Corrosion of Nickel-based Alloy G30 in the Stratum Water Containing H2S/CO2

The influences of temperature and CO2 pressure on the corrosion of nickel-based alloy G30 in the stratum water containing H2S/CO2 were investigated with the aid Mott-Schottky analysis and scanning electron microscopy（SEM） of electrochemical impedance spectroscopy（EIS）, The results indicate that alloy G30 is in the passive state in the stratum water, which is related to the formation of the passive film on its surface. This passive film can significantly protect the substrate from further corrosion. And the film protection is enhanced with decreasing temperature and CO2 pressure. Auger electron spectrometry（AES） and X-ray photoelectron spectrometry（XPS） results reveal that the passive film shows the double-layer structure, i.e. the inner chromium oxide and the outer iron/nickel spinel oxides or hydroxides with Mo oxides dispersing throughout the inner and outer scale.     

双极性半导体钝化膜空间电荷电容分析(II)

将双极性半导体钝化膜空间电荷电容等效为钝化膜/溶液界面处电容和内层钝化膜/外层钝化膜界面处的np结电容的串联, 根据前期研究建立的半导体富集态、耗尽态以及反型态空间电荷电容的统一计算公式, 给出了双极性钝化膜Mott-Schottky(M-S)曲线的非线性拟合方法. 并将这一方法应用于镍基合金G3高温高压H2S/CO2腐蚀后的钝化膜半导体特征研究. M-S曲线非线性拟合结果显示, 温度升高外层p型半导体钝化膜多数载流子浓度明显增高, 而内层n型半导体钝化膜的多数载流子浓度基本未变. 通过非线性拟合, 证明本文所给出的M-S曲线非线性拟合方法能够同时给出钝化膜内外层多个半导体性质参数,为揭示钝化膜形成及破坏机制提供更多信息. 结合X射线光电子能谱(XPS)分析, 讨论了钝化膜结构变化机制及np结在抑制腐蚀过程中的作用.     

Impedance spectroscopy study of passive layers on the surface of lead-tin and lead-tin-calcium alloys anodically oxidized in 4.8 M sulfuric acid solution

The nature of passive films, which were formed at various potentials in 4.8 M H₂SO₄ solution on the lead-tin and lead-tin-calcium alloys, is studied by the method of impedance spectroscopy. At the potentials of 1.3 and 1.7 V, the electrode impedance is presented by the equivalent circuit, which corresponds to the formation of a bilayer film consisting of lead(II) sulfate and oxide on the electrode surface. Lead(II) oxide, which forms under the layer of lead sulfate, determines a high resistance of passive layer on the electrodes of lead alloys under investigation. An introduction of tin into the lead alloys significantly decreases the resistance of passive layers. An addition of calcium to the lead-tin alloy raises the impedance of the system. At a potential of 2.05 V, a single-layer compact passive film forms on the electrodes of the test lead alloys. It consists predominantly of lead oxides PbO _x (1 < x ≤ 2), which exhibit a higher electron conductivity. An introduction of tin into the lead alloys decreases the resistance of formed films; calcium has almost no effect on the resistance of passive film under these conditions.     

Influence of Cr on the Electronic Properties of Passive Film on B30 Alloy in NaOH Solution

The influence of Cr on the electronic properties of the passive film on B30 alloy in NaOH solution was studied via electrochemical impedance spectra(EIS), potentiodynamic curve and Mott-Schottky plot. The Cr doped in the passive film on B30 alloy was detected by X-ray photoelectron spectroscopy(XPS). XPS results show that Cr₂O₃ appeared on the passive film, which implied the enhanced anti-corrosion of B30 alloy. The passive film showed a p-type semi-conductive character. The acceptor density(N_A) was in an order of magnitude of 10²² cm^-3, and N_A decreased with the increment of Cr. EIS results show that the film resistance(R_f) increased with increasing the amount of Cr. The diffusion coefficient(D₀) was calculated to be in a range of 10^-16-10^-17 cm^-2/s on the basement of point defect model(PDM).     

Corrosion resistances of passive films on low‐Cr steel and carbon steel in simulated concrete pore solution

The passive ranges of carbon steel rebar and 3Cr steel rebar in saturated Ca(OH)₂‐simulated concrete pore solution with pH 12.6 were determined by means of cyclic voltammetry and potentiodynamic polarization curves. Chronopotentiometry was used to obtain steady‐state conditions for the formation of passive films on rebar samples at different anodic potentials. Electrochemical impedance spectroscopy, Mott–Schottky and X‐ray photoelectron spectrometer curves were employed to compare the formed passive films at different potentials. Additionally, cyclic polarization curves were used to compare the corrosion resistances of formed passive films on the two rebars in saturated Ca(OH)₂‐simulated concrete pore solution with different concentration of Cl^?. The results show that the passive ranges of the two rebars are all between ?0.15 and +0.6 V, and more stable passive films can be formed on both rebars at the anodic potential of +0.3 V. In the absence of Cl^?, the stability and corrosion resistance of the passive film formed on the 3Cr rebar are better than those of CS rebar. The passive film of 3Cr steel has the relatively better pitting corrosion resistance than carbon steel in saturated Ca(OH)₂‐simulated concrete pore solution that contains different concentration of Cl^?. Copyright © 2016 John Wiley & Sons, Ltd.     

