T∕CNS 6-2018 核電廠金屬材料高溫高壓水中電化學試驗方法

1、ICS 77.060H 25T/CNS 62018核電廠金屬材料局溫局壓水中電化學試驗方法Test method for electrochemistry in high temperature pressurizedwater of metallic materials for nuclear power plants2018-03-15 發(fā)布2018-05-30 實施中國核學會 發(fā)布T/CNS 62018目 次tuW Ii Mffl l2規(guī)范性引用文件13 術語和定義 14 試驗儀器和設備15 試樣制備和要求26 試驗條件和步驟 37 試驗結果觀察及評定48 質量保證49試驗報告4附錄A

2、（資料性附錄）高溫高壓水循環(huán)回路系統(tǒng)及高壓釜結構 5附錄B （資料性附錄）電化學工作站推薦參數(shù)6T/CNS 62018本標準按照GB/T 1.12009給出的規(guī)則起草。本標準由中國核學會提出。本標準由核工業(yè)標準化研究所歸口。本標準起草單位：中國科學院金屬研究所、核工業(yè)標準化研究所、中國核動力研究設計院、上海交通 大學、國家電投集團科學技術研究院。本標準主要起草人：韓恩厚、王儉秋、酈曉慧、王家貞、李毅豐、張志明、張宏偉、姜峨、杜東海、 白亞奎。I學兔兔標準下載學兔兔標準下載T/CNS 62018核電廠金屬材料高溫高壓水中電化學試驗方法1范圍本標準規(guī)定了核電廠用金屬材料在高溫高壓水中電化學試驗方法

3、。 本標準適用于核電廠用金屬材料在350 C以下水介質中電化學試驗。2規(guī)范性引用文件下列文件對于本文件的應用是必不可少的。凡是注日期的引用文件，僅注日期的版本適用于本文 件。凡是不注日期的引用文件，其最新版本(包括所有的修改單)適用于本文件。GB/T 150.42011壓力容器 第4部分：制造、檢驗和驗收GB/T 101232001金屬和合金的腐蝕基本術語和定義GB/T 241962009金屬和合金的腐蝕 電化學試驗方法 恒電位和動電位極化測量導則ASTM G3一2014 腐燭測試中電化學測量的通用導則 Standard Practice for Conventions Applicable

4、to Electrochemical Measurements in Corrosion TestingASTM G5一2014 動電位陽極極化測量參考測試方法 Reference Test Method for Making Po- tentiodynamic Anodic Polarization MeasurementsASTM G311972 實驗室均勻腐燭測試通用導則 Standard Practice for Lab Immersion Corrosion Testing of MetalsASTM G591997(2014) 動電位極化電阻測量標準測試方法 Standard Te

5、st Method for Conducting Potentiodynamic Polarization Resistance MeasurementsASTM G611986鐵基、鎳基和鈷基合金局部腐蝕敏感性的循環(huán)動電位極化標準測試方法 Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Measurements for Localized Corrosion Susceptibility of Iron-，Nickel-，or Cobalt-Based AlloysASTM G1021989(20

6、15)利用電化學測試計算腐蝕速率及其相關信息的標準規(guī)程 Standard Practice for Calculation of Corrosion Rates and Related Information from Electrochemical MeasurementsASTM G1061989(2015)電化學阻抗測量用算法和設備的驗證標準實施規(guī)程 Standard Practice for Verification of Algorithm and Equipment for Electrochemical Impedance MeasurementsASTM G199一2009 (

7、2014)電化學噪聲測試標準方法 Standard Guide for ElectrochemicalNoise Measurement 3術語和定義GB/T 101232001和GB/T 241962009界定的術語和定義適用于本文件。4試驗儀器和設備4.1高壓釜4.1.1高壓釜釜體、釜蓋應采用不銹鋼或鎳基合金等耐蝕合金制造，釜體一般為整體結構，特殊情況下學兔兔標準下載T/CNS 62018也可為焊接結構，但應進行無損檢測。4.1.2釜體與釜蓋之間及釜上引出的各測試孔均需具有良好的密封性能，在試驗過程中不準許有泄漏 現(xiàn)象。4.1.3高壓釜應設有安全保護裝置，并定期檢查安全保護裝置的可靠性。4

