Text

Response to Request for Additional Information Related to the License Amendment Request on Change of Containment Building Sump Buffering Agent from Trisodium Phosphate to Sodium Tetraborate
	ML062570173
Person / Time
Site:	Fort Calhoun
Issue date:	09/06/2006
From:	Reinhart J; Omaha Public Power District
To:	; Document Control Desk, Office of Nuclear Reactor Regulation
References
	LIC-06-0105 WCAP-16596-NP, Rev 0
	Download: ML062570173 (162)
	v • d • e

Omaha Publ~cPower Distnct 444 South 16th Street Mall Omaha NE 68102-2247 September 6,2006 LIC-06-0105 U. S. Nuclear Regulatory Commission Attn: Document Control Desk Washington, DC 20555-0001

References:

1. Docket No. 50-285

2. Letter from Jeffrey A. Reinhart (OPPD) to Document Control Desk (NRC) dated August 21, 2006, Fort Calhoun Station, Unit No. 1 License Amendment Request (LAR) "Change of Containment Building Sump Buffering Agent from Trisodium Phosphate to Sodium Tetraborate" (LIC-06-0088) (ML062340039)

SUBJECT:

Response to Request for Additional Information Related to the License Amendment Request on Change of Containment Building Sump ~ u f f e r i n ~

Agent from Trisodium Phosphate to Sodium Tetraborate Reference 2 provided the Omaha Public power District's request for a license amendment to support changing the containment building sump buffering agent from Trisodium Phosphate to Sodium Tetraborate. Attachment 1 to this letter provides additional information requested in an email dated August 31, 2006. Attachment 1 contains a copy of WCAP-16596, "Evaluation of Alternative Emergency Core Cooling System Buffering Agents." This report is non-proprietary.

I declare under penalty of perjury that the foregoing is true and correct. (Executed on September 6,2006.)

No commitments are made to the NRC in this letter. If you have additional questions, or require further information, please contact Thomas R. Byrne at (402) 533-7368.

Fort Calhoun Station Employment with Equal Opportunity

U.S. Nuclear Regulatory Commission LIC-06-0105 Page 2

Attachment:

1. Response to Request for Additional Information Related to the License Amendment Request on Change of Containment Building Sump Buffering Agent from Trisodium Phosphate to Sodium Tetraborate c: Director of Consumer Health Services, Department of Regulation and Licensure, Nebraska Health and Human Services, State of Nebraska

LIC-06-0105 Page 1 ATTACHMENT 1 Response to Request for Additional Information Related to the License Amendment Request on Change of Containment Building Sump Buffering Agent from Trisodium Phosphate to Sodium Tetraborate b

WCAP-16596, "Evaluation of Alternative Emergency Core Cooling System Buffering Agents"

Westinghouse Non-Proprietary Class 3 WCAP-16596-IVP July 2006 Revision 0 Evaluation of Alternative Emergency Core Cooling System Buffering Agents

WESTINGHOUSE NON-PROPRIETARY CLASS 3 WCAP-16596-NP, Revision 0 Evaluation of Alternative Emergency Core Cooling System Buffering Agents Richard D. Reid Kurtis R. Crytzer Chemistry, Diagnostics & Materials Engineering

Ann E. Lane Timothy S. Andreychek Containlnent Systems Applications July 2006 Approved: *William J. Rinkacs, Manager Containment Systems Applications

Gordon C. Bischoff PWR Owners Group Programs

Electronically approved records are authenticated in the Electronic Document Management System This work performed under PWROG Project Number PA-SEE-0285.

WESTINGHOUSE NON-PROPRIETARY CLASS 3 111 LEGAL NOTICE This report was prepared as an account of work performed by Westinghouse Electric Company LLC. Neither Westinghouse Electric company LLC, nor any person acting on its behalf:

A. Makes any warranty or representation, express or implied including the warranties of fitness for a particular purpose or merchantability, with respect to the accuracy, completeness, or usefulness of the information contained in this report, or that the use of any information, apparatus, method, or process disclosed in this report may not infringe privately owned rights; or B. Assumes any liabilities with respect to the use of, or for damages resulting from the use of, any information, apparatus, method, or process disclosed in this report.

COPYRIGHT NOTICE This report has been prepared by Westinghouse Electric Company LLC and bears a Westinghouse Electric Company copyright notice. As a member of the PWR Owners Group, you are permitted to copy and redistribute all or portions of the report within your organization; however, all copies made by you must include the copyright notice in all instances.

DISTRIBUTION NOTICE This report was prepared for the PWR Owners Group. This Distribution Notice is intended to establish guidance for access to this information. This report (including proprietary and non-proprietary versions) is not to be provided to any individual or organization outside of the PWR Owners Group program participants without prior written approval of the PWR Owners Group Program Management Office. However, prior written approval is not required for program participants to provide copies of Class 3 Non Proprietary reports to third parties that are supporting implementation at their plant, and for submittals to the NRC.

WCAP- 16596-NP, Rev. 0 July 2006

WESTINGHOUSE NON-PROPRIETARY CLASS 3 iv PWR Owners Group Member Participation* for PWROG Project Authorization PA-SEE-0285 Utility Member Plant Site(s)

Yes No AmerenUE Callaway (W) X American Electric Power D.C. Cook 1&2 (W) X Arizona Public Service Palo Verde Unit 1, 2, & 3 (CE) X Constellation Energy Group Calvert Cliffs 1 & 2 (CE) X Constellation Energy Group Ginna (W) X Dominion Connecticut Millstone 2 (CE) X Dominion Connecticut Millstone 3 (W) X Dominion Kewaunee Kewaunee (W) X Dominion VA North Anna 1 & 2, Suny 1 & 2 (W) X Duke Energy Catawba 1 & 2, McGuire 1 & 2 (W) X Duke Energy Oconee 1,2, 3 (B&W) X Entergy Nuclear Northeast Indian Point 2 & 3 (W) X Arkansas 2, Waterford 3 (CE), X Entergy Operations South Arkansas I (B&W)

Exelon Generation Co. LLC Braidwood 1 & 2, Byron 1 & 2 (W), X TMI I (B&W)

FirstEnergy Nuclear Operating Co Beaver Valley 1 & 2 (W), Davis-Besse (B&W)

Florida Power & Light Group St. Lucie 1 & 2 (CE) X Florida Power & Light Group Turkey Point 3 & 4, Seabrook (W) X Nuclear Management Company Prairie Island 1&2, Pt. Beach 1&2 (W) X Nuclear Management Company Palisades (CE) X Omaha Public Power District Fort Calhoun (CE) X Pacific Gas & Electric Diablo Canyon 1 & 2 (W) X Progress Energy Robinson 2, Shearon Harris (W), X Crystal River 3 (B&W) -

PSEG - Nuclear Salem 1 & 2 (W) X Southern California Edison SONGS 2 & 3 (CE) X South Carolina Electric & Gas V.C. Summer (W) X So. Texas Project Nuclear Operating Co. South Texas Project 1 & 2 (W) X WCAP- 16596-NP, Rev. 0 July 2006

WESTINGHOUSE NON-PROPRIETARY CLASS 3 v Southern Nuclear Operating Co. Farley 1 & 2, Vogtle I & 2 (W) l x l l Tennessee Valley Authority Sequoyah 1 & 2, Watts Bar (W) X TXU Power Comanche Peak 1 & 2 (W) X Wolf Creek Nuclear Operating Co. Wolf Creek (W) X

This is a list of participants in this project as of the date the final deliverable was completed. On occasion, additional members will join a project. Please contact the PWROG Program Management Office to verify participation before sending documents to participants not listed above.

WCAP- 16596-NP, Rev. 0 July 2006

WESTINGHOUSE NON-PROPRIETARY CLASS 3 vi PWR Owners Group International Member Participation* for PWROG Project / Task PA-SEE-0285 Participant Utility Member Plant Site(s)

Yes I NO British Energy I Sizewell B I X (

1u Electrabel (Be1 ian Utilities) l 1c Kansai Electric Co., LTD l Kori 1, 2, 3 & 4 X Korea Hydro & Nuclear Power Corp.

Yonggwang 1 & 2 (W) 1 Korea Hydro & Nuclear Power Corp. Yonggwang 3 , 4 , 5 & 6 Ulchin 3. 4 & 5 (CE) 1 Nuklearna Electrarna KRSKO 1 x 1 1 X

Ringhals AB Ringhals 2, 3 & 4 (W) X Spanish Utilities Asco 1 & 2, Vandellos 2, X Almaraz 1 & 2 (W)

Taiwan Power Co. Maanshan 1 & 2 (W) X Electricite de France 54 Units X

This is a list of participants in this project as of the date the final deliverable was completed. On occasion, additional members will join a project. Please contact the PWROG Program Management Office to verify participation before sending documents to participants not listed above.

WCAP- 16596-NP, Rev. 0 July 2006

WESTINGHOUSE NON-PROPRIETARY CLASS 3 vii TABLE OF CONTENTS EXECUTIVE

SUMMARY

.................................................................................................................................. xii 1.0 Report Overview ............................................................................................................................................13 2.0 Introduction ...................................................................................................................................................14 2.1 Background .............................................................................................................................................. 14 2.2 Program Objective .....................................................................................................................................15 2.3 Buffer Properties ........................................................................................................................................ 15 2.4 References ..................................................................................................................................................16 3.0 Selection of Candidate Buffering Agents ...................................................................................................17 3.1 References .................................................................................................................................................. 18 4.0 Test Plan ........................................................................................................................................................ 19 4.1 Phase 1: Dissolution Testing ...................................................................................................................... 19 4.2 Phase 2: pH Adjustment of Boric Acid Solutions...................................................................................... 19 4.3 Phase 3: Dissolution in Boric Acid as a Function of Temperature .........................:..............................20 4.4 Phase 4: Aluminum and Calcium Addition ................................................................................................ 21 4.5 Phase 5: Corrosion Testing ........................................................................................................................ 22 4.6 Phase 6: Environmental Effects Testing .................................................................................................... 23 4.7 Phase 7: Boric Acid Solubility Testing ...................................................................................................... 24 4.8 References .................................................................................................................................................. 24 5.0 Test Results ................................................................................................................................................ 25 5.1 Phase 1: Dissolution Testing Results ......................................................................................................... 25 5.2 Phase 2: pH Adjustment of Boric Acid Solutions Results ......................................................................... 25 5.3 Phase 3: Dissolution in Boric Acid as a Function of Temperature Results ............................................... 27 5.4 Phase 4: Aluminum and Calcium Addition Results ................................................................................... 27 5.5 Phase 5: Corrosion Testing Results ........................................................................................................... 33 5.6 Phase 6: Environmental Effects Testing .................................................................................................... 34 5.7 Phase 7: Boric Acid Solubility Testing Results ......................................................................................... 36 WCAP.16596.NP, Rev . 0 July 2006

WESTINGHOUSE NON-PROPRIETARY CLASS 3 vlll 5.8 References ..................................................................................................................................................

36 6.0 Evaluation of Buffering Agent Criteria ......................................................................................................... 37 6.1 Precipitation under Post-LOCA Conditions .............................................................................................. 37 6.2 Quantity Required to Adjust pH >8.0 ........................................................................................................ 38 6.3 Dissolution Rate ........................................................................................................................................ 38 6.4 Affordability and Availability .................................................................................................................... 39 6.5 Corrosiveness .............................................................................................................................................

39 6.6 Effect on Boric Acid Solubility ............................................................................................................... 39 6.7 Environmental Stability ............................................................................................................................. 39 6.8 Habitability Concerns ................................................................................................................................ 40 6.9 OxideICRUD Release ................................................................................................................................ 40 6.10 References ............................................................................................................................................43 7.0 Conclusions and Recommendations .............................................................................................................. 44 7.1 References ..................................................................................................................................................

45 8.0 Considerations for Buffer Replacement ........................................................................................................ 46 8.1 pH Requirements ...................................................................................................................................... 46 8.2 Recommended Evaluations ........................................................................................................................ 46 8.3 References ..................................................................................................................................................

48 Appendix A: Detailed Results of Phase 2 Testing ............................................................................................. 49 Appendix B: Detailed Results of Phase 3 Testing .............................................................................................. 66 Appendix C: Detailed Results of Phase 4 Testing .............................................................................................. 69 C.l Phase 4 Detailed Test Results ............................................................................................................. 70 C.2 Phase 4A and 4B Test Report ................................................................................................................... 90 Appendix D: Detailed Results of Phase 5 Testing ............................................................................................ 125 Appendix E: Detailed Results of Phase 6 Testing ............................................................................................. 145 E .1 Environmental Effects Testing with 100% Humidity ..........................................................................146 E.2 Environmental Effects Testing with 30% Humidity ............................................................................ 149 WCAP.16596.NP, Rev . 0 July 2006

WESTINGHOUSE NON-PROPRIETARY CLASS 3 ix Appendix F: Detailed Results of Phase 7 Testing .............................................................................................

154 WCAP-16596-NP, Rev. 0 July 2006

WESTINGHOUSE NON-PROPRIETARY CLASS 3 x LIST OF TABLES Table 3-1 : Properties of Candidate ECCS Buffering Agents ...............................................................................18 Table 5-1: Phase 1 Dissolution Testing Results ................................................................................................... 25 Table 5-2: Phase 2 pH Adjustment of 2500 ppm Boric Acid Solution Results ................................................... 26 Table 5-3: Phase 3 Dissolution Testing Results as a Function of Temperature ...................................................27 Table 5-4: Phase 4 Calcium Addition Precipitate Formation ...............................................................................28 Table 5-5: Phase 4 Aluminum Addition Precipitate Formation .........................................................................29 Table 5-6: Measured Settling Rates of Aluminum and Calcium Precipitates .....................................................30 Table 5-7: Calculated Filter Cake Coefficients ................................................................................................... 31 Table 5-8: Phase 5 Corrosion ofAluminum and Carbon Steel Metal Coupons ................................................ 33 Table 5-9: Phase 6 Environmental Effects Testing Results .................................................................................. 35 Table 5-10: Phase 7 Determination of Buffer Impact on Boric Acid Solubility .................................................36 Table 6-1: Summary of Characteristics of Candidate ECCS Buffering Agents ...................................................42 WCAP.16596.NP. Rev . 0 July 2006

WESTINGHOUSE NON-PROPRIETARY CLASS 3 xi LIST O F FIGURES Figure 5-1 : Mass of Buffer Candidate Required to Achieve Desired pH ............................................................ 26 Figure 5-2: Precipitate Formation with Calcium Addition ..................................................................................28 Figure 5-3 : Precipitate Formation with Aluminum Addition ...............................................................................29 Figure 5-4: Buffering Capacity of NaTB and TSP for Boric Acid Addition ...................................................32 Figure 5-5: Buffering Capacity of NaTB and TSP for Hydrochloric Acid Addition ...........................................33 WCAP.l6596.NP, Rev . 0 July 2006

WESTINGHOUSE NON-PROPRIETARY CLASS 3 xii EXECUTIVE

SUMMARY

The PWR Owners Group (PWROG) has commissioned this program to evaluate candidate replacement buffering agents for trisodium phosphate (TSP) and sodium hydroxide (NaOH) in PWR Emergency Core Cooling Systems (ECCS). The results of this evaluation identify recommended alternative buffering agents for plants now using TSP and NaOH for post-accident buffering in order to reduce the risk of sump screen plugging due to the formation of chemical products. A reduction in the potential for chemical precipitate formation may allow plants to more easily demonstrate design margin for new or existing sump screens, which will assist plants in meeting the December 2007 deadline for corrective actions set by the NRC in Nuclear Regulatory Commission (NRC) Generic Letter (GL) 2004-02.

The primary goal of this program is to identify suitable buffering agents to reduce precipitate generation under post-accident conditions. In addition, the properties of the candidate buffers must be comparable to those of the buffers currently in use. In order to qualify the alternative buffers, the candidates were subjected to a selection process which involved both evaluation of literature data and a series of tests. Specifically, the report presents the following conclusions from this evaluation process.

Selection of Candidates Candidate buffering agents were selected for testing based on the criteria established in Section 2.3. Sodium tetraborate decahydrate (NaTB) and sodium metaborate tetrahydrate (NaMB) were selected because of the advantage that NaTB is already in use in Ice Condenser PWR plants. Sodium tripolyphosphate (NaTPP) and sodium gluconate (NaGlu) were also selected for testing because of their abiIity to act as sequestering agents, which may serve to inhibit precipitation.

Test Phase Results Seven phases of tests were conducted to determine the acceptability of the selected candidates. Sodium gluconate was eliminated due to its inability to achieve a target pH of 8.0. Although sodium tripolyphosphate provided the best results in the precipitation testing phase, NaTPP formed the least amount of precipitate with the addition of aluminum and calcium, the corrosion testing showed that NaTPP may cause significant release of iron and aluminum from containment structural materials. In the environlnental effects testing, in which the candidates were exposed to elevated temperature for 30 days, sodium tetraborate maintained its form as did TSP, while the sodium metaborate formed a liquid.

Conclusions and Recommendations The sodium tetraborate and sodium metaborate buffers were determined from the test phases to be the most comparable alternatives to TSP and NaOH. Due to the results of the environmental effects test, in which sodium metaborate dissolved, sodium tetraborate would be recommended as the best alternative to TSP.

However, sodium metaborate in solution form would be a suitable replacement for NaOH solution. The testing confirmed that TSP is an excellent buffering agent for plants with a low loading of calcium-bearing materials.

WCAP-16596-NP, Rev. 0 July 2006

13 WESTINGHOUSE NON-PROPRIETARY CLASS 3 1.0 REPORT OVERVIEW The purpose of this report is to evaluate alternative buffering agents for use in PWR Emergency Core Cooling Systems (ECCS) which may decrease chemical precipitate formation post-LOCA.

The information contained in this report supports the resolution of GSI-191 through replacement of the buffering agent in order to reduce potential post-accident chemical effects in containment sump fluids.

Section 2 of this report presents an introduction to the alternate buffer program, the background of the chemical effects issue, the buffer properties of concern to be evaluated for each candidate, and also provides the objective of this program.

Section 3 describes the review of literature data performed in order to identify candidate buffers for the test program based on the criteria for buffer properties.

Section 4 outlines the Test Plan for comparison of the candidate buffers with the buffering agents currently employed in US PWRs.

Section 5 presents the results of the bench scale acceptability tests performed according to the Test Plan.

Section 6 performs an evaluation of the buffering agent criteria provided in Section 2.3. For each candidate buffer, precipitation under post-LOCA conditions, the quantity required to adjust the pH to > 8.0, the dissolution rate, affordability and availability, corrosiveness, the effect on boric acid-solubility, environmental stability, habitability concerns, and the potential for oxide1CRUD release are discussed.

Section 7 presents the conclusions and recommendations developed from the results of the test phases in Section 5 and the evaluation of the buffering agent criteria performed in Section 6.

Finally, Section 8 discusses considerations for replacement of the buffering agent with a suggested alternative, including pH requirements and necessary evaluations.

