扫描微电极法测量金属微区腐蚀电位电流分布——Ⅰ 扫描微电极测量系统

扫描微电极法测定金属微区腐蚀电位及电流密度分布是研究金属局部腐蚀的重要手段。本文在评述了目前利用扫描电极测量金属表面电位分布的各种方法基础上,建立了新的实验系统。文中阐述了本方法的电化学理论基础,提出了获得外径低达数微米且具有良好电化学性能的 Ag/igCl参比电极,设计制造了微参比电极在样品表面附近自动扫描的机械装置,研制了具有高输入阻抗,强抗干扰能力的电位分布测定仪器,还介绍了测量电流密度分布等方法。本实验系统具有较高的测量精度,整套装置简易可行,能满足测量实际腐蚀体系的要求。     

局部腐蚀微区电化学测试技木的研究

本文研究了KCl-Ag/AgCl微参比电极、微Cl~-选择电极和钨微电极的制备与性能,初步的结果表明:微参比电极具有稳定的电位及较小的温度系数;在没有其它卤离子存在的情况下,微Cl~-电极的电位与logαci~-有良好的线性关系,溶液酸度的改变和其它离子的存在对这一线性关系影响不大;在酸性条件下,在NaCl或MgCl_2溶液中,钨微电极具有稳定的电位,这一电位与溶液pH值有良好的线性关系,而且与溶液浓度无关,当溶液中存在的其他离子浓度不高时,对上述线性关系也没有影响。将上述微电极应用于缝隙腐蚀和应力腐蚀研究,得到一些现场跟踪测量的结果,这些结果可与其他作者用其它方法所获得的结果相印证。     

腐蚀疲劳裂纹尖端电化学行为的研究

采用微电极体系和试样背后打孔技术，对３００Ｍ超高强度钢在３．５％ＮａＣｌ水溶液中腐蚀疲劳裂纹尖端微区溶液电化学行为进行研究，在极化和无极化条件下分别测试裂化溶液的电位△Ｅ和ｐＨ值的变化，结果发现，无极化条件下，裂尖ｐＨ下降，电位上升，裂尖前沿电位和ｐＨ值随裂化分布不均匀，在极化条件下，裂尖电化学特征随极化电位变化而表现不同，基于裂尖电化学行为规律，对腐蚀疲劳裂放展规律进行解释。     

剥离PE防腐层破损点下钢质管线的阴极保护

基于长输管线三层聚乙烯(3PE)防腐层失粘剥离现场开挖调查的情况,构建剥离防腐层下管道表面微区环境腐蚀模拟研究实验装置,研究华南酸性土壤环境条件剥离防腐层下管体表面的阴极保护和微区环境特征,采用微电极技术监测剥离区管线钢表面的局部电位和环境p H值的变化。结果表明,剥离区管线的有效保护距离随阴极保护电位负移而增加;在高电阻率酸性土壤环境中,剥离防腐层下的阴极保护仅限于破损点附近,剥离区深处管体处于自腐蚀状态;剥离防腐层下阴极保护有效性及其屏蔽程度可由剥离防腐层下微区溶液p H值判定。     

W-Ni-Fe合金微观组织与冲击性能研究

在不同混料时间相同烧结工艺下制备了两件钨合金。采用金相显微镜、扫描电子显微镜以及能谱技术对两件钨合金的微观组织以及成分进行了表征,并对其进行了冲击性能测试。微观组织观察表明两件钨合金晶粒形貌、尺寸差别不大,钨颗粒晶粒尺寸介于10⁵0μm。微区成分测试表明两件样品钨颗粒微区成分基本相同,而粘结相区差别较大。混料时间较长的钨合金粘结相区W元素含量较高,Ni、Fe、Co元素含量较低;而混料时间较短的钨合金微区成分正好相反。冲击韧性测试表明混料时间较长的钨合金冲击韧性明显降低。冲击断口显示混料时间较长的钨合金粘结相区撕裂棱较短,而混料时间较短的钨合金粘结相区撕裂棱较长。     

