FeS膜的离子性对基体金属腐蚀的影响

本文采用动电位扫描法研究了Ａ３钢在油田污水中的腐蚀速度，以及Ｓ＾２－对腐蚀速度的影响，通过测膜电位曲线的方法，研究了ＦｅＳ膜的离子选择性，阐述了ＦｅＳ膜的离子选择性对基体金属腐蚀行为的影响。研究表明，金属表面的ＦｅＳ膜是一种双极结构膜，促进腐蚀。     

碳钢表面稀土转化膜的XPS和AES研究

用浸渍法在Ａ３钢表面上获得了稀土转化膜，此膜呈均匀的金黄色，有良好的装饰效果。硫酸铜点滴、盐水浸泡、硫化氢气体等加速腐蚀试验以及膜层的电化学测试均证实此膜具有一定的耐蚀性能。膜层的ＸＰＳ９Ｘ射线光电子光谱）分析结果表明，膜层由铁、铈、氧等元素组成；在膜层的表面，铁以Ｆｅ＾３＋，铈以Ｃｅ＾４＋状态存在，在膜层的内部，铁以Ｆｅ＾３＋及Ｆｅ＾３＋，铈以Ｃｅ＾３＋和Ｃｅ＾４＋状态存在；从ＡＥＳ（俄歇Ｆｅ＾     

丙炔醇聚合股对铁在酸性溶液中的缓蚀作用

应用电化学交流阻抗谱技术研究了Ｆｅ／Ｈ_２ＳＯ_４与Ｆｅ／Ｈ_２ＳＯ_４＋Ｈ_２Ｓ体系中丙炔醇（ＰＡ）聚合膜的形成及其缓蚀作用,同时利用ＳＥＭ、ＡＦＭ及ＥＤＸ对ＰＡ聚合不同时期铁表面腐蚀形貌进行观测与成分分析．结果表明,Ｆｅ／Ｈ_２ＳＯ_４与 Ｆｅ／Ｈ_２ＳＯ_４＋ Ｈ_２Ｓ体系中 ＰＡ可逐渐聚合成膜,从而有效抑制基体的腐蚀,使电极表面较为平整,微米尺度下呈现规则的块状结构;但Ｆｅ／Ｈ_２ＳＯ_４体系中宏观上ＰＡ并未形成连续的保护膜,导致电极表面局部发生腐蚀;而Ｆｅ／Ｈ_２ＳＯ_４＋Ｈ_２Ｓ体系中,Ｈ_２Ｓ、ＨＳ－在电极表面的吸附减缓了ＰＡ聚合成膜,但长时间腐蚀后,由于硫化物的生成覆盖在ＰＡ聚合膜上,使其具有长期缓蚀效能．     

氟化物及二氧化铈添加剂对润滑脂的抗磨和极压性能的影响

利用ＳＲＶ的磨损试验机考察了作为高温固体润滑剂的ＣｅＦ３，ＣａＦ３，（ＣＦ）ｎＣＯ２以及Ｓｂ２Ｏ３对锂基脂摩擦学性能的影响，应用透射电镜分析了添加剂对皂的纤维结构的影响，铜片腐蚀实验考察了添加剂的腐蚀性，热失重分析研究了添加剂的热分解行为，自动划痕试验机测量了摩擦表面反应膜的结合强度，并对磨痕进行了Ｘ光光电子能谱分析。     

聚苯胺和聚吡咯膜电极对Fe（Ⅱ）和Sb（Ⅲ）电催化作用

Ｆｅ（Ⅱ）和Ｓｂ（Ⅲ）的氧化还原峰电流在聚苯胺（ＰＡｎ）和聚吡啶（ＰＰｙ）膜电极上比在铂丝电极上高出一倍至数倍。在膜电极上氧化峰电位与还原峰电位之差值（△Ｅｐ）也比在铂丝电极上显著减小．说明两种膜电极对Ｆｅ（Ⅱ）和Ｓｂ（Ⅲ）离子的电极反应有较好的电催化活性。在电位扫描速度较低时，两种离子在聚合物膜电极上的氧化和还原反应的催化活性相近。     

