热镀锌板无铬钝化技术研究进展

采用传统的铬酸盐钝化处理技术,能够在金属表面获得一层耐蚀性能优异且具有自修复性的钝化膜。但是由于六价铬毒性很大,对人类的健康有很大危害,近年来六价铬钝化工艺已经被限制使用,因此开发新型环保的无铬钝化技术已成为目前的研究热点。现有热镀锌板的无铬钝化工艺可大致分为有无机钝化、有机钝化、无机/有机复合钝化三种类型。详细介绍了这三种无铬钝化类型的机理及其研究进展,主要阐述了现有制备镀锌板表面无铬钝化膜层的钼酸盐钝化、钨酸盐钝化、硅酸盐钝化、植酸钝化、单宁酸钝化、有机硅烷钝化、有机树脂钝化和无机盐/有机树脂复合钝化等工艺的原理,并对这几种无铬钝化工艺的特点进行了总结,阐明了不同无铬钝化工艺获得的钝化膜层的结构特点。通过与铬酸盐钝化膜的性能相比较,进一步分析了各种无铬钝化膜层的优缺点。最后提出综合利用无机钝化和有机钝化的优点,研发新型环保的无机/有机复合钝化处理工艺是热镀锌钢板无铬钝化技术未来的发展趋势。     

锌镀层钝化处理的研究现状及展望

介绍了锌镀层铬酸盐钝化和三价铬钝化的原理及应用前景;分别概述了高铬钝化、低铬彩色钝化、低铬蓝白钝化、军绿色钝化的优缺点;重点介绍低铬钝化和三价铬钝化的发展,并进行了展望.     

铝合金三价铬钝化液的研制和应用

分析了铝合金三价铬钝化液的钝化机制,研究了复合盐钝化剂用量、钝化处理时间和温度对钝化膜质量的影响。结果表明,经铝合金三价铬钝化液钝化后的试样,其抗腐蚀性能优于铬酸钝化液,可在常温下进行处理,且处理时间较短,有利于减轻铬酸钝化液中六价铬离子对环境的影响。     

Cu-Ni合金BTA复配体系钝化处理工艺研究

采用苯并三氮唑(BTA)复配钝化体系对B10 Cu-Ni合金进行钝化处理,以提高其在含硫化物环境介质中的耐腐蚀性能,并研究工艺参数对钝化膜耐蚀性的影响规律.利用动电位极化曲线和电化学阻抗谱研究钝化膜的耐腐蚀性能,采用X射线光电子能谱分析钝化膜的化学成分.实验结果表明,在BTA与磺基水杨酸组成的复配体系中形成的钝化膜比BTA单一体系中形成的钝化膜具有更高的耐蚀性,这是磺基水杨酸与基体合金反应形成的络合物膜与Cu(I)BTA膜协同作用的结果;钝化处理的时间和温度是影响钝化膜耐蚀性的重要工艺参数,延长钝化时间和提高钝化温度均可以提高钝化膜的耐蚀性,60℃高温条件下5 min的钝化处理即能够达到常温条件下3 h的钝化处理效果.     

载波钝化及其后处理对不锈钢钝化膜组成及稳定性的影响

一、前言钝化是不锈钢得以广泛应用的前提之一,人们不断地探索提高钝化膜稳定性的新途径。一些学者认为,交变电场对钝化膜具有破坏作用。这种看法有一定的片面性。我们曾发现,在直流钝化电位基础上叠加一定频率,幅值和波形的交变电场对不锈钢进行载波钝化,所得到的载波钝化膜再经适当的后处理,其稳定性远远优于相同条件下得到的直流钝化膜,其中最佳的载波钝化及后处理条件可使不锈钢钝化膜稳定性提高5个数量级左右。本工作通过AES等分析手段,从钝化膜组成变化角度探讨载波钝化及后处理提高钝化膜稳定性的原因。     

镀锌层无铬(Ⅵ)钝化的现状与发展趋向

概述了国内外镀锌层无铬（Ⅵ）钝化工艺的新进展，包括三价铬钝化、钼酸盐钝化、钨酸盐钝化、钛盐钝化、单宁酸钝化、植酸钝化．亡艺，及在研究上有较大进展的改性硅酸盐钝化、稀土金属盐钝化、有机硅烷钝化及无机-有机物复合型钝化等工艺。并在此基础上进一步提出了镀锌层无铬钝化的发展方向。     

压铸锌合金用三价铬钝化液的开发和应用

分析了一种高效、环保压铸锌合金用三价铬钝化液的主要成分及其操作工艺条件,优化了钝化液工作的参数,包括钝化液pH值、钝化温度和钝化时间的影响.研究结果表明,经三价铬钝化液处理后的锌合金,其钝化膜层均匀,色泽白亮、略显淡蓝色,耐中性盐雾腐蚀时间超过96h;该三价铬钝化液不仅有利于减轻原六价铬钝化液中六价铬对环境的污染,而且价格便宜、操作工艺简单.     