WCAP-16596-NP, Rev. 0 July 2006

14 WESTINGHOUSE NON-PROPRIETARY CLASS 3

2.0 INTRODUCTION

In February 2006, the PWR Owners' Group (PWROG) authorized testing to evaluate alternative buffering agents for use in the Emergency Core Cooling System (ECCS) at PWRs (Reference 2.4-1). The purpose of the testing is to identify candidate replacements for trisodium phosphate (TSP) and sodium hydroxide (NaOH) currently used in this application at most plants.

Laboratory testing to support this program is being conducted at the Fauske and Associates facility in Burr Ridge, IL under an approved test plan (Reference 2.4-2).

A replacement for TSP is desirable due to the potential interaction of phosphate with metals dissolved from containment materials under accident conditions, particularly calcium, to produce amorphous metal phosphate precipitates. A replacement for NaOH is desirable due to the enhanced corrosion of aluminum alloys in NaOH solutions, and resultant generation of amorphous aluminum-containing precipitates, including aluminum oxyhydroxide and metal aluminosilicates. Past testing has shown that such amorphous precipitates do not settle readily and are difficult to filter, and thus are likely to contribute to sump strainer head loss under accident conditions (References 2.4-3-2.4-6).

The primary goal of the alternative buffering agent test program is to identify suitable buffering agents to minimize precipitate generation under post-accident conditions. This goal may be accomplished by selecting buffering agents that do not react directly with dissolved species to produce precipitate, as well as selecting buffering agents that reduce the dissolution/corrosion of containment materials or maintain dissolved metals in solution to prevent precipitation. In addition to minimizing precipitate generation, the candidate buffer properties must be comparable to those of the chemicals currently used.

2.1 BACKGROUND

The conditions in Pressurized Water Reactor (PWR) containment buildings are designed to both contain radioactive materials releases and facilitate core cooling in the event of a Loss of Coolant Accident (LOCA). The cooling process requires water discharged from the break and containment spray to be collected in a sump for recirculation by the Emergency Core Cooling System (ECCS) and Containment Spray System (CSS). Typically, a containment sump contains one or more screens in series that protect the components of the ECCS and CSS from debris that could be washed into the sump. Debris generated by the action of the discharged water and the latent containment debris inside containment may be transported to the containment sump and downstream of the sump to the ECCS and CSS components when the ECCS and CSS are realigned from injecting water from the Refueling or Borated Water Storage Tank (RWST or BWST). There is a concern that this debris may form a debris bed at the sump screen that would sufficiently impede the recirculating flow as to challenge long-term core cooling requirements.

The NRC identified its concern regarding maintaining adequate long-term core cooling in Generic Safety Issue (GSI) 191 (Reference 2.4-7). Generic Letter (GL) 2004-02 (Reference 2.4-8), issued in September 2004, identified actions that utilities must take to address the sump blockage issue. The NRC's position is that plants must be able to demonstrate that WCAP-16596-NP, Rev. 0 July 2006

15 WESTMGHOUSE NON-PROPRIETARY CLASS 3 debris transported to the sump screen after a LOCA will not lead to unacceptable head loss for the recirculation pumps, will not impede flow through the ECCS and CSS, and will not adversely affect the long-term operation of either the ECCS or the CSS. Generic Letter 2004-02 also identifies that all mitigating actions by plants be implemented by the end of December 2007 if required to enable licensees to demonstrate acceptable ECCS and CSS performance.

A major concern in evaluating the effects of the debris transported to the sump screen is the chemical products which may form in a post-LOCA sump environment. Materials present in containment may dissolve or corrode when exposed to the reactor coolant and spray solutions.

This behavior would result in oxide particulate corrosion products and the potential for the formation of precipitates due to changes in temperature and reactions with other dissolved materials. These chemical products may become another source of debris loading to be considered in sump screen performance and downstream effects.

The results of the Integrated Chemical Effects Test (ICET) program (Reference 2.4-9) and the PWROG sponsored Chemical Effects Bench Testing (Reference 2.4-5) indicate two main contributors to precipitate formation following a LOCA. The high pH of the NaOH buffered sump solution post-LOCA may cause significant metal corrosion, resulting in oxide particulate corrosion products and the potential for formation of metal silicates. Also, the reaction of TSP with dissolved metals may form metal phosphate precipitates. Recent tests performed at Argonne National Laboratory (ANL) (Reference 2.4-6) demonstrate that chemical products, specifically calcium phosphate precipitates, may contribute significantly to head loss across simulated sump screen debris beds.

2.2 PROGRAM OBJECTIVE The objective of this program is to evaluate candidate buffering agents as potential alternatives to trisodium phosphate (TSP) or sodium hydroxide (NaOH) used in Emergency Core Cooling Systems (ECCS) in operating Pressurized Water Reactors (PWR). Replacement of the existing buffering agent may reduce the quantity of precipitate formation and the resulting impact on head loss of the chemical precipitates. The information contained in this report may be utilized by plants considering replacement of the buffering agent as part of their GSI-191 resolution.

2.3 BUFFER PROPERTIES This program is being conducted in order to identify alternative buffering agents which minimize the potential for chemical precipitate formation following a LOCA. Thus, possible reactions between materials in containment and the buffer candidates will be evaluated as part of the program. In addition to minimizing precipitate generation, the following properties must be comparable to those of the chemicals currently in use (Reference 2.4-1):

1. Quantity required to adjust pH to target value

2. Dissolution rate in water at post-LOCA sump temperatures

3. Affordability and ready availability WCAP-16596-NP, Rev. 0 July 2006

16 WESTINGHOUSE NON-PROPRIETARY CLASS 3

4. No demonstrated deleterious effects, e.g., corrosion to key containment structural materials

5. Does not adversely affect the solubility of boric acid, or lead to an increase in boric acid precipitation on structures

6. Resistant to degradation from radiation, elevated temperatures and humidity, i.e., long storage life in containment environment

7. Non-hazardous material, i.e., does not create habitability concerns during storage or handling

8. Will not cause significant release of metal oxide deposits from the fuel or primary coolant system surfaces The candidates for this test program were selected considering both potential precipitate formation and the criteria listed above. Their properties were evaluated through the testing given in the Test Plan provided in Section 4.0 and literature research results provided in Section 3.0.

2.4 REFERENCES

2.4-1 PWROG PA-SEE-0285, "Alternate Buffer for ECCS," February 2006.

2.4-2 LTR-CDME-06-65, "Test Plan: Evaluation of Alternative Buffering Agents for ECCS Application," March 2006.

2.4-3 LA-UR-05-0124, "Integrated Chemical Effects Test Project: Test # l Data Report,"

June 2005.

2.4-4 LA-UR-05-6996, "Integrated Chemical Effects Test Project: Test #3 Data Report,"

October 2005.

2.4-5 WCAP-16530-NP, Revision 0, "Evaluation of Post-Accident Chemical Effects in Containment Sump Fluids to Support GSI-191," February 2006.

2.4-6 Oras, J., et al., "Chemical Effectsmead Loss Testing Quick Look Report, Tests ICET 3-4 to 11," January 20,2006.

2.4-7 Generic Safety Issue 191 (GSI-19 l), "Assessment of Debris Accumulation on Pressurized Water Reactor (PWR) Sump Performance."

2.4-8 NRC Generic Letter 2004-02, "Potential Impact of Debris Blockage on Emergency Recirculation During Design Basis Accidents at Pressurized-Water Reactors, September 13,2004.

2.4-9 Test Plan: Characterization of Chemical and Corrosion Effects Potentially Occurring Inside a PWR Containment Following a LOCA, Revision 13, July 20, 2005.

WCAP-16596-NP, Rev. 0 July 2006

17 WESTINGHOUSE NON-PROPRIETARY CLASS 3 3.0 SELECTION OF CANDIDATE BUFFERING AGENTS A review of literature data was performed to identify candidate alternative buffering agents. This review identified three primary classes of potential alternatives:

1. Borates: this class includes salts of tetraborate, metaborate, and octaborate. A distinct advantage of this class is that sodium tetraborate is already in use in Ice Condenser plants.

' 2. Polymeric (condensed) phosphates: this class includes salts of tripolyphosphate, pyrophosphates and metaphosphates (e.g., sodium hexametaphosphate).

3. Sequestering (chelating) agents: this class includes chemicals capable of sequestering metal ions dissolved fiom containment materials, thereby inhibiting precipitation, such as salts of citrate and ethylenediaminetetraacetate (EDTA). It should be noted that some polymeric phosphates are excellent sequestering agents for calcium and magnesium.

Other potential classes of materials that were considered include carbonates, amines, and salts of other strong oxyacids or weak acids. Carbonates were dismissed due to the potential for precipitation of metal carbonates (Reference 3.1-1). Armnes were dismissed due primarily to habitability concerns and the fact that most commonly used amines are volatile liquids, so that storage and handling would be challenging. Salts of other strong oxyacids (e.g, sodium nitrate) or other weak acids (e.g., sodium acetate) could be effective buffers, but offer no benefits relative to the borates.

Any of the sodium or potassium borate salts would be suitable candidates as alternatives to sodium hydroxide or trisodium phosphate. Sodium tetraborate decahydrate (Borax, Na2B407.10H20)has been selected for testing since it is currently used in nuclear plant applications. Sodium metaborate tetrahydrate (NaB02.4H20)has been selected since it provides a higher pH than other borates (Reference 3.1-2).

A number of polymeric (or condensed) phosphates are readily available commercially. These include sodium pyrophosphate, sodium trimetaphosphate, sodium tripolyphosphate and sodium hexametaphosphate. All of the condensed phosphates are good sequestering agents for alkali earth metals (e.g., calcium and magnesium), and are used for this purpose in detergents (Reference 3.1-1). However, they may slowly hydrolyze to produce orthophosphate (poi3),and are thus chemically equivalent to TSP, i.e., may interact with metals to form metal phosphate precipitates. Neither sodium hexametaphosphate (Calgon) nor sodium trimetaphosphate will produce the desired final buffered pH (the pH of 1% solutions is -7), and therefore neither is a good candidate. Sodium pyrophosphate decomposes at 94OC (201OF) and is therefore not a good candidate. Therefore, sodium tripolyphosphate has been the only condensed phosphate selected for testing.

A wide variety of other sequestering agents are available for consideration. However, most available sequestering agents are not specific to calcium and may mobilize radionuclides (e.g.,

WCAP-16596-NP, Rev. 0 July 2006

cobalt-60) from the oxides on the fuel and other surfaces within the primary coolant system. For example, citrate and EDTA are used for the chemical decontamination of primary systems (Reference 3.1-3). Of the sequestering agents commonly used for calcium, sodium gluconate may serve as an effective buffering agent and would not result in significant release of radionuclides.

The candidates selected for testing as potential alternatives to sodium hydroxide or trisodium phosphate as ECCS buffering agents are summarized in Table 3-1 with their properties (Reference 3.1-4).

Table 3-1: Properties of Candidate ECCS Buffering Agents PH Molecular Decomposition Buffering Agent (1% solution) Weight (glmol) Temperature ("C)

Sodium tetraborate decahydrate (NaTB) 9.2 381.4 >600 Sodium metaborate tetrahydrate (NaMB) 11.0 137.9 >900"'

Sodium tripolyphosphate (NaTPP) 8.0 367.9 622 Sodium gluconate (NaGlu) 10.0 218.1 206 Sodium hydroxide (NaOH) >14 40.0 > 1000 Trisodium phosphate dodecahydrate (TSP) 12.0 380.1 >1000'~)

(1) Above 52°C the waters of hydration may be liberated.

(2) Above 100°C the waters of hydration may be liberated.

3.1 REFERENCES

3.1-1 Newell, S. B., Chemistry: An Introduction, Little, Brown and Company, 1977.

3.1-2 U. S. Borax Product Profile, "So&um Metaborate, 8 Mol," February 2002.

3.1 -3 Recent Developments in Decontamination Technology, EPRI Radiation Control Seminar, Seattle, WA, August 1999.

3.1-4 Dean, J. A. (ed.), Lange's Handbook of Chemistry, 15Ih~ d i t i o nMcGraw-Hill,

, 1999.

WCAP-16596-NP, Rev. 0 July 2006

19 WESTINGHOUSE NON-PROPRIETARY CLASS 3 4.0 TESTPLAN A test plan was developed in order to compare the candidate buffer properties to those of the buffering agents currently in use (Reference 4.8-1). Some of the buffer properties compared through testing include the buffer's dissolution behavior, potential for precipitate generation, resistance to temperature and humidity, and impact on boric acid solubility. The test program has been arranged in phases so that only candidates that meet the criteria established for each phase are tested in subsequent phases. Note, if specific criterion for a given test phase is not met, testing of candidate buffers may continue at the test director's discretion.

4.1 PHASE 1: DISSOLUTION TESTING During this phase, the rate of dissolution in water at 150°F will be determined for a 1 weight percent solution of each candidate buffering agent. The dissolution rate of trisodium phosphate will also be determined for comparison. Sodium hydroxide is added as a solution, so comparison testing is not applicable.

Perform the following steps for each candidate buffering agent and for trisodium phosphate:

1. Heat 1 liter of demineralized water to 15055°F (6653°C).

2. Add 10 grams of the test chemical.

3. Record the time required for complete dissolution (determined visually).

4. Allow the solution to cool to 25°C.

5. Measure pH and verify solution is free of precipitates.

Acceptance criteria:

1. Complete dissolution in less than 2 hours2.314815e-5 days 5.555556e-4 hours 3.306878e-6 weeks 7.61e-7 months or less than three times the amount of time required for dissolution of trisodium phosphate dodecahydrate, whichever is less;

2. pH > 8.0 after cooling; and

3. no visible precipitates after cooling.

4.2 PHASE 2: PH ADJUSTMENT OF BCIRIC ACID SOLUTIONS During this phase, the quantity of each candidate buffering agent required to adjust boric acid solutions to a range of pH values will be determined. Three different boric acid concentrations will be used.

1. Prepare 1 liter of stock boric acid solutions containing 2000 ppm, 2500 ppm and 3000 ppm boron by dissolving 11.4294 g, 14.2994 g and 17.1592 g of boric acid (H3B03) in demineralized water; measure and record the pH of the stock solutions.

Perform the following steps for each candidate buffering agent and for trisodium phosphate and sodium hydroxide:

2. Prepare 250 milliliters of titrant solution containing X ppm boron and 50 g/L of the test chemical. The addition quantities will be:

WCAP-16596-NP, Rev. 0 , July 2006

WESTMGHOUSE NON-PROPRIETARY CLASS 3 Boric acid = (250 mL/1000 ml/L)

X ppd1000 * (61.83 g H3B03/10.81 g B)

Test Chemical = 50 g/L * (250 mL11000 ml/L)

Where X is the boron concentration being tested, 2000, 2500 or 3000.

3. Titrate 50 milliliter aliquots of the appropriate stock boric acid solution with the corresponding test solution; after the pH exceeds 7.0, measure and record pH after each 2 milliliter addition; terminate the titration when pH reaches a maximum or reaches 10.0, whichever occurs first.

4. Perform steps 2 and 3 for each boron concentration.

5. For each boric acid solution, determine the quantity (in grams) of each test chemical required to reach pH values of 8.0, 8.5, 9.0, 9.5 and 10.0. This will be:

mL titrant required

0.05 g/mL

6. Note the formation of any precipitates during the titrations.

Acceptance Criteria:

1. Ability to achieve a maximum pH of at least 8.0 in all three boric acid solutions;

2. quantity required to achieve a pH of 8.0 no more than two times that required using

. trisodium phosphate dodecahydrate (on a weight basis); and

3. no visible precipitates formed during titrations.

4.3 PHASE 3: DISSOLUTION IN BORIC ACID AS A FUNCTION OF TEMPERATURE During this phase, the dissolution rate of the candidate buffering agents in a nominal boric acid solution will be determined as a function of temperature.

1. Prepare 1 liter of stock 2500 ppm boron solution using boric acid (see step 1 of Phase 2);

measure and record the pH of the stock solution.

Perform the following steps for each candidate buffering agent and for trisodium phosphate:

2. Heat 100 milliliters of the boric acid solution to 100*5"F (38*3"C).

3. Add the quantity of the test chemical required to achieve a pH of 8.0, as determined in Phase 2 testing.

4. Record the time required for complete dissolution (determined visually).

5. Allow the solution to cool to 25°C and verify it is free of precipitates.

6. Repeat steps 2 to 4 at 150f 5°F (66*3"C) and at 200f 5°F (93*3"C).

Acceptance criteria:

1. At each temperature, complete dissolution in less than 2 hours2.314815e-5 days 5.555556e-4 hours 3.306878e-6 weeks 7.61e-7 months or less than three times the amount of time required for dissolution of trisodium phosphate, whichever is less;

2. no visible precipitates observed either immediately after dissolution or during cooling.

WCAP-16596-NP, Rev. 0 July 2006

21 WESTINGHOUSE NON-PROPRIETARY CLASS 3 4.4 PHASE 4: ALUMINUM AND CALCIUM ADDITION During this phase, calcium and aluminum salts will be added to solutions containing the candidate buffers to determine whether precipitates form.

1. Prepare 1 liter of stock 2500 ppm boron solution using boric acid (see step 1 of Phase 2);

measure and record the pH of the stock solution.

2. Prepare 100 milliliter stock solutions containing 10000 ppm aluminum (Al) and 10000 ppm calcium (Ca). Any soluble salts may be used, such as aluminum nitrate for aluminum or calcium chloride for calcium. The addition quantities are determined as:

A1 or Ca salt (g) = (llfraction A1 or Ca in salt)

0.1 L

10 g/L Perform the following steps for each candidate buffering agent and for trisodium phosphate and sodium hydroxide:

3. Heat 95 milliliters of the stock boric acid solution to 150*5OF (66*3OC).

4. Add the quantity of the test chemical required to achieve a pH of 8.5, as determined in Phase 2 testing.

5. Add 5 milliliters of stock A1 or Ca solution; note the formation of any precipitates.

6. Transfer the solution to a 100 mL graduated cylinder.

7. Allow the solution to cool to 25OC; note the formation of any precipitates during cooling.

8. After 1 , 2 and 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , record the volume of any precipitates formed.

9. Perform steps 3 to 8 using both A1 and Ca.

Acceptance criteria:

1. For Al, the volume of precipitate generated is no more than generated using sodium hydroxide or trisodium phosphate; and

2. no precipitate generated on addition of Ca.

Phase 4ABB: Determination of Threshold Valuesfor Precipitate Formation in NaTB and NUMB The initial results of Phase 4 testing showed that precipitates formed on addition of calcium and aluminum to solutions containing NaTB and NaMB. This result was contrary to the results of previous testing conducted in both the PWROG program (Reference 4.8-2) and the ICET program (Reference 4.8-3). Specifically, at lower levels of dissolved calcium and aluminum, and at lower pH, no precipitates were observed with NaTB in the presence of either calcium or aluminum. Therefore, follow-on testing was performed to determine threshold values for precipitate formation, and to examine the effect of pH.

During this phase, calcium and aluminum salts were added at various concentrations to solutions containing the candidate buffers to determine whether precipitates would form. In Phase 4A, 75 ppm solutions were tested, and in Phase 4B, solutions of varying concentrations were tested.

