XPS研究Ti32Mo在浓盐酸溶液中钝化膜结构

用XPS研究了Ti32Mo在70℃,4 mol/L盐酸溶液阳极电位为+0.2 V和+0.9 V时的钝化膜结构和组成.结果表明,钝化膜是由表层和过渡层组成的双层结构.对于阳极电位为+0.2 V的试样,钝化膜富集因子f(Mo)随溅射深度由最外层的1.60变化到8 nm时的1.20;而对于阳极电位为+0.9 V的试样,钝化膜富集因子f(Mo)在1.1-1.22之间变化.钝化膜的表层还可以分为两个亚层Ⅰ和Ⅱ.钝化膜的组成主要是Ti和Mo各种价态的氧化物、氢氧化物和氯化物.     

XPS研究Ti32Mo在浓盐酸溶液中钝化膜结构

用XPS研究了Ti32Mo在70℃、4 mol/L盐酸溶液阳极电 位为02 V和09 V时的钝化膜结构和组成.结果表明，钝化膜是由表层和过渡层组成的双层结构.对于阳极电位为02 V的试样，钝化膜富集因子f(Mo)随溅射深度增加，由最外层的175变化到8 nm时的140；而对于阳极电位为09 V的试样，钝化膜富集因子f(Mo)在132～142之间变化.钝化膜的表层可成Ⅰ和Ⅱ两个亚层，其组成主要是Ti和Mo不同价态的氧化物、氢氧化物和氯化物.     

磁场和CI~-对铁在中性Na_2SO_4溶液中阳极极化行为的影响

用动电位扫描法研究了外加磁场及Cl~-对铁在中性0.5mol/LNa_2SO_4溶液中阳极极化行为的影响。结果表明:有、无磁场下铁在含Cl~-的Na_2SO_4溶液中的阳极极化曲线都呈现活化-钝化-过钝化特征,虽然Cl~-会阻碍钝化膜的形成过程;外加磁场使E_p和E_F正移并增大i_(max)和i_(min),使钝化区范围缩小。Cl~-与磁场同时存在时对钝化膜的破坏有协同作用。     

普通低碳钢与细晶粒钢钝化膜在碱性介质中的耐蚀性

应用循环伏安与动电位极化曲线确定普通低碳钢与细晶粒钢在碱性介质(模拟混凝上孔隙液)中的钝化区域.利用计时电流法在选取的阳极极化电位下使钢筋生成稳定的钝化膜,并通过电化学阻抗谱、Mott-Schottky曲线比较了钢筋在不同阳极电位下形成的钝化膜的优劣性;其次,循环极化曲线对比分析了在有无Cl~-存在时普通低碳钢与细晶粒钢钝化膜的耐蚀性.结果表明,2种钢筋的公共钝化电位区域为-0.25—+0.6V,在选取的+0.3V阳极极化电位下2者均能形成更稳定的钝化膜.在无Cl~-存在的条件下,细晶粒钢钝化膜的稳定性与耐蚀性均略优于普通低碳钢;但有Cl~-存在时,细晶粒钢抑制Cl~-点蚀的能力稍弱于普通低碳钢.影响细晶粒钢钝化膜耐蚀性的主要原因是晶界数量与微量元素含量.     

Cl~-对高氮不锈钢在0.5mol/L NaOH溶液中腐蚀行为的影响

利用动电位极化曲线、电化学阻抗谱和恒电位极化电流响应曲线对一种高氮不锈钢在含不同浓度Cl~-的0.5mol/L NaOH溶液中的腐蚀行为进行了研究。结果表明:高氮不锈钢在含Cl~-的0.5mol/L NaOH中具有良好的耐蚀性,极化曲线表现出阳极钝化特征,Cl~-浓度对点蚀电位无显著影响,钝化电流密度随Cl~-浓度的增加而增大;当Cl~-浓度增加到1.00mol/L时,高氮不锈钢表面生成的钝化膜呈n型半导体,仍具有良好的保护性,钝化膜的载流子密度随着Cl~-浓度的增加而增大。     

椭圆偏振法研究镍表面的钝化膜

用椭圆偏振法研究了镍在硼酸盐缓冲溶液中,于初始钝化处(-0.5V,SCE)、稳定钝化处(0.4V)和钝化/过钝化交界处(0.8V)恒电位阳极极化时所生成的钝化膜。分析了钝化膜的厚度、生长动力学规律、成份和生长机理。结果表明:钝化膜的厚度、成份和生长机理都与外加电位有关;在所研究的电位下,钝化膜都具有双层结构;膜生长都先生成外层膜,随后在其下面再生成一层内层膜;内层膜的生长都服从线性规律,外层膜的生长规律分别为线性规律、抛物线规律和对数规律。     

