T∕CNS 6-2018 核电厂金属材料高温高压水中电化学试验方法

1、ICS 77.060H 25T/CNS 62018核电厂金属材料局温局压水中电化学试验方法Test method for electrochemistry in high temperature pressurizedwater of metallic materials for nuclear power plants2018-03-15 发布2018-05-30 实施中国核学会 发布T/CNS 62018目 次tuW Ii Mffl l2规范性引用文件13 术语和定义 14 试验仪器和设备15 试样制备和要求26 试验条件和步骤 37 试验结果观察及评定48 质量保证49试验报告4附录A

2、（资料性附录）高温高压水循环回路系统及高压釜结构 5附录B （资料性附录）电化学工作站推荐参数6T/CNS 62018本标准按照GB/T 1.12009给出的规则起草。本标准由中国核学会提出。本标准由核工业标准化研究所归口。本标准起草单位：中国科学院金属研究所、核工业标准化研究所、中国核动力研究设计院、上海交通 大学、国家电投集团科学技术研究院。本标准主要起草人：韩恩厚、王俭秋、郦晓慧、王家贞、李毅丰、张志明、张宏伟、姜峨、杜东海、 白亚奎。I学兔兔标准下载学兔兔标准下载T/CNS 62018核电厂金属材料高温高压水中电化学试验方法1范围本标准规定了核电厂用金属材料在高温高压水中电化学试验方法

3、。 本标准适用于核电厂用金属材料在350 C以下水介质中电化学试验。2规范性引用文件下列文件对于本文件的应用是必不可少的。凡是注日期的引用文件，仅注日期的版本适用于本文 件。凡是不注日期的引用文件，其最新版本(包括所有的修改单)适用于本文件。GB/T 150.42011压力容器 第4部分：制造、检验和验收GB/T 101232001金属和合金的腐蚀基本术语和定义GB/T 241962009金属和合金的腐蚀 电化学试验方法 恒电位和动电位极化测量导则ASTM G3一2014 腐烛测试中电化学测量的通用导则 Standard Practice for Conventions Applicable

4、to Electrochemical Measurements in Corrosion TestingASTM G5一2014 动电位阳极极化测量参考测试方法 Reference Test Method for Making Po- tentiodynamic Anodic Polarization MeasurementsASTM G311972 实验室均匀腐烛测试通用导则 Standard Practice for Lab Immersion Corrosion Testing of MetalsASTM G591997(2014) 动电位极化电阻测量标准测试方法 Standard Te

5、st Method for Conducting Potentiodynamic Polarization Resistance MeasurementsASTM G611986铁基、镍基和钴基合金局部腐蚀敏感性的循环动电位极化标准测试方法 Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Measurements for Localized Corrosion Susceptibility of Iron-，Nickel-，or Cobalt-Based AlloysASTM G1021989(20

6、15)利用电化学测试计算腐蚀速率及其相关信息的标准规程 Standard Practice for Calculation of Corrosion Rates and Related Information from Electrochemical MeasurementsASTM G1061989(2015)电化学阻抗测量用算法和设备的验证标准实施规程 Standard Practice for Verification of Algorithm and Equipment for Electrochemical Impedance MeasurementsASTM G199一2009 (

7、2014)电化学噪声测试标准方法 Standard Guide for ElectrochemicalNoise Measurement 3术语和定义GB/T 101232001和GB/T 241962009界定的术语和定义适用于本文件。4试验仪器和设备4.1高压釜4.1.1高压釜釜体、釜盖应采用不锈钢或镍基合金等耐蚀合金制造，釜体一般为整体结构，特殊情况下学兔兔标准下载T/CNS 62018也可为焊接结构，但应进行无损检测。4.1.2釜体与釜盖之间及釜上引出的各测试孔均需具有良好的密封性能，在试验过程中不准许有泄漏 现象。4.1.3高压釜应设有安全保护装置，并定期检查安全保护装置的可靠性。4

