非晶态Fe－W合金镀层的表面改性

将Ｆｅ－Ｗ非晶态镀层在铬酸盐钝化液中进行化学钝化与电化学钝化，使之形成含铬钝化膜。阳极极化曲线说明，钝化后镀层的孔蚀电位向正向移动了约１．６８Ｖ；Ｆｅ－Ｗ非晶镀层在氯化钠溶液中浸泡近１ｈ表面发生严重腐蚀，而经钝化处理的镀层浸泡１个月，表面无变化，仍具有金属光泽。     

非晶态Fe—W合金镀层的表面改性

将Ｆｅ－Ｗ非晶态镀层在铬酸盐钝化液中进行化学钝化与电化学钝化，使之形成含多种钝化膜。阳极极化曲线说明，反镀层的孔蚀电位向正向移动了１．６８Ｆ；Ｆｅ－Ｗ非晶镀层在氯化钠溶液中浸泡近１ｈ表面发生严重腐蚀，而经钝化处理的镀层浸泡１个月，表面无变化，仍具有金属光泽。     

铝合金稀土转化膜成膜工艺研究

应用正交实验设计 ,开发并研究了LY1 2铝合金 4价铈盐转化膜的成膜工艺及其膜层的耐蚀性能 .实验表明 :经稀土转化处理的铝合金其点蚀电位升高 ,自然腐蚀电位有所降低 ,从而降低了点蚀敏感性 ;试样极化阻力提高 70倍以上 ,耐蚀性能大大提高 ,与铬酸盐相当 ;另外 ,还结合电化学测试和表面分析 ,初步探讨了铝合金稀土转化膜的耐蚀机理     

镀锡层上钛-磷复合体系钝化膜的制备与表征

通过钛盐与磷酸盐体系复配的方法,在镀锡层表面得到了一种钛-磷复合体系钝化膜. 利用扫描电子显微镜(SEM)、X射线光电子能谱 (XPS)、盐雾试验、Tafel极化曲线和EIS交流阻抗谱测试等方法,研究了所得钝化膜的表面形貌、组成与耐蚀性能. 结果表明,得到的钝化膜层的主要组成成分为Ti₃(PO₄)₄nH₂O和TiO₂,在镀锡层表面结晶细致并有封孔的作用,因此有很好的耐蚀性能.     

电镀锌钢硅烷-有机膦酸复合钝化膜的制备及性能表征

利用N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷(AAPTMS)、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(GPTMS)和1-羟基亚乙基-1,1-二膦酸(HEDP),在电镀锌钢基体上制备了一种新型硅烷-有机膦酸复合钝化膜.X射线光电子能谱、傅立叶变换红外光谱以及中性盐雾试验、动电位极化曲线和电化学阻抗谱测试表明:该复合钝化膜主体结构由Si—O—Si、Si—O—P等组成;120 h中性盐雾试验后白锈面积小于5%,达到铬酸盐彩色钝化膜水平;且其腐蚀反应呈现更为明显的阳极扩散控制特征,属于物理阻挡机制.     

双环戊二烯基二(芳氧基)钛、锆、铪衍生物的13C核磁共振谱

第Ⅳ副族金属的双环戊二烯基二卤化物及取代双环戊:二烯基二卤化物的¹³C NMR谱已有一些报道.但关于双环戊二烯基二(芳氧基)钛、锫、铪类型化合物的¹³C NMR谱则尚未见系统报道.我们研究其¹³C NMR谱,目的在于探讨第Ⅳ副族的不同金属以及芳环对位不同取代基对¹³C化学位移的影响.我们发现环戊二烯环的¹³C化学位移随金属周期数的增加而有规律地移向高场.同时,在钛、锆、铪三个系列的化合物中,不论是芳环还是环戊二烯环,其相应碳原子的¹³C化学位移之间存在着非常好的线性关系,相关系数等于或优于0.99.     

