26.514 28.287 26.469 28.177 26.665 Experiment No. 7 7 7 17b 17b 17b T (mils) 0.071 0.097 0.006 <0.001 <0.001 <0.001 R (mils per year) 1.031 1.416 0.092 <0.013 <0.013 <0.013

Table 5-29 Corrosion Rate of I690 in Vapor above Air Saturated Demineralized Water Coupon I 690-5 I 690-8 I 690-1 I 690-5 W1 (g) 27.910 28.024 28.611 27.911 W3 (g) 27.912 28.058 28.611 27.911 Experiment No. 11 11 17a 17a T (mils) <0.001 <0.001 <0.001 <0.001 R (mils per year) <0.013 <0.013 <0.013 <0.013

405 SS
Table 5-30 Corrosion Rate of 405 SS in Air Saturated Demineralized Water Coupon 405-5 W1 (g) 6.347 W3 (g) 6.347 Experiment No. 7 T (mils) <0.001 R (mils per year) <0.014

1010 Carbon Steel

Table 5-31 Corrosion Rate of 1010 CS in Air Saturated Demineralized Water

5-19

EPRI Proprietary Licensed Material Experimental Results R (mils per year) 3.173 2.809 3.592 2.793 2.049

Coupon 1010-8 1010-9 1010-10 1010-1 1010-2

W1 (g) 21.531 21.100 21.388 21.033 23.278

W3 (g) 21.433 21.013 21.278 20.947 23.215

Experiment No. 7 7 7 17b 17b

T (mils) 0.217 0.192 0.246 0.191 0.140

Table 5-32 Corrosion Rate of 1010 CS in Vapor Above Air Saturated Demineralized Water Coupon 1010-4 1010-5 W1 (g) 21.380 21.195 W3 (g) 21.355 21.168 Experiment No. 11 11 T (mils) 0.055 0.061 R (mils per year) 0.632 0.691

A569 Carbon Steel

Table 5-33 Corrosion Rate of A569 CS in Air Saturated Dimeralized Water Coupon A 569-6 A 569-9 W1 (g) 20.234 20.193 W3 (g) 20.132 20.114 Experiment No. 7 7 T (mils) 0.228 0.177 R (mils per year) 3.334 2.579

Table 5-34 Corrosion Rate of A569 CS in Vapor above Air Saturated Demineralized Water Coupon A 569-7 A 569-8 A 56910 A 569-1 A 569-2 A 569-3 W1 (g) 20.492 20.538 20.337 20.238 20.412 20.178 W3 (g) 20.481 20.525 20.326 20.200 20.397 20.156 Experiment No. 11 11 11 17a 17a 17a T (mils) 0.024 0.027 0.024 0.086 0.035 0.049 R (mils per year) 0.278 0.311 0.275 1.263 0.512 0.714

A36 Carbon Steel

Table 5-35 Corrosion Rate of A36 CS in Air Saturated Demineralized Water Coupon W1 (g) W3 (g) Experiment T (mils) R (mils per

5-20

EPRI Proprietary Licensed Material Experimental Results year) A 36-5 A 36-7 A 36-8 A 36-1 A 36-2 A 36-3 23.374 23.275 23.334 21.083 23.042 23.054 23.281 23.261 23.180 21.004 22.963 22.970 No. 7 7 7 17b 17b 17b 0.214 0.032 0.358 0.181 0.182 0.194 3.130 0.461 5.228 2.645 2.662 2.831

Table 5-36 Corrosion Rate of A36 CS in Vapor above Air Saturated Demineralized Water Coupon A 36-3 A 36-6 A 36-9 W1 (g) 23.109 23.325 23.379 W3 (g) 23.091 23.304 23.358 Experiment No. 11 11 11 T (mils) 0.0435 0.0486 0.050 R (mils per year) 0.496 0.554 0.565

E-7018 Weld Metal

Table 5-37 Corrosion Rate of E-7018 in Air Saturated Demineralized Water Coupon E 7018-1 E 7018-2 E 7018-3 W1 (g) 21.698 21.780 21.402 W3 (g) 21.593 21.668 21.306 Experiment No. 17b 17b 17b T (mils) 0.234 0.250 0.216 R (mils per year) 3.419 3.657 3.158

