锆合金氧化膜弹性模量的测定

氧化膜的内应力对锆合金的腐蚀行为有重要影响，弹性模量是计算分析氧化膜内应力的关键物性参数。由于测试困难，锆合金氧化膜的弹性模量通常根据块体材料的数据进行估计。本文利用纳米压痕法测试分析了多种条件下锆合金氧化膜的弹性模量和硬度，研究发现其表面和截面的弹性模量与硬度数值存在差异。与纯水相比，在含锂水介质中腐蚀，锆合金氧化膜的弹性模量及硬度偏小。      

锆合金在高温高压水中的腐蚀

本文介绍了国产锆-2、锆-4合金在温度大于300℃的水或蒸汽中的腐蚀——氧化与吸氢;认为两种合金耐氧化性能相似,在反应堆工质中使用,具有足够的耐蚀性。水中添加少量氢氧化锂(含锂1—2ppm)或硼酸(含硼800ppm),对合金腐蚀无明显影响。在高温水中,锆-4在腐蚀300天后的吸氢增重约为锆-2的1/3—1/2;而在341℃蒸汽中,锆-4减少吸氢的优越性并不明显。水中加氢增加了锆-4的吸氢速率,但并没有达到妨碍使用的程度。预生氧化膜不能改善合金的耐长期腐蚀性能。具有热流的锆合金管与不锈钢定位架接触处的隙缝会导致危险的局部腐蚀,但在中性水条件下,腐蚀深度很浅,并不影响锆合金的长期使用。     

PWR一回路水质中800合金的腐蚀研究

用320℃含600 mg/kg硼和2 mg/kg锂的高氧含量水溶液模拟PWR一回路水质,研究了800合金在一回路水中的腐蚀特性。结果表明,800合金试样在被侵蚀1500 h之后,表面生成一层很薄的氧化膜,去除氧化膜后,计算出其均匀腐蚀速率为4.03×10?4 mm/a,基体中TiN缺陷处容易引起点蚀,管状试样内环出现明显的晶间腐蚀现象。     

两种锆合金显微组织与腐蚀机理研究

根据国产C锆合金与低锡Zr-4合金在纯水以及LiOH水溶液中的高压釜腐蚀试验的结果，采用透射电镜（TEM）观察基体和氧化膜显微组织，通过分析氧化增重数据，对C锆合金的腐蚀机理进行了研究。提出了3种腐蚀机理:即Nb元素有效抑制阴离子空位浓度提高，可减少氧元素扩散速率；缺陷阱的数量影响氧扩散带来的腐蚀，且空位阱数量与第二相颗粒总表面积成正比；第二相粒子氧化膨胀造成氧化膜压应力松弛，降低其稳定性并失去保护能力。      

N36锆合金包壳堆内腐蚀模型研究

本文利用池边检查数据，基于阿累尼乌斯方程建立了N36锆合金包壳堆内腐蚀最佳估算模型。由于缺乏腐蚀转折前数据，N36锆合金包壳腐蚀转折前氧化膜厚度只是时间的函数，腐蚀转折后氧化膜厚度是包壳温度和时间的函数。通过在最佳估算腐蚀模型上添加工程因子，建立了不同加工工艺N36锆合金包壳腐蚀模型。N36锆合金包壳腐蚀包络模型在最小腐蚀转折点的基础上建立。模型验证结果表明，N36锆合金包壳腐蚀模型与验证数据符合较好，能够用于N36锆合金堆内腐蚀行为模拟。     

321不锈钢在低酸度硝酸铀酰溶液中的腐蚀特性

用称量法和电化学法研究了321不锈钢在不同浓度和pH值的硝酸铀酰溶液中的高温均匀腐蚀和电化学府蚀行为。均匀腐蚀试验结果表明．在选定的腐蚀条件下，321不锈钢样品在960h内，其表面光洁度无明显变化．腐蚀速率小于0．04mg/m^2.h，在低酸度的硝酸铀酰溶液中耐蚀。用腐蚀电入学法研究了321不锈钢在有溶解氧的硝酸铀酰溶液中的腐蚀电化学特性，测量了电极的腐蚀电位、腐蚀电流密度。经AES分析表明，电化学腐蚀后的样品在腐蚀膜中有一定量的铀．深度剖析含铀腐蚀膜的厚度为10—15nm。     

钛合金在硼、锂介质中的缝隙腐蚀行为分析

钛合金作为新型蒸汽发生器的主要结构材料，其耐缝隙腐蚀性能受到关注，而钛合金在硼、锂介质中的缝隙腐蚀行为研究较少。本文采用微型腐蚀回路对钛合金TA16和TA17在硼、锂介质中的5000 h缝隙腐蚀行为进行了研究，获得了2种材料的缝隙腐蚀敏感性，并对试验后钛合金氧化膜成分和结构进行了分析。结果表明：在缝隙腐蚀模拟件上未观察到缝隙腐蚀现象，TA16、TA17在硼、锂介质中对缝隙腐蚀不敏感；模拟件缝隙内、外的氧化物存在一定差异，缝隙外的颗粒状微晶钛铁矿(FeTiO₃)与钛合金缝隙腐蚀无关。     

