Degradation of corrosion resistance of Zircaloy-4 in LiOH aqueous solution

To investigate the degradation of corrosion resistance of Zircaloy-4 in LiOH aqueous solution, SIMS (secondary ion mass spectrometry) analysis was performed to examine the profiles of Li+, K+, and OH- in oxide layers formed in the same concentration (0.1 mol/L) LiOH and KOH solutions. Even though the oxide layers have an equal thickness, the penetration depth of K+ is shallower than that of Li+, and the penetration depth of OH- corroded in KOH solution is also shallower than that corroded in LiOH solution. It shows that the diffusion of OH- into oxide layer is accompanied by the corresponding cation. The difference of degradation effect of LiOH and KOH solutions on the corrosion resistance of Zircaloy-4 was discussed.     

LiOH水溶液加速Zr-4合金腐蚀的研究

将Zr-4合金样品分别放在盛有350℃，0．1mol／L的LiOH和KOH水溶液的高压釜中进行腐蚀，当2种样品的氧化膜厚度相同时，用二次离子质谱仪(SIMS)测量Li^ ,K^ 和OH^-在氧化膜剖面上的浓度分布，发现进入氧化膜的Li^ 比K^ 深而且记数强度高，同时在LiOH水溶液中腐蚀的样品，其氧化膜中OH^-的强度也比在KOH水溶液中腐蚀的样品高，这表明OH^-在氧化膜中的分布和扩散与其对应的阳离子有关。根据以上结果讨论了Zr-4合金在LiOH水溶液中耐腐蚀性能降低的原因。     

Detrimental role of LiOH on the oxide film formed on Zircaloy-4

To understand the degradation behavior of Zircaloy-4 corroded in LiOH aqueous solution, X-ray diffraction was performed to analyze the crystal structure of Zircaloy-4 oxide formed in three different media. Second ion mass spectrometry (SIMS) was utilized to measure the penetration of Li⁺ and OH⁻ into the oxide film when Zircaloy-4 is exposed in LiOH aqueous solution. It was found that the SIMS depth profile of OH⁻ in the oxide film is in accord with that of Li⁺, which indicates that there exists OH⁻ in the oxide film. Based on the results, it is put forward that OH⁻ diffuses faster than O⁻² in the oxide films, which can enhance the corrosion rate of Zircaloy-4 and the transformation from tetragonal zirconia (t-ZrO₂) to monoclinic zirconia (m-ZrO₂). OH⁻ plays a detrimental role on the oxide film formed on Zircaloy-4.     

Stress corrosion cracking of zirconium and Zircaloy-4 in halide aqueous solutions

Zirconium and Zircaloy-4 in 1 M NaCl, 1 M KBr and 1 M KI aqueous solutions were found to be susceptible to stress corrosion cracking (SCC) only at potentials above the pitting potential. In all the tested systems the following steps were found: first electrochemical breakdown of the passive film, followed by intergranular attack due to anodic dissolution assisted by stresses; and finally a fast transgranular propagation. This last step was identified as the “true” SCC process. The analysis of the possible mechanisms involved during this process led to the conclusion that the surface-mobility SCC mechanism can be used to explain the experimental results found in the present work.     

不同介质对Zr-4合金氧化膜结构的影响

为了解释锆合金在LiOH水溶液中耐腐蚀性能降低的原因，将3组粉状Zr-4合金样品分别放在500℃空气中、500℃过热蒸汽中和350℃的0．1mol／L LiOH水溶液中进行腐蚀，当氧化膜厚度约为1．5gm时，用XRD分析这3组样品的晶体结构。将一片状Zr-4合金样品在350℃的0．04mol／L LiOH水溶液中腐蚀2d，用SIMS检测Li^ 和OH^-在氧化膜剖面上的分布。根据实验结果提出OH^-在氧化膜中比O^-2扩散速度快，使t—ZrO2加速向m-ZrO2转变，导致Zr-4合金腐蚀速度加快。     

Plasma electrolytic oxidation and corrosion protection of Zircaloy-4

The compositions and morphologies of coatings formed by plasma electrolytic oxidation (PEO) on Zircaloy-4 in silicate electrolyte, using an AC current regime, have been determined for a range of formation times. The coatings consist of zirconia with incorporated silicon species, with the distributions of coating species related to the types of discharges. Potentiodynamic polarization in 6 M nitric acid at 100 °C indicated that the corrosion resistance is mainly provided by the thin barrier layer next to the substrate.     