X80管线钢焊接接头的模拟重构及电偶腐蚀行为表征

利用离散、热模拟处理和模块化重构的微电极阵列对X80管线钢焊接接头进行模拟重构,并联用经典电化学测试技术和微电极阵列测试技术研究了X80钢模拟焊接接头及孤立分区在CO2饱和的NACE溶液中的电偶腐蚀行为。结果表明,在NACE溶液中,孤立的细晶区开路电位最正,腐蚀倾向小,而焊缝的电位最负,腐蚀倾向大;各部分的腐蚀电流密度大小关系为:部分相变区细晶区粗晶区母材焊缝;模拟X80钢焊接接头组织中,粒状贝氏体与铁素体的混合组织的开路电位最正,极化电阻最小。当各组成部分耦合后,模拟焊接接头中的焊缝和粗晶区作为主要阳极,腐蚀加速;细晶区和部分相变区作为主要阴极,腐蚀减缓;邻近热影响区的母材微电极以阳极性电流为主,远离热影响区的母材微电极以阴极性电流为主。提出电偶腐蚀强度因子用于表征电偶腐蚀强度。孤立的焊缝区的自腐蚀电流密度虽最小,但在电偶腐蚀的加速作用下,焊缝与粗晶区作为模拟焊接接头的薄弱环节,首先因腐蚀而失效。     

腐蚀疲劳裂纹尖端电化学行为的研究

本文采用微电极体系和试样背面打孔技术,对300M超高强度钢在3.5%NaCl水溶液中腐蚀疲劳裂纹尖端微区溶液电化学行为进行研究。在极化和无极化条件下分别测试裂尖溶液的电位△E和pH值的变化。结果发现,无极化条件下,裂尖pH值下降,电位上升,裂尖前缘电位和pH值随裂尖扩展而分布不均匀,在极化条件下,裂尖电化学特征随极化电位变化而表现不同。基于裂尖电化学行为规律、对腐蚀疲劳裂纹扩展规律进行解释。     

高强铝合金裂纹尖端在3.5%NaCl溶液中的微区电化学特性

采用毛细管微电极测试方法、扫描Kelvin探针技术和数值分析方法,对2024-T351高强铝合金裂纹尖端在3.5%NaCl溶液中的微区电化学特性和腐蚀行为进行了研究.结果表明,裂纹尖端的腐蚀电位较远离裂纹尖端的基体位置更负,裂纹尖端处的电化学活性明显增加.在外加应力的作用下,裂纹尖端处表面氧化膜的厚度减薄,其稳定性和保护性变弱.裂纹尖端处优先发生阳极溶解,浸泡24 h后在裂纹尖端处出现腐蚀产物的堆积.由于腐蚀电位和电化学活性的差异,在裂纹尖端(阳极)和远离裂纹尖端的基体(阴极)之间可形成电偶对,进一步促进裂纹尖端局部区域内腐蚀过程的进行.     

高强铝合金裂纹尖端在3.5%NaCl溶液中的微区电化学特性

采用毛细管微电极测试方法、扫描Kelvin探针技术和数值分析方法,对2024 T351高强铝合金裂纹尖端在3.5%NaCl溶液中的微区电化学特性和腐蚀行为进行了研究.结果表明,裂纹尖端的腐蚀电位较远离裂纹尖端的基体位置更负,裂纹尖端处的电化学活性明显增加.在外加应力的作用下,裂纹尖端处表面氧化膜的厚度减薄,其稳定性和保护性变弱.裂纹尖端处优先发生阳极溶解,浸泡24 h后在裂纹尖端处出现腐蚀产物的堆积.由于腐蚀电位和电化学活性的差异,在裂纹尖端(阳极)和远离裂纹尖端的基体(阴极)之间可形成电偶对,进一步促进裂纹尖端局部区域内腐蚀过程的进行.     

电化学方法和丝束电极在局部腐蚀研究中的应用

综述了常规电化学方法和扫描微探针技术的测试原理和应用现状,重点探讨了丝束电极在金属不同类型局部腐蚀研究中的应用。丝束电极技术能够获得不同位置点腐蚀电位、电流密度,从而获得界面等电位图和电流分布图等信息。丝束电极技术与常规电化学方法和微区扫描探针技术联合应用,可克服丝束电极技术只能测量宏观尺度电流电位分布不均的缺点,扩展丝束电极技术的研究范围。     

CO2局部腐蚀测试及评价方法研究

局部腐蚀测试及评价方法一直是困扰腐蚀界的一大难题.本文针对CO2局部腐蚀的特征,研发了一种测量CO2局部腐蚀蚀孔大小的测试装置.它能准确测定蚀孔的有关几何参数,定量评定局部腐蚀的破坏程度;并且根据CO2局部腐蚀的特征,建立一种评定CO2局部腐蚀的方法,分别采用平均最深腐蚀孔深度和计算腐蚀孔体积的方法对CO2腐蚀的3种局部腐蚀形态进行评价;通过对CO2点蚀的测量及评价,验证了局部腐蚀测试装置的有效性和评价方法的准确性.     