不同晶粒度螺纹钢的电化学行为及其钝化膜的Mott-Schottky 研究

利用交流阻抗谱和极化曲线研究比较了四组不同晶粒尺寸的螺纹钢在模拟海水液(3.5% NaCl)中短期电化学腐蚀行为; 利用硼酸缓冲液中钝化膜的Mott-Schottky 理论比较了各试样在不同阳极极化电位下的钝化膜的优劣性. 结果表明, 在14 d 的模拟海水短期浸泡期间, 细晶粒螺纹钢在后期表现出较大阻抗值和较小的自腐蚀电流密度, 耐蚀性能优于粗晶粒试样. 在硼酸缓冲液中形成的钝化膜表现出典型的n 型半导体性能, 公共钝化区间为-0.15～0.8 V. 在选取的-0.1, 0.2, 0.5 V 三个不同极化电位下, 细晶粒螺纹钢在硼酸缓冲液中的钝化膜稳定性、耐蚀性弱于粗晶粒螺纹钢. 在0.5 V 的外加电压下试样钝化膜的内层膜消失, 钝化膜的施主浓度最低, 膜最为致密、稳定.     

高功率镍氢电池La1-xMgx(NiCoAl)3.6金属氢化物电极的电化学性能研究

MH-Ni电池具有电化学比能量高、耐过充/放电性能好、无记忆效应和环境友好等优点而得到广泛应用.金属氢化物电极是MH-Ni电池的核心材料,其研究工作主要集中在稀土AB₅系、钛系、锆系和镁基等合金作为MH-Ni电池金属氢化物电极方面.但这些体系合金的电化学容量低.     

镁合金在含F－的NaOH溶液中钝化行为的电化学研究

采用极化曲线、电容-电位曲线、Mott-Schottky分析以及电化学阻抗(EIS)等电化学方法研究了镁合金在含F^－ NaOH溶液中的阳极钝化行为. 结果表明, 在－1.2～1.8 V的电位范围内, 镁合金在含F^－的NaOH溶液中发生阳极钝化. 所形成的钝化膜表现出n型半导体的导电特性. 在0.7～1.8 V的电位范围内, 随着F^－浓度增大, 镁合金的阳极极化电流密度呈现出随着电位升高而逐渐增大的趋势, 随着F^－浓度增大这一趋势逐渐减弱. 并且F^－浓度的增大使得镁合金表面空间电荷层电容和钝化膜的载流子密度都不断减小. 通过极化曲线和电化学阻抗共同说明, 在5%的Na₂SO₄溶液中, NaOH溶液中阳极钝化后的镁合金随着钝化体系中F^－浓度的增加其耐蚀性逐渐减弱.     

烟酸在铁钝化膜层表面的吸附机理

循环伏安法结合原位拉曼光谱的表征结果表明,烟酸在铁钝化膜层表面的吸附行为归因于其具有形成稳定膜层复合物的性能,烟酸将间隙离子FeⅡ转化为稳定的晶格离子FeⅢ,从而降低铁钝化膜的溶解性.旋转电极电化学晶体微天平的分析结果表明烟酸在活化态和钝化态铁表面的吸附行为遵循LangmuirFreundlich热力学规律,并由此计算出过程中的吸附常数、标准自由能和非均质分布常数.研究认为有机分子在钝化膜表面为化学型吸附,可导致钝化膜破坏的间隙离子被烟酸固定在八面体空位晶格中形成稳定晶型结构,并通过扫描电镜(SEM)和衰减全反射红外光谱(ATR FTIR)分析对结论进行了再次验证.     

钼酸盐封闭后处理的热镀锌钢板硅烷膜的耐蚀性

为进一步增强硅烷膜的耐蚀性, 将硅烷化热镀锌钢板用钼酸盐溶液进行封闭后处理, 并采用扫描电子显微镜(SEM)、中性盐雾(NSS)实验、盐水全浸实验和电化学技术研究了所得复合膜层的表面形貌和耐蚀性能. 结果表明: 经钼酸盐溶液封闭处理后, 硅烷膜的孔隙被填充, 在锌层表面形成了由硅烷膜和钼酸盐转化膜构成的连续完整致密的复合膜; 复合膜的耐蚀性能明显提高, 且与钼酸盐溶液的封闭时间有关, 封闭60 s时所形成的复合膜的耐蚀性最佳. 在5%(w, 质量分数)NaCl溶液中的电化学测量结果表明: 硅烷化热镀锌钢板经钼酸盐溶液封闭处理后, 同时抑制了腐蚀过程中的阳极和阴极反应, 但主要是抑制阴极反应, 导致腐蚀电流密度明显减小, 发挥了单一硅烷膜和单一钼酸盐转化膜腐蚀防护的协同效应, 腐蚀防护效率高达99.1%; 随浸泡时间延长, 试样低频扩散阻抗先增大后减小, 表明膜层具有一定的“自愈”能力, 其耐蚀性优于常规铬酸盐钝化膜.     