候选材料在650 ℃超临界水中的腐蚀行为研究

研究了3种候选材料（347、HR3C和In-718）在650 ℃、25 MPa去离子水中的均匀腐蚀行为,使用场发射扫描电镜（FEG-SEM）和能谱（EDS）观察了不同腐蚀时间的表面氧化膜形貌与合金元素分布,使用掠入射X射线衍射（GIXRD）分析了氧化膜相结构。结果表明,3种材料腐蚀失重均符合抛物线规律,347的失重为HR3C和In 718的40倍以上;3种材料氧化膜均以Ni(Cr, Fe) ₂O₄为主,In-718点蚀严重,347氧化膜明显脱落,HR3C氧化膜较均匀致密;高温超临界水中,提高合金的Cr含量有助于增强均匀腐蚀性能,添加Nb有损合金的点蚀抗力。     

锆合金氧化膜及基体中氧的扩散

锆合金氧化膜及基体中氧的扩散系数是锆合金腐蚀动力学中的重要参数,目前文献报道的氧在锆及氧化膜中的扩散系数数值差异较大。本文通过真空退火试验,得到不同温度下氧化膜中氧浓度分布,计算了氧在锆合金基体中的扩散系数;通过氧化膜的等效扩散模型,由腐蚀转折前的腐蚀增重曲线,估算锆合金氧化膜中氧的扩散系数,得到Zr-Sn-Nb合金基体中氧的扩散系数随温度的变化规律为D_Zr(cm²/s)=0.18exp(-180 000/RT);通过转折前的腐蚀增重曲线,估算得到氧化膜中氧的扩散系数随温度的变化规律为D_ox(cm²/s)=3×10^-7exp(-101 550/RT)。     

锆合金氧化膜的内应力计算

锆合金氧化膜中的内应力是锆合金腐蚀动力学中的重要影响因素,目前没有统一的方法得到氧化膜中内应力的大小,且数值差异较大。在传统的实验和理论方法的基础上,建立ZrO₂/Zr合金双层氧化弯曲几何模型,计算不同腐蚀状态下氧化膜中的内应力大小,得到内应力变化规律并分析其影响因素,为锆合金氧化膜内应力研究提供了一种较为可靠的方法。      

Systematic approach to predicting corrosion of zirconium alloys in the water coolant of nuclear reactors

A method of semiempirical prediction of corrosion of cladding zirconium alloys as a function of the operating conditions and composition is presented. The laws of thermodynamics and chemical kinetics of the oxidation reactions of a multicomponent zirconium alloy form the physicochemical basis of the computational method. The method is based on a model developed at the All-Russia Research and Design Institute of Integrated Power Technology for the corrosion of commercial and experimental zirconium alloys in water media under autoclave and reactor conditions taking account of the composition of the alloy and the water chemistry. The model is verified on the basis of independent tests performed on a series of zirconium alloys under autoclave and reactor conditions. The method developed makes it possible to predict the corrosion of fuel-element cladding made from zirconium alloys with fuel burnup to 80 MW·days/kg under the conditions of one- and two-phase VVER and RBMK coolant.     

CAP1400燃料组件用新锆合金研究

在Zr-Sn-Nb系合金的基础上添加微量合金元素Ge和Si等,采用真空电弧熔炼,制备了多种新锆合金。使用透射电子显微镜(Transmission electron microscope,TEM)对合金基体进行显微组织分析,分别通过堆外高压釜腐蚀试验、定氢分析仪和万能材料试验机对合金的腐蚀、吸氢和拉伸性能进行评估。结果表明,常规工艺处理后,SZA-4和SZA-6合金均发生了完全再结晶,第二相细小、均匀弥散分布在晶粒内和晶界上;SZA-4和SZA-6合金在三种水化学条件下均具有优良的耐腐蚀性能,SZA-6合金的耐腐蚀性能优于参考合金,SZA-4合金的耐腐蚀性能略优于SZA-6合金;SZA-6合金的吸氢性能略优于SZA-4合金;两种合金的拉伸性能满足设计要求。基于SZA-4和SZA-6合金优良的耐腐蚀、吸氢和力学性能,未来将有望用于CAP1400自主化燃料组件。     

316NG不锈钢在硼-锂溶液中的电化学腐蚀行为研究

利用电化学方法获得316NG不锈钢（316NG）在300℃、pH=5~8硼-锂溶液中的极化曲线和交流阻抗（EIS），并绘制相应水化学条件下的电位-pH图。结果表明:碱性条件下钝化区尤其是二次钝化区极化电流急剧减小，pH=7~8时阳极极化表现出3次钝化现象，偏碱性条件极化阻抗显著高于偏酸性和近中性条件，说明碱性条件下316NG表面钝化膜保护效果更佳。pH=5时电化学极化后样品表面主要生成Cr₂O₃和Fe₂O₃；碱性条件下（pH=6~8）样品表面氧化膜为分层结构:最外层为Fe₃O₄，随深度增加开始出现NiFe₂O₄，内层成分主要为FeCr₂O₄。随着电导率升高，溶液电阻、电荷传递电阻和钝化膜电阻均显著降低。依据极化曲线绘制的电位-pH图与文献结果相吻合。      