漆树漆酶的催化氧化作用 (ⅹⅢ)──Fe~(2+)离子对漆酶催化氧化反应的影响()

以５,６－二溴－２,３－二氰基氢醌为底物,在ｐＨ４．５０条件下,用分光光度法考察了ＦｅＳＯ４对漆树漆酶催化氧化反应的影响．结果表明,在本文实验条件下ＳＯ２－４离子对酶促反应的影响基本可以忽略,而Ｆｅ２＋离子对漆酶的催化氧化反应则有明显的竞争性抑制作用．研究证实,Ｆｅ２＋离子的抑制作用是通过它还原酶促反应的产物半醌自由基阴离子来实现的     

钝性合金摩擦电化学性质的影响因素

研究了不同Ｃｒ含量的Ｆｅ－Ｃｒ合金在Ｈ２ＳＯ４溶液体系中的摩擦腐蚀过程,重点了载荷,摩擦速度,Ｃｒ含量及Ｈ２ＳＯ４溶液浓度对摩擦电流密度的影响。结果表明：当摩擦仅作用在金属部分表面时,在钝化电位区,外加载荷和摩擦速度对摩擦电流密度有较大的影响。     

漆树漆酶的催化氧化作用（ⅫⅡ）

以５,６－二溴－２,３－二氰基氢醌为底物,在ＰＨ４．５０条件下,用分光光度法考察了ＦｅＳＯ４对漆树漆酶催化氧化反应的影响。结表明,在本文实验条件下ＳＯ４＾２－离子对酶促反应的影响基本可以忽略,而Ｆｅ＾２离子对漆酶的催化氧化反应则有明显的竞争性抑制作用,研究证实,Ｆｅ＾２＋离子的抑制作用是通过它还原酶促反应的产物半醌自由基阴离子来实现的。     

全氟磺酸膜的离子选择性

研究了Ｎａｆｉｏｎ１１７膜（一种全氟磺酸膜）对阳离子的选择性,测定了含Ｋ＾＋,Ｎｉ＾２＋及Ｆｅ＾３＋的Ｎａｆｉｏｎ１１７膜的离子选择性系数,实验发现含Ｈ＾＋,Ｋ＾＋,Ｐｂ＾２＋,Ｎｉ＾２＋,Ｃｏ＾２＋,Ｆｅ＾３＋等离子的膜都能较好符合Ｎｅｒｎｓｔ响应。膜对一价离子的选择性优于二价及三价离子。     

应用D411树脂精制用於离子膜制碱的二次盐水的研究（Ⅰ）

本文研究了Ｄ４１１树脂对饱和食盐水中Ｃａ，Ｍｇ，Ｆｅ离子静态和动态的吸附性能，并研究了Ｄ４１１树脂精制离子膜制碱用二次盐水的离佳条件。     

金属腐蚀监测的光波导传感方法研究

本文提出一种用于金属腐蚀监测的光波导传感方案 ,用金属膜层局部取代光波导的介质包层 ,构成腐蚀敏感膜 ,从而获取金属腐蚀信息 .依据波导理论选用 72 1比色皿上的石英玻璃作为光波导材料 ,利用电化学方法在波导材料内表面上形成Fe C合金腐蚀敏感膜 ,并用XRD、EDX等对膜层结构进行分析 .在电化学腐蚀膜的同时 ,用光学方法记录光波导输出光功率的变化 ,实验结果表明电化学方法与光学方法获取的腐蚀信息同步 ,证实了所提传感方案可行     