Effect of Surface State on Nodular Corrosion Resistance of Zircaloy-4 Alloy

The effect of surface state on the nodular corrosion resistance of Zircaloy-4 alloy was investigated in superheated steam at 500 °C/10.3 MPa by autoclave tests. The microstructures of oxide films on the corroded specimens were observed by TEM and SEM. The results indicate that surface strained layer delays the appearance of nodular spots on the specimen surfaces and improves the nodular corrosion resistance. The columnar grains orientation of the oxide films formed on the specimens with surface strained layer was more consistent than that on the specimens without surface strained layer when a comparison was made on the same orientation of the grain surfaces. Such a kind of oxide microstructure formed on the specimens with surface strained layer can hinder the diffusion of oxygen ions along the grain boundaries and delay the growth of oxide films, therefore retard the formation process of nodular spots. This indicates that the microstructure of the initial oxide films has an important influence on the subsequent growth of the oxide films.     

Zr-4合金氧化膜显微组织与疖状腐蚀机制研究

经过不同热处理后的几种Zr-4合金样品,在550 ℃/25 MPa超临界水中腐蚀时都不同程度地发生了疖状腐蚀.用扫描电镜研究了氧化膜的显微组织.提出Zr-4合金发生疖状腐蚀的机制:Zr-4合金腐蚀生成的部分氧化膜具有微孔和微裂纹少、比较致密的特性,生长到一定程度后,在应力作用下,局部薄弱区发生平行于O/M界面的开裂并不断扩大,造成表层氧化膜破裂,腐蚀介质水进入裂纹中,形成有效的供氧源,使局部腐蚀加速,发生不均匀腐蚀,这种不均匀腐蚀在适当条件下发展成疖状腐蚀.氧化膜局部产生了可向O/M界面提供充足氧的直接供氧源,是引发锆合金产生疖状腐蚀的最密切因素.所有与发生疖状腐蚀有关的其它因素,如合金元素、第二相的大小和分布、氧化膜生长各向异性等,都是通过对氧化膜相关性质的影响而发生作用.     

Analysis of microstructure and corrosion behavior of laser surface alloyed zircaloy-4 with niobium

The influence of laser surface alloying (LSA) with niobium (Nb) on the corrosion and mechanical properties of Zircaloy-4 was examined by potentiodynamic polarization testing in a chloride solution at 80°C and microhardness testing. The results are discussed with the structural and compositional variations in the LSA layer determined by X-ray diffraction (XRD), a scanning electron microscope (SEM) and a wavelength dispersive spectrometer (WDS). The LSA on Zircaloy-4 precoated with Nb produced a Nb-alloyed layer 200~300 μrn thick with 1.3~2.5 wt.% Nb, depending on the laser beam power. The alloyed layer was composed of a mixed structure of α-Zr and β-Zr phases with the (β-Zr phase increasing with the Nb content in the alloyed layer. The LSA with Nb increased the microhardness of Zircaloy-4, which was attributed primarily to the grain-size refinement of rapid cooling and, also, to the solid solution hardening with Nb. The resistance to the localized corrosion of Zircaloy-4 in a chloride solution significantly improved through LSA with Nb, which was attributed to the combined effects of the fine rapidly cooled microstructure and to the Nb alloying.     