镍基合金825在超临界水中的腐蚀性能研究

研究了镍基合金825在550 ℃/25 MPa、600 ℃/25 MPa和650 ℃/25 MPa超临界水（SCW）中的应力腐蚀开裂敏感性,以及在超临界650 ℃/25 MPa、次临界290 ℃/15.2 MPa水中的均匀腐蚀性能。通过慢应变速率拉伸实验得到了相应的应力-应变曲线,结果表明,随温度的升高,825的机械强度和塑性逐渐下降;实验后试样的SEM图像表明,825在3种工况下的应力腐蚀开裂倾向大小关系为600 ℃＞550 ℃＞650 ℃。825在SCW条件下的腐蚀实验表明,其腐蚀增重大致符合幂函数生长规律;而其在次临界条件下的腐蚀增重变化却呈现出先减后增的特征。     

Electrochemical impedance spectroscopic study of passive zirconium

Spent, unreproccessed nuclear fuel is generally contained within the operational fuel sheathing fabricated from a zirconium alloy (Zircaloy 2, Zircaloy 4, or Zirlo) and is then stored in a swimming pool and/or dry storage facilities until permanent disposal in a licensed repository. During this period, which begins with irradiation of the fuel in the reactor during operation, the fuel sheathing is exposed to various, aggressive environments. The objective of the present study was to characterize the nature of the passive film that forms on pure zirconium in contact with an aqueous phase [0.1 M B(OH)₃ + 0.001 M LiOH, pH 6.94] at elevated temperatures (in this case, 250 °C), prior to storage, using electrochemical impedance spectroscopy (EIS) with the data being interpreted in terms of the point defect model (PDM). The results show that the corrosion resistance of zirconium in high temperature, de-aerated aqueous solutions is dominated by the outer layer. The extracted model parameter values can be used in deterministic models for predicting the accumulation of general corrosion damage to zirconium under a wide range of conditions that might exist in some repositories.     

Transmission electron microscopy examination of oxide layers formed on Zr alloys

A transmission electron microscopy investigation was performed on oxides formed on three zirconium alloys (Zircaloy-4, ZIRLO and Zr-2.5Nb) in pure water and lithiated water environments. This research is part of a systematic study of oxide microstructures using various techniques to explain differences in corrosion rates of different zirconium alloys. In this work, cross-sectional transmission electron microscopy was used to determine the morphology of the oxide layers (grain size and shape, oxide phases, texture, cracks, and incorporation of precipitates). These characteristics were found to vary with the alloy chemistry, the corrosion environment, and the distance from the oxide/metal interface. These are discussed and used in conjunction with observations from other techniques to derive a mechanism of oxide growth in zirconium alloys.     

基于Fe-H2O、Cr-H2O、Zr-H2O体系的高温电位-pH理论计算

本文从热力学角度出发,利用能斯特方程进行计算,研究了423、573 K温度条件下Fe-H₂O体系、Cr-H₂O体系及Zr-H₂O体系的电位-pH图（E-pH图）,从理论上说明了铁、铬、锆3种反应堆结构材料的主要组成元素在高温高压水中,受电位、pH影响的腐蚀行为倾向,为后续在堆内水化学环境中进行材料电化学腐蚀试验研究以预防材料的腐蚀、延长材料的使用寿命提供了数据参考。      

Hydrazine and Hydrogen Co-injection to Mitigate Stress Corrosion Cracking of Structural Materials in Boiling Water Reactors, (III)

The effects of hydrazine on the corrosion of Zircaloy-2 were examined in supercritical water. Hydrazine could be used as a reducing agent to control the corrosive environment for the coolant of boiling water reactors (BWRs). Before the corrosion test, the applicability of supercritical water for corrosion testing of zirconium alloys was studied. Supercritical water was found to be a useful solvent for testing corrosion based on the following facts: (1) the weight gain of Zircaloy-2 in supercritical water followed the same cubic law with the activation energy of 133 kJ/mol as that in water and steam did, and (2) the weight gain in supercritical water at 723 K and 24.5 MPa was more than 8 times greater than that in water at 561 K and 7.8 MPa depending on immersion time. The corrosion tests in supercritical water at 723 K and 24.5 MPa under γ-irradiation for 1,000 h were conducted to study the effects of adding nitrogen and ammonia on the corrosion of Zircaloy-2. Nitrogen and ammonia are decomposed products of hydrazine. The measured weight gain, oxide film thickness, and amount of hydrogen pick-up had slight differences between cases with and without the additives. Based on these data, it was concluded adding hydrazine to the coolant has little influence on the corrosion of Zircaloy-2 used in BWR cores.