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奥氏体不锈钢应变电化学过程的控制研究
牛林
学位类型博士
导师曹楚南
1998
学位授予单位中国科学院金属腐蚀与研究所
学位授予地点中国科学院金属腐蚀与研究所
关键词奥氏体不锈钢 电化学参数 塑性应变 应力腐蚀裂纹
摘要本论文从水溶液体系应力腐蚀开裂的电化学特征出发,着重研究各种因素如有机添加剂、电位扰动、进一步理解奥氏不锈钢的应力腐蚀开裂机理,从而达到在一定程度上控制金属应变电化学过程的目的。考虑反应速度的浓度效应和温度效应,分别研究了酸性氯化物溶液浓度和温度对奥氏体不锈钢SCC敏感性的影响,以确定敏感的SCC体系。通过添加一系列有机含氮化合物和炔氧化合物、研究它们对奥氏体不锈钢SCC敏感性影响的差异,选择了两种明显降低SCC敏感性的缓蚀剂。利用慢应变速率技术、扫描电镜并结合电化学极化曲线和阻抗方法,对321奥氏体不锈钢在酸性氯化物溶液中的应力腐蚀开裂敏感性以及相关的电化学参数进行了动态实时测量,在影响应力腐蚀开裂的断裂力学特征与电化学参数之间建立了联系。研究了苯并三氮唑和丙炔醇对该体系应力腐蚀开裂的缓蚀作用,发现苯并三氮唑和丙炔醇能抑制321不锈钢在酸性氯化物溶液中的应力腐蚀开裂敏感性。它们对于321不锈钢在酸性氯化物溶液中腐蚀的缓蚀作用主要是抑制腐蚀的阳极过程,缓蚀作用来自覆盖金属表面活性位置的效应。通过慢拉伸过程中的阻测量可以颢金属表面的反应活性变化。结果表明,拉伸试样的表面活性挖地随延伸率直线增大,而缓蚀剂使这种增大明显减缓。稳定的金属表面络合物抑制了腐蚀的阳极反应产物(MOH)_(ad)和(MCI)_(ad)的形成,从而起到缓蚀作用。在慢应变速率拉伸过程中通过恒电位、电位扫描和阶跃的扰动极化方式,研究了321奥氏体不锈钢在酸性氯化物溶液中的应力腐蚀开裂敏感性及断裂特征。结果表明,阳极极化促进321不锈钢在酸性氯化物溶液中的应力腐蚀开裂,而阴极极化抑制过程的发生与发展,因此该体系的应力腐蚀开裂符合阳极溶解机理。阶跃频率高的循环电位阶跃极化造成的应力腐蚀。氢致开裂起主导作用。在慢拉伸过程中对金属施加徨电位扫描或电位阶跃极化时,扫描速度越慢(稳态),或阶跃频率超高,均能使材料断裂敏感性提高。相同电位范围内,高频率循环电位阶跃比循环电们扫描导致更低的材料断裂延伸率。这一工作为研究电位因素对应力腐蚀开裂的影响开拓了一个新的领域。经滑移-溶解-再钝化模型为基础,推导得出了应力腐蚀裂纹扩展速度与裂尖应变速度和电位之间的理论关系。理论计算表明,在裂纹增长速度与裂尖应变速度的关系曲线中有两个特征区域。在区域1随裂尖应变速度增加而增加。在区域2不随裂尖应变速度变化。用SSRT技术测量了304L不锈钢的裂纹增长速度。当电位控制在区域2的阳极区时,理论计算值与区域2的得到的SCC速度比较一致。该工作为力学和环境因素影响应力腐蚀裂纹扩展速度的实验研究提供了理论指导。研究了弹、塑性应变对奥氏体不锈钢学行为的影响,从热力学送气和学参数的关系出发,分析了不锈钢的应变学行。静态无载荷试样和动态慢拉伸试样的电化学行为明显不同。不同形变阶段金属力学化学活性存在明显差别。弹性应变只对金属阳极溶解过程产生作用,而不影响阴极过程。形变强化和位错塞积群的形成对金属的力学化学活性起着决定性的作用。
其他摘要On the basis of the electrochemical characteristic of stress corrosion cracking in aqueous solution system, the effects of various environmental and mechanical parameters, such as organic additives, potential perturbation, temperature and strain rate etc., on the susceptibility of stress corrosion cracking for austenitic stainless steel have been studied. The purpose is to further understand the stress corrosion cracking mechanisms and to control the metallic straining electrochemical processes. From the point of view of concentration and temperature on reaction rate, the effects of concentration and temperature of the acidic chloride solution on the susceptibility of stress corrosion cracking have been studied, and the systems susceptible to stress corrosion cracking were determined. The inhibitors action of a series of organic compounds on the susceptibility has been compared. Two inhibitors which markedly decrease the stress corrosion cracking susceptibility were selected. The SCC susceptibility of 321 austenitic stainless steel in acidic chloride solution and the inhibiting effect of both benzotriazole(BTA) and propargyl alcohol(PA) on stress corrosion and general corrosion were studied by slow strain rate testing(SSRT), combined with transient current measurements during intermediate strain rate testing (ISRT) under potentiostatic condition, scanning electron microscopy(SEM), potentiodynamic polarization measurements and in situ electrochemical impedance spectroscopy(EIS) measurements. The relationships between the mechanical properties and electrochemical parameters which affected the stress corrosion cracking have been established. The results indicated that the inhibiting action of BTA and PA can be attributed to their adsorption and inhibiting the anodic dissolution of the metal by the effect of blocking the active sites on the metal surface. The change