8、.1.4釜體、釜蓋等高溫承壓構件應按照GB/T 150.4-2011進行無損檢測，經(jīng)檢測合格后方可使用。 4.1.5釜內導管及試樣支架推薦采用耐高溫耐腐蝕材料加工，如采用不銹鋼、鎳基合金等材料制成。 試樣固定在試樣架上，應保證試樣與試樣架、試樣與釜體、試樣與試樣之間均處于絕緣狀態(tài)。 4.1.6高壓釜應配備相應的冷卻水循環(huán)系統(tǒng)，以保護外部參比電極及其他不耐高溫的試驗部件。 4.1.7推薦的高溫高壓水循環(huán)回路系統(tǒng)及高壓釜結構參見附錄A。4.2加熱及控溫裝置4.2.1推薦采用電加熱方式。4.2.2加熱裝置及控溫儀器應具有滿足試驗要求的升溫速率，在試驗溫度下能長期保溫，并且穩(wěn)定、可 靠、操作方便。盡量

9、保持高壓釜內溫度均勻，并確保高壓釜內熱電偶在試樣附近，以便實吋監(jiān)測試樣試 驗溫度。4.2.3 控溫精度：1 C。4.3電化學工作站4.3.1電化學工作站應滿足高溫高壓水中開路電位、動電位極化曲線、電化學阻抗譜等測試要求。 4.3.2電化學工作站的推薦參數(shù)參見附錄B。4.4 電極系統(tǒng)4.4.1電化學試驗一般采用三電極體系，包括工作電極、輔助電極和參比電極。4.4.2高溫高壓水中電化學試驗所用參比電極推薦采用外置式壓力平衡Ag/AgCl電極，也可采用Cu/ Cu2()/陶瓷或Fe/FesOj陶瓷等耐高溫固體參比電極。對于外置式壓力平衡Ag/AgCl參比電極，電解 質KC1溶液推薦濃度0.1 mol

10、/L(25 C時該濃度的Ag/AgCl電極相對標準氫電極的電位為0.286 6 V)。 4.4.3為了保證參比電極電位穩(wěn)定，應配備電極冷卻循環(huán)水系統(tǒng)，確保參比電極芯部溫度相對恒定，且 不超過50 C。試驗前后檢測并校正參比電極電位，必要時更換電解液，保證試驗期間電極電位穩(wěn)定。 4.4.4輔助電極推薦選用金屬鉑片，推薦尺寸20 mmX20 mm，輔助電極采用鉑絲點焊，并用聚四氟乙 烯熱縮管包覆后引出高壓釜。各個電極之間的距離應保持恒定。4.4.5當采用0.1 mol/L KC1溶液作電解液的Ag/AgCl參比電極時，推薦按照式(1)將測得的電極電 位轉換為標準氫電極電位：Eshe E 0|)s

11、十0.286 6 0.001 X (T T,.) -1- 1.745 X 10 X ( T Tr)2 3.03 X 10 9 X (T T r)3 (1 ) 式中：T 試驗溫度，單位為攝氏度(C);T,.25 C ；EO|)S 實測工作電極相對于參比電極的電位，單位為伏特(V)；Eshe相對于標準氫電極的電位，單位為伏特(V)。5試樣制備和要求5.1試樣尺寸5.1.1 推薦標準試樣尺寸:10 mmX 10 mmX 1 mm。5.1.2如進行不同面積比的其他電化學試驗，可根據(jù)試驗要求改變試樣尺寸。3學兔兔標準下載T/CNS 620185.2 試樣加工試樣的加工應采用對材質影響小的方法。推薦用水砂

12、紙將試樣表面依次磨到2000號，或根據(jù)試驗 要求處理樣品表面，確保最終去除樣品表面加工影響層，然后用分析純級丙酮或酒精洗凈。5.3試樣連接5.3.1高溫電化學試樣一般不進行試樣封裝，因此需嚴格控制樣品尺寸及表面狀態(tài)。5.3.2試樣引線推薦采用與試樣化學成分相同或近似的金屬絲，引線表面包覆聚四氟乙烯熱縮管，聚 四氟乙烯管熱縮后與導線之間不應存在縫隙，試樣引線點焊在試樣側面，并確保焊點附近導線裸露面積 盡量小，焊點長度不宜超過3 mm。5.3.3點焊后，應注意打磨樣品表面由焊接引起的其他損傷部位，該部位表面粗糙度與樣品最終粗糙 度要求相同。當試驗溫度超過300 1時，推薦在導線聚四氟乙烯熱縮管外面