Zr_(56)Cu_(19)Ni_(11)Al_9Nb_5非晶合金的腐蚀行为

通过浸泡法、动电位极化法、扫描电镜(SEM)、能谱分析(EDX)和X射线光电子能谱(XPS),研究了Zr_(56)Cu_(19)Ni_(11)Al_9Nb_5非晶合金分别在3.5%的NaCl、1mol/L的NaOH和1mol/L的H_2SO_4溶液中的腐蚀和电化学性能。结果表明,试样在3.5%的NaCl、1mol/L的NaOH和1mol/L的H_2SO_4溶液中浸泡2 256h后,肉眼未发现明显腐蚀。SEM观察发现试样发生局部腐蚀,耐腐蚀性在3.5%的NaCl溶液中最差,在1mol/L的NaOH溶液中次之,在1mol/L的H_2SO_4溶液中最好。动电位极化测试结果表明,在3.5%的NaCl溶液中未发生钝化,由于Cl~-的破坏作用,钝化膜发生局部溶解,腐蚀电流密度最大,耐腐蚀性最差。在1mol/L的NaOH和1mol/L的H_2SO_4溶液中发生钝化,生成致密而稳定的钝化膜,且在1mol/L的H_2SO_4溶液中自腐蚀电位和点蚀电位更高,腐蚀电流密度更小,钝化区更宽,钝化膜的稳定性和保护性能更好,耐腐蚀性更好。EDX和XPS分析表明,试样在3.5%的NaCl、1mol/L的NaOH和1mol/L的H_2SO_4溶液中的腐蚀产物主要为ZrO_2、Cu_2O、Al_2O_3、NiO和Nb_2O_5。     

316L奥氏体不锈钢在不同电位下的点蚀和再钝化行为研究

目的研究外加电位对316L奥氏体不锈钢点蚀和再钝化行为的影响。方法采用循环极化、恒电位极化,电化学阻抗谱(EIS)等多种电化学测试方法,研究了系列电位与混合电位对316L奥氏体不锈钢点蚀敏感性的影响,并采用扫描电子显微镜(SEM)、X射线光电子能谱(XPS)观察分析钝化膜点蚀形貌和元素含量。结果在60℃的饱和CO_2的10 g/L NaCl溶液中,316L奥氏体不锈钢的钝化区间为-0.394～0.168 V,但电位在-0.100～0.168V之间,即亚稳态点蚀区时,电流出现一定的波动。在钝化区极化时,316L奥氏体不锈钢的稳态电流密度非常低,随外加电位的升高而略有增加,极化后试样表面无点蚀;在亚稳态点蚀区,极化的电流密度较高,极化后,试样表面出现明显的点蚀坑;混合区极化时,电位从0.1 V转换到-0.1 V时,电流密度急剧下降,并稳定在一个较低的电流值。XPS结果表明,在钝化区电位极化后,Cr、Mo元素含量有所升高,而Fe元素发生了选择性溶解。结论 Cr、Mo元素是耐蚀性元素,其氧化物或氢氧化物的存在可促进钝化膜的局部修复,因此电位转换到低电位后,试样表面发生再钝化现象,钝化膜的稳定性增强,材料的耐蚀能力提高。     

微量Cl~-对316L不锈钢在沸腾乙酸—甲酸混合介质中的腐蚀行为的影响

通过腐蚀失重测量、极化曲线测试和AES分析,研究了微量Cl~-对316L不锈钢在沸腾的84％乙酸—10％甲酸—6％水中的腐蚀行为的影响。结果表明,微量Cl~-(50ppm)的吸附对316L的活性溶解有抑制作用。Cl~-浓度再高则腐蚀速度增大。316L在阳极极化时呈现钝化行为,阳极钝化膜富铬、贫铁,Cl~-使钝化膜的铬、铁含量降低,铬/铁比也降低,从而氧/(铬+铁)比升高,膜的保护性能降低,一定条件下可诱发孔蚀。常温下恒电位阳极极化使Cl~-在表面吸附并进入钝化膜内,温度升高则吸附作用减弱。     

硼酸缓冲溶液中pH值和Cl~-浓度对Cu腐蚀行为的影响

在硼酸缓冲溶液中,采用动电位极化、电化学阻抗谱(EIS)和半导体电容分析方法分别研究了Cu电极的极化行为及其表面人工Cu_2O钝化膜的化学稳定性.结果表明,低pH值、高Cl~-浓度均造成Cu_2O钝化膜的破坏和溶解.高Cl~-浓度时,Cu_2O钝化膜的半导体性质由p型转变为n型,使Cl~-更容易进入钝化膜与Cu~+络合,并破坏钝化膜从而加速腐蚀.高pH值、低Cl~-浓度有利于Cu_2O钝化膜稳定.     