of reactivity on the metal surface can be monitored by the impedance measurements during SSRT. The results showed that the reactivity of the surface of tensile specimens increased directly proportional to the strain, while the addition of inhibitors obviously retarded the increase rate. By applying constant potential polarization, potential sweep and step perturbation polarization during SSRT, the SCC susceptibility and fracture characteristic of type 321 austenitic stainless steel in acidic chloride solution have been studie. The results indicated that the anodic polarization promoted the SCC of the stainless steel, whereas cathodic polarization inhibited the initiation and propagation of the cracks. Therefore, the SCC of this metal/environment system seems to follow anodic dissolution mechanism. However, hydrogen played a decisive role in the SCC of this metal/environment system under high frequency cyclic potential step perturbation. When cyclic potential scan or cyclic potential step was applied to the metal specimen during SSRT, the slower the scan rate was(quasi-steady state), or the higher the step frequency, the higher the fracture susceptibility. Within the same polarized potential ranges, fracture elongation in cyclic potential step was lower than that in cyclic potential scan. This work opened up a new field to study the effect of potential factor on the SCC. Based on the model of slip-bare metal dissolution-repassivation and crack-tip strain analysis, a theoretical equation of stress corrosion cracks growth rate as a function of crack-tip strain rate and potential for 304L stainless steel in acidic chloride solution was deduced and proposed. The theoretical prediction showed that there are two regions in the curve of crack growth rate with the crack-tip strain rate. In region 1, the crack growth rate increased with increasing crack-tip strain rate. In region 2, the crack growth rate was independence of the crack-tip strain rate. The crack growth rate of 304L stainless steel in acidic chloride solution has been measured by slow strain rate testing(SSRT) technique. The theoretical calculation was consistent with the experimental SCC growth rate in region 2 when potential was controlled in anodic region. This work provided a theoretical guideline for the experimental study of crack growth rate influenced by strain rate at crack tip and potential. The effect of elastic and plastic strain on the electrochemical behavior of austenitic stainless steel has been studied. Based on the relationships between thermodynamic criteria and electrochemical parameters, the straining electrochemical behaviors of stainless steel have been analyzed. The results showed that the changes of open circuit potential and EIS with time for unstressed specimen were obviously different from those of dynamic slow tensile specimen. The elastic strain only affected the anodic dissolution process of metal and had no effect on the cathodic process. The strengthened deformation and the formation of dislocation block played a key role in the mechanical-chemical effect.
页数111
语种中文
文献类型学位论文
条目标识符http://ir.imr.ac.cn/handle/321006/17645
专题中国科学院金属研究所
推荐引用方式
GB/T 7714
牛林. 奥氏体不锈钢应变电化学过程的控制研究[D]. 中国科学院金属腐蚀与研究所. 中国科学院金属腐蚀与研究所,1998.
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