13、包套氧化鋯陶瓷管，以提高 導線絕緣特性。6試驗條件和步驟6.1溶液配制6.1.1采用電導率小于1 MS/cm的去離子水或蒸餾水配制試驗溶液。6.1.2根據(jù)試驗要求配制試驗溶液，宜采用分析純級試劑。6.2試驗條件6.2.1按照試驗要求確定試驗溫度。6.2.2對于動態(tài)循環(huán)高壓釜，溶液應充滿高壓釜腔，外加壓力高于該溶液飽和蒸汽壓，調節(jié)高壓泵選擇 合適的溶液流量，確保高壓釜內溶液在1 h內至少徹底更換1次。6.2.3 推薦升溫速率為70 C/h100 C/h。6.2.4溶液體積與試樣表面積的比值宜大于100 mL/cm2。6.2.5相同試驗條件下平行試樣不少于3個。6.2.6達到試驗溫度后保溫時間不宜

14、少于48 h，亦可根據(jù)試驗需要對試驗保溫時間進行調整。6.2.7高溫高壓水中電化學試驗參數(shù)的選擇，根據(jù)具體試驗項目和試驗要求，參照GB/T 24196- 2009,ASTM G32014.ASTM G52014、ASTM G311972、ASTM G611986、ASTM G591997 (2014)、ASTM G1992009(2014)、ASTM 01021989(2015)和 ASTM 01061989(2015)中的相關 規(guī)定執(zhí)行。6.3試驗步驟6.3.1試驗前精確測量每個試樣的尺寸，測量精度取決于試驗要求，推薦使用游標卡尺測量，并計算其 表面積。6.3.2安裝試樣，并保持測試面正對輔

15、助電極，且每個試樣與輔助電極的距離相同。擰緊固定螺栓，確 保高壓釜密閉，向高壓釜內充人高純氮氣，排出釜腔內的空氣，然后注人試驗溶液排出高純氮氣。6.3.3試驗前應調節(jié)試驗溶液水化學參數(shù)，根據(jù)試驗條件調節(jié)溶解氧、溶解氫含量，并在試驗報告中 注明。6.3.4確保測溫、測壓及安全保護裝置均處于正常狀態(tài)后，開始加壓并確保壓力/達到設定值，確認無 泄漏后開始加熱升溫。6.3.5系統(tǒng)穩(wěn)定后根據(jù)試驗要求規(guī)定的時間進行電化學測試。6.3.6試驗完成后，首先對高壓釜停止加熱，等降溫至室溫時，方可降壓打開高壓釜，防止循環(huán)回路中 的溶液因壓力降低發(fā)生汽化。#T/CNS 620187試驗結果觀察及評定利用相關軟件處理

16、電化學測試源文件，并根據(jù)試驗要求繪制或擬合出試驗條件下的開路電位、鈍化 電流密度、電化學交流阻抗譜等試驗結果，具體數(shù)據(jù)處理和結果評定可參照GB/T 241962009、 ASTM G32014、ASTM G52014、ASTM G311972、ASTM G61 1986、ASTM G591997 (2014)、ASTM 01992009(2014) .ASTM 01021989(2015)和 ASTM 01061989(2015)中的相關 規(guī)定執(zhí)行。8質量保證8.1試驗人員要求本標準所規(guī)定的試驗涉及高溫高壓特殊工況，試驗人員應具備相關高溫高壓水循環(huán)系統(tǒng)基本操作 技能及電化學專業(yè)背景知識，以提高