WCAP-16596-NP, Rev. 0 July 2006

WESTINGHOUSE NON-PROPRIETARY CLASS 3

1. 1 liter of stock 2,500 pprn boron solution was prepared using boric acid (see step 1 of Phase 2); the pH of the stock solution was measured and recorded. Additional stock boron solution was prepared as needed.

2. 50 milliliter stock solutions containing 5,000 pprn aluminum, 7,500 pprn aluminum, 5,000 pprn calcium, and 7,500 pprn calcium were prepared. Note, 10,000 pprn solutions were used for initial Phase 4 test in^. Aluminum nitrate was used for aluminum and calcium chloride was used for calcium. The addition quantities were determined as:

Salt (g) = (llfraction A1 or Ca in salt)

0.05 L

5 g/L[for 5,000 ppm]

Salt (g) = (llfraction A1 or Ca in salt)

0.05 L

7.5 g/L[for 7,500 ppm]

The following steps were performed for sodium tetraborate and sodium metaborate:

3. 100-x milliliters of the stock boric acid solution were heated to 150*5OF (66*3"C) using a hot plate with stirring, where x was the volume of stock A1 or Ca solution added in step 5.

4. The quantity of the test chemical required to achieve a pH of 8.5 was added, as determined in Phase 2 testing.

5. Sufficient stock 5,000 pprn or 7,500 pprn A1 or Ca solution was added to achieve varying quantities of dissolved A1 or Ca; the formation of any precipitates was noted.

Concentrations ranged from 75 pprn to 476 pprn for A1 and from 75 pprn to 380 pprn for Ca.

6. The solution was transferred to a 100 mL graduated cylinder.

7. The solution was allowed to cool to 25OC; the formation of any precipitates during cooling was noted.

8. After 1 , 2 and 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the volume of any precipitates formed was recorded.

9. Steps 3 to 8 were performed using both A1 and Ca.

10. Steps 3 to 9 were repeated, adjusting the metal concentration as required to find the precipitate threshold concentration.

Phase 4C: Determination ofpH Effects on Precipitation in NuTB and NUMB During this phase, the steps in Phase 4 were repeated with pH adjusted to 7.0, 7.5 and 8.0, rather than 8.5.

4.5 PHASE 5: CORROSION TESTING During this phase, the effects of the buffering agents on key structural materials will be determined. The materials to be tested are A508 carbon steel and commercially pure aluminum metal (A1 100).

1. Prepare 5 liters of stock 2500 pprn boron solution using boric acid (71.497 g); measure and record pH.

Perform the following steps for each candidate buffering agent and for trisodium phosphate and sodium hydroxide:

2. Weigh and dimension duplicate A508 and commercially pure aluminum corrosion coupons.

WCAP-16596-NP, Rev. 0 July 2006

23 WESTINGHOUSE NON-PROPRIETARY CLASS 3

3. To 500 milliliters of stock solution, add sufficient test chemical to achieve a pH 8.0 solution.

4. Transfer 250 milliliters of the test solutions to two test vessels; the test vessels should be fitted with lids to reduce liquid loss due to evaporation during the test.

5. Heat the test solutions to 150*5OF (66*3"C).

6. Insert duplicate A508 coupons in one test vessel and duplicate aluminum coupons in the other test vessel.

7. Maintain the vessel temperature at 150*5OF (66*3"C) for two weeks.

8. Cool the test solutions and measure pH and dissolved iron or aluminum, as applicable.

9. Remove the corrosion specimens

10. Rinse with demineralized water, followed by acetone or ethanol, dry and weigh.

11. Descale the corrosion coupons and repeat step 10.

12. Determine weight loss as a function of coupon surface area (scaled and descaled).

Acceptance criteria:

1. General corrosion no greater than observed with sodium hydroxide or trisodium phosphate;

2. No indication of localized corrosion, such as pitting.

4.6 PHASE 6: ENVIRONMENTAL EFFECTS TESTING During this phase, the effects of elevated temperature during storage will be evaluated. ]Vote, this test phase may be initiated in parallel with Phase 1 testing. Dissolution testing (step 6) need only be performed on candidates that meet criteria established for Phases 1 to 5.

Perform the following steps for each candidate buffering agent and for trisodium phosphate:

1. Place 10 grams of each candidate buffer in individual glass beakers and cover with a watch glass.

2. Place the beakers in an oven set at 150f5OF (66*3"C).

3. Maintain oven temperature for 30 days.

4. After 30 days exposure, remove the candidate buffers and physically examine.

5. Repeat Phase 1 dissolution tests.

Acceptance criteria:

1. Complete dissolution in less than 2 hours2.314815e-5 days 5.555556e-4 hours 3.306878e-6 weeks 7.61e-7 months or less than three times the amount of time required for dissolution of trisodium phosphate, whichever is less;

2. pH > 8.0 after cooling; and

3. no visible precipitates after cooling.

WCAP-16596-NP, Rev. 0 July 2006

24 WESTINGHOUSE NON-PROPRIETARY CLASS 3 4.7 PHASE 7: BORIC ACID SOLUBILITY TESTING The purpose of this test phase is to determine the solubility limit of boric acid in the presence of the candidate buffering agents. For consistency, the solubility limit will be determined at an initial pH value of 7.0 in a solution with an initial boron concentration of 2500 ppm.

1. Prepare 1 liter of stock 27.5% boric acid solution (275 g boric acid + 725 g demineralized water); measure and record pH.

Perform the following steps for each candidate buffering agent and for trisodium phosphate and sodium hydroxide:

2. Using phase 2 data, determine the quantity of the test chemical required to achieve a pH of 7.0 in 100 rnL of 2500 ppm B solution.

3. Heat the solution to boiling (expected to be near 103°C).

4. Add 19.23 (i.e., 27.5%/1.43%) times the quantity of test chemical determined in step 3 to the test solution; this will simulate concentration during core boiling.

5. Maintain solution at or near boiling, and add boric acid in -0.5 g increments to determine solubility limit.

Acceptance criteria:

1. Presence of the buffering agent does not decrease the solubility of boric acid.

4.8 REFERENCES

4.8-1 LTR-CDME-06-65, Revision 1, "Test Plan: Evaluation of Alternative Buffering Agents for ECCS Application," April 2006.

4.8-2 WCAP-16530-NP, Revision 0, "Evaluation of Post-Accident Chemical Effects in Containment Sump Fluids to Support GSI-191," February 2006.

4.8-3 LA-UR-05-9 177, "Integrated Chemical Effects Test Project: Test #5 Data Report,"

January 2006.

WCAP-16596-NP, Rev. 0 July 2006

25 WESTINGHOUSE NON-PROPRIETARY CLASS 3 5.0 TEST RESULTS Bench scale acceptability tests were performed at Fauske &Associates, Inc. in May 2006 according to the Test Plan presented in Section 4 above. The results of each of the test phases are provided below (Reference 5.8-1).

5.1 PHASE 1: DISSOLUTION TESTING RESULTS This test phase determined the dissolution time for each buffer candidate. The results are presented in Table 5-1 below. The rate of dissolution for each buffer candidate was comparable to that for TSP. All of the tested buffers met the requirement established for complete dissolution in less than 3 times the dissolution time for TSP. The shortest time to achieve complete dissolution was 2:20 minutes for TSP, while the longest time was 5:17 min for sodium tripolyphosphate. In addition, with the exception of sodium gluconate, all of the buffers met the requirement for a pH greater than or equal to 8.0 upon cooling. Although the regulatory requirement for minimum pH is 7.0, a value of 8.0 was used in evaluation of the buffering agents since many plants target higher ECCS coolant pH values.

Table 5-1: Phase 1 Dissolution Testing Results Time for Temperature of p~ of Solution Buffering Agent Mass [gl Dissolution Water [OC] @ 25°C

[min]

Sodium tetraborate decahydrate 10.0016 66.9 2:21 9.22 Sodium metaborate tetrahydrate 10.0513 68.2 2:32 10.20 Sodium tripolyphosphate 10.0169 68.8 5: 17 9.24 Sodium gluconate 10.0240 67.5 3:22 6.93 Trisodium phosphate dodecahydrate 10.0344 67.4 2:20 11.90 Sodium gluconate was eliminated as a candidate from hture testing due to failure to meet the pH requirement.

5.2 PHASE 2: PH ADJUSTMENT OF BORIC ACID SOLUTIONS RESULTS During this test phase, titrations were performed to determine the quantity of each buffering agent required to adjust the boric acid solution to a pH of 8.0, 8.5,9.0,9.5, and 10.0 for boric acid concentrations of 2000 ppm, 2500 ppm, and 3000 ppm boron. The detailed test results for this phase are given in Appendix A. Figure 5.1 presents the mass of each buffer required to obtain pH values between 6.0 and 9.0 for a boric acid solution concentration of 2500 ppm.

WCAP- 16596-NP, Rev. 0 July 2006

26 WESTMGHOUSE NON-PROPRIETARY CLASS 3 Figure 5-1: Mass of Buffer Candidate Required to Achieve Desired pH Mass of Buffer Candidate Required to Achieve Desired pH 6 7 8 OH of buffer candidate1 boron solution Table 5-2 provides the mass of each buffering agent required to achieve a pH of 7.5, 8.0, and 8.5 for a boric acid concentration of 2500 ppm.

Table 5-2: Phase 2 pH Adjustment of 2500 ppm Boric Acid Solution Results Mass required to Mass required to Mass required to Buffering Candidate achieve a pH of 7.5 achieve a pH of 8.0 achieve a pH of 8.5

[g/Ll [g/Ll lg/Ll Sodium tetraborate decahydrate 3.669 10.89 31.63 Sodium metaborate tetrahydrate 2.219 5.543 11.99 Sodium tripolyphosphate 8.597 na na Sodium hydroxide 0.5301 1.156 2.176 Trisodium phosphate dodecahydrate 4.177 9.939 19.14 From the results above, a similar quantity of sodium metaborate, sodium tetraborate and trisodium phosphate are required to adjust the pH of the boric acid solution, while more sodium tripolyphosphate and much less sodium hydroxide are required to achieve the same target pH values. Because the pH values of 8.0 and 8.5 were not able to be achieved in the 2500 ppm boric acid solution with sodium tripolyphosphate; this buffer did not meet the requirement for a pH of 8.0 established in the Test Plan. However, sodium tripolyphosphate was maintained in the following test phases, as a minimum target pH of 7.0 may be sufficient for some plants.

WCAP-I 6596-NP, Rev. 0 July 2006

27 WESTINGHOUSE NON-PROPRIETARY CLASS 3 5.3 PHASE 3: DISSOLUTION IN BORIC ACID AS A FUNCTION OF TEMPERATURE RESULTS This test phase determined the dissolution rate of the buffering agents in a 2500 ppm boric acid solution at temperatures of 100°F (38"C), 150°F (66"C), and 200°F (93°C). Similar to the first test phase, the dissolution rates for the buffer candidates were found to be comparable to those for TSP, so all buffers met the acceptance criterion and were included in the next test phase.

Appendix B contains the detailed results of this testing, while Table 5-3 below compares times for dissolution of the candidates at each temperature.

Table 5-3: Phase 3 Dissolution Testing Results as a Function of Temperature Buffering Agent 1 Sodium tetraborate decahydrate (NaTB) 1 1:40 1 0:44 1 0:29 1 1 Sodium metaborate tetrahydrate (NaMB) 1 1:37 1 1:06 1 0:37 1 1 Sodium tripolyphosphate (NaTPP) / 2:24 1 1:42 1 0:49 1

) Trisodium phosphate dodecahydrate (TSP) 1 2:27 1 155 ( 0:42 1 5.4 PHASE 4: ALUMINUM AND CALCIUM ADDITlON RESULTS WCAP-16530 (Reference 5.8-2) demonstrated that the main metals that contribute to precipitate formation in PWR containment sumps are aluminum and calcium. Thus, aluminum and calcium salts were combined with 2500 ppm boric acid solutions and each candidate buffering agent in this test phase in order to determine whether precipitates would form. Although silicate is also a significant contributor to precipitate formation, no precipitates have been identified that contain both buffering agent anions and silicate.

5.4.1 Phase 4 Testing Results For the addition of 500 ppm dissolved calcium from calcium chloride, a significant amount of precipitate formed with TSP, while very little precipitate formed with sodium tripolyphosphate and sodium hydroxide. A crystalline-appearing precipitate formed with sodium tetraborate and sodium metaborate. However, the volume of precipitate formed was less than observed for TSP.

See Table 5-4 for the quantity of precipitate formation for each buffer. Figure 5-2 shows the precipitate formation approximately 48 hours5.555556e-4 days 0.0133 hours 7.936508e-5 weeks 1.8264e-5 months after the addition of calcium.

WCAP-16596-NP, Rev. 0 July 2006

28 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Table 5-4: Phase 4 Calcium Addition Precipitate Formation Volume of Volume of Volume of pH of Liquid Precipitate Precipitate Precipitate Buffering Candidate After Ca Liquid Appearance After 1 Hour After 2 After 24 Addition

[ml] Hours [ml] Hours [ml]

Sodium tetraborate decahydrate 29 29 24 8.44 Suspended precipitate particles Sodium metaborate tetrahydrate 13 13 12 8.44 Suspended precipitate particles Sodium tripolyphosphate 0 0 1 7.32 Slightly cloudy Sodium hydroxide 0 0 177 ppm (NaTB) or 75 ppm (NaMB) for aluminum and >254 ppm for calcium (both NaTB and NaMB). In the case of calcium, a reduction in the solution pH resulted in dissolution of the precipitate. At lower pH values (8.0 and lower), precipitation did not occur upon addition of calcium up to the maximum concentration of 700 ppm tested. For the additional testing with aluminum, pH had no discernible effect on precipitate formation.

5.4.3 Precipitate Characterization Settling and filterability tests, similar to those conducted in Reference 5.8-2, were performed on the precipitates generated from the aluminum and calcium metal additions to the alternate buffer solutions as described in Section 5.4.1 (Reference 5.8-3). These tests provide a measure of the potential impact of the generated precipitates on containment sump screen head loss. In general, a higher settling rate and higher filter cake coefficient indicate that the precipitate will be less detrimental in causing a high pressure drop across the screen.

Precipitates with high settling rates may settle to the bottom of containment instead of remaining in suspension, and thus would not contribute to sump screen head loss. Also, the settling rate provides some measure of the particle size andlor morphology which may contribute to the pressure drop across the screen. In addition, high filter cake coefficients indicate that a precipitate in suspension will easily pass through a filter, avoiding contributing to head loss at the sump screen.

Table 5-6 below presents the measured settling volume of the precipitates formed in the Phase 4 testing and the calculated average settling rates. Little or no precipitate formed when aluminum was added to the NaTPP solution or when calcium was added to the NaOH solution, so these combinations are not presented below, Table 5-6: Measured Settling Rates of Aluminum and Calcium Precipitates Volume of PPT (ml) Average Settling Buffering Agents Rate 15 min 1 hr 2 hr 3 hr 4 hr (mmlhr)

Candidates NaMB w/ A1 10.3 10.3 10.3 10.3 10.3 ND"'

with A1 NaTB w/ A1 10.3 10.3 10.3 10.3 10.3 ND NaMB wl Ca 0.8 0.7 0.6 0.6 0.6 4(2)

Candidates NaTB wl Ca 1.4 0.9 0.8 0.8 0.7 69 with Ca NaTPP wl Ca 10.4 9.9 5.7 4.2 2.1 9 Current NaOH wl A1 10.1 10.1 10.0 9.9 9.9 - 0.5 Buffers with TSP wl A1 10.4 10.4 10.4 10.4 10.4 ND A1 or Ca TSP wl Ca 9.7 8.2 6.7 5.4 4.3 10 WCAP- 16596-NP, Rev. 0 July 2006

(I) ND = No measurable settling occurred over the four hour observation period.

(2) The initial settling was instantaneous for the precipitates formed when calcium was added to the NaMB solution. An average settling rate of 4 rnm/hr was calculated after this initial settling occurred.

Table 5-7 presents the calculated filter cake coefficients from the filterability testing. In the Phase 4 testing, no precipitate was visible from the addition of aluminum to the NaTPP solution.

However, this solution did cause a pressure drop across the test filter in the filterability testing, so a filter cake coefficient was determined. A filter cake coefficient was not calculated for the precipitate formed from the combination of NaMB and calcium because no pressure drop occurred when the precipitate was added to the test loop.

Table 5-7: Calculated Filter Cake Coefficients Mass PPT (g)

Overall, the precipitates formed from the addition of aluminum to the buffer solutions did not appear to settle over the four hour observation period. The calcium precipitates settled more quickly, with the calcium precipitates formed in the NaTB and NaMB solutions settling faster than those in the TSP and NaTPP solutions. An average settling rate of 69 d h r was calculated for the NaTB with calcium precipitate, and the initial settling of the NaMB with calcium precipitate occurred prior to the first volume measurement. In contrast, the calculated settling rates for the calcium precipitates formed in the TSP and NaTPP solutions were 10 d h r and 9 mmfhr, respectively.

In the filterability testing, the filter cake coefficients for the aluminum precipitates formed from the candidate buffers, NaTB, NaMJ3 and NaTPP, appeared higher than those calculated for TSP and NaOH. Also, the filter cake coefficients for the precipitates generated from the calcium addition to the TSP, NaOH, and NaTPP solutions were lower than those determined for NaTB and NaMB. The calcium precipitate formed in NaTB had a filter cake coefficient of -2.0 while the calcium precipitate formed in NaMB caused no discernible head loss.

WCAP- 16596-NP, Rev. 0 July 2006

32 WESTMGHOUSE NON-PROPRIETARY CLASS 3 The settling and filterability characteristics of the precipitates formed from the alternate buffers were examined in this section to provide a comparison among the buffer and metal combinations tested. These results do not provide an accurate measure of the precipitate contribution to sump screen head loss.

5.4.4 Buffering Capacity Although not the primary intent of this testing, behavior of the buffering agents on addition of acidic aluminum nitrate solution provides data on the relative buffering capacity of the candidates. Examination of the pH values after liquid addition in Table 5-5 show that NaTB and TSP have nearly identical buffering capacity, with a pH change from 8.5 to about 8.0 after aluminum nitrate addition. The pH change for NaMB was slightly greater (8.5 to 7.7). As expected due to the limited buffering capacity of NaOH, the pH change was much greater (8.5 to 6.9). The initial pH of the NaTPP solution was lower (7.5), so a direct comparison of the buffering capacity of this agent is not possible.

To further examine the buffering capacity of NaTB relative to TSP, stock solutions of 1500 ppm boric acid were prepared and the pH was adjusted to 7.5 with either NaTB or TSP. In one test, solid boric acid (a weak acid) was added in 300 ppm increments and the resulting pH was measured. In a second test, hydrochloric acid (a strong acid) was added in 73 ppm increments.

The results of this testing showed that NaTB and TSP have comparable buffering capacity (see Figures 5-4 and 5-5).