8、.1.4釜体、釜盖等高温承压构件应按照GB/T 150.4-2011进行无损检测，经检测合格后方可使用。 4.1.5釜内导管及试样支架推荐采用耐高温耐腐蚀材料加工，如采用不锈钢、镍基合金等材料制成。 试样固定在试样架上，应保证试样与试样架、试样与釜体、试样与试样之间均处于绝缘状态。 4.1.6高压釜应配备相应的冷却水循环系统，以保护外部参比电极及其他不耐高温的试验部件。 4.1.7推荐的高温高压水循环回路系统及高压釜结构参见附录A。4.2加热及控温装置4.2.1推荐采用电加热方式。4.2.2加热装置及控温仪器应具有满足试验要求的升温速率，在试验温度下能长期保温，并且稳定、可 靠、操作方便。尽量

9、保持高压釜内温度均匀，并确保高压釜内热电偶在试样附近，以便实吋监测试样试 验温度。4.2.3 控温精度：1 C。4.3电化学工作站4.3.1电化学工作站应满足高温高压水中开路电位、动电位极化曲线、电化学阻抗谱等测试要求。 4.3.2电化学工作站的推荐参数参见附录B。4.4 电极系统4.4.1电化学试验一般采用三电极体系，包括工作电极、辅助电极和参比电极。4.4.2高温高压水中电化学试验所用参比电极推荐采用外置式压力平衡Ag/AgCl电极，也可采用Cu/ Cu2()/陶瓷或Fe/FesOj陶瓷等耐高温固体参比电极。对于外置式压力平衡Ag/AgCl参比电极，电解 质KC1溶液推荐浓度0.1 mol

10、/L(25 C时该浓度的Ag/AgCl电极相对标准氢电极的电位为0.286 6 V)。 4.4.3为了保证参比电极电位稳定，应配备电极冷却循环水系统，确保参比电极芯部温度相对恒定，且 不超过50 C。试验前后检测并校正参比电极电位，必要时更换电解液，保证试验期间电极电位稳定。 4.4.4辅助电极推荐选用金属铂片，推荐尺寸20 mmX20 mm，辅助电极采用铂丝点焊，并用聚四氟乙 烯热缩管包覆后引出高压釜。各个电极之间的距离应保持恒定。4.4.5当采用0.1 mol/L KC1溶液作电解液的Ag/AgCl参比电极时，推荐按照式(1)将测得的电极电 位转换为标准氢电极电位：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 试验温度，单位为摄氏度(C);T,.25 C ；EO|)S 实测工作电极相对于参比电极的电位，单位为伏特(V)；Eshe相对于标准氢电极的电位，单位为伏特(V)。5试样制备和要求5.1试样尺寸5.1.1 推荐标准试样尺寸:10 mmX 10 mmX 1 mm。5.1.2如进行不同面积比的其他电化学试验，可根据试验要求改变试样尺寸。3学兔兔标准下载T/CNS 620185.2 试样加工试样的加工应采用对材质影响小的方法。推荐用水砂

12、纸将试样表面依次磨到2000号，或根据试验 要求处理样品表面，确保最终去除样品表面加工影响层，然后用分析纯级丙酮或酒精洗净。5.3试样连接5.3.1高温电化学试样一般不进行试样封装，因此需严格控制样品尺寸及表面状态。5.3.2试样引线推荐采用与试样化学成分相同或近似的金属丝，引线表面包覆聚四氟乙烯热缩管，聚 四氟乙烯管热缩后与导线之间不应存在缝隙，试样引线点焊在试样侧面，并确保焊点附近导线裸露面积 尽量小，焊点长度不宜超过3 mm。5.3.3点焊后，应注意打磨样品表面由焊接引起的其他损伤部位，该部位表面粗糙度与样品最终粗糙 度要求相同。当试验温度超过300 1时，推荐在导线聚四氟乙烯热缩管外面

