热镀锌层钛盐钝化膜耐蚀性能的研究

以钛盐为主盐,加入双氧水、硝酸(磷酸)、络合剂等配制无铬钝化液,经钝化后在镀锌层表面获得一层均匀的无铬钝化膜.通过电化学试验、盐雾腐蚀试验、大气暴露试验等测试手段对比研究了铬酸盐钝化膜、钛盐钝化膜、镀锌层的耐蚀性能以及影响钝化膜耐蚀性的因素.结果表明:镀锌层经钛盐钝化后耐蚀性能明显改善,在中性盐雾箱内可以通过48 h连续喷雾而不产生白锈.     

AZ31B型镁合金表面钛盐化学转化膜

研究了一种镁合金表面无铬钝化的钛盐环保型化学转化膜处理工艺。利用中性盐雾试验和极化曲线法测试了转化膜的耐蚀性能,采用SEM、EDS等方法对膜的形貌、元素组成进行了研究。结果表明,钛盐转化处理后在镁合金表面形成含钛氧化物膜层,该膜层有良好的耐蚀性能。     

高择优取向碱性锌酸盐镀锌层的耐蚀性

采用盐水浸泡试验,电化学测试和盐雾试验研究了碱性锌酸盐体系中获得的高择优取向镀锌层和随机取向镀锌层的耐蚀性能,对比了不同取向镀锌层三价铬和六价铬钝化膜的耐蚀性;采用盐雾试验对比了两种取向镀锌层和氰化镀锌层的耐蚀性。结果表明,高择优取向镀锌层的耐蚀性优于随机取向镀锌层;两种取向的镀锌层经三价铬钝化比六价铬钝化耐蚀性要好;经三价铬钝化处理后的高择优取向镀锌层耐盐雾时间可达720h。     

镀锡板无铬钝化工艺研究

基于钛锆-磷硅无铬钝化体系,采用正交试验方法,改变钝化液浓度、干燥温度和时间,成功获得了高性能无铬钝化膜,并确定了无铬钝化最佳工艺。通过测定试验样板的抗酸抗硫性能、涂漆附着力性能和电化学耐蚀性能,发现其综合性能接近铬酸盐钝化产品。     

镀锌层三价铬黑色钝化膜的耐蚀性能

制备了一种环保、不含六价铬的三价铬黑色钝化液,选择适当的封闭剂,研究其在镀锌层表面钝化后的耐腐蚀性能。通过醋酸铅点滴试验、塔菲尔极化曲线测试、电化学阻抗测试检测钝化膜的耐蚀性及采用扫描电子显微镜观察其表面形貌。结果表明:镀锌层表面经三价铬黑色钝化后再进行封闭处理,弥补了Cr3+钝化后无自愈能力的缺点,显著提高了镀锌层钝化膜的耐腐蚀性能,而且达到了Cr6+黑色钝化的外观效果。     

硅烷-钼复合无铬钝化膜的耐蚀性及标准曲线构建

为更好地指导新型硅烷-钼复合无铬钝化膜的工业化生产,研究钝化膜的耐蚀性能,构建皮膜量标准曲线。分别使用X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)分析钝化膜的物相组成和表面元素价态。利用中性盐雾试验和电化学测试,探讨钝化膜的耐蚀性能。采用X射线荧光光谱法(XRF),绘制和构建皮膜量标准曲线。结果表明:硅烷-钼复合无铬钝化膜层中Si、Mo元素能分别与Zn形成化学键,膜层结合性较好。膜层耐蚀性在一定范围内随着膜层皮膜量升高而升高,当皮膜量高于800 mg/m2时,耐蚀性趋于稳定,其耐蚀性与稳定性接近Cr6+。此外,皮膜量与XRF射线强度呈线性关系,斜率为3.413。     

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。     

机械镀锌层钝化工艺研究

针对目前机械镀锌的钝化多为借鉴电镀锌、热浸镀锌的钝化工艺,其工艺不稳定、处理效果差等问题,本文借助醋酸铅点滴实验法分析了机械镀锌层的出光、钝化工艺。采用盐水浸泡试验、电化学极化法分析了机械镀锌层钝化膜的耐腐蚀性能。研究结果表明,采用由柠檬酸、乙二醇、OP-10组成的出光液对镀层腐蚀较弱,出光后镀层表面光亮,钝化膜醋酸铅点滴发黑时间短。优化并确定了机械镀锌层的无铬亮白钝化、低铬蓝白钝化和低铬亮白钝化三种钝化液组成,三种钝化膜均能提高镀层的耐蚀性能,改善镀层的外观光泽性。其中低铬亮白钝化处理后的钝化膜耐腐蚀性能最佳。     