Figure 5-4: Buffering Capacity of NaTB and TSP for Boric Acid Addition Buffer Capacity in 1500 ppm Boron NaTB and TSP H3BO3Addition 1500 2000 2500 3000 3500 Boron (pprn)

-NaTB -TSP WCAP-16596-NP, Rev. 0 July 2006

33 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure 5-5: Buffering Capacity of NaTB and TSP for Hydrochloric Acid Addition Buffer Capacity in 1500 pprn Boron NaTB andTSP - HCI Addition 1M HCI Added (pprn)

-NaTB T S P 5.5 PHASE 5: CORROSION TESTING RESULTS In the corrosion testing the effects of the buffering agents on key structural materials, which are typically comprised of aluminum or carbon steel, were determined. A508 carbon steel and commercially pure aluminum (A1 100) metal coupons were purchased for this test phase. The coupons were submerged for two weeks at an elevated temperature in a 2500 ppm boric acid solution buffered to a pH value of 8.0 with each buffering agent, with the exception of sodium tripolyphosphate which was tested at an initial pH of 7.5. ICP (Inductively Coupled Plasma) analysis was then performed on the solutions to measure the quantity of iron or aluminum dissolved from the metal coupons.

Appendix C presents the detailed results from this test phase including the aluminum and carbon steel coupon mass loss and images of the metal coupons after two weeks of exposure to the buffering agent and boric acid solutions. Table 5-8 below presents the average coupon mass loss.

Table 5-8: Phase 5 Corrosion of Aluminum and Carbon Steel Metal Coupons I Steel corrosion(') Aluminum Buffering Agent

~orrosion(')(g/m2)

I Sodium tetraborate decahydrate (NaTB) 1 1.03 I 35.1 I I Sodium metaborate tetrahydrate (NaMB) I 0.62 1 9.49 I I Sodium tripolyphorphate (NaTPP) I 54.8 I 24.5 I I Trisodium phosphate dodecahydrate (TSP) I 1.OO I 2.92 I I Sodium hydroxide (NaOH) I 1.04 I 14.8 1 (1) Average descaled weight loss of two specimens WCAP- 16596-NP, Rev. 0 July 2006

34 WESTINGHOUSE NON-PROPRIETARY CLASS 3 From the results presented above, sodium tripolyphosphate caused the greatest corrosion to steel.

For the remaining buffering agents, material loss was very low (1 g/m2 or less). Aluminum corrosion was higher in the presence of sodium tetraborate and sodium tripolyphosphate than observed with TSP, while aluminum corrosion was lower in the presence of sodium metaborate than observed with sodium hydroxide.

The fact that dissolved silicate will also inhibit corrosion of submerged aluminum should be considered in the evaluation of the significance of the increased corrosion of submerged aluminum in the presence of sodium tetraborate and sodium tripolyphosphate relative to TSP. It should be noted that the inhibitory effects of phosphate and silicate are not included in the PWROG chemical model since these effects have not been quantified for all chemistry conditions.

The initial acceptance criteria established for this test phase was general corrosion no greater than observed with TSP or sodium hydroxide and no indication of localized corrosion. Sodium tripolyphosphate did not satisfy the criteria for either steel or aluminum. Sodium tetraborate and sodium metaborate satisfied both criteria for corrosion to carbon steel, and sodium metaborate satisfied both criteria for aluminum. While no indication of localized corrosion to aluminum was observed with sodium tetraborate, general corrosion was higher than observed with either TSP or sodium hydroxide. Based on the acceptable performance in other test phases, acceptable corrosion behavior with steel, and on consideration of silicate passivation of submerged aluminum, sodium tetraborate was retained in the test program.

5.6 PHASE 6: ENVIRONMENTAL EFFECTS TESTING In this phase of testing, the effects of elevated temperature and humidity during storage on the buffering agents were determined by placing samples in an oven at 150°F (66°C) and 30%

relative humidity. After 30 days of exposure at these conditions, the buffers were subjected to dissolution testing similar to that conducted in Phase 1.

The TSP was observed to be clumped together at the end of the 30 days but still appeared granular. The sodium tetraborate and sodium tripolyphosphate buffers formed a solid clump but were able to be removed from the test beaker. The sodium metaborate also formed a solid clump which appeared more crystalline and did not separate easily from the beaker. In addition, a significant decrease in the volume of the sodium metaborate was observed.

The time for dissolution after exposure to the elevated temperature and humidity for 30 days slightly increased for TSP from 2 minutes, 20 seconds for fresh product to 2 minutes, 37 seconds.

The time for dissolution of the remaining buffering agents met the acceptance criterion of less than three times the time required for dissolution of TSP. Also, for all buffers tested, the pH of the solution after cooling was greater than 8.0 and no visible precipitates were observed. Table 5-9 summarizes the results of the environmental effects testing.

An initial test was performed at 100% humidity by placing a beaker of water in the oven. This condition was found to be too severe. After 2 weeks, the sodium tetraborate remained a solid, but both the trisodium phosphate and sodium metaborate had dissolved. Upon cooling, the trisodium phosphate solidified, but the sodium metaborate did not.

WCAP-16596-NP, Rev. 0 July 2006

35 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Table 5-9: Phase 6 Environmental Effects Testing Results Mass of Temperature of Dissolution Time pH of Resulting Buffer Candidate Dissolution Water at Addition Observations

[min] Solution Sample [gl ["CI Sodium tetraborate decahydrate 7.6877 67.9 3:29 9.21 Most of clump broke up when added to the water All of the loose sample was dissolved in 2:59 Sodium metaborate tetrahydrate 7.4978 67.1 4:39 10.07 while sample that was still stuck to glass from the beaker took 4:39 Trisodium phosphate dodecahydrate 4.8797 66.9 2:37' 11.39 Dissolved in the same fashion as in phase 1 Sodium tripolyphosphate 10.119 66.6 2:47 8.91 Most of clump broke up when added to the water WCAP- 16596-NP, Rev. 0 July 2006

36 WESTINGHOUSE NON-PROPRIETARY CLASS 3 5.7 PHASE 7: BORIC ACID SOLUBILITY TESTING RESULTS The impact on boric acid solubility of the candidate buffers was determined in this test phase.

Table 5-10 demonstrates that all of the buffer candidates, in addition to the TSP and NaOH buffers, increase the solubility of boric acid.

Table 5-10: Phase 7 Determination of Buffer Impact on Boric Acid Solubility Mass of Boric % Increase in Mass of Test Initial Weight Final Weight Test Chemical Acid Dissolved Boric Acid Chemical [g] % Boric Acid % Boric Acid Is1 Solubility Sodium tetraborate decahydrate 2.1907 27.73 30.1687 29.85 7.65 Sodium metaborate tetrahydrate 1.5415 27.55 31.1107 30.37 10.24 Sodium tripolyphosphate 4.5097 27.47 35.9081 33.53 22.06 Sodium hydroxide 0.3994 27.58 30.7523 30.63 11.06 Trisodium phosphate dodecahydrate 2.5050 27.56 33.5439 32.07 16.36