An insight into the passivation of cupronickel alloys in chloride environment

Cupronickels offer enhanced corrosion protection in marine environments by the formation of passive films on the surface. Cyclic voltammetric studies were carried on cupronickels in chloride solutions at pH 6.3 to understand the role of chloride ions in passive film formation. Increase in nickel content of the alloy and of chloride ions in solution decreases film resistance. Chloride ions take part in reduction of the passive film to copper. A solid-state model for passive film formation involving chloride ions has been attempted.     

XPS and AES analysis of passive films on Fe-25Cr-X (X = Mo, V, Si and Nb) model alloys

Corrosion resistance of stainless steel is due to the presence of a thin passive film of typically 1–2 nm thickness. The influence of ternary alloying elements on the composition of passive films on Fe-Cr alloys and their pitting corrosion resistance has been investigated. Iron-chromium alloys were analyzed by XPS and AES with model alloys (Fe-25Cr-X with X = at % Mo, Si, V and Nb) formed in sulphate solution in the presence and absence of chloride ions. All ternary alloying elements increase the pitting potential compared to the corresponding binary alloy. Films formed in chloride containing sulphate solution contain both electrolyte anions. Scanning Auger microscopy reveals that for a two phase system such as Fe-25Cr-11Nb, the dendritic phase is enriched with chromium, while essentially all of the niobium is located in the interdendritic eutectic.     

XPS and AES analysis of passive films on Fe-25Cr-X (X = Mo,V, Si and Nb) model alloys

Corrosion resistance of stainless steel is due to the presence of a thin passive film of typically 1-2 nm thickness. The influence of ternary alloying elements on the composition of passive films on Fe-Cr alloys and their pitting corrosion resistance has been investigated. Iron-chromium alloys were analyzed by XPS and AES with model alloys (Fe-25Cr-X with X = at % Mo, Si, V and Nb) formed in sulphate solution in the presence and absence of chloride ions. All ternary alloying elements increase the pitting potential compared to the corresponding binary alloy. Films formed in chloride containing sulphate solution contain both electrolyte anions. Scanning Auger microscopy reveals that for a two phase system such as Fe-25Cr-11Nb, the dendritic phase is enriched with chromium, while essentially all of the niobium is located in the interdendritic eutectic.     

The effect of passivated potential on the passive films formed on pure chromium in borate buffer solution

The effect of passivated potential on corrosion resistance of the chromium in borate buffer solution was investigated. The electrochemical results showed that corrosion resistance of the passive film on the chromium electrode decreased with the increasing of passivated potential. The Mott–Schottky analysis showed that more acceptor concentrations in passive film due to higher passivated potential deteriorated corrosion resistance of the chromium electrode. The results from XPS showed that more chromium hydroxides were formed in higher passivated potential, while less chromium oxides were formed. More acceptor concentrations in passive films reduced corrosion resistance of the chromium electrode in borate buffer solution. Copyright © 2016 John Wiley & Sons, Ltd.     

690合金在300 ℃含硫模拟碱性水化学中的腐蚀行为

690 合金作为压水堆核电站蒸汽发生器传热管的一种关键材料, 其在碱性环境下还原态硫导致的钝化膜的腐蚀退化是引发应力腐蚀开裂的关键原因之一. 本文采用动电位极化曲线, 结合扫描电镜(SEM)、俄歇能谱(AES)、二次离子飞行时间质谱(ToF-SIMS)研究了690合金在300 ℃模拟碱性水化学中的腐蚀行为, 并分析了硫代硫酸根与硫酸根对钝化膜特性的影响. 实验结果表明: 300 ℃碱性溶液中690合金表面钝化膜为外层的多孔层与内层的紧密层组成的双层结构, 所加入的硫酸盐种类对690合金的耐蚀性有较大影响; 硫代硫酸根使690合金钝化电流密度增加, 过钝化电位降低, 即钝化膜的耐蚀性降低; 此外, 硫代硫酸根使钝化膜中的Cr含量降低而Ni 含量提高, 硫代硫酸根会在合金表面电化学还原成为更低价态的硫进入钝化膜, 使钝化膜中的硫化物增多也是导致钝化膜防护性能变差的原因; 而硫酸根与钝化膜的作用较弱, 对钝化膜的影响较小.     