Zr-4合金疖状腐蚀与晶粒取向的关系

Zr-4大晶粒样品在高压釜中经过500℃/10.3 MPa过热蒸气腐蚀,研究了不同晶粒表面上氧化膜厚度与晶粒取向的关系。结果表明:样品腐蚀时氧化膜的生长表现出明显的各向异性特征,晶粒表面取向在(10■0)和(11■0)之间时,氧化膜生长速率最快,腐蚀3 h后最先出现疖状腐蚀斑,当腐蚀时间延长至30 h时,晶粒表面的极点在反极图中间位置的那些晶粒表面上也逐渐产生疖状腐蚀斑,而晶粒表面取向在(0001)晶面附近时氧化膜生长速率最慢,即使腐蚀30 h也没有产生疖状腐蚀斑。结果表明:当第二相大小和分布以及Fe,Cr合金元素在α-Zr中的固溶含量相同的情况下,Zr-4合金的耐疖状腐蚀性能与样品表面的晶粒取向有着密切的关系。     

固溶时效处理对Mg-4Sm-3Gd-0.5Zr合金显微组织和耐蚀性能的影响

利用光学显微镜、X射线衍射仪和扫描电镜等方法研究了固溶时效处理前后Mg-4Sm-3Gd-0.5Zr合金(质量分数,%)的显微组织、物相组成和腐蚀形貌,并在质量分数为3.5%的NaCl溶液中进行了静态失重和电化学测试。结果表明,铸态Mg-4Sm-3Gd-0.5Zr合金由α-Mg基体和沿晶界分布的粗大网状共晶相Mg₄₁Sm₅和Mg₅Gd组成,固溶时效处理并没有改变共晶相的种类,但网状共晶组织消失,并且晶内有大量细小弥散的第二相析出,晶界更加清晰。试验合金采用525 ℃×8 h固溶+225 ℃×8 h时效处理后,腐蚀速率从0.185 mg·cm^-2·h^-1降低至到0.116 mg·cm^-2·h^-1,自腐蚀电流密度从1.599×10^-4A·cm^-2降低到0.924×10^-4 A·cm^-2,耐蚀性能明显提高。     

Electrochemical and XPS studies and the potential scan rate dependent pitting corrosion behavior of Zircaloy-2 in 5% NaCl solution

Electrochemical studies of Zircaloy-2 in 5% NaCl solution were carried out using polarization and electrochemical impedance spectroscopy (EIS). Scan rate dependent pitting behavior of Zircaloy-2 was observed when polarization experiments were carried out at different scan rates (5 mV/min, 50 mV/min and 500 mV/min). Polarization resistance, double layer capacitance, and the thickness of passive film were calculated from the EIS study. The slope of the Bode plot in the capacitive region showed non-ideal behaviour, suggesting formation of pits. A distribution of chloride concentration was seen at the surface of the electrode when the test solution was sampled from different parts of the sample surface and analyzed for chloride. Inclusion of chloride ions in the passive film was observed from the XPS study and the chloride concentration increases with the higher anodic polarization. The outermost layer of the passive film was rich in hydroxide and oxy-hydroxide. A bi-layer passive film structure on the alloy surface is proposed.     

Zr-4合金表面变形纳米结构TEM研究

利用透射电镜对Zr-4合金表面进行高能喷丸处理所致纳米结构的微观组织演变特征进行了研究.结果表明,经过喷丸处理变形后,Zr-4合金表面形成一层平均晶粒尺寸为几纳米至十几纳米的致密纳米层,随着离表面距离的增加,晶粒尺寸也不断增加.通过对Zr-4合金的变形行为以及微观结构组织演变的观察和分析,探讨了纳米晶的形成机制.     

Zr-4合金的阳极氧化膜与高压釜预生膜对比研究

利用电化学极化曲线测量、氧化增重测量、往复式摩擦磨损实验,对分别通过阳极氧化和高压釜氧化生成的2种不同Zr-4合金表面氧化膜的耐腐蚀、耐高温氧化和抗摩擦性能进行测试和对比评价.实验表明,2种氧化膜都有效地改善了Zr-4合金的性能（耐腐蚀,耐高温氧化等）,它们对Zr-4合金的改善程度相近.XRD,XPS,RBS,SEM等方法分析表明,阳极氧化膜厚度约1μm,分为疏松水合层和ZrO2致密层2部分,ZrO2由四方相和单斜相组成;高压釜预生膜厚度约0.9μm,分为最外H2O层、疏松水合层和ZrO2致密层3部分,ZrO2只以单斜相存在.研究结果为现行核工业中对Zr-4合金的预处理方法提供了一个新的思路.     