5.8 REFERENCES
5.8-1 FAV06-48, Revision 0, "Evaluation of Alternative Buffering Agents for ECCS Application: Bench Scale Acceptability Tests," May 2006.
5.8-2 WCAP-16530-IVP, Rev. 0, "Evaluation of Post-Accident Chemical Effects in Containment Sump Fluids to Support GSI-191," February 2006.
5.8-3 LTR-CSA-06-52, "Settling and Filterability Tests on Precipitates from Alternate Buffer Testing," July 2006.
WCAP-16596-NP, Rev. 0 July 2006
37 WESTINGHOUSE NON-PROPRIETARY CLASS 3 6.0 EVALUATION OF BUFFERING AGENT CRITERIA This section provides the evaluation of the buffering agents for the criteria presented in Section 2.3. Ji the evaluation, the buffering agents are rated as EXCELLENT, GOOD or POOR for each criterion. A designation of EXCELLENT indicates the buffering agent is markedly superior to the other agents evaluated for the parameter of interest. A designation of POOR indicates that the performance of the buffering agent is markedly inferior for that attribute. The results of this evaluation are summarized in Table 6-1.
6.1 PRECIPITATION UNDER POST-LOCA CONDITIONS Sodium Hydroxide (NaOH): due to the transient high pH conditions that may exist when NaOH is used, large quantities of dissolved aluminum and silicon may be released from containment materials (Reference 6.10-1). These dissolved species will eventually precipitate as sodium aluminum silicate and aluminum oxyhydroxide. Thus, sodium hydroxide is rated as POOR for precipitate formation.
Trisodium Phosphate (TSP): most metal phosphates are insoluble at the range of pH and temperature that would exist in the containment sump post-LOCA. However, in the presence of trisodium phosphate, aluminum would preferentially precipitate as an aluminum silicate or oxyhydroxide, and release of most other metals is low in the presence of trisodium phosphate.
The exception is release of calcium from calcium-bearing materials such as calcium silicate insulation. Ji the presence of these calcium-bearing materials, release of calcium will result in formation of calcium phosphate (References 6.10-1 and 6.10-2). Thus, TSP is rated as GOOD for precipitate formation in the absence of calcium-bearing minerals, but POOR in the presence of such materials.
Sodium Tetraborate (NaTB): sparingly soluble metal borates may form at elevated pH and elevated levels of dissolved aluminum or calcium (see Section 5.4 and Reference 6.10-3).
However, pH is easily maintained at 8.0 or less using NaTB, and in most cases dissolved aluminum/calcium concentrations will not exceed the threshold values. Thus, NaTB is rated as GOOD for precipitate formation.
Sodium Metaborate (NaMB): NaMB has the same chemical behavior as NaTB with respect to precipitate formation (References 6.10-4 and 6.10-5), and is therefore rated as GOOD for precipitate formation.
Sodium Tripolyphosphate (NaTPP): NaTPP is a good sequestering agent for most metals, particularly calcium and aluminum which are the predominant metals present in the coolant under post-LOCA conditions. Sequestration inhibits formation of precipitates, as a result, no metal precipitates would form in the presence of NaTPP. Therefore, NaTPP is rated as EXCELLENT for precipitate formation.
WCAP- 16596-NP, Rev. 0 July 2006
38 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Sodium Gluconate (iVaGlu): similar to NaTPP, NaGlu is a good sequestering agent for calcium and aluminum and would therefore be expected to be rated as EXCELLENT for precipitate formation. However, precipitate formation in the presence of NaGlu was not evaluated due to inability of NaGlu to establish a pH>7.0 in the presence of boric acid.
6.2 QUANTITY REQUIRED TO ADJUST PH >8.0 Sodium Hydroxide: as a strong base, very little NaOH is required to buffer boric acid solutions to a pH>8.0, relative to the other buffering agents tested. However, this effect also results in correspondingly lower buffering capacity when NaOH is used as the buffering agent. Therefore, plants using NaOH generally have higher target pH values than those using other buffering agents. Overall, NaOH is rated as EXCELLENT based solely on the minimal quantity required to rapidly raise pH.
Trisodium Phosphate: a manageable quantity of TSP is required to adjust the pH of boric acid solutions to >8.0. In this program, TSP is used as the yardstick by which the other buffering agents are rated. Thus, TSP is rated as GOOD for quantity required to adjust pH>8.0.
Sodium Tetraborate: the quantity of NaTB required to adjust the pH of the boric acid solutions tested (2000,2500 and 3000 ppm) is comparable to the quantity of TSP required, up to pH 8.0.
Above this value, relatively more NaTB is required to achieve an equivalent pH. Thus, NaTB is rated as GOOD for quantity required to adjust pH>8.0.
Sodium Metaborate: at a boron concentration of 2500 ppm, the quantity of NaMB required to adjust pH to 8.0 is about half of the quantity of TSP required. Thus, NaMB is rated as EXCELLENT for quantity required to adjust pH>8.0. Note, as an alternative to sodium hydroxide in liquid form, a comparable volume of NaMB solution would be required to achieve an equivalent pH.
Sodium Tripolyphosphate: at a boron concentration of 2500 ppm, the highest pH achievable using NaTPP is 7.6, and more than twice as much NaTPP as TSP is required to reach a pH value of 7.5 in the presence of 2500 ppm boron. Thus, NaTPP is rated as POOR for quantity required to adjust pH>8.0. NaTPP would be rated as GOOD if the nominal pH target were reduced to 7.5.
Sodium Gluconate: it was not possible to adjust the pH of boric acid solutions tested to >7.0 using NaGlu. Thus, NaGlu is rated as POOR for quantity required to adjust pH>8.0.
6.3 DISSOLUTION RATE All of the buffering agents tested dissolved in boric acid solutions in six minutes or less, even after exposure to simulated containment conditions for 30 days. Thus, all buffering agents are rated as GOOD with respect to dissolution rate. Note, this parameter is not applicable to sodium hydroxide since NaOH is applied as a solution, rather than as a solid material.
WCAP-16596-NP, Rev. 0 July 2006
39 WESTINGHOUSE NON-PROPRIETARY CLASS 3 6.4 AFFORDABILITY AND AVAILABILITY Affordability and ready availability were considered in the initial selection of the buffering agents for testing. NaOH, TSP and NaTB are rated as EXCELLENT since they are already in use in PWR applications. All other buffering agents are rated as GOOD.
6.5 CORROSIVENESS Sodium Hydroxide: under the transient high pH and high temperature conditions that may exist during the first several hours of a LOCA event, corrosion to aluminum metal may be elevated in the presence of NaOH. However, overall corrosion to aluminum and other metals when NaOH is used as the buffering agent is comparable to other agents tested. Thus, NaOH is rated as GOOD for corrosiveness.
Trisodium Phosphate: when TSP is used as the buffering agent, corrosion to steel is low and comparable to other agents tested. However, corrosion to aluminum is markedly lower. Thus, TSP is rated as EXCELLENT for corrosiveness.
Sodium Tetraborate: compared to the results obtained with other buffering agents, corrosion to submerged aluminum is higher in the presence of NaTB, but not excessive. Corrosion to steel is comparable. Thus, NaTB is rated as GOOD for corrosiveness.
Sodium Metaborate: corrosion to both steel and aluminum is low in the presence of NaMB, and comparable to other agents tested. Thus, NaMB is rated as GOOD for corrosiveness.
Sodium Tripolyphosphate: corrosion to steel is more than 50 times higher in the presence of NaTPP than observed with any of the other buffering agents tested. Corrosion to aluminum is also higher, but the difference is not as marked. Thus, NaTPP is rated as POOR for corrosiveness.
Sodium Gluconate: due to the inability to provide the required pH adjustment, corrosiveness of NaGlu was not evaluated.
6.6 EFFECT ON BORIC ACID SOLUBILITY All of the buffering agents tested increased the solubility of boric acid, and thus all are rated as GOOD. The increase in solubility ranged from 7.65% for NaTB to 22.06% for NaTPP. At a consistent initial pH of 7.0, the relative ranking of the buffering agents was NaTPP > TSP >
NaOH > NaMB > NaTB.
6.7 ENVIRONMENTAL STABILITY Sodium Hydroxide: since NaOH is provided as a liquid, the environmental stability of this buffering agent was not tested. However, since NaOH is already in use, the environmental stability is considered GOOD.
WCAP-16596-NP, Rev. 0 July 2006
40 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Trisodium Phosphate: slight clumping of TSP occurred during exposure to simulated storage conditions for 30 days. However, the clumped product readily dissolved and provided the expected pH adjustment. As demonstrated by years of use in a PWR environment, TSP has good radiation stability. Thus, TSP is rated as GOOD for environmental stability.
Sodium Tetraborate: as with TSP, clumping of NaTB occurred during exposure to simulated storage conditions for 30 days. However, the clumped product readily dissolved and provided the expected pH adjustment. As demonstrated by years of use in a PWR environment, NaTB has good radiation stability. Thus, NaTB is rated as GOOD for environmental stability.
Sodium Metaborate: during initial tests at 100% humidity, NaMB completely and irreversibly dissolved. Under more moderate conditions, some dissolution of NaMB occurred, and recrystallization resulted in a solid clump that could not be mechanically removed from the test vessel. However, the solid material dissolved readily and provided the expected pH adjustment.
Borates have good radiation stability, as demonstrated by long-term use of NaTB and sodium pentaborate in PWR and BWR applications (Reference 6.10-6). Overall, NaMB is rated as POOR for environmental stability when used as a solid. However, NaMB is highly soluble and could be used in liquid form in the same manner as NaOH. Under this usage condition NaMB would be rated as GOOD for environmental stability.
Sodium Tripolyphosphate: as with TSP and NaTB, clumping of NaTPP occurred during exposure to simulated storage conditions for 30 days. However, the clumped product readily dissolved and provided the expected pH adjustment. Based on the chemical similarity to TSP, NaTPP is expected to have good radiation stability (References 6.10-4 and 6.10-5). Thus, NaTPP is rated as GOOD for environmental stability.
Sodium Gluconate: due to the inability to provide the required pH adjustment, the environmental stability of NaGlu was not evaluated.
6.8 HABITABILITY CONCERNS None of the buffering agents evaluated are considered hazardous during storage, or produce hazardous vapors. Concentrated sodium hydroxide solution is highly corrosive and extreme care must be taken in handling (Reference 6.10-7). Borates are poisonous at elevated concentration, so care must be taken in handling NaTB and NaMB during product transfer (Reference 6.10-8 and 6.10-9). TSP, NaTPP and NaGlu are relatively benign, and present minimal hazards during handling, e.g., dusts are irritants to the eyes and respiratory tract (References 6.10-10, 6.10-1 1, and 6.10-12).
6.9 OXIDEICRUD RELEASE With the exception of the sequestering agents, NaTPP and NaGlu, the buffering agents evaluated will not increase mobilization of radionuclides from the primary coolant system components or fuel. Therefore, NaOH, TSP, NaTB and NaMB are rated as GOOD for oxideiCRUD release.
For NaOH, NaTB and NaMB, this conclusion is based on the fact that borates are present in the coolant during operation (Also note that the addition of NaOH to boric acid produces sodium WCAP-16596-NP, Rev. 0 July 2006
41 WESTINGHOUSE NON-PROPRIETARY CLASS 3 borate). For TSP, this conclusion is based on the experience with use of TSP as a'water treatment chemical in PWR applications for many years. Exposure of the contaminated oxides to N ~ T P P or NaGlu may result in some mobilization of radionuclides. However, at elevated pH this effect would be expected to be minimal. In the absence of specific test data, NaTPP and NaGlu are rated as POOR for oxide1CRUD release.
While minimization of oxide1CRUD release is not a regulatory requirement for the buffering agent, it should be considered since the primary side components (including fuel) typically contain in excess of 10,000 curies of gamma-emitting radioisotopes, so a significant release of oxideICRLTD would result in elevated dose rates throughout containment.
WCAP-16596-NP, Rev. 0 July 2006
42 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Table 6-1: Summary of Characteristics of Candidate ECCS Buffering Agents Buffering Agent Criterion NaOH TSP NaTB NaMB NaTPP NaGlu Precipitate Formation poor(') ~ood(~' Exc Good Exc No Data Quantity Required to Adjust pH >8.0 Exc Good Good Exc Poor Poor Dissolution Rate NIA'~' Good Good Good Good Good AffordabilityIAvailability Exc Exc Exc ' Good Good Good Corrosiveness Good Exc Good Good Poor No Data Effect on Boric Acid Solubility Good Good Good Good Good No Data Environmental Stability Good Good Good Good No Data Habitability Concern Good Exc Good Good Exc Exc OxideICRUD Release I ~ood I ~ood 1 ~ood ( ~ood I poor 1 poor (1) NaOH rated "Poor" due to elevated A1 production.
(2) TSP rated "Poor" under elevated Ca conditions.
(3) NaOH provided as a 50% solution.
(4) NaMB rated "Poor" based on behavior of solid material; "Good" rating as a liquid solution.
WCAP-16596-NP, Rev. 0 July 2006
43 WESTINGHOUSE NON-PROPRIETARY CLASS 3 6.10 REFERENCES 6.10-1 WCAP-16530-NP, Rev. 0, "Evaluation of Post-Accident Chemical Effects in Containment Sump Fluids to Support GSI- 191," February 2006.
6.10-2 LA-UR-05-6996, "Integrated Chemical Effects Test Project: Test #3 Data Report,"
October 2005.
6.10-3 U. S. Borax Product Profile, "Borax Decahydrate," January 2002.
6.10-4 Greenwood, N. N. and Earnshaw, A., Chemistry of the Elements (2nd Edition), Elsevier, 1998.
6.10-5 EPRI Report NP-5558-SL, Rev. 1, "Boric Acid Application Guidelines for Intergranular Corrosion Inhibition," December 1990.
6.10-6 Eagle Picher Technical Bulletin EP-SSGC-NAPB, Rev. 3, "Enriched Sodium Pentaborate," July 2002.
6.10-7 Mallinckrodt-Baker MSDS Number S4037, "Sodium Hydroxide Solutions (more than 10% NaOH)," October 2004.
6.10-8 U. S. Borax MSDS, "Borax Decahydrate," May 2000.
6.10-9 U. S. Borax MSDS, "Sodium Metaborate, 8 Mol," May 2000.
6.10- 10 Mallinckrodt-Baker MSDS Number S4770, "Sodium Phosphate, Tribasic, 12-Hydrate,"
November 2005.
6.10-1 1 Arcos Organics MSDS ACC-01559, Rev. 5, "Sodium Tripolyphosphate," March 2003.
6.10-12 Hydrochem Industrial Services MSDS M097, "Sodium Gluconate," December 2000.
WCAP-16596-NP, Rev. 0 July 2006
44 WESTINGHOUSE NON-PROPRIETARY CLASS 3
7.0 CONCLUSION
S AND RECOMMENDATIONS The results of the evaluation presented in this report, as summarized in Section 6, indicate that sodium tetraborate decahydrate (Borax) is the best alternative to trisodium phosphate for plants with high loadings of calcium-bearing materials in containment. For plants without a high loading of calcium-bearing materials, TSP is determined to be the superior candidate based on the rankings in Table 6-1. For high-calcium plants, use of sodium tetraborate would eliminate concerns with precipitation of calcium phosphate. Calculations show that changing from TSP to NaTB buffering would reduce the total precipitate formation by more than 40 percent for a plant with a high loading of calcium-bearing materials. Additional considerations to support replacement of TSP with NaTB are:
NaTB provides a comparable buffering capacity to TSP with a comparable quantity of buffering agent, so that no modification to the existing buffer delivery scheme would be required; No new types of precipitates would form at a target pH of 8.0 or less, irrespective of the calcium loading; Corrosion to steel structural materials would be comparable to that expected with TSP; As with TSP, NaTB addition increases the solubility of boric acid, and thereby provides contingency against boric acid precipitation under post-accident conditions; Sodium tetraborate has been evaluated for other potential chemical effects as part of the PWROG Program (Reference 7.1-1) and the ICET program (Reference 7.1-2); and Sodium tetraborate is already in use at ice condenser plants.
The results of this evaluation also show that sodium metaborate, in solution form, would be a suitable replacement for sodium hydroxide solution. The room temperature solubility of NaMB is >40% (Reference 7.1-3). Calculations show that changing from NaOH to NaMB buffering, combined with a target pH change from 8.5 to 7.5, would reduce the total precipitate formation by about 50 percent. The primary advantages of replacement of NaOH with NaMB are:
The more moderate pH of NaMB solutions would reduce aluminum corrosion during the first several hours post-LOCA (per Reference 7.1-3, the pH of an 18% NaMB solution is 12.0, compared to >14.0 for 18% NaOH);
In combination with boric acid, NaMB has a higher buffering capacity than NaOH, thereby allowing sufficient margin to allow a lower target pH for the final sump chemistry conditions and a concomitant decrease in release of aluminum and silica from containment materials; WCAP-I 6596-NP, Rev. 0 July 2006
45 WESTINGHOUSE NON-PROPRIETARY CLASS 3 NaMB and NaOH provide a nearly identical increase in the solubility of boric acid, and thereby provides comparable contingency against boric acid precipitation under post-accident conditions; Under more moderate sump conditions, long-term corrosion of aluminum is less in the presence of NaMB than that experienced when NaOH buffering is used, while corrosion to carbon steel is low and essentially identical to NaOH; and Once dissolved in the containment sump fluid, the chemistry of the boric acid/NaMB buffer system is similar to that of the boric acid/NaTB system, thus existing evaluations of NaTB may be used to evaluate post-accident chemical effects.
7.1 REFERENCES
7.1-1 WCAP-16530-NP, Rev. 0, "Evaluation of Post-Accident Chemical Effects in Containment Sump Fluids to Support GSI-191," February 2006.
7.1-2 LA-UR-05-9177, "Integrated Chemical Effects Test Project: Test #5 Data Report,"
January 2006.
7.1-3 U. S. Borax Product Profile, "Sodium Metaborate, 8 Mol," February 2002.
WCAP- 16596-NP, Rev. 0 July 2006
46 WESTINGHOUSE NON-PROPRIETARY CLASS 3 8.0 CONSIDERATIONS FOR BUFFER REPLACEMENT If a plant elects to replace their existing buffering agent, there are several major considerations, including the pH requirements for the equilibrium sump solution post-accident, the quantity of the replacement buffer necessary to meet these requirements, and the potential for additional evaluations to determine the replacement buffer impact.
8.1 PH REQUIREMENTS A major concern in determining both the type and quantity of buffering agent required to mitigate post-accident consequences is the target pH of the sump solution. A minimum pH is required for fission product removal and to prevent stress corrosion craclung; however, as the pH increases, so does the total precipitate formation (Reference 8.3-1). In addition, the concern for hydrogen generation due to corrosion of aluminum increases with pH.
NRC Branch Technical Position MTEB 6-1 (Reference 8.3-2) provides a minimum pH criteria of 7.0 to avoid stress corrosion cracking based on a Westinghouse report (Reference 8.3-3). This report demonstrates that with a solution pH of 7.0 the time for initiation of craclung of stainless steel is 7.5 and 10 months for sensitized and non-sensitized specimens, respectively.
Reference 8.3-2 also discusses an Oak Ridge National Laboratory report in which a minimum pH of 6.5 is recommended in order to reduce the likelihood of stress corrosion craclung (Reference 8.3-4).
In addition, Standard Review Plan Section 6.5.2 (Reference 8.3-5) provides a requirement for the pH of the sump solution to be sufficiently high to prevent significant long-term iodine reevolution. Thus, the equilibrium sump solution pH, after mixing and dilution with the primary coolant and ECCS injection should be equal to or greater than that required to prevent iodine reevolution. A minimum pH of 7.0 is specified in Reference 8.3-5 to provide long-term iodine retention and is conservatively based on Reference 8.3-6 which shows that at a pH of 6.0 or higher there is minimal conversion of iodine compounds to the volatile form of iodine.
8.2 RECOMNIENDED EVALUATIONS 8.2.1 Chemical Model Reanalysis If a plant decides to pursue replacement of the existing TSP or NaOH buffer with one of the recommended buffer candidates, the first step would be to perform the chemical model evaluation presented in Reference 8.3-1 to determine the impact on the chemical precipitate formation. The main concern for precipitate formation with the trisodium phosphate buffer is calcium phosphate, which forms due to the reaction of calcium-bearing materials with phosphate.
For a change from TSP to sodium tetraborate, the quantity of chemical products which form will be reduced because the calcium phosphate precipitate will not form. In order to evaluate this change using the chemical model, the selection for TSP, which allows the calcium release to be assumed to form calcium phosphate, should not be made.
WCAP-16596-NP, Rev. 0 July 2006
47 WESTINGHOUSE NON-PROPRIETARY CLASS 3 The elevated pH values which may be reached post-accident with the sodium hydroxide buffer lead to a significant amount of aluminum precipitate formation (Reference 8.3-1). Thus, a reduction in the final sump pH would aid in mitigating the precipitate formation; however, due to the limited buffering capacity of NaOH, it is not desirable to reduce the quantity of NaOH used to buffer the sump solution. Sodium metaborate is recommended as a suitable replacement for sodium hydroxide for plants which need to reduce the sump pH in order to alleviate the formation of chemical products and would prefer to maintain the current buffer delivery system.
Again, the chemical model may be used to determine the precipitate formation for sodium metaborate. First, the reduced pH transient for the replacement buffer must be determined.
Then, because sodium metaborate once dissolved behaves sufficiently similar to both TSP and sodium tetraborate, the dissolution testing results used to develop the chemical model in Reference 8.3-1 will also apply to NaMB.
8.2.2 Determination of Replacement Buffer Quantity If a plant elects to replace the buffering agent, an essential step is the calculation of the amount of the replacement buffering agent required post-LOCA to achieve a desired pH. The determination of the required quantity is dependent upon the target pH, the ECCS boron concentration, and the sump volume. Equations are provided below for a target pH of 7.5 for replacement buffers sodium tetraborate and sodium metaborate.
For boron concentrations of 2000 to 3000 ppm, the amount of sodium tetraborate decahydrate required to achieve a target pH of 7.5 may be determined as:
NaTB (kg/m3) = 6.62 - 0.0076 [B] + 2.56 E-06 [B]~,
where [B] is the boron concentration in the ECCS in ppm.
For example, for a boron concentration of 2500 ppm, 3.62 kg/m3 NaTB would be required to achieve a pH of 7.5. For a sump volume of 1,415 m3 (50,000 ft3), this equates to 5122 kg (11,282 pounds) of NaTB.
For boron concentrations of 2000 to 3000 ppm, the amount of sodium metaborate tetrahydrate required to achieve a target pH of 7.5 may be determined as:
NaMB (kg/m3)= 9.34 - 0.0077 [B] + 1.94 E-06 [B]~,
where [B] is the boron concentration in the ECCS in ppm.
For example, for a boron concentration of 2500 ppm, 2.22 kg/m3 NaMB would be required to achieve a pH of 7.5. For a sump volume of 1,415 m3 (50,000 ft3), this equates to 3,141 kg (6,927 pounds) of NaMB. This equates to 6,382 liters (1,686 gallons) of 40 weight percent solution.
WCAP-16596-NP, Rev. 0 July 2006
48 WESTINGHOUSE NON-PROPRIETARY CLASS 3 8.2.3 Evaluation of Buffer ~ e ~ l a c e m e Impactnt This test program was designed to qualify alternative buffers by comparing the candidate buffer properties to those of the buffers currently in use. Thus, the replacement of the existing buffer with an evaluated alternative is intended to have minimal impact on plant analyses.
Buffering agents are used to buffer the boric acid solution in order to meet the pH requirements discussed in Section 8.1. The areas of concern for pH include radiological consequences, stress corrosion cracking, hydrogen generation, and Equipment Qualification (EQ) concerns. The evaluation of the replacement buffer impact on these areas should be minor as long as the equilibrium sump solution pH remains unchanged and the time to reach this pH is similar.
Additional analyses may be required if a plant desires to change their target pH or if the time for complete dissolution of the replacement buffer is significantly longer.
8.3 REFERENCES
8.3-1 WCAP-16530-NP, Rev. 0, "Evaluation of Post-Accident Chemical Effects in Containment Sump Fluids to Support GSI-19 1 ," February 2006.
8.3-2 Branch Technical Position MTEB 6-1, "pH for Emergency Coolant Water for PWRs,"
Revision 2, July 1981.
8.3-3 D.D. Whyte and L.F. Picone, "Behavior ofAustenitic Stainless Steel in Post Hypothetical Loss of Coolant Environment," WCAP-7798-L, Westinghouse Nuclear Energy Systems, November 1971.
8.3-4 J.C. Griess and E.E. Creek, "Design Considerations of Reactor Containment Spray Systems - Part X, the Stress Corrosion Cracking of Types 304 and 3 16 Stainless Steel in Boric Acid Solutions," ORNL-TM-24 12, Part X, Oak Ridge National Laboratory, May 1971.
8.3-5 NUREG-0800, US Nuclear Regulatory Commission Standard Review Plan, Office of Nuclear Reactor Regulation, Section 6.5.2 Containment Spray as a Fission Product Cleanup System, Revision 3, December 2005.
8.3-6 C. C. Lin, "Chemical Effects of Gamma Radiation on Iodine in Aqueous Solutions,"
Journal ofInorganic and Nuclear Chemistiy, 42, pp. 1101-1107.
WCAP-16596-NP, Rev. 0 July 2006
49 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Appendix A: Detailed Results of Phase 2 Testing WCAP-16596-NP, Rev. 0 July 2006
50 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Boron Concentration: 2000 ppm Preparation of 1 liter of stock 2000 ppm boron solution:
Mass of H3BO3:11.4178 g Preparation of 250 ml of titrant solution:
Mass of H3Bo3:2.8619g Mass of Na2B407.10H20:12.5622 g
pH of solution: 8.80 0' 10 20 30 40 50 60 70 Volume of Titrant Solution [ml]
pH Value 1 Volume of Titrant Mass ofTest
[mu I Chemical [g]
- did not completely dissolve WCAP-16596-NP, Rev. 0 July 2006
51 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Boron Concentration: 2000 ppml Preparation of 1 liter of stock 2000 ppm boron solution:
Mass of H3BO3:11.4178 g pH of solution:4.90 Preparation of 250 ml of titrant solution:
Mass of H3B03:2.8571 g Mass of 1Va2B407. 10H20:10.9644 g pH of solution:8.76 Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test pH Value
[mu Chemical [g]
1 Repeated previous test with less sodium tetraborate decahydrate to assure it completely dissolved.
WCAP-16596-NP, Rev. 0 July 2006
52 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Boron Concentration: 2500 pprn Preparation of 1 liter of stock 2500 ppm boron solution:
Mass of H3BO3:14.3040 g pH of solution:4.67 Preparation of 250 ml of titrant solution:
Mass of H3B03:3.5769g Mass of Na2B407.1OHZO:11.5024 g pH of solution: 8.67 Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test 1 pH Value
[mu Chemical [g]
WCAP-16596-NP, Rev. 0 July 2006
53 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Boron Concentration: 3000 ppm Preparation of 1 liter of stock 3000 ppm boron solution:
Mass of H3BO3:17.1472 g Preparation of 250 ml of titrant solution:
Mass of H3B03:4.2892g Mass of Na2B407.10H20: 12.5208 g Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test pH Value
[mil Chemical [g]
8.0 22.9 1.15 WCAP-16596-NP, Rev. 0 July 2006
54 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Boron Concentration: 2000 pprn Preparation of 1 liter of stock 2000 pprn boron solution:
Mass of H3BO3:11.4178 g pH of solution:4.90 Preparation of 250 rnl of titrant solution:
Mass of H3B03:2.8593g Mass of NaB02 . 4H20:10.2493 g pH of solution:9.55 Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test pH Value
[dl Chemical [g]
WCAP-16596-NP, Rev. 0 July 2006
55 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Boron Concentration: 2500 ppm Preparation of 1 liter of stock 2500 ppm boron solution:
Mass of H3B03: 14.3040 g pH of solution:4.67 Preparation of 250 ml of titrant solution:
Mass of H3B03:3.5810 g Mass of NaB02 . 4H20:10.2034 g pH of solution: 9.41 I ! ! ! ! ! ! ! ! .
6 - - _ _ - _ L ~ ~ ~ _ _ _ L _ _ _ _ ~ ~ L - _ _ - - - L ~ ~ ~ ~ ~ ~ L ~ ~ ~ ~ ~ ~ I ~ ~ ~ ~ ~ ~ J - -
5 ----1------1------1------!------L------L------III----!------
Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test pH Value 0.85 9.0 WCAP-I 6596-NP, Rev. 0 July 2006
56 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Boron Concentration: 3000 ppm Preparation of 1 liter of stock 3000 ppm boron solution:
Mass of H3BO3:17.1472 g pH of solution:4.55 Preparation of 250 ml of titrant solution:
Mass of H3B03:4.2806g Mass of NaB02 . 4H20:12.5170 g
pH of solution:9.44
- did not dissolve WCAP-16596-NP, Rev. 0 July 2006