In situ study on the effects of Ni and Mo on the passive film formed on Fe–20Cr alloys by photoelectrochemical and Mott–Schottky techniques

Effects of alloying elements (Ni and Mo) on the structure of passive film formed on Fe–20Cr alloys in pH 8.5 buffer solution were explored by analyzing the in situ electronic properties measured using the photoelectrochemical technique and Mott–Schottky analysis. The passive film formed on Fe–20Cr–10Ni was found to be mainly composed of Cr-substituted γ-Fe₂O₃ from similarities in photocurrent response for the passive films formed on the alloy and Fe–20Cr. On the other hand, the photocurrent spectra for the passive films of Fe–20Cr–15Ni–(0, 4)Mo alloys exhibited the spectral components associated with NiO and Mo oxide (MoO₂ and/or MoO₃) in addition to that induced by Cr-substituted γ-Fe₂O₃. Mott–Schottky plots for the passive films formed on Fe–20Cr–(10, 15)Ni and Fe–20Cr–15Ni–4Mo confirmed that the passive films on Fe–20Cr–(10, 15)Ni–(0, 4)Mo alloys have a base structure of Cr-substituted γ-Fe₂O₃ with variation of densities of shallow and deep donors depending on the Ni and Mo contents in the alloys. We suggest that the passive film formed on Fe–20Cr–(10, 15)Ni and Fe–20Cr–15Ni–4Mo alloys are composed of (Cr, Ni, Mo)-substituted γ-Fe₂O₃ when the concentrations of Ni and Mo are below critical values. However, NiO and Mo oxide (MoO₂ and/or MoO₃) would be precipitated in the passive films when the concentrations of Ni and Mo exceed critical values.     

不锈钢钝化膜耐蚀性与半导体特性的关联研究

通过极化曲线、交流阻抗谱和钝化膜半导体特性等电化学测量，研究了经电化学阳极氧化处理的不锈钢钝化膜在0.5 mol•L^-1 NaCl溶液中耐蚀性能与其半导体特性的关系，进一步探索电化学改性处理不锈钢钝化膜的耐蚀机理. 结果表明，不锈钢钝化膜在负于平带电位范围表现为p型半导体，在高于平带电位范围表现为n型半导体，这主要与组成钝化膜的Fe和Cr氧化物半导体性质有关. 与自然条件下形成的不锈钢钝化膜比较，发现经过电化学阳极氧化后不锈钢钝化膜具有较低的施主与受主浓度，平带电位负移，说明阴离子在钝化膜表面发生吸附. 低的施主与受主浓度及钝化膜表面负电荷的增强，可有效排斥侵蚀性Cl^－在钝化膜表面的特性吸附，有利于提高不锈钢的耐局部腐蚀性能.     

Electric properties and pitting susceptibility of passive films formed on iron in chromate solution

Electric properties and pitting susceptibility of passive films formed on iron in 0.01 M Na₂CrO₄ solution was investigated by using Mott–Schottky analyses, electrochemical noise analyses and anodic polarization curve measurements. It was found that the passive films were very disordered n-type semiconductors with two level donors, shallow and deep. The donor concentrations decreased as the passive film was formed at more positive potentials. The passive films were susceptible to pitting in the solution containing 0.05 M chloride ions. The pitting susceptibility of the passive film was improved as the donor concentration in the passive film decreased.     

多晶Fe60Ni40合金阳极钝化膜的XPS研究

过渡金属Fe、Ni或其合金由于它们具有磁性和在工业上被用作催化剂等，它们与氧化腐蚀性气体02、C12等的作用已被广泛研究［‘－3］．含Ni的不锈钢和含Ni50％的FeNi基合金在酸性溶液中表现出比铁更好的耐腐蚀性并增强了氧化钝化层的附着力，放它们在溶液的腐蚀与钝性研究已引起广泛的兴趣，甚至包括对F6Ni基非晶合全玻璃的腐蚀与钝性研究【4一刊，用不同的方法研究溶液状态下的自然氧化膜或阳极钝化膜，得出的结果不同，对腐蚀与钝性解释也很不一致，硼酸一础砂或磷酸一磷酸盐缓冲液在工业上被广泛用作清洗剂、缓蚀剂或成膜剂等·因此，…     

铬对碳钢在NaHCO_3/NaCO_3缓冲溶液中所成钝化膜半导体性能的影响

应用电化学阻抗谱技术研究铬对碳钢钝化膜半导体性能的影响.实验表明,在碳酸氢钠/碳酸钠缓冲溶液中碳钢形成的钝化膜具n型半导体特性,而含有3%铬的碳钢钝化膜则呈n-p型半导体特性,随着成膜电位的增加,以上两种钝化膜之Mott-Schottky直线部分的斜率均呈增大的趋势,表明成膜电位升高,膜内的杂质密度减小,但铬的加入使得碳钢钝化膜的施主密度增加约一个数量级,从而增加了碳钢点蚀发生的趋势.EIS分析表明:铬的加入降低了钝化膜的传递电阻R1和膜电阻R2,特别是膜电阻R2下降达3个数量级,这就有可能增加碳钢在高pH值环境中的腐蚀.     