The corrosion behavior of hard W–C system chemical vapor deposition layers in HCl and H<Subscript>2</Subscript>S aqueous solutions

The results of a study of anticorrosion performance of low carbon containing tungsten-based hard chemical vapor deposition (CVD) coatings with microhardness from 5 to 17 GPa are presented in this work. Their high corrosion resistance in hydrochloric acid and hydrogen sulfide solutions is noted, as their corrosion rate does not exceed 6 μm per year in hydrochloric acid solution and 15 μm per year in hydrochloric acid solution saturated with hydrogen. The open circuit potentials correspond to tungsten (VI) oxide formation so the corrosion process supposedly runs in passive state. Taking into account the low porosity of the CVD layers, which is lower than 0.02%, these coatings are promising for application as anticorrosion wear-resistant coatings for chemical and oil and gas apparatus responsible units.     

稀土对电沉积Ni-W合金组织和性能的影响

通过电沉积技术在45~#钢基体表面上制备了Ni-W-Er_2O_3复合镀层,利用SEM、EDS及XRD等分析了镀层的组织结构和表面形貌,采用磁性厚度仪、显微硬度计、电化学工作站等测试手段对合金镀层的厚度、显微硬度以及耐蚀性能进行了精确测定。结果表明:所制备的合金镀层组织致密,晶粒细小,未见有明显缺陷存在,镀层与基体结合良好;稀土氧化物Er_2O_3的加入可以保证基体材料获得高硬度、高W含量且具有良好耐蚀性能的Ni-W-Er_2O_3复合镀层,且当添加量为16 g/L时,其综合性能最优。     

Elektrochemische Meßmethoden zur Untersuchung der Spannungs- und Schwingungsrißkorrosion

Electrochemical measuring methods for studying stress-corrosion cracking and corrosion fatigue An apparatus is described for the investigation of local corrosion phenomena with simultaneous static and dynamic loading. The apparatus enables measurements to be made of potential variations in time, interdependance of current density and potential, and current density variation at constant potential. It is shown that stress corrosion cracking of carbon steel in boiling Ca(NO₃)₂, solution and of soft iron in NaOH is a clear local corrosion process. Analogous results are obtained with austenitic stainless steel in an activating medium. Corrosion fatigue of passive austenitic steels can be produced in SO, saturated water or in ferroammonium sulphate solution. Between corrosion fatigue and stress corrosion cracking there is a number of analogies but there are also differences. Stress corrosion cracking strongly depends from material composition but may be produced by almost any medium, while corrosion fatigue is possible in certain media only, but is not related with a particular metal composition.     

A Digital Microreflectometrical Video 3D-Probe for the Corrosion Studies

A reflectometrical video microprobe method for studying three-dimensional (3D) structures in spatially nonuniform surface films at metal/electrolyte interfaces is described. By forming microscopical video image of a probe microsite on the electrode surface and measuring the intensity distribution for reflected optical signal over the image area, one can obtain, in a real time, a three-dimensional image of the relief, thickness, and properties of islets, nuclei of a new phase, and secondary deposits over the selected area on the electrode surface. Practical considerations on developing an inexpensive PC-controlled microscopical video probe setup are given. The method is tested in a nondestructive study of microtopography of corrosion films formed on X18H10T chromic steel during its corrosion in iron chloride solution. The method is sensitive to thin films; it provides highly informative control of tangential nonuniformity of the film thickness over the studied microsite on the surface.     