Controlled Conditions without Oxygen Scavengers

Two experiments were run with nitrogen sparging used to remove dissolved oxygen and pH control using ammonia. No oxygen scavengers were used in these tests. The test conditions are summarized in Table 5-1. Experiment No. 10 used a continuous nitrogen sparge throughout the entire test period. Experiment No. 16 used an initial nitrogen sparge to reduce the dissolved oxygen to <20 ppb. The nitrogen was discontinued except for five minute nitrogen sparges four times during the subsequent 25 day test period. In Experiment No. 10, the dissolved oxygen was always <20 ppb, where in Experiment No. 16, it was <20 ppb for only a short period in between the sparge procedures. I600
Table 5-38 Corrosion Rate of I600 in pH Controlled Low Dissolved Oxygen Water Coupon W1 (g) W3 (g) Experiment T (mils) R (mils per year)

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EPRI Proprietary Licensed Material Experimental Results No1. 10

I 600-5

23.824

23.834

<0.001

<0.013

1-continuous nitrogen sparge Table 5-39 Corrosion Rate of I690 in pH Controlled Low Dissolved Oxygen Water Coupon I 690-2 W1 (g) 26.469 W3 (g) 26.468 Experiment No.1 10 T (mils) 0.001 R (mils per year) <0.013

1-continuous nitrogen sparge

1010 Carbon Steel

Table 5-40 Corrosion Rate of 1010 CS in pH Controlled Low Dissolved Oxygen Water Coupon 1010-7 1010-9 1010-3 1010-4 1010-5 W1 (g) 21.036 21.013 21.131 21.313 21.111 W3 (g) 21.003 20.988 21.042 21.212 21.020 Experiment No.1,2 10 10 16b 16b 16b T (mils) 0.074188 0.058434 0.1991 0.226362 0.203793 R (mils per year) 0.846 0.667 2.907 3.305 2.975

1-Experiment No. 10: continuous nitrogen sparge 2-Experiment No. 16b: initial nitrogen sparge, followed by periodic sparging

Table 5-41 Corrosion Rate of 1010 CS in Vapor above pH Controlled Low Dissolved Oxygen Water Coupon 1010-6 1010-7 1010-8 W1 (g) 21.192 20.969 20.036 W3 (g) 21.178 20.954 20.010 Experiment No.2 16a 16a 16a T (mils) 0.030 0.033 0.059 R (mils per year) 0.440 0.480 0.858

2-initial nitrogen sparge, followed by periodic sparging

A569 Carbon Steel

Table 5-42 Corrosion Rate of A569 CS in pH Controlled Low Dissolved Oxygen Water Coupon W1 (g) W3 (g) Experiment T (mils) R (mils per year)

5-22

EPRI Proprietary Licensed Material Experimental Results No.1,2 10 10 16b 16b 16b 16b

A 569-6 A 569-9 A 569-4 A 569-5 A 569-6 A 569-7

20.132 20.114 20.222 20.230 20.060 20.405

20.108 21.408 20.134 20.141 19.966 20.330

0.054 <0.001 0.196 0.199 0.208 0.166

0.612 <0.014 2.868 2.900 3.041 2.427

1-Experiment No. 10: continuous nitrogen sparge 2-Experiment No. 16b: initial nitrogen sparge, followed by periodic sparging Table 5-43 Corrosion Rate of A569 CS in Vapor above pH Controlled Low Dissolved Oxygen Water Coupon A 569-8 A 569-9 W1 (g) 20.525 21.408 W3 (g) 20.508 21.390 Experiment No.2 16a 16a T (mils) 0.038 0.040 R (mils per year) 0.561 0.584