弱碱性介质中氯离子对铜电极腐蚀行为的影响

应用循环伏安法、X射线光电子能谱法、电化学阻抗谱法以及现场椭圆偏光法研究了在弱碱性介质中添加Cl－对铜电极腐蚀行为的影响.结果表明, Cl－的加入能加剧铜电极的腐蚀,使腐蚀电流以及现场椭圆偏振参数Δ的变化范围都增大1个数量级, Cl－对Cu2O的掺杂将使铜电极的表面膜变得疏松,膜的耐蚀性变差.椭圆偏光实验不仅与电化学和能谱实验的结果一致,而且还能定性地、清楚地分辨出铜电极腐蚀过程中Cu2O的生成、Cl－对Cu2O的掺杂、CuO的生成等不同阶段;同时,利用恰当的模型还能定量地确定各个阶段铜电极表面膜的组成、厚度的变化,从而为研究铜电极的腐蚀与防护机理提供更多有用信息.     

Characteristics of a surface plasmon resonance sensor combined with a poly(vinyl chloride) film-based ionophore technique for metal ion analyses.

The characteristics of a surface plasmon resonance (SPR) sensor prepared by coating a metal film evaporated on a prism with a polymer film containing tetra-n-butyl thiuram disulfide (TBTDS) were studied. The differences in the sensitivity, selectivity, and detection limit for a Zn2+ ion of the SPR sensor were reported as a function of the thickness of the polymer film, the kind of a metal film, and the kind of a polymer film. The thinner was the polymer film, the higher was the sensitivity, and the lower was the detection limit. The Ag film gave to the SPR sensor higher sensitivity than the Au film. TBTDS contained in the poly(vinyl chloride) (PVC) film slightly improved the selectivity toward the Zn2+ ion. A non-conditioned poly(methyl methacrylate) (PMMA) film containing TBTDS gave a lower detection limit of 1.0 x 10(-6) mol/l, which is similar to that obtained by using an ion selective electrode (ISE) method, than the PVC film. The PVC film, however, gave higher concentration resolution than the PMMA film.     

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.     

Analysis of corrosion scales formed on steel at high temperatures in hydrocarbons containing model naphthenic acids and sulfur compounds

Corrosive naphthenic acids and sulfur compounds in crude oils present a major challenge for refineries from a corrosion perspective. Although it is accepted that some sulfur compounds may form protective FeS scales on the metal surface and deter corrosion, attempting to correlate the characteristics of FeS scale with its protective properties has not been successful. Given the complex chemical compositions of real crudes, model sulfur compound and model naphthenic acids were used to mimic the corrosion by crude fractions in the present study. The iron sulfide scale formed by the model sulfur/acid compounds was challenged by naphthenic acids under high‐velocity conditions to examine its protectiveness against corrosion. Moreover, the scale was analyzed with transmission electron microscope/energy dispersive X‐ray spectroscopy technique, and a layer of iron oxide formed on the 5Cr steel was found when naphthenic acids were present in the solution. The iron oxide layer appeared to be important for maintaining protection against naphthenic acid corrosion, and further analysis revealed that it was composed of magnetite. Copyright © 2015 John Wiley & Sons, Ltd.     

邻苯二胺、邻氨基酚的电化学聚合及聚合的膜性质

邻苯二胺(ODB), 邻氨基酚(OAP)在酸性水溶液中易电聚合, 可形成致密的聚合膜。聚邻苯二胺(PODB)在PH<4时具有电活性, 其氧化还原反应与电变色效应对应。聚邻苯二胺,聚邻氨基酚(POAP)膜电极电位在pH=4～10范围对pH有Nernst响应, 电极系数分别为59mV/pH和57mV/pH。响应时间小于3分钟。PODB, POAP膜能与Ni~(2+), Co~(2+)过渡金属离子形成稳定的聚合络合膜。此膜在碱性介质中具有稳定的循环伏安行为, 膜中的金属离子可被H~+交换。PODB电极的—NH_2基可再修饰引入醌/氢醌功能团。     

Optical detection of Cu ion using a SQ-dye containing polymeric thin-film on Au surface