Highly increased capacitance and thermal stability of anodic oxide films on oxygen-incorporated Zr-Ti alloy

Heat treatment of Zr-24 at% Ti alloy with barrier-type dielectric anodic oxide films was conducted at 473 K in air to examine the thermal stability of the dielectric oxide films for possible electrolytic capacitor application. The anodic oxide film was formed by anodizing of the alloy at 50 V for 30 min in 0.1 mol dm^?3 ammonium pentaborate electrolyte. The anodic oxide film of 125 nm thickness was crystalline, containing both monoclinic and tetragonal ZrO₂ phase. It was found that marked thickening of the oxide film with generation of cracks occurred during heat treatment at 473 K. Thus, the dielectric loss was largely increased along with the capacitance increase. In contrast, the anodic oxide film formed on the oxygen-incorporated alloy remained uniform, and no significant increase in dielectric loss was observed even after the heat treatment. The capacitance of the anodic film became as high as 4.8 mF m^?2, which was nearly twice that on Ta. The high capacitance was associated with the preferential formation of tetragonal ZrO₂ phase in the anodic oxide film on the oxygen-incorporated alloy. Findings indicated that the oxygen-incorporated Zr-Ti alloy is a promising novel material for capacitor application.     

非晶Fe40Ni40P14B6合金阳极钝化膜的电子能谱研究

应用表面分析技术XPS和AES（包括深度分布）分析了非晶Fe40Ni40P14B6合金在H3BO3－Na2B4O7（pH＝9．20）缓冲溶液中不同钝化势或不同钝化时间形成的阳极钝化膜的元素化学状态、结构和化学组成，探讨了加入Ⅲ、Ⅴ族B、P对非晶FeNi基合金钝化成膜的影响，并给出了阳极钝性成膜的一种机制．     

Corrosion behavior of PEO-treated AZ31 Mg alloy in chloride solution

Corrosion behavior and resistance of plasma electrolyte oxidation (PEO)-treated AZ31 Mg alloy were investigated by immersion and potentiodynamic polarization tests in 0.5 M NaCl solution in view of the PEO film thickness and sealing treatment of the PEO films in boiling water. The PEO films were formed using pulse current for various durations in 1 M NaOH?+?0.5 M NaF solution. Filiform corrosion was observed during the immersion test while pitting corrosion occurred during the potentiodynamic polarization test, irrespective of sealing treatment of the PEO films. Corrosion resistance of AZ31 Mg alloy was improved remarkably by the formation of thicker PEO films and their sealing treatments.     

镁合金阳极氧化膜的结构、成分及其耐蚀性

采用电压-时间曲线、膜厚-时间曲线、X射线衍射法、扫描电镜、能量色散谱仪、X射线光电子能谱法、全浸腐蚀实验和极化曲线等方法分别研究了AZ91D铸镁合金阳极氧化成膜动力学过程、阳极氧化膜的表面形貌、结构、元素组成、元素价态以及相成分和膜层的耐蚀性.结果表明,在阳极氧化的4个阶段中,由于各个阶段所生成膜的厚度、结构和成分等均不同,因此膜的耐蚀性相差很大;镁合金阳极氧化时耐蚀性最好的膜层是在阳极氧化过程中的第阶段和第阶段的交界处所生成的膜层;镁合金阳极氧化膜中含有Mg,O,Si,B和少量的Al,Na元素,膜层主要由MgO,MgSiO₃和Mg3B2O6组成.     

非晶Fe40Ni40P14B6合金阳极钝化膜的电子能谱研究

应用表面分析技术ＸＰＳ和ＡＥＳ（包括深度分布）分析了非晶Ｆｅ４０Ｎｉ４０Ｐ１４Ｂ６合金在Ｈ３ＢＯ３－Ｎａ２Ｂ４Ｏ７（ＰＨ＝９．２０）缓冲溶液中不同钝化时间形成的阳极钝化膜的元素化学状态、结构和化学组成，探讨了加入Ⅲ、Ｖ族Ｂ、Ｐ对非晶ＦｅＮｉ基合金钝化金钝化成膜的影响，并给出了阳极钝性成膜的一种机制。