2-initial nitrogen sparge, followed by periodic sparging

A36 Carbon Steel

Table 5-44 Corrosion Rate of A36 CS in pH Controlled Low Dissolved Oxygen Water Coupon A 36-5 A 36-8 A 36-4 A 36-5 A 36-6 A 36-7 W1 (g) 23.281 23.179 23.208 23.188 23.237 23.208 W3 (g) 23.260 23.153 23.108 23.110 23.127 23.094 Experiment No.1,2 10 10 16b 16b 16b 16b T (mils) 0.049 0.062 0.231 0.181 0.256 0.263 R (mils per year) 0.562 0.705 3.378 2.645 3.733 3.838

1-Experiment No. 10: continuous nitrogen sparge 2-Experiment No. 16b: initial nitrogen sparge, followed by periodic sparging

5-23

EPRI Proprietary Licensed Material Experimental Results

Table 5-45 Corrosion Rate of A36 CS in Vapor above pH Controlled Low Dissolved Oxygen Water Coupon A 36-8 A 36-9 W1 (g) 23.153 23.358 W3 (g) 23.139 23.340 Experiment No.2 16a 16a T (mils) 0.032 0.0407 R (mils per year) 0.470 0.595

2-initial nitrogen sparge, followed by periodic sparging

E-7018 Weld Metal

Table 5-46 Corrosion Rate of E-7018 in pH Controlled Low Dissolved Oxygen Water Coupon E 70183 W1 (g) W3 (g) Experiment No.1 10 T (mils) R (mils per year)

21.475

21.450

0.056

0.641

1-continuous nitrogen sparge

E-70-S Weld Metal

Table 5-47 Corrosion Rate of E-70-S in pH Controlled Low Dissolved Oxygen Water Coupon E 70s-3 E 70s-1 E 70s-2 E 70s-3 W1 (g) 21.743 21.360 21.563 21.667 W3 (g) 21.722 21.219 21.465 21.569 Experiment No.1,2 10 16b 16b 16b T (mils) 0.047149 0.313957 0.218988 0.219658 R (mils per year) 0.538 4.584 3.197 3.207

1-Experiment No. 10: continuous nitrogen sparge 2-Experiment No. 16b: initial nitrogen sparge, followed by periodic sparging

5-24

EPRI Proprietary Licensed Material

6
DISCUSSION OF RESULTS
The primary purpose of this section is to review and compare the results of the current experimental program with other relevant data obtained in the literature review reported in section 2 of this report. It is important to recognize that the current experimental program is not yet complete so that many important questions identified in the gap analysis are still unanswered. Furthermore, it is recognized that additional testing to investigate galvanic and other local corrosion processes is necessary before any formal recommendations can be made to change the existing secondary water lay-up guidance. Recommendations for future work related to general corrosion are discussed later in this section. The first conclusion that can be reached from the experimental work performed in this study is that the corrosion resistant alloys I600, I690 and 405 SS experience low and acceptable general corrosion rates under all of the dearated conditions tested. Although there were a couple of I600 measurements with higher than acceptable corrosion rates (probably as a result of experimental error), the majority of the data was at the limit of detection in this program. A general caution, however, as noted above is that galvanic and local corrosion should be evaluated before any overall general conclusion with respect to these alloys is drawn. Under aerated conditions without pH control both I600 and I690 experienced relatively high general corrosion rates for some specimens, but below LLD for other specimens. The remainder of this section discusses the corrosion measurements for the carbon steels; 1010, A569 and A36. Less testing of the weld metals E-70-S and E-7018 was performed but the results were all similar to the carbon steels. The results for individual carbon steels were presented in Section 5. For the purpose of evaluating the reproducibility of the experimental results, it is useful to show the results for all of the carbon steels on one graph since their corrosion behavior is expected to be similar. Figure 6-1 includes all of the hydrazine data for the three carbon steels tested, 1010, A-569 and A-36. A trend line is also drawn through the dataset for discussion purposes.