A study of the chemical composition of the passive film on a Ti-Mo alloy in HCI and H2SO4

The composition of the passive film on Ti-15Mo alloy, formed in 1 mol/L and 4mol/L HCI and 2 mol/L H₂SO₄ solutions at 70 °C (160 °F) under anodic polarization is investigated by XPS and electrochemical techniques. Anodic polarization potential is found to have an obvious influence on the content of Mo in the film. At lower anodic polarization potentials, the surface of the passive film is enriched in Mo. However, at higher anodic polarization potentials, the surface is diluted in Mo. The anions of the electrolytes influence the composition of the passive film. In HCI solution, chloride ions are incorporated with the passive film during its formation. The passive film consists of a compound containing chloride and oxide ions. While in H₂SO₄ solution, the passive film only consists of titanium-molybdenum oxide. Sulfide ions and other sulfur are not incorporated. Ti-Mo alloys have a better passivity than pure Ti in HCI and H₂SO₄ solutions. This passivity is related to the enrichment of Mo in the surface of the passive film.     

Depassivation-repassivation behavior of type-312L stainless steel in NaCl solution investigated by the micro-indentation

Repassivation behavior of type-312L stainless steel containing 6% of molybdenum was examined in NaCl solution using in situ micro-indentation technique, together with type-304 and 316L stainless steels. High stability of the passive film formed on the type-312L stainless steel was also examined by depth profiling analysis of passive films using glow discharge optical emission spectroscopy (GDOES). In 0.9 mol dm⁻³ NaCl solution at 296 K the type-304 and 316L stainless steels are passive only up to 0.3 V (SHE), above which pitting corrosion occurs. In contrast, no pitting corrosion occurs on type-312L stainless steel. Despite the significant difference of the pitting corrosion resistance, the repassivation kinetics of the three stainless steels, examined by micro-indentation at 0.3 V (SHE), is similar. The presence of molybdenum in the stainless steel does not influence the repassivation kinetics. The charge required to repassivate the ruptured type-312L stainless steel surface increases approximately linearly with the potential, even though the passivity-maintaining current increased markedly at potentials close to the transpassive region. Repassivation occurs without accompanying significant dissolution of steel, regardless of the stability of passive state. Depth profiling analyses of the passive films on the type-312L stainless steels formed at several potentials revealed that molybdenum species enrich in the outer layer of the passive film, below which chromium-enriched layer is present. The permeation of chloride ions may be impeded by the outer layer containing molybdate, enhancing the resistance against the localized corrosion of the type-312L stainless steel.     

Electrochemical and XPS studies of the passive film formed on stainless steels in borate buffer and chloride solutions

The passivity of AISI 304L and AISI 316L stainless steels in a borate buffer solution, with and without the addition of chloride ions, was studied using cyclic voltammetry and potentiodynamic measurements. The passive layers formed by electrochemical oxidation at different passivation potentials on both the stainless steels were studied by X-ray photoelectron spectroscopy, their compositions were analysed as a function of depth, and the cationic fraction of the passive film was determined. The passive films established on the two stainless steels in the borate buffer solution at pH = 9.3 contained the oxides of two main elements, i.e., Fe and Cr. The oxides of the alloying elements Ni and, optionally, Mo, also contribute to the passive layer. In the presence of chloride ions a strong chromium enrichment was observed in the passive layers.     

椭圆偏振法研究双相不锈钢的钝化膜

作者用椭圆偏振法结合交流阻抗法研究了耐海水腐蚀的双相不锈钢05Cr20Ni9Mc4Cu2Si3N在3.5％NaCl溶液中的钝化膜。结果表明:在自腐蚀及恒电位阳极极化(+0.2和+0.6V,vs.Ag/AgCl)条件下所生成的钝化膜都是双层的,但两者的生长机制不同。在自腐蚀状态下,内层吸收膜的折射率为2.5,主要由Fe_2O_3和Cr_2O_3组成;在恒电位下,内层膜是折射率约为1.2左右的吸附膜。两种条件下生成的外层膜,折射率都在1.7左右,主要由FeOOH,CrOOH或Cr(OH)_3组成,且可能具有非晶态结构。在恒电位下内、外层钝化膜的生长都服从对数规律。在自腐蚀状态下,内层膜的生长近似服从对数规律,外层膜的生长则不服从对数规律。     

Uniformity of passive films formed on ferrite and martensite by different inorganic inhibitors