17、試驗可操作性及結果可信度。8.2 試驗系統(tǒng)校準要求定期對高溫高壓水循環(huán)系統(tǒng)中的壓力容器及溫度、壓力、水化學參數(shù)等測試用傳感器或探頭進行檢 測或計量標定，定期更換探頭電解液等耗材，保證相關試驗參數(shù)和結果的可信度。8.3其他要求如采用靜態(tài)釜系統(tǒng)進行試驗，應注明試驗裝置參數(shù)和條件。9試驗報告試驗報告應包括但不限于以下內容：a) 本標準編號；b) 材料名稱、熱處理狀態(tài)；c) 試樣形狀尺寸、表面狀態(tài)、取樣位置、取樣方向；d) 試驗參數(shù)，如：溶液成分、溶解氧/溶解氫濃度、pH值、電導率、試驗溫度及保溫時間、壓力及 高壓釜參數(shù)等；e) 試驗結果，包括開路電位、極化曲線、鈍化電流密度、電化學交流阻抗譜數(shù)據(jù)擬合

18、結果等；f) 試驗異常記錄；g) 試驗人員和日期。1T/CNS 620185附錄 A（資料性附錄）高溫高壓水循環(huán)回路系統(tǒng)及高壓釜結構圖A.1高溫高壓水動態(tài)循環(huán)回路工作電極參比電極釜體輔 溶循入圖A.2局溫局壓水循環(huán)動態(tài)局壓釜不意圖附錄B（資料性附錄）電化學工作站推薦參數(shù)推薦的電化學工作站參數(shù)見表B.1。表B.1電化學工作站推薦參數(shù)參數(shù)范圍輸出槽壓士 22 V恒電位掃描電壓范圍士 11 V電壓最小分辨率1電流量程600 fA600 mA電流最小分辨率20 aA輸人阻抗100 TfK 電容0.2 pF電化學交流阻抗頻率范圍10 mHz100 kHz數(shù)據(jù)采集頻率0 Hz1 000 Hz9ICS 77

19、.060H 25Association Standard of Chinese Nuclear SocietyT/CNS 62018Test method for electrochemistry in high temperature pressurized water of metallic materials for nuclearpower plants核電廠金屬材料高溫高壓水中電化學試驗云法(English Translation)Issue date：2019-05-27Implementation date：2019-09-01Issued by Chinese Nuclear

20、SocietyContentsForeword 91 Scope 102 Normative references 103 Terms and definitions 114 Apparatus 115 Specimen preparation andrequirements 136 Test condition and procedures 147 Results and assessment 158 Quality assurance 159 Test report 16Annex A (informative) High temperature high pressure loop sy

21、stem and autoclavestructures 17Annex B (informative) Recommended parameters for electrochemical workstation 18T/CNS 62018ForewordChinese Nuclear Society is in charge of this English translation. In case of any doubt about the contents of English translation,the Chinese original shall be considered a

22、uthoritative.This standard is drafted in accordance with the rules given in the GB/T 1.12009 Directives for standardization Part 1 : Structure and drafting of standars.This standard was proposed by Chinese Nuclear Society.This standard was prepared by Institute for Standardization of Nuclear Industr

23、y.#T/CNS 62018Test method for electrochemistry in high temperature pressurized water of metallic materials for nuclear power plants1 ScopeThis standard specifies the electrochemical test methods of metallic materials used in nuclear power plant in high temperature high pressure water.This standard i

24、s applicable to electrochemical test for metallic materials used in nuclear power plant in aqueous medium under 350 C.2 Normative referencesThe following referenced documents are indispensible for the application of this document.For dated references,only the edition cited applies.For undated refere

25、nces,the latest edition of the referenced document (including any amendments) applies.GB/T 150.42011，Pressure vesselsPart 4： Fabrication，inspection and testing，and acceptance GB/T 101232001，Corrosion of metals and alloysBasic terms and definitionsGB/T 241962009, Corrosion of metals and alloysElectro

26、chemical test methodsGuidelines for conducting potentiostatic and potentiodynamic polarization measurementsASTM G32014, Standard practice for conventions applicable to electrochemical measurements in corrosion testingASTM G52014, Reference test method for making potentiodynamic anodic polarization m

27、easurementsASTM G311972, Standard practice for lab immersion corrosion testing of metalsASTM G591997(2014), Standard test method for conducting potentiodynamic polarization resistance measurementsioT/CNS 62018ASTM G611986, Standard test method for conducting cyclic potentiodynamic polarization measu