6-25

EPRI Proprietary Licensed Material Discussion of Results

Corrosion Rates, mpy

3.5 3 2.5 2 1.5 1 0.5 0 0.01 1

All Carbon Steels

Hydrazine Log. (Hydrazine)

100

10000

1000000

Concentration, ppm
Figure 6-1 Summary of all Carbon Steel data with Hydrazine additions

Figure 6-1, in addition to showing the trend with hydrazine concentration gives a good representation of how repeatable individual test measurements were in this program. These results illustrate that individual measurements are quite reproducible when exposed to the same test solution in an individual test vessel. In other words, the scatter at each concentration level is quite low suggesting that experimental measurement error is quite low. At the 1 ppm concentration level, the scatter is larger and this may in fact be due to real differences in corrosion rates. On the other hand, the general trend of the data although linear on the corrosion rate vs. log concentration plot does exhibit a fair amount of scatter around the trend line. This suggests that the run to run variation in the corrosion rate is much greater. In other words, if multiple tests were repeated in different test vessels with the same solution composition and metals, the results may not be as repeatable. At any rate, the experimental results appear to be more than adequate to show the general trend as a function of solution composition and material type.

Effect of Solution pH on Corrosion Rates

Figures 6-2 through 6-4 show the effect of solution pH on the corrosion rates of the three carbon steels tested under deaerated conditions. The test results for I600, I690 and 405SS are not shown here since all the test results were at or near the limit of detection of corrosion. There was insufficient data to show correlations for either of the weld metals, E-70-S or E-7018. The three carbon steels tested did not show any strong correlation with pH. The data for all three oxygen scavengers is shown in the figures. Since measurements were only made at two pHs for both DEHA and carbohydrazide, conclusions with respect to pH should not be drawn from this data alone. Hydrazine measurements were made at several pHs and thus this data is believed to 6-26

EPRI Proprietary Licensed Material Discussion of Results

be more representative. Two important points should be considered with respect to the hydrazine data. First, as shown in Table 5-1, the average solution pH did not correspond directly with the hydrazine concentration. In some cases, the pH was due to the scavenger alone and in some cases ammonia was added to control the pH >9.0. Secondly, the pH reported in Figures 6-2 through 6-4 is the average pH for the entire test period (typically 30 days). As described in Section 5 and as shown in the Appendix, the pH varied considerably during the test. Nonetheless, there is no clear correlation of corrosion data with pH. It is reasonable to conclude from this data that for oxygen free solutions over the range of pH from about 9.2-10.6 (e.g. approximately 1.5 pH units), the effect of oxygen scavenger concentration, over the practical range considered, is much more pronounced than the effect of solution pH on the observed carbon steel corrosion rate.

1010 Corrosion Rates

Corrosion Rates, mpy

3.5 3 2.5 2 1.5 1 0.5 0

8.8 9 9.2 9.4 9.6 9.8 10 10.2 10.4 10.6

Hydrazine DEHA Carbohydrazide No Scavenger

pH (25C)

Figure 6-2 1010 Corrosion Rate as a Function of Average Solution pH

6-27

EPRI Proprietary Licensed Material Discussion of Results

A569 Corrosion Rates

Corrosion Rate, mpy
3.5 3 2.5 2 1.5 1 0.5 0
8.8 9 9.2 9.4 9.6 9.8 10 10.2 10.4 10.6

Hydrazine DEHA Carbohydrazide No Scavenger

pH (25C)
Figure 6-3 A569 Corrosion Rate as a Function of Average Solution pH

A36 Corrosion Rates

3.5 3 2.5 2 1.5 1 0.5 0
8.8 9 9.2 9.4 9.6 9.8 10 10.2 10.4 10.6

Corrosion Rate,mpy

Hydrazine DEHA Carbohydrazide No Scavenger

pH (25C)
Figure 6-4 A36 Corrosion Rate as a Function of Average Solution pH

Comparison to Literature Data

In section 2, a detailed literature review of available corrosion data relevant to lay-up conditions was presented. Although the experimental program conducted here was designed to fill gaps in