A comparison of uniformity of passive films formed on ferrite and martensite by three kinds of inorganic inhibitors, chromate, bicarbonate and nitrite, has been made by anodic polarization curve and AC impedance measurements. It was found, by anodic polarization curve analyses, that there was different pitting susceptibility of passive films formed on ferrite and martensite by chromate or bicarbonate. In the solution containing chloride ions, the broken potential of the passive film formed on ferrite by chromate or bicarbonate was more negative than that on martensite. However, the passive films formed on both ferrite and martensite by nitrite had similar pitting susceptibility. Their broken potentials were almost the same. The difference in pitting susceptibility of the passive films was explained by Mott-Schottky analyses. It was found that the passive film formed on ferrite by chromate or bicarbonate had a higher donor concentration than the passive film on martensite. The passive films with higher donor concentrations were more sensitive to chloride ions. However, the passive films formed on both ferrite and martensite by nitrite had the same donor concentration. A uniform passive film can be formed on a martensite mild steel with ferrite bands by nitrite.     

不同电位-pH条件下钼的表面膜的XPS和AES研究

采用 X 射线光电子能谱(XPS)和俄歇电子能谱(AES)方法分析了钼在不同溶液及不同电位-pH 条件下所生成的表面膜。结果表明:(1)在低电位区生成的钝化膜是一种低价(很可能是4价)的氧化物或水合氧化物,在无氧溶液中稳定,膜极薄但保护性很好;(2)在较高电位的过钝化区所生成的表面膜的最终稳态物质是无水 MoO_3;(3)在 FeCl_2溶液中较高电位的第二钝化区中所生成的表面膜,其外层为 Fe_2O_3,内层则可能是由 FeMoO_4组成。AES 和XPS 分析结果证实了本文作者之一(杨武,与 A.Pourbaix 先生合作)早先绘制的 Mo-H_2O系电位-pH 平衡图以及所提出的在钢的局部腐蚀发展过程中钼的阻蚀作用机理的有效性。     

304L不锈钢钝化膜半导体性能研究

利用极化曲线、电容测量法和X射线光电子能谱(XPS)研究了304L不锈钢在0.5 mol/L NaHCO3溶液中所形成的钝化膜的半导体性能,同时对影响钝化膜半导体性能的因素进行了讨论.结果表明：在电位小于-0.4 V范围内,膜呈p型半导体特性;当电位处于-0.4 V至0.26 V范围内膜呈n型半导体特性.随着测试频率的降低及成膜电位的负移,Mott-Schottky曲线的斜率减小,表明膜内的杂质密度增加。氯离子的加入使得M S直线的斜率减小,增加膜内的杂质密度,容易造成点蚀的发生.XPS测试结果表明钝化膜主要由内层的铬氧化物和外层的铁氧化物组成,这与以前的研究结果相一致.     

XPS studies on passive film formed on stainless steel in a high-temperature and high-pressure methanol solution containing chloride ions

The composition and structure of passive film formed on 316L SS immersed in an anhydrous methanol solution (water content < 0.05 wt%) containing 0.42 wt% LiCl at 323-473 K were investigated by X-ray photoelectron spectroscopy (XPS), and compared with those of film formed in an aqueous solution. The passive film formed in the methanol solution was mainly composed of Fe and Cr oxides, and it possessed a double-layered structure consisting of an Fe oxide-rich outer layer and a Cr oxide-rich inner layer. Dissolution of the Fe-rich layer and densification of the Cr-rich inner layer were observed, especially at high temperatures. However, these were suppressed in an aerated methanol solution at 423 K or below, probably due to the barrier effect of adsorbed oxygen. No Ni compound contributed to composing the passive film, even at higher temperatures. The ratio of OH⁻ to O²⁻ was small and decreased with an increase in temperature (the presence of oxygen suppressed the decrease, especially at 423 K or below). The chloride ions were concentrated in the Fe-rich outer layer, and they penetrated more deeply than that in the aqueous solution into the passive film formed in the methanol solution.     

氯和氢对新型超高强度Cr12Ni4Mo2Co14钢在酸性环境中电化学腐蚀行为的影响

采用极化曲线、电化学阻抗和Mott-Schottky等电化学试验研究了酸性环境中Cl~-和氢对一种新型超高强度Cr12Ni4Mo2Co14钢电化学腐蚀行为的影响。结果表明:Cl-和氢均对Cr12Ni4Mo2Co14钢的阳极钝化区产生影响,随着Cl~-含量和氢含量的增加,点蚀电位负向移动,钝化区间缩短;Cl-通过占据氧空位促进钝化膜中形成Schottky空位对,而金属离子空位聚集会引起钝化膜的破坏;与未充氢Cr12Ni4Mo2Co14钢相比,充氢Cr12Ni4Mo2Co14钢中的施主和受主密度均有所提高,导致阳离子空位浓度提高,局部阳离子空位的聚集可诱导钝化膜的击穿。