双一[γ一（三乙氧基硅）丙基]四硫化物处理热镀铝锌层的耐蚀性研究

采用双-[γ-(三乙氧基硅)丙基]四硫化物(BTESPT)硅烷钝化液对热镀铝锌钢板进行了钝化处理.研究了在5%NaCl溶液中未钝化、硅烷钝化及铬酸盐钝化热镀铝锌钢板的极化曲线和电化学交流阻抗谱.通过中性盐雾试验比较了硅烷钝化膜与铬酸盐钝化膜的耐蚀性能.结果表明:经硅烷钝化液钝化后的热镀铝锌钢板,其腐蚀电位和电流密度下降,极化电阻增大,硅烷钝化膜抑制了热镀铝锌钢板的腐蚀过程,使得耐蚀性能远远高于铬酸盐钝化后的热镀铝锌钢板.     

无铬钝化与三价铬钝化的研究进展

六价铬钝化工艺,毒性大,严重污染环境,电镀行业研究并采用无毒或低毒的钝化工艺势在必行.目前无铬钝化和三价铬钝化已取得积极的进展,三价铬钝化已应用于生产,并获得良好的效果.无铬钝化作为环保工艺,是将来钝化工艺发展的新方向.结合近年来无铬钝化和三价铬钝化的发展,对无铬钝化、三价铬钝化及封闭处理等进行了较详细的阐述.     

镀锌钝化生产工艺优化

在钝化产品的实际生产中,钝化盐雾时间是评价钝化产品防锈能力的主要指标,钝化产品在生产过程中会出现钝化能力过剩的问题,同时该问题也导致了钝化液吨耗过高,造成生产成本增加。文章对解决钝化能力过剩的问题进行了探讨,对钝化工艺的原有工艺参数进行了优化。     

Improvement on the pitting corrosion resistance of 304 stainless steel via duplex passivation treatment

A remarkable improvement in the pitting corrosion resistance of 304 stainless steel was attempted using a novel duplex passivation treatment method. First, chemical passivation in nitric acid followed electrochemical passivation via potential polarization of step cycling in sodium nitrate electrolyte. Compared with traditional chemical passivation, breakdown potential was increased from 0.31 V_SCE to positive than 0.9 V_SCE at 70°C in a solution bearing 0.6 M [Cl^?] concentration. The critical pitting temperature was enhanced from 21.5°C to above 70°C in a solution with 6 M [Cl^?] concentration. Impedance analysis and X‐ray photoelectron spectroscopy results show that a more compact passive film with a higher ratio of chromium oxide on iron oxide was achieved by electrochemical passivation compared with chemical passivation. Morphology observation suggested that the potential polarization of step cycling slightly increased the dissolution of inclusions after being subjected to chemical passivation. The probable reason for the improvement on pitting resistance is discussed in detail based on inclusion dissolution and the protectiveness in passive film.     

304不锈钢环保型酸洗钝化工艺及其性能研究

采用化学浸泡法和动电位扫描法研究了304不锈钢在环保型酸洗钝化工艺下所得钝化膜的耐点蚀性能,运用X射线光电子能谱(XPS)分析了钝化膜的组成和结构.结果表明:由正交试验优选出的最优配方和工艺可大大提高304不锈钢表面钝化膜的耐点蚀性能;304不锈钢表面钝化膜中的Cr、Fe、Ni分别以Cr2O3、FeO、NiO的形式存在;钝化处理后,试片表面钝化膜中的铬元素和镍元素的含量明显增加.综合考虑,不锈钢柠檬酸钝化的最佳工艺为:柠檬酸质量分数4%,氧化剂X体积分数5%,乙醇体积分数2.5%,温度40℃,钝化时间60min.     

硼酸-硼砂缓冲液中铁的孔蚀及缓蚀剂PC-604作用的光电化学研究

采用光电化学方法对纯铁在ｐＨ＝８．４的硼酸－硼砂缓冲液中的孔蚀现象及缓蚀剂ＰＣ－６０４的作用进行了研究。结果表明,加入不同量的缓蚀剂后,铁表面饨化膜的禁带宽度没有发生变化,但是光电流信号却随缓蚀剂量的增加而增大了。从光电流暂态谱的研究中首次提出了钝化膜的膜参数的概念,并用以衡量钝化膜的抗孔蚀能力。     

温度对Cr26Mo1超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响

通过循环极化曲线、Mott-Schottky曲线以及电化学阻抗谱等方法研究了温度对Cr26Mol超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响.结果表明:随着温度升高,Cr26Mol超纯高铬铁素体不锈钢的自腐蚀电位降低,腐蚀电流密度增大,点蚀电位下降,钝化膜阻抗降低.Cr26Mol不锈钢钝化膜的半导体类型和性质在不同温度下发生改变.Cr26Mol不锈钢发生点蚀的孕育期随着温度的升高而缩短,点蚀敏感性增加,已发生点蚀的试样不能够自修复.     