6-28

EPRI Proprietary Licensed Material Discussion of Results

the available data rather than to repeat measurements, it is useful to compare the data from this study to the literature data where a comparison can be made. The majority of the data from the experimental program conducted here was under dearated conditions (dissolved oxygen <20 ppb). Figure 3-3 included corrosion data for carbon steel under low oxygen conditions. The data from this study (1010, A569, A36) is plotted with the data from Figure 3-3 below. No definitive conclusions or correlations can be drawn from the combination of this data other than the observation that the corrosion rates reported here are of the same order as previously reported. This increases our confidence in the use of the data from this experimental program for evaluating lay-up chemistries. Figure 3-1 was a summary of available data using oxygen scavengers under aerated conditions. No comparable measurements were made in this program, however Experiment # 16 was conducted under partially aerated conditions with pH control using NH3. In Experiment #16, the test vessel was initially sparged with nitrogen and 3 times for 5 minutes during the remainder of the test. For the majority of the test, the coupons were exposed to aerated conditions since the test vessel re-saturated with air quickly after the nitrogen purge. The data for the three carbon steels (1010, A569, and A36) is included with the original data from Figure 3-1 on Figure 6-6 below. The results from this program (with no oxygen scavenger present) suggest that pH control alone may be as effective as nominally 100 ppm hydrazine at a similar pH level. This conclusion is very tentative however, since the exact experimental conditions from the literature are not well known. In addition, it must be noted that Experiment #10, under nominally the same conditions at Experiment #16 except continuous nitrogen purge was used to maintain oxygen less than 25 ppb, had carbon steel corrosion rates about 5-times lower than Experiment #16b as indicated in Table 5-40. These new results underscore the importance of minimizing or eliminating dissolved oxygen from the system.

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EPRI Proprietary Licensed Material Discussion of Results

3.5

3 Carbon Steel Corrosion Rate, mpy

2.5

See Figure 3-3 for references to literature data

1.5

0.5

0 8.8 9 9.2 9.4 9.6 9.8 pH N2H4 CH DEHA N2H4 This Study DEHA This Study CHZ This Study 10 10.2 10.4 10.6 10.8

Figure 6-5 Comparison of Corrosion Data from This Study to Literature Data (Dearated Conditions)

6-30

EPRI Proprietary Licensed Material Discussion of Results

8 7 Carbon Steel Corrosion Rate, mpy 6 5 4 3 2 1 0 9.6 9.7 9.8 9.9 10 10.1 pH N2H4 CH This Study 10.2 10.3 10.4 10.5 10.6 10.7 360 ppm [1] 36 ppm [1] 0 ppm 80 ppm [17]

30 ppm [17]

Figure 6-6 Comparison of Corrosion Data from This Study to Literature Data (Aerated Conditions)

Recommendations for Future Work

In addition to the general conclusions stated above, it is also clear from the test results that the introduction of oxygen markedly increases the corrosion rate and that the corrosion rate in the vapor space above air saturated demineralized or pH controlled water is much lower than in the water. Although this is not unexpected, the results from Experiments No. 10, 16 and 17 show this effect for all three carbon steels. This observation coupled with the earlier ones leads to some recommendations for future general corrosion testing. Although localized corrosion testing is also planned in the future, the scope of that testing is not discussed here. The following table contains recommendations for future general corrosion experiments. The list is not prioritized, however consideration would need to be given to which experiments should be completed first so that the design of future experiments could be refined.

6-31

EPRI Proprietary Licensed Material Discussion of Results

Figure 6-7 Future General Corrosion Test Recommendations Experiment Series A Materials Carbon Steels & Weld Metals-in liquid Test Conditions Low Oxygen, vary pH with NH3. No oxygen scavenger Comments The experiments completed to date suggest that acceptable corrosion rates (e.g. less than allowance) can be achieved in dearated solutions without oxygen scavengers. The influence of pH is important and should be explored in a controlled manner. The importance of oxygen control is clear from the current set of results. Tests to determine the dependence on concentration and/or the presence of a threshold concentration above which corrosion increases rapidly is needed. Experiment #16 was initially designed to simulate the plant practice of initial dearation at the beginning of the layup period. The test apparatus will need to be re-designed to better simulate plant conditions. Similar to Series C except use oxygen scavenger to reduce oxygen conentration

Carbon Steels & Weld Metals-in liquid

Fixed pH (~9.5), vary oxygen from 0-200 ppb. No oxygen scavenger

Carbon Steels & Weld Metals-in vapor and liquid

Initial nitrogen purge, fixed pH, with and without oxygen scavengers Initial Aerated conditions, fixed pH with oxygen scavenger