13、包套氧化锆陶瓷管，以提高 导线绝缘特性。6试验条件和步骤6.1溶液配制6.1.1采用电导率小于1 MS/cm的去离子水或蒸馏水配制试验溶液。6.1.2根据试验要求配制试验溶液，宜采用分析纯级试剂。6.2试验条件6.2.1按照试验要求确定试验温度。6.2.2对于动态循环高压釜，溶液应充满高压釜腔，外加压力高于该溶液饱和蒸汽压，调节高压泵选择 合适的溶液流量，确保高压釜内溶液在1 h内至少彻底更换1次。6.2.3 推荐升温速率为70 C/h100 C/h。6.2.4溶液体积与试样表面积的比值宜大于100 mL/cm2。6.2.5相同试验条件下平行试样不少于3个。6.2.6达到试验温度后保温时间不宜

14、少于48 h，亦可根据试验需要对试验保温时间进行调整。6.2.7高温高压水中电化学试验参数的选择，根据具体试验项目和试验要求，参照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)中的相关 规定执行。6.3试验步骤6.3.1试验前精确测量每个试样的尺寸，测量精度取决于试验要求，推荐使用游标卡尺测量，并计算其 表面积。6.3.2安装试样，并保持测试面正对辅

15、助电极，且每个试样与辅助电极的距离相同。拧紧固定螺栓，确 保高压釜密闭，向高压釜内充人高纯氮气，排出釜腔内的空气，然后注人试验溶液排出高纯氮气。6.3.3试验前应调节试验溶液水化学参数，根据试验条件调节溶解氧、溶解氢含量，并在试验报告中 注明。6.3.4确保测温、测压及安全保护装置均处于正常状态后，开始加压并确保压力/达到设定值，确认无 泄漏后开始加热升温。6.3.5系统稳定后根据试验要求规定的时间进行电化学测试。6.3.6试验完成后，首先对高压釜停止加热，等降温至室温时，方可降压打开高压釜，防止循环回路中 的溶液因压力降低发生汽化。#T/CNS 620187试验结果观察及评定利用相关软件处理

16、电化学测试源文件，并根据试验要求绘制或拟合出试验条件下的开路电位、钝化 电流密度、电化学交流阻抗谱等试验结果，具体数据处理和结果评定可参照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)中的相关 规定执行。8质量保证8.1试验人员要求本标准所规定的试验涉及高温高压特殊工况，试验人员应具备相关高温高压水循环系统基本操作 技能及电化学专业背景知识，以提高

17、试验可操作性及结果可信度。8.2 试验系统校准要求定期对高温高压水循环系统中的压力容器及温度、压力、水化学参数等测试用传感器或探头进行检 测或计量标定，定期更换探头电解液等耗材，保证相关试验参数和结果的可信度。8.3其他要求如采用静态釜系统进行试验，应注明试验装置参数和条件。9试验报告试验报告应包括但不限于以下内容：a) 本标准编号；b) 材料名称、热处理状态；c) 试样形状尺寸、表面状态、取样位置、取样方向；d) 试验参数，如：溶液成分、溶解氧/溶解氢浓度、pH值、电导率、试验温度及保温时间、压力及 高压釜参数等；e) 试验结果，包括开路电位、极化曲线、钝化电流密度、电化学交流阻抗谱数据拟合

18、结果等；f) 试验异常记录；g) 试验人员和日期。1T/CNS 620185附录 A（资料性附录）高温高压水循环回路系统及高压釜结构图A.1高温高压水动态循环回路工作电极参比电极釜体辅 溶循入图A.2局温局压水循环动态局压釜不意图附录B（资料性附录）电化学工作站推荐参数推荐的电化学工作站参数见表B.1。表B.1电化学工作站推荐参数参数范围输出槽压士 22 V恒电位扫描电压范围士 11 V电压最小分辨率1电流量程600 fA600 mA电流最小分辨率20 aA输人阻抗100 TfK 电容0.2 pF电化学交流阻抗频率范围10 mHz100 kHz数据采集频率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核电厂金属材料高温高压水中电化学试验云法(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