In this study, we have fabricated Cu²⁺ ion sensor using a squarylium dye (SQ-dye) containing polymeric thin-film. Surface Plasmon Resonance (SPR) was used as a signal amplifier to achieve high sensitivity and large linear dynamic range for detection of Cu²⁺ ion. High selectivity to Cu²⁺ ion was obtained by the effective electro-static interaction between SQ-dye and Cu²⁺ ion in the polymeric film. The optimal analytical condition of high selectivity and sensitivity in the wider linear dynamic range obtained in this study may be a result of the cooperative ‘hard-soft’ metal ion-ligand interaction and effective detection of refractive index changes by the complexation of Cu²⁺ ion and SQ-dye in SPR measurement. Among 10 different alkali metal, alkaline earth metal, and transition metal ions, SQ-dye in poly(vinylchloride)–poly(vinyl acetate)–poly(vinyl alcohol) (PVC–PVAc–PVA) copolymer film showed the highest selectivity to Cu²⁺ ion. Although the interaction between SQ-dye and metal ions has not been well understood, both cooperative ‘hard-soft’ metal ion-ligand interaction and size-selective recognition of Cu²⁺ ion to SQ-dye may contribute to high selectivity. Furthermore, additional sensitivity in the detection of Cu²⁺ ion by SPR was obtained by matching the wavelength of probing radiation of SPR and absorption maximum of SQ-dye at 675 nm, which allow to detect small changes in the refractive index by complex formation on the sensing surface. This result may apply in development of the Cu²⁺ ion selective sensor for medical, biochemical, and environmental applications.     

Utilization of biowaste as an eco-friendly biodegradable corrosion inhibitor for mild steel in 1 mol/L HCl solution

This report focuses on the application of a biodegradable biowaste [human hair-(HHR)], to produce a mild steel corrosion inhibitor. The performance of HHR extract in inhibiting metallic corrosion in 1 mol/L HCl was investigated. The analysis of the metal corrosion behavior using electrochemical and weight loss techniques revealed that HHR exhibits an efficient corrosion-mitigating effect via adsorption on the metal surface following a Langmuir isotherm. Tafel-plot results revealed the mixed-mode corrosion protection behavior of HHR. Surface analysis using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and Fourier transform infrared (FT-IR) spectroscopy provided evidence for the precipitation of a protective HHR film on the metal surface.     

SRB和CO2共存环境中X60管线钢腐蚀电化学特征

对X60管线钢在硫酸盐还原菌(SRB)和CO2共存环境中进行浸泡实验, 对浸泡不同时间后的腐蚀形态及膜层的组成进行观察和分析, 并对膜层覆盖的X60钢的腐蚀电化学参数特征进行分析. 结果表明, SRB吸附形成的微生物膜覆盖程度加大导致X60钢电位正移, 腐蚀产物FeS和FeCO3含量增加导致X60钢电位负移. X60钢表面膜层中腐蚀产物含量较低时, 仅有一个与电极电位有关的时间常数, 当膜层中腐蚀产物的含量高时, 增加了与腐蚀产物膜有关的时间常数. 在浸泡初期, 随微生物膜覆盖程度增加, X60钢的电荷传递电阻增大; 随腐蚀产物含量增加, 电荷传递电阻先下降后增大. 随浸泡时间的延长, X60钢双电层电容和膜层电容均增大.     

Electrochemical Behavior and Nonlinear Mott-Schottky Characterization of a Stainless Steel Passive Film

The electrochemical behavior of 304-stainless steel in solutions with different pH values and chloride concentrations was investigated by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and a nonlinear Mott-Schottky analysis method. The results showed that the corrosion behavior of 304-stainless steel was affected by various factors, such as pH, chloride ion concentration, and dissolved oxygen. The pit initiation and propagation stage were observed in EIS plots through the addition of sodium chloride. In addition, the effect of pH on the passive film dominated one of the film growth kinetic reactions. The effect of chloride ion concentration was caused by the generation of more cation vacancies, leading the passive film more susceptible to pitting, which was also demonstrated by X-ray Photoelectron Spectroscopy. The results are consistent with the point defect model.