温度对Cr26Mol超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响

通过循环极化曲线、Mott-Schottky曲线以及电化学阻抗谱等方法研究了温度对Cr26Mo1超纯高铬铁素体不锈钢在3.5%NaCl溶液中耐点蚀性能的影响.结果表明:随着温度升高,Cr26Mo1超纯高铬铁素体不锈钢的自腐蚀电位降低,腐蚀电流密度增大,点蚀电位下降,钝化膜阻抗降低.Cr26Mo1不锈钢钝化膜的半导体类型和性质在不同温度下发生改变.Cr26Mo1不锈钢发生点蚀的孕育期随着温度的升高而缩短,点蚀敏感性增加,已发生点蚀的试样不能够自修复.     

HCO3–对超级13Cr马氏体不锈钢钝化行为及点蚀行为的影响

目的研究在0.1 mol/L NaCl硼酸缓冲溶液中,研究HCO_3~–对超级13Cr马氏体不锈钢的钝化及点蚀行为的影响。方法采用动电位极化、恒电位极化、Mott-Schottky曲线、电化学阻抗谱等电化学测试手段,并结合3D超景深显微镜进行点蚀形貌观察,研究超级13Cr马氏体不锈钢的电化学腐蚀行为。结果随着HCO_3~–浓度的增加,超级13Cr的钝化区间变宽,点蚀电位向正向移动,稳态点蚀发生的敏感性降低。HCO_3~–减少了超级13Cr亚稳态点蚀数量,降低了亚稳态点蚀电流密度峰值的平均值。随着HCO_3~–浓度的增大,超级13Cr钝化膜电阻Rf升高,电荷转移电阻Rct升高,钝化膜电容Cf逐渐减小。HCO_3~–使得超级13Cr钝化膜半导体特性由n型转变为n+p型双极性,且随着溶液中HCO_3~–浓度的增大,钝化膜中的施主密度ND和受主密度NA减小。结论 HCO_3~–的加入使得超级13Cr不锈钢钝化膜厚度增大,钝化膜内点缺陷密度降低,对基体的保护作用增强,抑制了超级13Cr的亚稳态和稳态点蚀发生。     

铬镀层及其阴极化修饰镀层的钝化行为

用电沉积方法在ＡＩＳＩ ４３０不锈钢上得到铬、铬钯交替镀层和铬钯复合镀层，凭借钯的阴极修饰效应，含钯的铬镀层在除氧的非氧化性酸中具有自钝化能力，极化曲线和阻抗频谱测定表明，在相庆铬镀层处于活化－钝化的电位区间，含钯镀层都表现出净阴极电流；活化溶解与钝化过程随电位的相对发展变化可由低频段容抗圈的演变来推定，铬钯复合镀层具有更大的钝化膜阻抗。     

氢对纯镍钝化膜的影响

研究了氢对纯镍阳极极化和钝化膜形成及耐蚀性能的影响。结果表明：预充氢会降低纯镍的自腐蚀电位,使其出现明显的活化区和临界钝化电流,缩短钝化区域;提高钝化电流密度和延长钝化膜的形成时间。固溶氢降低钝化膜的稳定性,增大膜的自活化能力;并导致钝化膜出现明显的孔蚀,膜的孔蚀电位随固溶氢含量的增加而降低。     

XPS analysis of the passive film formed on austenitic stainless steel coated with conductive polymer

Improvement of the passivation behavior of Type 304 austenitic stainless steel (SS) by coating with conductive polymers (CPs), like polyaniline (PANI) and poly(o-phenylenediamine) (PoPD), followed by exposure in an acid solution has been demonstrated. The passive films formed on SSs (after peeling off the polymer layer) are compared with those formed during anodic polarization under the same exposure condition. The passive films beneath the CPs are thicker and less hydrated than those formed on uncoated stainless steel. The polymer layer enhances the enrichment of chromium and nickel in the entire passive oxide, forming a more protective film than that formed during anodic polarization. The elemental distribution within the passive film is different in the two modes of passivation. The type of the polymer influences on the composition of the passive film. The best passivation is obtained by PoPD, with the passive film resulting in significant resistance of the SS to pitting corrosion in the 3% NaCl solution. The oxide film of this steel is characterized, in its inner and outer layers, by the highest ratio of Cr(OH)₃/Cr₂O₃ and the lowest content of iron species.     

An XPS study of anodic behavior of amorphous nickel-phosphorus alloys containing chromium,molybdenum or tungsten in 1 m CHl

The surfaces of amorphous Ni-18P, Ni-IOCr-20P, Ni-9Mo-19P and Ni-5W-18P alloys immersed or anodically polarized in 1 M HCl solution were analyzed in connection with their corrosion and anodic behavior. All alloys were more corrosion-resistant than crystalline nickel metal because of formation of phosphate-containing surface films on the Ni-18P, Ni-9Mo-19P and Ni-5W-18P alloys and because of spontaneous passivation due to formation of passive hydrated chromium oxyhydroxide film on the Ni-10Cr-20P alloy. The latter alloy was stable up to the transpassive region of chromium although intrusion of phosphate in the film was responsible for the higher passive current density in comparison to the amorphous Fe-Cr-13P-7C alloy of the same chromium content. The formation of thick porous phosphate films containing nickel, and molybdenum or tungsten by anodic polarization was not effective in passivating the Ni-18P, Ni-9Mo-19P and Ni-5W-18P alloys, and they suffered pitting corrosion by anodic polarization.