28、rements for localized corrosion susceptibility of Iron-，Nickel-，or Cobalt-Based AlloysASTM G1021989 (2015 )，Standard practice for calculation of corrosion rates and related information from electrochemical measurementsASTM G1061989(2015) 9 Standard practice for verification of algorithm and equipmen

29、t for electrochemical impedance measurementsASTM G199 2009(2014)，Standard guide for electrochemical noise measurement3 Terms and definitionsFor the purposes of this document, the terms and definitions given in GB/T 101232001 and GB/T 241962009 apply.4 Apparatus4.1 Autoclave4.1.1 The body and cover o

30、f an autoclave shall be made of corrosion-resistant alloys such as stainless steel and nickel-based alloy. In general, the autoclave body shall be integral, and welding is allowed under special circumstances but non-destructive test is required.4.1.2 The contact surface between autoclave body and it

31、s cover shall be sealed,as well as the holes through the cover.Any leakage is not permitted during the test.4.1.3 Safety protection devices are required for the autoclave,and they shall be inspected regularly.4.1.4 Non-destructive tests for autoclave body9cover and other temperature and pressure bea

32、ring components are required as specified in GB/T 150.42011，and the autoclave can only be used if it is acceptable.4.1.5 The tube and specimen holder in the autoclave are recommended to be made of high-temperature-resistant and corrosion-resistant materials such as stainless steel and nickel-based a

33、lloy. Fix specimens on the holders, keep the insulation between specimens and their holders and the autoclave.4.1.6 Cooling water circulation loop is required for the autoclave to protect the electrodes and other devices that are not high temperature resistant.liT/CNS 620184.1.7 The recommended high

34、 temperature high pressure water loop system and autoclave schematic see Annex A4.2 Heating and temperature control device4.2.1 Electrical heating is recommended.4.2.2 Heating and temperature control device shall have a suitable heating rate to meet the test requirement, keep the test temperature fo

35、r long period，and be stable, reliable and easy to operate.The temperature in the autoclave shall be distributed homogeneously.The thermal couple shall be placed near the specimen to monitor the specimen temperature instantaneously.4.2.3 The temperature accuracy shall be controlled within 1 C.4.3 Ele

36、ctrochemistry workstation4.3.1 Electrochemistry workstation shall meet the requirements for open circuit potential,potentio- dynamic polarization curve and electrochemical impedance spectroscopy test etc.4.3.2 Recommended parameters for electrochemistry workstation see Annex B.4.4 Electrode system4.

37、4.1 A three-electrode system is usually applied for electrochemistry test，including working electrode (WE),counter electrode (CE) and reference electrode (RE).4.4.2 The external pressure-balance Ag/AgCI reference electrode is recommended for electrochemical test in high temperature high pressure wat

38、er,and Cu/Cu2O/ceramic or Fe/Fe3O4/ceramic solid reference electrode is also applicable.For the external pressure-balance Ag/AgCI reference electrode, the concentration of KCI electrolyte is 0.1 mol/L as recommended.(the potential of Ag/AgCI electrode with 0.1 mol/L KCI electrolyte versus standard h

39、ydrogen electrode (SHE) is 0.286 6 V at 25 C.).4.4.3 Cooling water loop is required for the stability of reference electrode，and the temperature of the electrode core be lower than 50 C and relatively constant. The potential of reference electrode shall be measured and calibrated before and after te

40、st,and its electrolyte shall be changed in time for the potential stability during the test.4.4.4 A platinum sheet is recommended as counter electrode,and the recommended dimension is 20 mm (length) x 20 mm (width).Counter electrode is spot-welded with platinum wire and the wire is coated by polytet

41、rafluoroethylene (PTFE) heat-shrinkage tube.The coated wire is then pulled out the autoclave through testing hole on the cover.The distances among all the electrodes shall be constant.4.4.5 The potential measured by Ag/AgCI reference electrode with 0.1 mol/L KCI electrolyte is recommen-ded to transf

42、er into the potential versus standard hydrogen electrode by the following equation (1): Eshe = fobs + 0.286 6 - 0.001 x (T - Tr) + 1.745 x 10 7 x ( 7- Tr)2 3.03 x 10-9 x (T - Tr)3 where丁 test temperature,in C ；Tr 25 C ；Eobs measured potential of WE versus RE,in V；EShe potential versus SHE, inV.5 Spe

