1. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-0 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 0 Application of Hi-F Coat for Recontamination Reduction at Shimane Unit 1 Hitachi- ＧＥ Nuclear Energy, Ltd. M. Nagase, N. Usui, S. Oouchi Energy & Environmental Research Laboratory, Hitachi, Ltd. H. Hosokawa Chugoku Electric Power Company, Ltd. H. Kajitani, A. Yamashita, T. Minami

2. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-1 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 1 1 Background Dose rate reduction effects don’t last long after operation. Recontamination reduction is needed to keep low dose rate.

3. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-2 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 2 2 What is Hi-F Coat Formation of fine outer magnetite film before power operation ⇒ Reduction of inner oxide film formation to pick up Ｃｏ Hi-F Coat : Hitachi Ferrite Coating Film of Hi-F CoatOxide film in plants Chemical form OuterFe 3 O 4 Fe 3 O 4 、 Fe 2 O 3 、 Ni （ Co)Fe 2 O 4 Inner － CoCr 2 O 4 、 Cr 2 O 3 Size of particle ＜ 0.2μ ｍ 1 ～ 10μ ｍ Thickness of film ＜ 0.5μ ｍ 3 ～ 10μ ｍ Temperature 90 ℃ 280 ℃ Principal of recontamination reduction

4. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-3 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 3 3 Section photograph of film Formation of fine magnetite film （ thickness ：～ 0.3μm ） Vapor deposited carbon Base metal （ type 304 SS ） Film formed under NWC 200 ｈ (DO: 300 ppb) Film of Hi-F Caot Outer (magnetite particle ） Inner (chromite ） Coating layer (magnetite ） Vapor deposited carbon Base metal （ type 304 SS ）

5. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-4 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 4 4 Reduction effect of activity deposition （ laboratory data) ・ Remarkable reduction of 60 Ｃｏ deposition under HWC ・ Continuous effect after ６ times of heat and cool （ Stable) Hi-F Coat treatment NWC treatment Polished (no film) ～ 1/5 Amount of 60 Co deposition (Bq/cm 2 ) Time (h) DO:<10ppb, DH:50ppb, DH 2 O 2 :5ppb

6. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-5 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 5 5 Outline of treatment procedure Oxidation Decomposition, clean-up Final clean-up KMnO 4 Dissolution of chromium oxides Fe 2 O 3 ， MFe 2 O 4 (M : Fe, Ni, Co) Cr 2 O 3 Base metal Repeat C2H2O4N2H4C2H2O4N2H4 Dissolution of iron oxides Heat-up Reduction, clean-up Hi-F Coat treatment Decomposition Fe （ HCOO ） 2 H 2 O 2 N 2 H 4 Formation of fine ferrite (Fe 3 O 4 ) film ＨＯＰ method Hi-F Coat method Base metal

7. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-6 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 6 6 Outline of Hi-F Coat treatment equipments Only a little equipments are needed to decontamination equipments. Pump Cooler Ion exchange column Catalyst column Additional chemical injection system Filter Surge tank （ with heater ） Pump Target （ PLR piping etc. ）

8. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-7 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 7 7 Outline of Hi-F Coat treatment chemicals Only iron formate is added to HOP method chemicals. ChemicalConc. (ppm)Remarks HOP decon. process KMnO 4 200 ～ 300 For oxidation (COOH) 2 2000For reduction N2H4N2H4 ～ 600For ｐ H control H2O2H2O2 － For decomposition of chemicals Hi-F Coat treatment process Fe(HCOO) 2 Fe ：～ 250 Formic ion ： ～ 500 Raw material for film formation Formic acid is used for LOMI * process. H2O2H2O2 － For ion value control N2H4N2H4 200 ～ 500For ｐ H control * ： LOMI is one of chemical decontamination method.

9. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-8 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 8 8 Target of HOP decontamination & Hi-F Coat PLR piping ・ PLR pump inlet & outlet ・ Ring header ・ Riser piping (A & B loops) HOPHi-F Coat 1 st time 1 st &2 nd time2 nd time

10. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-9 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 9 9 Hi-F Coat treatment conditions ParameterPlanned valueMeasured value Fe conc.250±50 ppm 263 ～ 296 ppm N 2 H 4 conc. 200 ～ 600 ppm160 ～ 560 ppm

11. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-10 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 10 Hi-F Coat treatment results P P Surge tank Test piece unit Temporary piping

12. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-11 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 11 Hi-F Coat treatment results More than target value of 0.1μm （ 60μg/cm 2 ) was achieved. Sample itemApplicationSample No. Deposited amount （ μg/cm 2 ) Test piece 1 st time 1230 2270 2 nd time 3302 4192 3 rd time 5125 6132 4 th time 7402 8498 Temporary piping 2 nd timeA150 4 th timeB359

13. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-12 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 12 Surface observation (SEM) Before Hi-F Coat (After decon.) After Hi-F Coat ×1000 ×10000

14. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-13 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 13 Dose rate of PLR piping (1/2)

15. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-14 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 14 Dose rate of PLR piping (2/2)

16. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-15 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 15 Effect of dose rate reduction (1/4) Point 1: inlet piping

17. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-16 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 16 Effect of dose rate reduction (2/4) Point 2: inlet piping

18. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-17 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 17 Effect of dose rate reduction (3/4) Point 3: outlet piping

19. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-18 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 18 Effect of dose rate reduction (4/4) Point 4: outlet piping

20. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-19 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 19 Effect on chemical decontamination Hi-F Coat film was easy to be removed by chemical decontamination.

21. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-20 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 20 Effect of Zn injection on Hi-F Coat Farther Co deposition reduction can be expected with Zn injection. Hitachi laboratory data Time ： 500h Temp. ： 280 ℃ ECP ： -0.5V 024 Zn conc. (ppb) 0 20 40 60 80 100 Polished Hi-F Coat 60 Co deposition amount (Bq/cm 2 ) 6

22. All Rights Reserved. Copyright © 2008, Hitachi-GE Nuclear Energy, Ltd. 1-21 ※ この資料の複写、第 3 者への公開を固く禁じます。 All Rights Reserved. Copyright © 2009, Hitachi-GE Nuclear Energy, Ltd. 21 Summary 1.Hi-F Coat was first applied to Shimane Unit 1 after chemical decontamination. 2.Hi-F Coat treatment was successfully applied to the decontaminated surface. Deposited amount of film was about 270 μg/cm 2 which was more than target value of 60 μg/cm 2. 3.Recontamination was suppressed about 1/2 to 1/3 after one operation cycle. 4.Coated film was easy to be removed by chemical decontamination. 5.Farther dose rate reduction can be expected with Zn injection.