57 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Boron Concentration: 3000 ppm Preparation of 1 liter of stock 3000 ppm boron solution:
Mass of H3BO3:17.1472 g pH of solution:4.55 Preparation of 250 ml of titrant solution:
Mass of H3B03:4.2892g Mass of NaB02 . 4H20:10.1987 g pH of solution:9.29 Volume of Titrant Solution [ml]
Volume of Titrant Mass'of Test pH Value Chemical 0.473 30.5 1.24 9.0 120.0 4.895 WCAP-16596-NP, Rev. 0 July 2006
Test Chemical: Sodium tripolyphosphate Boron Concentration: 3000 ppm Preparation of 1 liter of stock 3000 ppm boron solution:
Mass of H3BO3:17.1472 g pH of solution:4.55 Preparation of 250 ml of titrant solution:
Mass of H3BO3:4.2865g Mass of Na5P3010:12.5086 g pH of solution:7.80 *
- not high enough to achieve pH of 8 WCAP-16596-NP, Rev. 0 July 2006
59 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tripolyphosphate Boron Concentration: 2500 ppm Preparation of 1 liter of stock 2500 ppm boron solution:
Mass of H3BO3:14.3040 g pH of solution:4.67 Preparation of 250 ml of titrant solution:
Mass of H3BO3:3.5739g Mass of Na5P3010: 12.8961 g pH of solution:7.88 A v A
A v
A v -
A 4b 4I 0 5 10 15 20 25 30 Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test pH Value
[mu Chemical [g]
WCAP-16596-NP, Rev. 0 July 2006
60 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium hydroxide Boron Concentration: 2000 ppm Preparation of 1 liter of stock 2000 ppm boron solution:
Mass of H3BO3:11.4178 g Preparation of 250 ml of titrant solution:
Volume of H20:234ml Mass of H3B03:2.8646g Mass of 50% NaOH:25.0414 g pH of solution: 12.77 Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test pH Value
[mu Chemical [g]
8.0 0.94 0.047 8.5 1.8 0.090 9.0 3.1 0.16 9.5 4.9 0.25 10.0 6.8 0.34 WCAP-16596-NP, Rev. 0 July 2006
61 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium hydroxide Boron Concentration: 2500 ppm Preparation of 1 liter of stock 2500 ppm boron solution:
Mass of H3BO3:14.3040 g Preparation of 250 ml of titrant solution:
Volume of H20:234 rnl Mass of H3BO3:3.5694 g Mass of 50% NaOH:24.9742 g pH of solution: 12.80 0 1 2 3 4 5 6 7 8 9 Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test pH Value
[mu Chemical [g]
WCAP-16596-NP, Rev. 0 July 2006
62 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium hydroxide Boron Concentration: 3000 ppm Preparation of 1 liter of stock 3000 ppm boron solution:
Mass of H3BO3:17.1472 g pH of solution:4.55 Preparation of 250 ml of titrant solution:
Volume of H20:234 rnl Mass of H3B03:4.2848 g Mass of 50% NaOH:25.0 188 g pH of solution: 12.66 I I I I 4
0 2 4 6 8 10 12 Volume of Titrant Solution [rnl]
Volume of Titrant Mass of Test pH Value 8.5 2.9 0.15 9.0 4.8 0.24 9.5 7.5 0.38 10.0 10.6 0.530 WCAP-16596-NP, Rev. 0 July 2006
63 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Trisodium phosphate dodecahydrate Boron Concentration: 2000 ppm Preparation of 1 liter of stock 2000 ppm boron solution:
Mass of H3BO3:11.4178 g pH of solution:4.90 Preparation of 250 ml of titrant solution:
Mass of H3B03:2.8553g Mass of Na3P04.12H20:12.5106 g pH of solution:9.89 Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test pH Value Chemical [ ]
8.5 20.1 1.01 9.0 51.8 2.59 WCAP-16596-NP, Rev. 0 July 2006
64 WESTTNGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Trisodium phosphate dodecahydrate Boron Concentration: 2500 ppm Preparation of 1 liter of stock 2500 ppm boron solution:
Mass of H3B03: 14.3040 g Preparation of 250 ml of titrant solution:
Mass of H3BO3:3.5775g Mass of Na3P04.12H20:12.5044 g Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test pH Value
[mil Chemical [g]
WCAP-16596-NP, Rev. 0 July 2006
65 WESTWGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Trisodium phosphate dodecahydrate Boron Concentration: 3000 ppm Preparation of 1 liter of stock 3000 ppm boron solution:
Mass of H3BO3:17.1472 g Preparation of 250 ml of titrant solution:
Mass of H3B03:4.2725g Mass of Na3P04.12H20:12.5107 g pH of solution:9.38 Volume of Titrant Solution [ml]
Volume of Titrant Mass of Test pH Value 8.5 44.2 2.21 WCAP-16596-NP, Rev. 0 July 2006
66 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Appendix B: Detailed Results of Phase 3 Testing WCAP-16596-NP, Rev. 0 July 2006
67 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Boron Concentration: 2500 ppm Desired pH: 8.0 Time for Temperature ["C] Mass Required [g] Mass Used [g] pH After Cooldown Dissolution [min]
38.6 1.089 1.0910 1:40 7.98 65.3 1.089 1.0902 0:44 7.97 94.2 1.089 1.0888 0:29 7.96 Test Chemical: Sodium metaborate tetrahydrate Boron Concentration: 2500 ppm Desired pH: 8.0 Time for Temperature ["C] Mass Required [g] Mass Used [g] pH After Cooldown Dissolution [min]
39.0 0.5543 0.5584 1:37 8.01 67.0 0.5543 0.5563 1:06 8.01 92.0 0.5543 0.5588 0:37 7.99 WCAP-16596-NP, Rev. 0 July 2006
68 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tripolyphosphate Boron Concentration: 2500 ppm Desired pH: 7.5 Time for Temperature ["C] Mass Required [g] Mass Used [g] pH After Cooldown Dissolution [min]
39.8 0.8597 0.8619 2:24 7.49 66.2 0.8597 0.8645 1:42 7.49 94.2 0.8597 0.8521 0:49 7.47 Test Chemical: Trisodium phosphate dodecahydrate Boron Concentration: 2500 ppm Desired pH: 8.0 Time for Temperature ['C] Mass Required [g] Mass Used [g] pH After Cooldown Dissolution [mini 39.0 0.9939 0.9943 2:27 7.99 66.3 0.9939 0.9901 1:55 7.98 91.5 0.9939 0.9934 0:42 7.98 WCAP-16596-NP, Rev. 0 July 2006
69 WESTINGHOUSE NON-PROPRIETARY CLASS 3
~ ~ p e n dC: i x Detailed Results of Phase 4 Testing WCAP-16596-NP, Rev. 0 July 2006
70 WESTNGHOUSE NON-PROPRIETARY CLASS 3 C.l PHASE 4 DETAILED TEST RESULTS Test Chemical: Sodium tetraborate decahydrate Boron concentration: 2500 ppm Desired pH: 8.5 Preparation of 100 ml of stock 10,000 ppm Ca solution:
Mass of CaC12:2.9004g Actual Concentration: 10,475 ppm pH of solution: 7.37 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.193 8 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of Ca solution:65.3 "C Temperature after addition of Ca solution: 63.0 "C Observations:
Precipitate was formed immediately upon addition of Ca solution.
After 60 minutes, there was 29 ml of precipitate at the bottom of the 100 ml graduated cylinder.
After 120 minutes, the temperature was 22.0 "C and there was 29 ml of precipitate at the bottom of the 100 ml graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , there was 24 ml of precipitate at the bottom of the 100 ml graduated cylinder. Also, some precipitate was still suspended in the liquid.
pH after addition of Ca: 8.44 WCAP- 16596-NP, Rev. 0 July 2006
WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure C-1: Overall and close-up views of precipitate formed by sodium tetraborate decahydrate and calciurn.
WCAP- 16596-NP, Rev. 0 July 2006
72 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium rnetaborate tetrahydrate Boron concentration: 2500 ppm Desired pH: 8.5 Preparation of 100 ml of stock 10,000 ppm Ca solution:
Mass of CaC12:2.9004 g Actual Concentration: 10,475 ppm pH of solution: 7.37 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.2165 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of Ca solution: 67.3 "C Temperature after addition of Ca solution:64.8 "C Observations:
Precipitate was formed immediately upon addition of Ca solution.
After 60 minutes, the temperature was 26.5 "C and there was 13 ml of precipitate at the bottom of the 100 ml graduated cylinder.
After 120 minutes, the temperature was 21.8 "C and there was 13 ml of precipitate at the bottom of the 100 ml graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , there was 12 ml of precipitate at the bottom of the 100 ml graduated cylinder. Also, some precipitate was still suspended in the liquid.
pH after addition of Ca: 8.44 WCAP-16596-NP, Rev. 0 July 2006
73 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure C-2: Overall and close-up views of precipitate formed by sodium metaborate tetrahydrate and calcium.
WCAP-16596-NP, Rev. 0 July 2006
74 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tripolyphosphate Boron concentration: 2500 ppm Desired pH: 7.5 Preparation of 100 ml of stock 10,000 ppm Ca solution:
Mass of CaC12:2.9004g Actual Concentration: 10,475 ppm pH of solution:7.37 Mass of buffering candidate:
Mass required: 0.8597 g Mass used: 0.865 1 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of Ca solution:68.6 "C Temperature after addition of Ca solution:65.8 "C Observations:
A very small amount of precipitate was formed immediately upon addition of Ca solution.
After 60 minutes, the temperature was 29.2 "C. The liquid was slightly cloudier than immediately after the addition of the Ca solution. No precipitate layer on the bottom of the graduated cylinder yet.
After 120 minutes, the temperature was 22.8 "C and there was a very thin layer of precipitate at the bottom of the 100 rnl graduated cylinder. The liquid is still cloudy.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , there was about 1 ml of precipitate at the bottom of the 100 ml graduated cylinder. The liquid was slightly cloudy.
pH after addition of Ca: 7.32 WCAP-16596-NP, Rev. 0 July 2006
75 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure C-3: Overall and close-up views of precipitate formed by sodium tripolyphosphate and calcium.
WCAP- 16596-NP, Rev. 0 July 2006
76 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium hydroxide Boron concentration: 2500 ppm Desired pH: 8.5 Preparation of 100 ml of stock 10,000 ppm Ca solution:
Mass of CaC12:2.9004g Actual Concentration: 10,475 ppm pH of solution:7.37 Mass of buffering candidate:
Mass required: 0.2176 g Mass used: 0.2354 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of Ca solution:68.7 "C Temperature after addition of Ca solution: 66.5 "C Observations:
Precipitate was formed immediately upon addition of Ca solution.
After 60 minutes, the temperature was 27.2 "C and there was no visible precipitate in the liquid.
After 120 minutes, the temperature was 22.4 "C and there was no visible precipitate in the liquid.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the liquid appeared slightly hazy and a very thin layer of precipitate was at the bottom of the graduated cylinder.
pH after addition of Ca: 8.47 WCAP-16596-NP, Rev. 0 July 2006
77 WESTINGHOUSE NON-PROPRIETARY CLASS 3
'igure C-4: Overall and close-up views of the precipitate formed by sodium hydroxide and calcium.
WCAP-16596-NP, Rev. 0 July 2006
78 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Trisodium phosphate dodecahydrate Boron concentration: 2500 ppm Desired pH: 8.5 Preparation of 100 ml of stock 10,000 ppm Ca solution:
Mass of CaC12:2.9004g Actual Concentration: 10,475 ppm pH of solution:7.37 Mass of buffering candidate:
Mass required: 1.914 g Mass used: 1.9787 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:67.8 "C Temperature at addition of Ca solution: 64.0 "C Temperature after addition of Ca solution:61.8 "C Observations:
Precipitate was formed immediately upon addition of Ca solution.
After 60 minutes, the temperature was 27.3 "C and there was 43 ml of precipitate at the bottom of the 100 ml graduated cylinder.
After 120 minutes, the temperature was 23.6 "C and there was 39 ml of precipitate at the bottom of the 100 ml graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , there was 3 1 ml of precipitate at the bottom of the 100 ml graduated cylinder.
pH after addition of Ca: 8.44 W C A P -16596-NP, Rev. 0 July 2006
79 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure C-5: Overall and close-up views of the precipitate formed by trisodium phosphate dodecahydrate and calcium.
WCAP-16596-NP, Rev. 0 July 2006
80 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Boron concentration: 2500 ppm Desired pH: 8.5 Preparation of 100 ml of stock 10,000 ppm A1 solution:
Mass of A1(N03)3. 9H20:13.8960 g Actual Concentration:9,994 ppm pH of solution:2.63 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1622 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution:64.5 "C Temperature after addition of A1 solution: 6 1.8 "C Observations:
Precipitate was formed immediately upon addition of A1 solution.
After 60 minutes, the temperature was 27.4 "C and there was 10 ml of precipitate at the bottom of the 100 ml graduated cylinder. The liquid above the precipitate was cloudy.
After 120 minutes, there was 9 ml of precipitate at the bottom of the 100 ml graduated cylinder. The liquid above the precipitate was still cloudy.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , there was 7 ml of precipitate at the bottom of the 100 ml graduated cylinder. The liquid above the precipitate was cloudy.
pH after addition of Al: 7.98 WCAP- 16596-NP, Rev. 0 July 2006
81 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure C-6: Overall and close-up views of the precipitate formed by sodium tetraborate decahydrate and aluminum.
WCAP- 16596-NP, Rev. 0 July 2006
82 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Boron concentration: 2500 ppm Desired pH: 8.5 Preparation of 100 ml of stock 10,000 ppm A1 solution:
Mass 0 f A l ( N 0 ~ .) 9H20:
~ 13.8960 g Actual Concentration:9,994 ppm pH of solution:2.63 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.2100 g Addtion of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:68.8 "C Temperature at addition of A1 solution:68.0 "C Temperature after addition of A1 solution: 65.4 "C Observations:
Precipitate was formed immediately upon addition of A1 solution.
After 60 minutes, the temperature was 28.6 "C and there was 21 ml of precipitate at the bottom of the 100 ml graduated cylinder. The liquid is still cloudy.
After 120 minutes, the temperature was 23.8 "C and there was 19 ml of precipitate at the bottom of the 100 ml graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , there was 15 ml of precipitate at the bottom of the 100 ml graduated cylinder. The liquid above the precipitate was cloudy.
pH after addition of Al: 7.70 WCAP-16596-NP, Rev. 0 July 2006
83 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure C-7: Overall and close-up views of the precipitate formed by sodium metaborate tetrahydrate and aluminum.
WCAP- 16596-NP, Rev. 0 July 2006
84 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tripolyphosphate Boron concentration: 2500 ppm Desired pH: 7.5 Preparation of 100 ml of stock 10,000 ppm A1 solution:
Mass 0 f A l ( N 0 ~ ) 9H20:
~ 13.8960 g Actual Concentration: 9,994 ppm pH of solution: 2.63 Mass of buffering candidate:
Mass required: 0.8597 g Mass used: 0.8690 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution:66.7 "C Temperature after addition of A1 solution: 64.3 "C Observations:
Upon addition of the A1 solution, the liquid was momentarily cloudy but then quickly went clear with stirring.
After 60 minutes, the temperature was 26.1 "C and the solution was clear and free of precipitate.
After 120 minutes, the solution was clear and free of precipitate.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was clear and free of precipitate.
pH after addition of Al: 6.02 WCAP-16596-NP, Rev. 0 July 2006
85 WESTINGHOUSE NON-PROPFUETARY CLASS 3 Figure C-8: Overall view of sodium tripolyphosphate and aluminum solution - no precipitate formed.
WCAP-16596-NP, Rev. 0 July 2006
86 WESTTNGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium hydroxide Boron concentration: 2500 ppm Desired pH: 8.5 Preparation of 100 ml of stock 10,000 ppm A1 solution:
Mass of A1(N03)3. 9H20:13.8960 g Actual Concentration:9,994 ppm pH of solution:2.63 Mass of buffering candidate:
Mass required: 0.2 176 g Mass used: 0.2309 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution:67.9 "C Temperature after addition of A1 solution:65.3 "C Observations:
Precipitate was formed immediately upon addition of A1 solution.
After 60 minutes, the temperature was 30.2 "C and there was 48 ml of precipitate at the bottom of the 100 ml graduated cylinder. The liquid above the precipitate is clear.
After 120 minutes, the temperature was 25.4 "C and there was 42 ml of precipitate at the bottom of the 100 ml graduated cylinder. The liquid is clear.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , there was 34 rnl of precipitate at the bottom of the 100 rnl graduated cylinder. The liquid was clear.
pH after addition of Al: 6.93 WCAP-16596-NP, Rev. 0 July 2006
87 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure C-9: Overall and close-up views of the precipitate formed by sodium hydroxide and aluminum.
WCAP-16596-NP, Rev. 0 July 2006
88 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Trisodium phosphate dodecahydrate Boron concentration: 2500 ppm
~ e s i r e pH:
d 8.5 Preparation of 100 ml of stock 10,000 ppm A1 solution:
Mass of A1(N03)3. 9H20:13.8960 g Actual Concentration:9,994 ppm pH of solution:2.63 Mass of buffering candidate:
Mass required: 1.914 g Mass used: 1.9830 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of Ca solution:68.3 "C Temperature after addition of Ca solution:65.9 "C Observations:
Precipitate was formed immediately upon addition of Ca solution.
After 60 minutes, the temperature was 29.5 "C and there was 32 ml of precipitate at the bottom of the 100 ml graduated cylinder. The liquid was slightly cloudy.
After 120 minutes, the temperature was 23.1 "C and there was 28 ml of precipitate at the bottom of the 100 ml graduated cylinder. The liquid was slightly cloudy.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , there was 23 ml of precipitate at the bottom of the 100 ml graduated cylinder, The liquid above the precipitate was slightly cloudy.
pH after addition of Al: 7.97 WCAP-16596-NP, Rev. 0 July 2006
WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figurt:C-10: Overall and close-up views of precipitate formed by trisodium phosphate dodecahydral and a1uminum.
WCAP-16596-NP, Rev. 0 July 2006
90 WESTINGHOUSE NON-PROPRIETARY CLASS 3 C.2 PHASE 4AAND 4B TEST REPORT PHASE 4A: LOW CONCENTRATION AL UMINUM AND CALCIUM ADDITION 1.1 Procedure During this phase, calcium and aluminum salts were added to solutions containing the candidate buffers to determine whether precipitates would form.
1. 1 liter of stock 2500 ppm boron solution was prepared using boric acid (see step 1 of Phase 2);
the pH of the stock solution was measured and recorded.
2. 100 milliliter stock solutions containing 1,000 ppm aluminum (Al) and 1,000 ppm calcium (Ca) were prepared. Note, 10,000 ppm solutions were used for initial Phase 4 testing. Aluminum nitrate was used for aluminum and calcium chloride was used for calcium. al he addition quantities were determined as:
Salt (g) = (llfraction A1 or Ca in salt)
0.1 L
1 g/L The following steps were performed for sodium tetraborate and sodium metaborate:
3. 95 milliliters of the stock boric acid solution were heated to 150+5"F (66+3OC) using a hotplate with stirring.
4. The quantity of the test chemical required to achieve a pH of 8.5 was added, as determined in Phase 2 testing.
5. 7.5 milliliters of stock A1 or Ca solution was added; the formation of any precipitates was noted.
This was the equivalent to 75 ppm Ca or A1 in the test solution.
6. The solution was transferred to a 100 mL graduated cylinder.
7. The solution was allowed to cool to 25'C; the formation of any precipitates during cooling was noted.
8. After 1 , 2 and 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the volume of any precipitates formed was recorded
9. Steps 3 to 8 were performed using both Al and Ca.
WCAP- 16596-NP, Rev. 0 July 2006
91 WESTINGHOUSE NON-PROPRIETARY CLASS 3 1.2 Preoaration of Stock Solutions Preparation of 1 L of stock 2,500 pprn boron solution:
Mass of H3B03required: 14.2993 g Mass of H3BO3used: 14.2917 g Actual Concentration: 2,499 pprn Preparation of 100 mL of stock 1,000 pprn A1 solution:
Mass of Al(N03)3 . 9H20 required: 1.3904 g Mass of Al(N03)3 . 9 H 2 0 used: 1.3936 g Actual Concentration: 1,002 pprn Preparation of 100 mL of stock 1,000 pprn Ca solution:
Mass of CaC12required:0.2769 g Mass of CaC12 used:0.2983 g Actual Concentration: 1,077 pprn WCAP- 16596-NP, Rev. 0 July 2006
92 WESTINGHOUSE NON-PROPRIETARY CLASS 3 1.3 Sodium Tetraborate and Sodium Metaborate with 75 pprn Aluminum and Calcium 1.3.1 Summary of Results At aluminum and calcium concentrations of 75 ppm, neither sodium tetraborate nor sodium metaborate formed precipitates that remained in the solution longer than approximately one second. The results of testing at this metal concentration can be seen in Figure 1.1 below which was taken approximately 7 2 hours2.314815e-5 days 5.555556e-4 hours 3.306878e-6 weeks 7.61e-7 months after the additions of the metal solutions.
Figure 1.1 Results of precipitate testing at metal concentrations of 75 ppm. (pictured above from left to right: sodium tetraborate decahydrate with 75 pprn Al, sodium tetraborate decahydrate with 75 pprn Ca, sodium metaborate tetrahydrate with 75 pprn Al, and sodium metaborate tetrahydrate with 75 pprn Ca)
WCAP-16596-NP, Rev. 0 July 2006
93 WESTINGHOUSE NON-PROPRIETARY CLASS 3 1.3.2 Detailed Results Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 73.3 ppm A1 (7.5 mL of stock 1,002 ppm A1 solution)
Initial Boron Concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Massused: 3.1671 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution: 65.8 "C Temperature after addition of A1 solution: 6 1.1 "C Observations:
A very small amount of precipitate formed at the location of aluminum solution addition. The precipitate quickly dissolved ( 4 s).
After 60 minutes, the temperature of the solution was 29.7"C and no precipitate was present.
After 120 minutes, no precipitate was present.
After 72 hours8.333333e-4 days 0.02 hours 1.190476e-4 weeks 2.7396e-5 months , no precipitate was present.
WCAP-16596-NP, Rev. 0 July 2006
94 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 78.8 ppm Ca (7.5 mL of stock 1,077 ppm Ca solution)
Initial Boron Concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1599 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:68.3 "C Temperature at addition of Ca solution:64.5 "C Temperature after addition of Ca solution: 60.1 "C Observations:
A very small amount of precipitate formed at the location of calcium solution addition. The precipitate quickly dissolved (<1 s).
After 60 minutes, the temperature of the solution was 30.3"C and no precipitate was present.
After 120 minutes, no precipitate was present.
After 72 hours8.333333e-4 days 0.02 hours 1.190476e-4 weeks 2.7396e-5 months , no precipitate was present.
WCAP-16596-NP, Rev. 0 July 2006
95 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Metal Concentration: 73.3 ppm A1 (7.5 rnL of stock 1,002 ppm A1 solution)
InitialBoron Concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.2201 g Addtion of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution:65.7 OC Temperature after addition of A1 solution:6 1.5 "C Observations:
A very small amount of precipitate formed at the location of aluminum solution addition. The precipitate quickly dissolved (<1 s).
After 60 minutes, the temperature of the solution was 30.2"C and no precipitate was present.
After 120 minutes, no precipitate was present.
After 72 hours8.333333e-4 days 0.02 hours 1.190476e-4 weeks 2.7396e-5 months , no precipitate was present.
WCAP-16596-NP, Rev. 0 July 2006
Test Chemical: Sodium metaborate tetrahydrate Metal Concentration: 78.8 pprn Ca (7.5 rnL of stock 1,077 ppm Ca solution)
Initial Boron Concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 1.199 g Massused: 1.1915g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:68.3 "C Temperature at addition of Ca solution:65.5 "C Temperature after addition of Ca solution: 6 1.5 "C Observations:
A very small amount of precipitate formed at the location of calcium solution addition. The precipitate quickly dissolved (<l s).
After 60 minutes, the temperature of the solution was 30.7"C and no precipitate was present.
After 120 minutes, no precipitate was present.
After 72 hours8.333333e-4 days 0.02 hours 1.190476e-4 weeks 2.7396e-5 months , no precipitate was present.
WCAP-16596-NP, Rev. 0 July 2006
PHASE 4B: HIGH CONCENTRATION AL UMINUM AND CALCIUM ADDITION 2.1 Procedure During this phase, calcium and aluminum salts were added to solutions containing the candidate buffers to determine whether precipitates would form.
1. 1 liter of stock 2,500 pprn boron solution was prepared using boric acid (see step 1 of Phase 2);
the pH of the stock solution was measured and recorded. Additional stock boron solution was prepared as needed.
2. 50 milliliter stock solutions containing 5,000 pprn aluminum, 7,500 pprn aluminum, 5,000 pprn calcium, and 7,500 pprn calcium were prepared. Note, 10,000 pprn solutions were used for initial Phase 4 testing. Aluminum nitrate was used for aluminum and calcium chloride was used for calcium. The addition quantities were determined as:
Salt (g) = (llfraction A1 or Ca in salt)
0.05 L
5 g/L[for 5,000 ppm]
Salt (g) = (llfraction A1 or Ca in salt)
0.05 L
7.5 glL[for 7,500 ppm]
The following steps were performed for sodium tetraborate and sodium metaborate:
3. 95 milliliters of the stock boric acid solution were heated to 150*5OF (66*3OC) using a hotplate with stirring.
4. The quantity of the test chemical required to achieve a pH of 8.5 was added, as determined in Phase 2 testing.
5. 5.0 milliliters of stock 5,000 pprn A1 or Ca solution was added; the formation of any precipitates was noted. This was the equivalent to approximately 250 pprn Ca or A1 in the test solution.
6. The solution was transferred to a 100 mL graduated cylinder.
7. The solution was allowed to cool to 2S°C; the formation of any precipitates during cooling was noted.
8. After 1 , 2 and 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the volume of any precipitates formed was recorded.
9. Steps 3 to 8 were performed using both A1 and Ca.
10. Steps 3 to 9 were repeated, adjusting the metal concentration as required to find the precipitate threshold concentration.
WCAP-16596-NP, Rev. 0 July 2006
98 WESTINGHOUSE NON-PROPRIETARY CLASS 3 2.2 Preparation of Stock Solutions Preparation of 1 L of stock 2,500 pprn boron solution:
Mass of H3B03required: 14.2993 g Mass of H3B03used: 14.2917 g Actual Concentration: 2,499 pprn Preparation of 1 L of stock 2,500 pprn boron solution:
Mass of H3BO3required: 14.2993 g Mass of H3BO3used: 14.2932 g Actual Concentration: 2,499 pprn Preparation of 1 L of stock 2,500 pprn boron solution:
Mass of H3BO3required: 14.2993 g Mass of H3B03used: 14.3052 g Actual Concentration: 2,50 1 pprn Preparation of 50 mL of stock 5,000 pprn A1 solution:
Mass of A1(N03)3. 9H20required:3.4760 g Mass of A1(N03)3. 9H20used:3.4727 g Actual Concentration:4,995 pprn Preparation of 50 mL of stock 5,000 pprn Ca solution:
Mass of CaC12required:0.6922 g Mass of CaC12used:0.7027 g Actual Concentration: 5,076 pprn Preparation of 50 mL of stock 7,500 pprn A1 solution:
Mass of A1(N03)3. 9H20 required:5.2140 g Mass 0 f A l ( N 0 ~ .) 9H20
~ used:5.23 19 g Actual Concentration: 7,526 pprn Preparation of 50 mL of stock 7,500 pprn Ca solution:
Mass of CaC12required: 1.0384 g Mass of CaC12used: 1.0522 g Actual Concentration: 7,600 pprn WCAP-16596-NP, Rev. 0 July 2006
99 WESTINGHOUSE NON-PROPRIETARY CLASS 3 2.3 Sodium Tetraborate and Aluminum 2.3.1 Summary of Results Sodium tetraborate precipitate testing was performed using various concentrations of aluminum solutions in order to determine a concentration threshold, below which no precipitate would form. The results of this testing can be seen in Figure 1.1 which was taken approximately 48 hours5.555556e-4 days 0.0133 hours 7.936508e-5 weeks 1.8264e-5 months after the addition of the aluminum solutions.
Figure 2.1 Sodium tetraborate precipitate testing with aluminum solutions at various concentrations.
(pictured above from left to right: 177 ppm Al, 250 ppm Al, 304 ppm Al, 376 ppm Al, and 476 ppm Al)
WCAP-16596-NP, Rev. 0 July 2006
100 WESTINGHOUSE NON-PROPRIETARY CLASS 3 While investigating the effects of aluminum concentration on the formation of precipitates, two experiments were performed at room temperature. These tests show that the formation of precipitates is dependent on the temperature of the solution at the time of the addition of the metal solution. (*) The results of these tests can be seen in Figures 1.2 and 1.3 which were taken approximately 48 hours5.555556e-4 days 0.0133 hours 7.936508e-5 weeks 1.8264e-5 months after the addition of the aluminum solution. When testing at room temperature less precipitates were formed than when tested at the elevated temperature.
Figure 2.2 Sodium tetraborate precipitate testing at an aluminum concentration of approximately 370 ppm. (pictured above from left to right: testing performed at room temperature, test performed at 66OC)
(*) These tests were out of the scope of the test plan.
WCAP-16596-NP, Rev. 0 July 2006
101 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure 2.3 Sodium tetraborate precipitate testing at an aluminum concentration of 476 ppm.
(pictured above from left to right: testing performed at room temperature, test performed at 66°C)
WCAP-16596-NP, Rev. 0 July 2006
102 WESTINGHOUSE NON-PROPRIETARY CLASS 3 2.3.2 Detailed Results Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 177 ppm A1 (3.5 rnL of stock 4,995 ppm A1 solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1567 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution:66.2 "C Temperature after addition of A1 solution:63.7 "C Observations:
Solution was uniformly cloudy upon addition of aluminum solution. Began clearing up.
After 60 minutes, the solution was slightly cloudy and no accumulation of precipitate was present.
After 120 minutes, the solution was slightly cloudy to clear and no accumulation of precipitate was present.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was clear to slightly cloudy and no accumulation of precipitate was present.
WCAP-I 6596-NP, Rev. 0 July 2006
103 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 250 ppm A1 (5.0 mL of stock 4,995 ppm A1 solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1752 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution:64.5 "C Temperature after addition of A1 solution:61.8 "C Observations:
Solution was uniformly cloudy upon addition of aluminum solution. Began clearing up.
After 60 minutes, the solution was slightly cloudy and no accumulation of precipitate was present.
After 120 minutes, the solution was slightly cloudy to clear and no accumulation of precipitate was present.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was slightly cloudy to clear and a very thin layer of precipitate was present at the bottom of the graduated cylinder.
WCAP-16596-NP, Rev. 0 July 2006
Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 304 ppm A1 (4.0 mL of stock 7,526 ppm A1 solution)
Initial Boron concentration:2,50 1 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1682 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 OC Temperature at addition of A1 solution:64.8 OC Temperature after addition of A1 solution: ---------
Observations:
Solution was uniformly cloudy upon addition of aluminum solution.
After 60 minutes, the solution was cloudy and approximately 3 mL of precipitate had accumulated at the bottom of the graduated cylinder.
After 120 minutes, the solution was cloudy and approximately 3 mL of precipitate was at the bottom of the graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was cloudy and approximately 2 mL of precipitate was at the bottom of the graduated cylinder.
WCAP-16596-NP, Rev. 0 July 2006
105 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 376 ppm A1 (5.0 mL of stock 7,526 ppm A1 solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1664 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 OC Temperature at addition of A1 solution: 64.5 OC Temperature after addition of A1 solution:6 1.9 OC Observations:
Solution was uniformly cloudy upon addition of aluminum solution.
After 60 minutes, the solution was cloudy and 7 mL of precipitate had accumulated on the bottom of the graduated cylinder.
After 120 minutes, the solution was cloudy and there was 7 mL of precipitate on the bottom of the graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was cloudy and there was 6 rnL of precipitate on the bottom of the graduated cylinder.
WCAP-16596-NP, Rev. 0 July 2006
Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 365 ppm A1 (7.5 mL of stock 4,995 ppm A1 solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1672 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:22.7 "C Temperature at addition of A1 solution:---------
Temperature after addition of A1 solution: ---------
Observations:
Solution was uniformly cloudy upon addition of aluminum solution.
After 60 minutes, the solution was slightly cloudy and there was no accumulation of precipitate at the bottom of the graduated cylinder.
After 120 minutes, the solution was slightly cloudy.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was slightly cloudy.
WCAP-16596-NP, Rev. 0 July 2006
107 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 476 ppm A1 (10.0 mL of stock 4,995 ppm A1 solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1667 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution: 65.2 "C Temperature after addition of A1 solution:6 1.0 "C Observations:
Solution was uniformly cloudy upon addition of aluminum Solution. There were also particles suspended in the solution.
After 60 minutes, the solution was cloudy and 13 mL of precipitate had accumulated on the bottom of the graduated cylinder.
After 120 minutes, the solution was cloudy and there was 13 mL of precipitate on the bottom of the graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was cloudy and there was 11 mL of precipitate on the bottom of the graduated cylinder.
WCAP-16596-NP, Rev. 0 July 2006
108 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 476 ppm A1 (10.0 rnL of stock 4,995 ppm A1 solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1770 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:22.8 OC Temperature at addition of A1 solution:---------
Temperature after addition of A1 solution:---------
Observations:
Solution was uniformly cloudy upon addition of aluminum solution.
After 60 minutes, the solution was cloudy and there was no accumulation of precipitate at the bottom of the graduated cylinder.
After 120 minutes, the solution was cloudy.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was cloudy.
WCAP-16596-NP, Rev. 0 July 2006
109 WESTINGHOUSE NON-PROPRIETARY CLASS 3 2.4 Sodium Tetraborate and calcium 2.4.1 Summary of Results Sodium tetraborate precipitate testing was performed using various concentrations of calcium solutions in order to determine a concentration threshold, below which no precipitate would form. The results of this testing can be seen in Figure 1.4 below which was taken approximately 48 hours5.555556e-4 days 0.0133 hours 7.936508e-5 weeks 1.8264e-5 months after the addition of the calcium solutions.
Figure 2.4 Sodium tetraborate precipitate testing with calcium solutions at various concentrations. (pictured above from left to right: 254 ppm Ca, 307 ppm Ca, and 380 ppm Ca)
WCAP-16596-NP, Rev. 0 July 2006
110 WESTINGHOUSE NON-PROPRIETARY CLASS 3 While investigating the effects of calcium concentration on the formation of precipitates, one experiment was performed at room temperature to determine whether the solution would behave in a similar fashion to that seen with the addition of aluminum. The result of this test can be seen in Figure 1.5 which was taken approximately 48 hours5.555556e-4 days 0.0133 hours 7.936508e-5 weeks 1.8264e-5 months after the addition of the aluminum solution. When testing at room temperature, precipitates were still formed. (*)
Figure 2.5 Sodium tetraborate precipitate testing at a calcium concentration of 483 ppm.
(' This test was out of the scope of the test plan.
WCAP-16596-NP, Rev. 0 July 2006
2.4.2 Detailed Results Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 254 ppm Ca (5.0 mI, of stock 5,076 ppm Ca solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1605 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of Ca solution:64.5 "C Temperature after addition of Ca solution: 6 1.6 "C Observations:
Localized precipitate was seen at the location of addition of the calcium solution. These solids quickly dissolved and the solution was clear.
After 60 minutes, the solution remained clear.
After 120 minutes, the solution was clear After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was clear.
WCAP-16596-NP, Rev. 0 July 2006
112 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 307 ppm Ca (4.0 mL of stock 7,600 ppm Ca solution)
Initial Boron concentration:2,501 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1736 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:68.9 "C Temperature at addition of Ca solution:64.4 "C Temperature after addition of Ca solution:---------
Observations:
The solution was uniformly cloudy upon addition of calcium solution. The solution appeared to become clearer.
After 60 minutes, the solution was clear with very small particles suspended in it. Also, the bottom of the graduated cylinder was scattered with precipitate particles.
After 120 minutes, the solution was clear with very small particles suspended in it. Also, more precipitate had accumulated on the bottom of the graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , there was approximately 1 mL of precipitate at the bottom of the graduated cylinder and some particles remained suspended in the solution.
WCAP-16596-NP, Rev. 0 July 2006
113 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 380 ppm Ca (5.0 mL of stock 7,600 ppm Ca solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Massused: 3.17368 Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:68.9 "C Temperature at addition of Ca solution:64.4 "C Temperature after addition of Ca solution: ---------
Observations:
The solution was uniformly cloudy upon addition of calcium solution.
After 60 minutes, the solution was slightly cloudy and 9 mL of precipitate had accumulated at the bottom of the graduated cylinder.
After 120 minutes, the solution was slightly cloudy and 9 mL of precipitate was at the bottom of the graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was slightly cloudy and 9 mL of precipitate was at the bottom of the graduated cylinder. There were also suspended particles in the solution.
WCAP-16596-NP, Rev. 0 July 2006
114 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Metal Concentration: 483 ppm Ca (10.0 mL of stock 5,076 ppm Ca solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 3.163 g Mass used: 3.1633 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:22.9 "C Temperature at addition of Ca solution: ---------
Temperature after addition of Ca solution:---------
Observations:
The solution was uniformly cloudy with suspended particles upon addition of calcium solution.
After 60 minutes, 44 rnL of precipitate had accumulated at the bottom of the graduated cylinder. There were suspended particles in the solution.
After 120 minutes, there was 40 mL of precipitate at the bottom of the graduated cylinder. There were suspended particles in the solution.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , there was 37 mL of precipitate at the bottom of the graduated cylinder. There were suspended particles in the solution.
WCAP-16596-NP, Rev. 0 July 2006
115 WESTNGHOUSE NON-PROPRIETARY CLASS 3 2.5 Sodium Metaborate and Aluminum 2.5.1 Summary of Results Sodium metaborate precipitate testing was performed using various concentrations of aluminum solutions in order to determine a concentration threshold, below which no precipitate would form. The results of this testing can be seen in Figure 1.6 which was taken approximately 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months after the addition of the aluminum solutions.
Figure 2.6 Sodium metraborate precipitate testing with aluminum solutions at various concentrations. (pictured above from left to right: 155 ppm Al, 200 ppm Al, 250 ppm Al, and 376 ppm Al)
WCAP-16596-NP, Rev. 0 July 2006
116 WESTINGHOUSE NON-PROPRIETARY CLASS 3 2.5.2 Detailed Results Test Chemical: Sodium metaborate tetrahydrate Metal Concentration: 155 ppm A1 (2.0 mL of stock 7,526 ppm A1 solution)
Initial Boron concentration:2,501 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.2097 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:68.9 "C Temperature at addition ofAl solution:65.8 "C Temperature after addition of A1 solution:63.4 "C Observations:
Solution was uniformly cloudy upon addition of aluminum solution. Began clearing up.
After 60 minutes, the solution was slightly cloudy to clear and no accumulation of precipitate was present.
After 120 minutes, the solution was slightly cloudy to clear.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was slightly cloudy to clear.
WCAP-16596-NP, Rev. 0 July 2006
117 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Metal Concentration: 200 ppm A1 (2.6 rnL of stock 7,526 ppm A1 solution)
Initial Boron concentration:2,501 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.2037 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution:65.9 "C Temperature after addition of A1 solution:63.6 "C Observations:
Solution was uniformly cloudy upon addition of aluminum solution. Began clearing up.
After 60 minutes, the solution was slightly cloudy and no accumulation of precipitate was present.
After 120 minutes, the solution was slightly cloudy.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was slightly cloudy.
WCAP- 16596-NP, Rev. 0 July 2006
118 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Metal Concentration: 250 ppm A1 (5.0 rnL of stock 4,995 ppm A1 solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.2136 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution: 66.2 "C Temperature after addition of A1 solution:63.7 "C Observations:
Solution was uniformly cloudy upon addition of aluminum solution.
After 60 minutes, the solution was cloudy and no accumulation of precipitate was present.
After 120 minutes, the solution was cloudy and there was approximately 3 mL of precipitate at the bottom of the graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was cloudy and there was approximately 3 mL of precipitate at the bottom of the graduated cylinder.
WCAP- 16596-NP, Rev. 0 July 2006
119 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Metal Concentration: 376 ppm A1 (5.0 mL of stock 7,526 ppm A1 solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.2007 g Addition of buffering candidate and A1 solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of A1 solution:65.8 "C Temperature after addition of A1 solution: 63.0 "C Observations:
Solution was uniformly cloudy upon addition of aluminum solution.
After 60 minutes, the solution was cloudy and 10 mL of precipitate had accumulated at the bottom of the graduated cylinder.
After 120 minutes, the solution was cloudy and there was 9 mL of precipitate at the bottom of the graduated cylinder.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was cloudy and there was 8 mL of precipitate at the bottom of the graduated cylinder.
WCAP-16596-NP, Rev. 0 July 2006
120 WESTINGHOUSE NON-PROPRIETARY CLASS 3 2.6 Sodium Metaborate and Calcium 2.6.1 Summary of Results Sodium metaborate precipitate testing was performed using various concentrations of calcium solutions in order to determine a concentration threshold, below which no precipitate would form. The results of this testing can be seen in Figure 1.7 below which was taken approximately 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months after the addition of the aluminum solutions.
Figure 2.7 Sodium metraborate precipitate testing with calcium solutions at various concentrations. (pictured above from left to right: 254 ppm Ca, 380 ppm Ca, 451 ppm Ca, and 480 ppm Ca)
WCAP-16596-NP, Rev. 0 July 2006
121 WESTINGHOUSE NON-PROPRIETARY CLASS 3 2.6.2 Detailed Results Test Chemical: Sodium metaborate tetrahydrate Metal Concentration: 254 ppm Ca (5.0 mI,of stock 5,076 ppm Ca solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.2155 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidated9.0 "C Temperature at addition of Ca solution:66.0 "C Temperature after addition of Ca solution: 63.6 "C Observations:
Solution was clear upon addition of calcium solution.
After 60 minutes, the solution was clear.
After 120 minutes, the solution was clear.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was clear.
WCAP-16596-NP, Rev. 0 July 2006
122 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Metal Concentration: 380 ppm Ca (5.0 mL of stock 7,600 ppm Ca solution)
Initial Boron concentration:2,499 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.2038 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of Ca solution:65.7 "C Temperature after addition of Ca solution:63.2 "C Observations:
Solution was clear upon addition of calcium solution.
After 60 minutes, the solution was clear.
After 120 minutes, the solution was clear.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was clear. A very thin layer of precipitate had accumulated at the bottom of the graduated cylinder.
WCAP-16596-NP, Rev. 0 July 2006
Test Chemical: Sodium metaborate tetrahydrate Metal Concentration: 45 1 ppm Ca (6.0 mL of stock 7,600 ppm Ca solution)
Initial Boron concentration:2,50 1 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.205 1 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:69.0 "C Temperature at addition of Ca solution: 65.8 "C Temperature after addition of Ca solution:---------
Observations:
Upon addition of calcium solution, localized cloudiness at the location of addition was observed. The solution was clear to slightly cloudy.
After 60 minutes, the solution was slightly cloudy, After 120 minutes, the solution was slightly cloudy.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was clear with suspended particles and there was approximately 1 mL of precipitate at the bottom of the graduated cylinder.
WCAP-16596-NP, Rev. 0 July 2006
124 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Metal Concentration: 480 ppm Ca (6.4 mL of stock 7,600 ppm Ca solution)
Initial Boron concentration:2,50 1 ppm Desired pH: 8.5 Mass of buffering candidate:
Mass required: 1.199 g Mass used: 1.2149 g Addition of buffering candidate and Ca solution:
Temperature at addition of buffering candidate:68.7 OC Temperature at addition of Ca solutioh: 66.1 OC Temperature after addition of Ca solution: ---------
Observations:
Upon addition of calcium solution, localized cloudiness at the location of addition was observed. The solution was clear to slightly cloudy.
After 60 minutes, the solution was slightly cloudy.
After 120 minutes, the solution was cloudy.
After 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months , the solution was clear with suspended particles.
Approximately 2 mL of precipitate had accumulated at the bottom of the graduated cylinder.
WCAP-16596-NP, Rev. 0 July 2006
125 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Appendix D: Detailed Results of Phase 5 Testing WCAP-16596-NP, Rev. 0 July 2006
127 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Steel Corrosion:
Buffer Candidate WCAP-16596-NP, Rev. 0 July 2006
128 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Initial Aluminum Coupon Masses and Dimensions Hole Diameter Type Number Mass [g] Length [mm] Width [mm] Thickness [mm]
[mml A L l 100 1 7.2713 51.O 19.0 2.9 9.6 A L l 100 2 7.2636 51.I 19.0 2.9 9.6 A L l 100 3 7.2493 51.O 19.0 2.9 9.6 A L l 100 4 7.2231 51.O 19.0 2.9 9.6 A L l 100 5 7.2427 51.O 19.0 2.9 9.6 A L l 100 6 7.2404 51.O 19.0 2.9 9.6 ALl 100 7 7.2897 51.I 19.1 29 9.6 A L l 100 8 7.2174 50.8 19.1 2.9 9.6 A L l 100 9 7.1894 51.O 19.0 2.9 9.6 ALI 100 10 7.2414 51.O 19.1 2.9 9.6 WCAP-16596-NP, Rev. 0 July 2006
Initial Carbon Steel Coupon Masses and Dimensions Hole Diameter Type Number Mass [g] Length [mm] Width [mm] Thickness [mm]
lmml A508CL2 1 23.0856 51.O 19.1 3.1 9.6 A508CL2 2 22.9719 51.O 19.2 3.1 9.6 A508CL2 3 22.7750 51.1 19.1 3.1 9.6 A508CL2 4 22.8077 51.1 19.1 3.1 9.6 A508CL2 5 22.6574 51.0 19.2 3.1 9.6 A508CL2 6 22.4625 50.9 19.2 3.1 9.6 A508CL2 7 22.0541 51.O 19.2 3.1 9.6 A508CL2 8 22.8778 51.O 19.1 3.1 9.6 A508CL2 9 22.8053 51.O 19.2 3.2 9.6 A508CL2 10 22.9240 51.1 19.2 3.1 9.6 WCAP-16596-NP, Rev. 0 July 2006
130 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Aluminum Coupons After 2 Weeks of Corrosion Pictured above from left to right: Sodium tetraborate decahydrate, Sodium metaborate tetrahydrate, Sodium tripolyphosphate, Trisodium phosphate dodecahydrate, Sodium hydroxide.
WCAP-16596-NP, Rev. 0 July 2006
131 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Aluminum Coupons After De-scaling Pictured above from left to right: Sodium tetraborate decahydrate, Sodium metaborate tetrahydrate, Sodium tripolyphosphate, Trisodium phosphate dodecahydrate, Sodium hydroxide.
WCAP-16596-NP, Rev. 0 July 2006
WESTINGHOUSE NON-PROPRIETARY CLASS 3 Carbon Steel Coupons After 2 Weeks of Corrosion Pictured above from left to right: Sodium tetraborate decahydrate, Sodium metaborate tetrahydrate, Sodium tripolyphosphate, Trisodium phosphate dodecahydrate, Sodium hydroxide.
Note: Coupons 5 and 6 are pictured face down because they were oriented face down in the corrosion flask and did not corrode uniformly.
WCAP-16596-NP, Rev. 0 July 2006
133 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Carbon Steel Coupons After De-scaling Pictured above from left to right: Sodium tetraborate decahydrate, Sodium metaborate tetrahydrate, Sodium tripolyphosphate, Trisodium phosphate dodecahydrate, Sodium hydroxide.
WCAP- 16596-NP, Rev. 0 July 2006
134 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Detailed Results Test Chemical: Sodium tetraborate decahydrate Preparation of 500 ml of 2500 ppm boron solution:
Boric acid required:7.1496 g Boric acid used:7.1379 g pH of solution:4.69 Addition of sodium tetraborate decahydrate:
Mass for pH of 8.0:5.4450 g Mass used: 5.4383 g pH of solution:8.01 Coupons used:
AL1100: 1&2 A508CL2: 1& 2 Observations after 2 weeks:
WCAP-16596-NP, Rev. 0 July 2006
Sodium tetraborate decahydrate test solutions after 2 weeks:
Solution that contained aluminum coupons Solution that contained steel coupons WCAP-16596-NP, Rev. 0 July 2006
136 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Preparation of 500 ml of 2500 ppm boron solution:
Boric acid required:7.1496 g Boric acid used:7.1760 g pH of solution:4.65 Addition of sodium metaborate tetrahydrate:
Mass for pH of 8.0:2.7715 g Mass used: 2.7518 g pH of solution:8.00 Coupons used:
AL1100: 3&4 A508CL2: 3&4 Observations after 2 weeks:
WCAP-16596-NP, Rev. 0 July 2006
137 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Sodium metaborate tetrahydrate test solution after 2 weeks:
Solution that contained aluminum coupons Solution that contained steel coupons WCAP-16596-NP, Rev. 0 July 2006
138 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tripolyphosphate Preparation of 500 rnl of 2500 pprn boron solution:
Boric acid required:7.1496 g Boric acid used:7.1770 g pH of solution:4.66 Addition of sodium tripolyphosphate:
Mass for pH of 7.5:4.2985 g Mass used: 4.2828 g pH of solution:7.49 Coupons used:
AL1100: 5&6 A508CL2: 5 & 6
, Observations after 2 weeks:
WCAP-16596-NP, Rev. 0 July 2006
139 WESTINGHOIJSE NON-PR(3PRIETARY CLASS 3 Sodium tripolyphosphate test solution after 2 weeks:
Solution that contained aluminum coupons Solution that contained steel coupons WCAP-16596-NP, Rev. 0 July 2006
140 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Trisodium phosphate dodecahydrate Preparation of 500 ml of 2500 ppm boron solution:
Boric acid required:7.1496 g Boric acid used:7.1342 g pH of solution:4.65 Addition of trisodium phosphate dodecahydrate:
Mass for pH of 8.0:4.9695 g Mass used: 4.8955 g pH of solution:7.99 Coupons used:
AL1100: 7&8 A508CL2: 7 & 8 Observations after 2 weeks:
WCAP-16596-NP, Rev. 0 July 2006
141 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Trisodium phosphate dodecahydrate test solution after 2 weeks:
Solution that contained aluminum coupons Solution that contained steel coupons WCAP-16596-NP, Rev. 0 July 2006
142 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium hydroxide Preparation of 500 ml of 2500 pprn boron solution:
Boric acid required:7.1496 g Boric acid used:7.1367 g pH of solution:4.66 Addition of sodium hydroxide:
Mass for pH of 8.0:0.5780 g Mass used: 1.2259 g of 50% NaOH pH of solution:8.00 Coupons used:
AL1100: 9 & 10 A508CL2: 9 & 10 Observations after 2 weeks:
WCAP-16596-NP, Rev. 0 July 2006
143 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Sodium hydroxide test solution after 2 weeks:
Solution that contained aluminum coupons Solution that contained steel coupons WCAP- 16596-NP, Rev. 0 July 2006
144 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Analvsis of Dissolved Iron and Aluminum WCAP-16596-NP, Rev. 0 July 2006
145 WESTINGHOUSE NON-PROPFUETARY CLASS 3 Appendix E: Detailed Results of Phase 6 Testing WCAP-16596-NP, Rev. 0 July 2006
146 WESTINGHOUSE NON-PROPRIETARY CLASS 3 It is important to note that two separate environmental effects tests were performed. Section E.l documents the results of environmental testing performed while simulating 100% relative humidity. Jn order to do this, a beaker of water was placed within the oven. Section E.2 documents the results of environmental testing performed without the beaker of water. The relative humidity for the test was approximately 30%.
E.l ENVIRONMENTAL EFFECTS TESTING WITH 100% HUMIDITY Start Date: 3-3 1-06 End Date: 4-13-06 Loading of Samples:
Mass of sodium tetraborate decahydrate used: 10.0934 g Mass of sodium metaborate tetrahydrate used: 10.0917 g Mass of trisodium phosphate dodecahydrate used: 10.1012 g 100 ml of deionized water Observations after 2 weeks:
Sodium tetraborate decahydrate was still a solid, but both sodium metaborate tetrahydrate and trisodium phosphate dodecahydrate were dissolved.
Upon cooling, the trisodium phosphate dodecahydrate solidified.
The pH of the sodium metaborate tetrahydrate solution was 11.78.
Figure E-1 : Sodium tetraborate decahydrate remained a solid but was a clump as opposed to a fine powder.
WCAP-16596-NP, Rev. 0 July 2006
WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure E Sodii metaborate tetrahydrate was completely dissolved.
Figure E The 1 3dium phosphate dodecahydrate sample was a liquid when it was n the oven.
WCAP- 16596-NP, Rev. 0 July 2006
WESTINGHOUSE NON-PROPRIETARY CLASS 3 Figure E- e trisodium phosphate dodecahydrate sample was a solid after it was cooled to I:oom temperah Figure E. le top-view of the trisodium phosphate dodecahydrate sample shows the surf ace after cooling.
WCAP-16596-NP, R.; 0 July 2006
149 WESTTNGHOUSE NON-PROPRIETARY CLASS 3 E.2 ENVIRONMENTAL EFFECTS TESTING WITH 30% HUMIDITY Start Date: 4-1 3-06 End Date: 5-12-06 Loading of Samples:
Mass of sodium tetraborate decahydrate used: 10.0443 g Mass of sodium metaborate tetrahydrate used: 10.0522 g Mass of trisodium phosphate dodecahydrate used: 10.0464 g Mass of sodium tripolyphosphate used: 10.0703 g Relative humidity in oven: - 30%
Observations after 30 days:
Sodium tetraborate decahydrate:
Solid clump Sample separated from side of beaker Clump of sample easily slid out of the beaker WCAP-16596-NP, Rev. 0 July 2006
150 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Sodium metaborate tetrahydrate Solid crystal-like clump Stuck to side of beaker Large decrease in volume Sample beaker had to be broken so that most of test sample could be dissolved (this resulted in having to add the test sample 'with a few pieces of glass stuck to sample)
WCAP-16596-NP, Rev. 0 July 2006
151 WESTINGHOUSE NON-PIIOPRIETARY CLASS 3 Trisodium phosphate dodecahydrate Still looks granular but is clunlped together Stuck to sides When removed, sample broke up into a powder again WCAP-16596-NP, Rev. 0 July 2006
152 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Sodium tripolyphosphate Solid clump Slight separation from side of beaker Clump of sample easily slid out of the beaker WCAP-16596-NP, Rev. 0 July 2006
153 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Dissolution results:
Mass of Temperature of Dissolution Time pH of Resulting Buffer Candidate Dissolution Water at Addition Observations
[min] Solution Sample [gl ["CI Sodium tetraborate decahydrate 7.6877 67.9 3:29 9.21 Most of clump broke up when added to the water All of the loose sample was dissolved in 2:59 Sodium metaborate tetrahydrate 7.4978 67.1 4:39 10.07 while sample that was still stuck to glass from the beaker took 4:39 Trisodium phosphate dodecahydrate 4.8797 66.9 2:37 11.39 Dissolved in the same fashion as in phase 1 Sodium tripolyphosphate 10.119 66.6 2:47 8.91 Most of clump broke up when added to the water WCAP-16596-NP, Rev. 0 July 2006
154 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Appendix F: Detailed Results of Phase 7 Testing WCAP-16596-NP, Rev. 0 July 2006
155 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tetraborate decahydrate Mass req'd for pH of 7.0: 0.1 140 g Observations WCAP-16596-NP, Rev. 0 July 2006
156 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium metaborate tetrahydrate Mass req'd for pH of 7.0: 0.08003 g Boric Acid Gross Mass Net Sample Actual Wt.%
Time rC1Addition lgl IS] Mass [g] Boric Acid Observations 115.2390 0.0000 - Mass of flask, stopper, stir bar 27.5694 142.8084 27.5694 100.00 Boric acid addition 215.3186 100.0796 27.55 Deionized water addition 2:15 - Heat on @ 5 2:30 53.2 2:40 73.5 2:50 96.1 Almost all dissolved 2:55 104.5 - Dissolved, pH = 1.08, heat @ 3 3:OO 104.1 215.8754 100.6364 27.40 1.5415 g of NaMT, pH = 2.55 3:04 102.9 0.5447 216.1 186 100.8796 27.87 Dissolved 3:08 103.5 0.6323 216.4969 101.2579 28.39 Dissolved 3:11 103.5 0.6768 216.9331 101.6941 28.93 Dissolved 3:14 103.4 0.5704 217.2731 102.0341 29.40 Dissolved WCAP-16596-NP, Rev. 0 July 2006
157 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium tripolyphosphate Mass req'd for pH of 7.0: 0.2339 g Observations WCAP-16596-NP, Rev. 0 July 2006
158 WESTMGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Sodium hydroxide Mass req'd for pH of 7.0 (50% NaOH): 0.0398 g Observations WCAP-16596-NP, Rev. 0 July 2006
159 WESTINGHOUSE NON-PROPRIETARY CLASS 3 Test Chemical: Trisodium phosphate dodecahydrate Mass req'd for pH of 7.0: 0.1299 g 0 bservations WCAP-16596-NP, Rev. 0 July 2006