钇对IN-939抗热腐蚀性的影响

本文研究了钇对铸造镍基高温合金IN—939热腐蚀性能的影响,采用75％Na_2SO_4—25％NaCl为付蚀介质的坩埚法,在温度为850℃与900℃,时间从10小时到300小时的范围内进行实验。 从热付蚀减重及渗透深度测得的动力学曲线表明:钇能改善合金热付蚀性。对热付蚀产物进行了金相显微镜和扫描电镜观察以及电子探针与X射线衍射分析。观察到含钇合金付蚀层的表面形貌与不含钇合金有明显区别,IN—939合金表面上形成的付蚀层为氧化铬和硫化铬等的多层结构,其下为铬的贫化区;而IN—939Y表面付蚀层是由大量的氧化铬少量的TiO_2,α—Al_2O_3及微量Y_2O_3、YCrO_3与硫化物组成。腐蚀层下没有贫铬现象,而出现贫钛区与沿晶界的内氧化物以及钇与钛的硫氧化物的分散质点。     

铸铁及其表面碳化钨涂层的电化学行为

考察了甲醇汽油发动机缸套材料铸铁及其表面碳化钨涂层在甲酸水溶液中的腐蚀性能,并研究了其电化学腐蚀行为;采用电化学腐蚀中的极化曲线和电化学阻抗来表征其电化学腐蚀性能。结果表明：碳化钨涂层可有效地改善甲醇汽油发动机缸套材料铸铁的耐腐蚀性能;与铸铁相比,碳化钨涂层的自腐蚀电位高、自腐蚀电流小;同时碳化钨涂层使铸铁表面电荷的传输电阻变大,抑制了铸铁在甲酸溶液中的自放电功能,阻碍了电化学腐蚀的进行,从而有效地保护发动机缸套材料铸铁。     

The hot corrosion of Co-25Cr-10Ni-5Ta-3Al-0.5Y alloy (S-57)

A cobalt-base alloy, Co-25 Cr-10 Ni-5 Ta-3 Al-0.5 Y (S-57), was subjected to hot corrosion in Mach 0.3 burner rig combustion gases at maximum alloy temperatures of 900 and 1000°C. Various salt concentrations were injected into the burner; 0.5, 2, 5 and 10 parts per million synthetic sea salt and 4 parts per million sodium sulphate (Na₂SO₄). The extent of corrosion was determined by measuring the maximum depth of corrosion in the alloy and the corrosion process was studied by metallography, X-ray diffraction, scanning electron microscopy, and electron microprobe analysis. While S-57 was found to possess only moderate oxidation resistance at these temperatures, this alloy resisted significant hot corrosion attack under all but the most severe test conditions. The process of the hot corrosion attack under the most severe conditions of this study was primarily sulphidation.     

Temperature,current density and cobalt concentration effects on electrodeposited anticorrosive cobalt-tungsten alloys using factorial experiment design and ANOVA techniques

ABSTRACT

Corrosion processes can compromise the durability of metallic materials. One way to minimise the effects of corrosion is to coat them with corrosion-resistant alloys. In this study, Co–W alloys were produced by electrodeposition and their anticorrosive performance was evaluated at different levels of current density, Co bath concentration and bath temperature, using factorial experiment design and ANOVA techniques. This evaluation consisted of measuring corrosion current and using electrochemical impedance spectroscopy. Adherent and corrosion resistant alloys were obtained at the lowest temperature of experimental design (25°C) and current density (10?mA?cm^?2) values. From the corrosion tests, X-ray Diffraction and Scanning Electron Microscopy analysis it was possible to conclude that the increase in the tungsten percentage in the composition of the alloy generated an increase in corrosion resistance. Although the alloys’ chemical composition has influence on the corrosion resistance, their physical aspect, such as the presence of cracks, are more significant for the resistance to corrosion.     

Morphological characterisation and spectroscopic studies of the corrosion behaviour of tungsten heavy alloys

Tungsten-based alloys have been used in a wide variety of industrial and military applications. These alloys are composed mainly of tungsten (88-95%) with various combinations of nickel, cobalt, iron and copper usually making up the remaining fraction.The corrosion behaviours of five munitions grade tungsten alloys of interest have been examined using immersion tests and wet-dry cycle tests to determine the mechanisms involved in the release of the metallic components. Analyses carried out using SEM, EDS and grazing incidence XRD techniques, show the release of tungsten as well as alloying elements due to galvanic corrosion resulting from the difference in electrode potential between the tungsten phase and the binder phase in all cases studied. The extent of corrosion was directly related with the dissolution of tungsten in the binder phase during the sintering stage of manufacture. In W-Ni-Co-Fe alloys binder phase corrosion was observed while the relatively noble tungsten phase was less affected. The reverse was observed for a W-Cu alloy.