Carbon Steels & Weld Metals- vapor and liquid

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EPRI Proprietary Licensed Material

A
CHEMISTRY MEASUREMENT DATA
The chemistry measurements where available are reported in this Appendix. Average pH values are reported for each experiment. It should be noted that because the vessels were relatively stagnant and in many cases excessive corrosion product existed in the test vessel, the values reported here should be considered approximate. For the cases where the dissolved oxygen is reported <0.020 ppm, it is felt that the dissolved oxygen was less than this value. In most cases the oxygen probe reported 0.0 ppm.
Table A-1 Experiment No. 1 Chemistry Data Time (days) 0 3 4 7 8 9 10 11 14 15 16 17 18 19 21 22 23 24 28 29 Avg. pH 10.60 10.87 10.73 10.68 10.59 10.50 10.55 10.50 10.33 10.40 10.38 10.38 10.38 10.40 10.60 10.58 10.58 10.52 10.47 10.44 10.02 D0 (mg/l) <0.020 0.31 <0.020 0.03 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 325 206 215 261 291 319 326 280.9 427 335 449 458 468.5 477 542.5 577 605 652 769 800

A-1

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-2 Experiment No. 2 Chemistry Data Time (days) 0 3 4 7 8 9 10 11 14 15 16 17 18 19 21 22 23 24 28 29 Avg. pH 10.40 9.78 9.53 9.17 9.23 9.21 9.27 9.35 9.04 9.13 9.20 9.27 9.27 9.53 9.44 9.36 9.34 9.29 9.24 9.22 8.92 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 90.1 91.7 100.2 119.35 121.65 126.4 130.7 73.2 167.5 167.4 168.1 169.5 170.5 171.7 186.7 193 198.8 206 229.5 235

A-2

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-3 Experiment No. 3 Chemistry Data Time (days) 0 3 4 7 8 9 10 11 14 15 16 17 18 19 21 22 23 24 28 29 Avg. pH 8.10 8.54 9.55 9.27 9.16 9.04 9.00 9.06 9.04 8.83 8.88 8.85 8.66 9.04 8.97 8.98 8.94 8.98 9.01 9.04 8.52 D0 (mg/l) 0.05 0.06 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 5.83 7.74 54.6 66.7 73.6 82.9 81 90.9 148.6 90.4 191 206.5 223 236 223 219 219 215 197.3 189.8

A-3

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-4 Experiment No. 4 Chemistry Data Time (days) 0 3 4 5 6 7 10 11 12 13 14 17 18 24 25 Avg pH 11.42 10.97 10.88 10.80 10.74 10.68 10.53 10.49 10.42 10.40 10.38 10.41 10.51 10.10 10.16 9.93 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 167.7 268 305 336 366.5 397 504 538 586 602 619 665 693 943 981

A-4

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-5 Experiment No. 5 Chemistry Data Time (days) 0 3 4 5 6 7 10 11 12 13 14 17 18 24 25 Avg. pH 10.77 10.26 10.29 10.21 10.17 10.16 10.11 10.08 10.08 9.90 9.87 9.90 9.75 9.41 9.46 9.4 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 117.3 175.7 178 193 173 172 152 139.7 136.1 272 299 371 383 504 568

A-5

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-6 Experiment No. 6 Chemistry Data Time (days) 0 3 4 5 6 7 10 11 12 13 14 17 18 24 25 Avg. pH 10.23 9.33 9.19 9.14 8.97 8.99 8.84 8.85 9.37 9.34 9.27 9.15 9.09 9.13 9.20 8.63 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 40.3 125.2 193.5 224 253 273 311 285 292 314 328 354 362 437 494

A-6

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-7 Experiment No. 8 Chemistry Data Time (days) 0 2 3 4 7 9 10 11 13 14 16 17 18 21 23 24 25 Avg. pH 10.34 10.13 10.14 10.32 10.25 10.14 10.08 10.15 9.78 10.24 10.2 10.08 10.04 9.56 9.48 9.8 9.92 9.48 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 97.9 143.3 173.8 203 284 353 353 367 249 373 394 362 237 124.1 55.9 166.8 79.8