v t e Letter Sequence Response to RAI
TAC:MD2864, (Approved, Closed)
Initiation Request, Request Acceptance... Administration Questions 4 October 2006 2 November 2006 Answers 6 September 2006 Results Approval, Approval Other:
MONTHYEAR2006-11-30 [Table View]

LIC-06-0105, Response to Request for Additional Information Related to the License Amendment Request on Change of Containment Building Sump Buffering Agent from Trisodium Phosphate to Sodium Tetraborate

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References:

SUBJECT:

Attachment:

SUMMARY

SUMMARY

2.0 INTRODUCTION

2.1 BACKGROUND

2.4 REFERENCES

3.1 REFERENCES

4.8 REFERENCES

5.8 REFERENCES

7.0 CONCLUSION

7.1 REFERENCES

8.3 REFERENCES

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LIC-06-0105, Response to Request for Additional Information Related to the License Amendment Request on Change of Containment Building Sump Buffering Agent from Trisodium Phosphate to Sodium Tetraborate

Text

References:

SUBJECT:

Attachment:

SUMMARY

SUMMARY

2.0 INTRODUCTION

2.1 BACKGROUND

2.4 REFERENCES

3.1 REFERENCES

4.8 REFERENCES

5.8 REFERENCES

7.0 CONCLUSION

7.1 REFERENCES

8.3 REFERENCES

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