43、cimen preparation and requirements5.1 Specimen dimension5.1.1 The recommended specimen dimension is 10 mm (length) x 10 mm (width) x 1 mm (thickness).5.1.2 For other electrochemical tests in different area ratio,the dimensions of the specimens may be altered according to the test requirements.5.2 Sp

44、ecimen preparationA method that has little effect on the material shall be used for specimen preparation. Water-proof abrasive paper is recommended to grind the specimen stepwise until 2000 # ,or treat the specimen surface in accordance with test requirement.Confirm the processing influence layer on

45、 the surface is removed finally,and then clean specimens with analytical acetone or ethanol.5.3 Specimen connection5.3.1 Specimens for high temperature electrochemistry test are not packed in general9so the dimension and surface condition shall be controlled strictly.5.3.2 The leading wire is recomm

46、ended to have the identical or similar chemical composition with the specimen,and shall be coated with PTFE heat-shrinkage tube.No gap is allowed between the PTFE tube and leading wire after heat shrinkage.The leading wire shall be spot-welded on the side of the specimen.The exposed area of wire aro

47、und the welding spot shall be as small as possible.The length of the welding spot shall be less than 3 mm.5.3.3 After spot-welding,other welding affected areas on the specimen shall be ground to achieve the same roughness as the specimen.When test temperature is higher than 300 C，the leading wire is

48、 recommended to be sleeved into zirconia tube after being coated with PTFE heat-shrinkage tube to maintain the insulation.6 Test condition and procedures6.1 Solution preparation6.1.1 Deionized or distilled water with a conductivity less than 1 uS/cm shall be used to prepare the test solution.6.1.2 A

49、nalytical reagents are recommended to prepare the solution in accordance with the test requirement.6.2 Test condition6.2.1 Test temperature shall be determined by test requirements.6.2.2 For dynamic circulation autoclave, its chamber shall be filled with solution. The applied pressure shall be highe

50、r than its saturated vapor pressure.The high pressure pump shall be adjusted to get the appropriate flow to ensure the solution in the autoclave be recycled at least once per hour.6.2.3 The heating rate is recommended as 70 oC/h100 C/h.6.2.4 The ratio of solution volume to specimen surface area shal

51、l be higher than 100 mL/cm2.6.2.5 At least three tests under the same condition shall be conducted.6.2.6 The holding time at the target temperature shall not be less than 48 h prior to the test.The holding time can be adjusted according to the test requirement.6.2.7 Electrochemical test parameters f

52、or high temperature high pressure water shall be chosen according to specific test items and test requirement and shall be in accordance with the relevant rules in GB/T 241962009,ASTM G32014,ASTM G52014,ASTM G311972,ASTM G611986,ASTM G591997(2014), ASTM G1992009 (2014), ASTM G1021989 (2015) and ASTM

53、 G1061989 (2015).6.3 Test procedures6.3.1 The dimension of each specimen needs to be measured precisely,and the accuracy depends on test requirements.A vernier caliper is recommended9and the surface area of the specimen shall be calculated.6.3.2 The specimens are installed to keep the measuring surf

54、ace facing directly to the counter electrode and all specimens should have the same distance to the counter electrode.The fixing bolts are screwed to keep the autoclave airtight.High purity nitrogen shall be blown into the autoclave chamber to expel the air inside,and the test solution is then pumpe

55、d to push out the nitrogen.6.3.3 The water chemistry parameters of the solution shall be adjusted before the test,especially the dissolved oxygen or hydrogen concentration.The above parameters shall be reported.6.3.4 After checking all the temperature and pressure measuring and protection devices, r

56、aise the pressure to the set value,and then start heating after confirming there is no leakage.6.3.5 When the system is stabilized, electrochemical test is conducted according to the required time.6.3.6 Stop heating after the test,and the autoclave should be opened once the temperature decreases to

57、room temperature in order to prevent solution from vaporizing avoid of vaporization of the solution due to pressure reduction.7 Result and assessmentSource files of the electrochemical test shall be processed using relevant software.Open circuit potential, passivation current density and electrochemical impedance spe