Fretting wear behavior of nitrogen implanted Zircaloy-4 alloy

1　ＩＮＴＲＯＤＵＣＴＩＯＮＺｉｒｃａｌｏｙ 4ｉｓｃｏｍｍｏｎｌｙｕｓｅｄｆｏｒｆｕｅｌｃｌａｄｄｉｎｇｏｆｐｒｅｓｓｕｒｅｄｗａｔｅｒｒｅａｃｔｏｒｓ (ＰＷＲ ) ,ｂｅｃａｕｓｅｉｔｈａｓａｌｏｗｔｈｅｒｍａｌｎｅｕｔｒｏｎｃｒｏｓｓｓｅｃｔｉｏｎ ,ｅｘｃｅｌｌｅｎｔｃｏｒｒｏｓｉｏｎｒｅｓｉｓｔａｎｃｅ,ａｄｅｑｕａｔｅｓｔｒｅｎｇｔｈａｎｄ ｇｏｏｄｆｏｒｍａｂｉｌｉｔｙ .Ｉｎａｎｕｃｌｅａｒｒｅａｃｔｏｒｈｅａｔｇｅｎｅｒａｔｅｄｉｎｔｈｅｆｕｅｌｅｌｅｍｅｎｔｉｓｅｘｔｒａｃｔｅｄｂｙｐｕ…     

激光表面处理对Zr－4合金板材疖状腐蚀的影响

研究了几种激光表面处理工艺对不同状态的Ｚｒ－４合金板材泡疖腐蚀的影响。实验结果表明：激光表面处理可以显著提高Ｚｒ－４合金抗疖状腐蚀性能；激光表面处理前Ｚｒ－４合金板材的状态（消除应力退火态、再结晶退火态、冷加工态）对激光表面处理后板材的疖状腐蚀性能的影响不明显     

激光表面处理对Zr—4合金板材疖状腐蚀的影响

研究了几种激光表面处理工艺对不同状态的Ｚｒ－４合金板材泡疖腐蚀的影响。实验结果表明：激光表面处理可以显著提高Ｚｒ－４合金抗疖状腐蚀性能；激光表面处理前Ｚｒ－４合金板材的状态（消除应力退火态、再结晶退火态、冷加工态）对激光表面处理后板材的疖状腐蚀性能的影响不明显     

Zr-4合金氧化膜的显微组织研究

Zr-4合金样品在高压釜中经过360℃/18.6 MPa高温去离子水腐蚀395天后,用扫描电镜观察了氧化膜的断口形貌,用高分辨透射电镜观察了氧化膜不同深度处的显微组织和晶体结构,研究了氧化膜的显微组织在腐蚀过程中的演化过程。氧化膜的晶体结构非常复杂,在靠近金属基体处除了稳定的单斜(m)晶体结构外,还存在非晶、立方(c)和四方(t)等亚稳相,晶体中还生成了很多缺陷。m/t和m/c晶体之间存在共格关系,满足(001)m//(110)t,(010)m//(1-10)t;以及(001)m//(002)c,(010)m//(020)c的取向关系。氧化膜中的晶体缺陷在应力、温度和时间作用下会发生扩散,并在氧化锆晶界上凝聚生成孔隙,弱化了晶粒之间的结合力并引起显微组织的演化。在内应力的作用下,孔隙之间的扩展和连结发展成微裂纹,氧化膜变得比较疏松,导致了耐腐蚀性能的变化和腐蚀加速。讨论了各种影响显微组织演化因素之间的关系,氧化膜显微组织的演化过程是不可避免的,寻找并控制能够延缓显微组织演化过程的因素是提高锆合金耐腐蚀性能的有效途径。     

Zr与固溶处理对Mg-1.5Zn-0.5Ca-0.8Ce合金耐腐蚀性能的影响

以Mg-1.5Zn-0.5Ca-0.8Ce合金作为研究对象,分别进行合金化和固溶处理,研究Zr的添加及固溶处理对镁合金Mg-1.5Zn-0.5Ca-0.8Ce耐腐蚀性能的影响,并探究合金化和热处理对镁合金耐腐蚀性能影响机理.结果表明:Zr的加入和固溶处理均有效提高了材料的耐腐蚀性,其中Mg-1.5Zn-0.5Ca-0....