Preparation and adhesive properties of colored Ti/Zr-based conversion coating on aluminum foil for lithium battery packaging

In this study, an aluminum (Al) foil used for lithium ion battery packaging film was treated with titanium (Ti)/zirconium (Zr) solution containing hexafluorotitanic acid and hexafluorozirconic acid using tannic acid as a colorant and metavanadate as an accelerator, respectively, and a golden conversion coating was successfully deposited on the surface of Al foil. The morphology and composition of the coating were characterized by scanning electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy, and the hydrophilicity was assessed by contact angle measurement. The effect of Ti/Zr treatment on the adhesion properties of Al foil was evaluated by T-peeling test and compared with that of traditional chromate-phosphate treatment. The results show that tannic acid contributes to the formation of the golden coating, and metavanadate accelerates the formation of the conversion coating. The results also indicate that the Ti/Zr-based conversion coating is mainly composed of Al₂O₃, Al (OH)₃, AlF₃, TiO₂/ZrO₂, NH₄VO₃, and V₂O₅. The Ti/Zr treatment cannot only improve the heat-sealing strength, but also the T-peeling strength by approximately 12 times compared with that of untreated Al foil. Thus, Ti/Zr treatment has the potential to replace the traditional chromate conversion treatment.     

Effect of Cu in electroless Ni–Cu–P coating on passivation process

Electroless Ni–P and Ni–Cu–P coatings were passivated by chromate conversion treatment respectively. The anticorrosive performances of passivated coatings were investigated by potentiodynamic polarization and electrochemical impedance spectroscopy measurements. The passivated Ni–Cu–P coating exhibited a high corrosion resistance with the i_corr of 0.236 μA/cm,² while the value of passivated Ni–P coating was only 1.030 μA/cm,² indicating the passive film could improve the corrosion resistance of Ni–Cu–P coating to a significant extent. High‐resolution X‐ray photoelectron spectroscopy was used to determine the chemical states of elements detected in the passive film. Compared with passivated Ni–P coating, the passive film on Ni–Cu–P coating exhibited a higher ratio of Cr₂O₃ to Cr(OH)₃ with the value of 72:28, which was the main factor for passivated Ni–Cu–P coating showing excellent corrosion resistance. The effect of Cu in electroless Ni–Cu–P coating on passivation process was discussed by the contrast experiment. Copyright © 2016 John Wiley & Sons, Ltd.     

Effects of Mn2+ on the chrome‐free colored Ti/Zr‐based conversion coating on 6063 aluminum alloy

The conversion coating with golden color and improved corrosion resistance had been prepared by adding Mn²⁺ in the Ti/Zr conversion coating solution. Comparing with that of conversion coating without Mn²⁺, the optimal treatment time of this conversion coating was much shorter and the corrosion resistance was obviously improved. The effect of Mn²⁺ on the formation of golden Ti/Zr conversion coating was thoroughly investigated by means of energy dispersive X‐ray spectroscopy, SEM, XPS, and Raman and electrochemical workstation. The results showed that the conversion coating had a double‐layer structure: the outer layer consisted of the metal‐organic complex and the inner layer was mainly made up of Na₃AlF₆. Mn²⁺ was oxidized into MnOOH in solution and precipitated on the substrate surface which provided the nucleus to Na₃AlF₆ crystal and accelerated Na₃AlF₆ crystal formation and also made the microstructure of conversion coating change to the cubic. The mechanism of the formation of the conversion coating can be deemed as nucleation, growth of Na₃AlF₆ crystal, and formation of metal‐organic complex. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of chromate conversion film on tinplate substrate by XPS and electrochemistry methods

The chromate conversion coating formed on commercial tinplate via a cathode electrolytic dichromate treatment has been studied by X‐ray photoelectron spectroscopy (XPS) and electrochemistry methods. Through the analysis of the XPS, it was shown that there existed Cr, O, and Sn in the chromate coating and the chromate film consisted mainly of Cr(OH)₃, Cr₂O₃, Sn, and SnO_x. The current density decreased with increasing of the electric charge. The corrosion resistance for tinplate is relative with the content of chromium in the passivation film. Copyright © 2009 John Wiley & Sons, Ltd.     