A-7

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-8 Experiment No. 9 Chemistry Data Time (days) 0 2 3 4 7 9 10 11 13 14 16 17 18 21 23 24 25 Avg. pH 9.86 9.45 9.2 9.22 9.01 8.85 8.85 8.73 9.48 9.95 9.77 9.69 9.58 9.31 9.4 9.43 9.31 8.84 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 114.4 170.1 190 199.8 224 249 260 249 334 394 451 490 478 532 570 563 574

A-8

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-9 Experiment No. 10 Chemistry Data Time (days) 0 2 3 4 7 9 10 11 13 14 16 17 18 21 23 24 25 Avg. pH 10.32 9.6 9.74 9.02 9.335 8.52 8.1 8.11 10.29 10.47 10 9.65 9.59 9.4 9.17 9.04 9.24 8.87 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 36.9 43.5 45.1 40.2 12.19 1.74 0.18 0.54 81.6 79.3 52.4 59.4 49.59 79 69.3 57.1 44.4

A-9

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-10 Experiment No. 12 Chemistry Data Time (days) 0 2 3 5 6 7 10 12 13 14 17 18 19 20 Avg. pH 9.13 9.97 9.87 9.52 9.41 9.22 9.1 9.41 9.2 9.01 9.5 9.26 9.38 9.17 8.74 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 10.14 63.8 0.21 0.09 0.17 64.7 75.2 93.1 115.2 129.7 171.1 238 181.4 197.8

A-10

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-11 Experiment No. 13 Chemistry Data Time (days) 0 2 3 5 6 7 10 12 13 14 17 18 19 20 Avg. pH 9.97 9.29 9.33 9.07 9.14 9.8 9.27 9.63 9.22 9.02 9.7 9.17 9.8 9.37 8.79 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 84.2 56.2 57.3 58.7 61.3 93.9 75.7 111.9 100.9 99.6 103.9 91.8 121.9 36

A-11

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-12 Experiment No. 14 Chemistry Data Time (days) 0 2 3 5 6 7 10 12 13 14 17 18 19 20 Avg. pH 10.11 9.45 9.7 9.27 9.24 9.18 10.02 9.49 9.36 9.21 9.09 9.06 9.4 9.28 8.79 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) 71.4 61.3 58.1 87.3 85.9 108.2 137.5 191.5 160.3 228 219 204 213 214

A-12

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-13 Experiment No. 15 Chemistry Data time (days) 0 2 3 5 6 7 10 12 13 14 17 18 19 20 Avg. pH 9.68 9.90 9.35 9.11 9.26 9.11 9.21 9.26 9.15 9.00 9.31 9.29 9.05 9.36 8.67 D0 (mg/l) <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 <0.020 Conductivity (s/cm) Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured Not Measured

A-13

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-14 Experiment No. 16 Chemistry Data Time (days) 0 1 3 5 7 11 12 13 14 18 19 21 25 Avg. pH 11.1 10.26 10.06 9.89 9.78 9.85 9.56 9.65 9.84 9.66 9.62 9.87 8.91 9.15 D0 (mg/l) <0.020 4.05 2.65 1.67 1.55 1.66 1.68 <0.020 1.40 1.23 1.37 1.55 1.58 Conductivity (s/cm) 78.0 100.4 172.2 205 216 212 217 230 320 366 393 449 411

A-14

EPRI Proprietary Licensed Material Chemistry Measurement Data

Table A-15 Experiment No. 17 Chemistry Data Time (days) 0 1 3 5 7 11 12 13 14 18 19 21 25 Avg. pH 6.14 5.56 5.57 5.55 5.58 5.43 5.38 5.84 5.55 5.62 5.76 5.71 6.05 5.67 D0 (mg/l) 5.99 3.41 3.87 3.64 3.15 3.06 3.18 3.30 2.98 3.27 2.99 3.91 4.15 Conductivity (s/cm) 4.32 7.21 9.55 11.28 13.17 17.07 19.66 20.20 21.60 27.40 28.80 31.00 48.40

A-15

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