Water‐based ZrO2 pretreatment for AA2024 aluminum alloy

Design, development and scale‐up of environmentally friendly coatings are very important in order to replace chromate‐based coatings for aluminum alloys. Sol–gel materials are candidates for use in protective coating applications, as it is possible to form highly adherent and chemically inert oxide films on metal substrates. ZrO₂ pretreatments were developed by means of sol–gel technology. An inorganic salt was employed as Zr precursor in an aqueous solution. The deposition was initially carried out on AA2024 by means of dip and spray technology at laboratory scale. Corrosion inhibitors were introduced to improve corrosion behavior of the films. At a later stage, coating deposition was carried out with a robot‐controlled air‐pressure gun in spraying cabins in order to evaluate industrial production of the pretreatments. Film morphology and composition were investigated by means of SEM‐EDXS and GDOES. The electrochemical behavior of the ZrO₂ pretreatments was investigated by means of potentiodynamic polarization. The water‐based ZrO₂ pretreatment investigated in this work is thin and well adherent on the substrate. Barrier properties are similar to those of chromate conversion coating. Results on samples produced with robot‐controlled air‐pressure gun indicate that ZrO₂ pretreatments are suitable for industrial application. Copyright © 2009 John Wiley & Sons, Ltd.     

In vitro bioactivity of titanium implants coated with bicomponent hybrid biodegradable polymers

In order to improve the bioactivity and biocompatibility of titanium (Ti) implants, we designed a novel biodegradable hybrid (polycaprolactone/polylactic acid, PCL/PLA) membrane to coat Ti surfaces. The bicomponent PCL/PLA membrane was applied to a Ti substrate starting with the coating of Ti samples with a porous PLA film layer using a dip-coating technique. This was followed by deposition of electrospun PCL nanofibers onto the Ti substrate, resulting in a PCL/PLA bicomponent hybrid coating layer. The cytocompatibility, bioactivity and corrosion performance of PCL/PLA-coated Ti samples was compared to PLA-coated Ti samples and untreated Ti samples. When placed in Hanks’ solution, apatite formed on the treated Ti samples but not on untreated Ti samples. When assessing Ti cytocompatibility and MC3T3-E1 osteoblast adherence, proliferation, and survival, our results showed superior performance by polymer-treated Ti samples compared to untreated Ti samples, and maximal osteoblast cell viability was achieved with the bicomponent PCL/PLA hybrid coating layer. Furthermore, during the potentiodynamic polarization test in simulated body fluid, the polymer-coated Ti samples showed corrosion resistance. Therefore, the approach described herein may serve as a basis for the development of polymer-coated Ti surfaces that can be used in dental or orthopedic implants.     

Development of Composition and Investigation of Properties of a New,Environmentally Friendly Molybdenum-Containing Decorative Protective Conversion Coating on Zinс-Plated Surfaces

The composition was developed for a new high-efficiency black environmentally friendly molybdenum-containing decorative protective conversion coating on zinс-plated surfaces. The corrosion resistance of this coating was investigated. It was proven theoretically and experimentally that the new coating is comparable in corrosion resistance and protective power to popular environmentally hazardous chromate coatings. A study of the physicochemical mechanism of the formation of a black molybdenum-containing coating on a zinс-plated surface determined that the new conversion coating comprises mainly molybdenum(V) oxide.     

EIS study on the corrosion performance of a Cr(III)-based conversion coating on zinc galvanized steel for the automotive industry

The corrosion performance of a new industrial Cr(III)-based conversion coating on zinc galvanized FeP04 steel for the automotive industry was studied. For comparison, the zinc galvanized steel submitted to a Cr(VI)-based passivation treatment was also examined. The corrosion behavior was assessed by means of potentiodynamic polarization and electrochemical impedance spectroscopy measurements in aerated 0.1 M NaCl solution. The behavior of untreated zinc galvanized FeP04 steel in aerated 0.1 M NaCl solution was also studied. The results obtained indicate that with the same thickness, the coating generated in the Cr(III) treatment bath exhibits better corrosion properties compared to the coating formed in the Cr(VI) treatment bath. The difference in the corrosion protection given by the two conversion coating types can be ascribed to the difference in the chromium content and coating composition.