硫酸铈对三价铬钝化膜耐腐蚀性的影响研究

目的研究硫酸铈对三价铬钝化膜耐蚀性能的影响。方法通过在三价铬镀铬盐溶液中分别添加0.3、0.5、0.8、1.0、1.5 g/L的硫酸铈,然后通过极化曲线测试,对比不同硫酸铈添加量的钝化膜的腐蚀电流密度,确定硫酸铈在三价铬镀铬盐溶液中的最佳添加量,然后分别制备未添加硫酸铈和添加最佳添加量硫酸铈的三价铬钝化膜,通过电化学工作站CHI660E测量Tafel极化曲线和电化学阻抗谱。分析钝化膜的电化学性能,研究不同钝化膜的耐腐蚀性。观察试样表面的微观形貌,对比添加硫酸铈和未添加硫酸铈的钝化膜的微观形貌。结果通过极化曲线测试发现,当硫酸铈的添加量为1.0 g/L时,钝化膜的腐蚀电流密度小于其余添加量的钝化膜,添加硫酸铈和未添加硫酸铈的钝化膜的耐蚀性能不同,添加硫酸铈后的钝化膜性能得到改善,且钝化膜膜层的微观形貌发生改变。结论添加硫酸铈后,三价铬钝化膜的耐腐蚀性能增强。当硫酸铈的添加量为1.0 g/L时,腐蚀电流密度最小,为3.835×10~(-6) A/cm~2,耐腐蚀性能优于其余钝化膜。     

镀锌层硅酸盐+虫胶复合转化膜的制备和表征

目的阻碍热镀锌板出现白锈,提高镀锌层的耐腐蚀性能。方法采用正交试验法优化出添加虫胶水溶液的有机无机复合钝化液。通过电化学Tafel极化曲线、交流阻抗(EIS)、乙酸铅点滴和中性盐雾试验,对比分析基体、硅酸盐+虫胶复合钝化膜与铬酸盐钝化膜的耐腐蚀性能。采用摩擦法测试对比分析基体和无铬钝化膜试样的附着性能,并通过扫描电子显微镜、X射线光电子能谱和红外光谱对形貌和结构进行分析。结果添加虫胶水溶液的复合钝化膜表面平整致密,72 h中性盐雾试验后的腐蚀面积小于10%。乙酸铅点滴试验和电化学测试显示,复合钝化膜的耐腐蚀性能较基体好。附着力试验测试显示,复合钝化膜具有良好的附着能力。结论因为复合钝化液中的虫胶与硅酸盐交织为O—Si—CH_2结构,与金属离子结合生成致密的膜层附着在镀锌层表面,使得复合钝化膜致密平整,且使腐蚀过程得到了强烈的抑制。     

Electrodeposited nickel/alumina composite coating on NdFeB permanent magnets

NdFeB magnets are highly susceptible to corrosion in various environments. A nickel/alumina composite coating for NdFeB magnets was investigated in this paper. The microstructures of electrodeposited nickel coating and nickel/alumina composite coating were determined by scanning electron microscope (SEM). The corrosion behavior of nickel coating and nickel/alumina composite coating in 3.5 wt% sodium chloride solution was studied by polarization curves and electrochemical impedance spectroscopy (EIS). The results show that the nickel coating and nickel/alumina composite coating can both provide adequate protection to the NdFeB substrate. Furthermore, the free corrosion potential of nickel/alumina composite coating is more positive and the passivation region is more obvious compared with nickel coating, and the capacitance loop diameter of nickel/alumina composite coating is significantly larger than that of nickel coating. With the increase in immersion time, a flat of passivation film is formed on the surface of nickel/alumina composite coating, resulting in excellent corrosion resistance after 288 h immersion in 3.5% sodium chloride solution according to EIS testing.     

Cr含量对Fe-Cr-Ni镀层电化学腐蚀性能的影响

以硫酸盐和氯化盐为主盐,将Cr以微粒形式悬浮于镀液中,电沉积Fe-Cr-Ni复合镀层,用电化学方法研究了镀液中Cr粉含量对电沉积Fe-Cr-Ni复合镀层在NaCl介质中的腐蚀行为的影响.结果表明:在镀层的浸泡试验中,溶液中Cr粉含量为100g/L获得的镀层自腐蚀电位是最负的.动电位扫描显示,镀层都有钝化性能.但对于溶液中Cr粉含量为100g/L获得的镀层出现明显的过钝化,其耐蚀性能较差.     

Corrosion protection of sintered NdFeB magnets by CAPVD Ti2N coating

Sintered NdFeB magnets have poor corrosion resistance and are readily susceptible to corrosion under different environmental conditions. Cathodic arc physical vapour deposited (CAPVD) titanium nitride coating for sintered NdFeB permanent magnets has been investigated in this paper. Tafel extrapolation was employed to study the corrosion behaviour in 3.5% NaCl solution at ambient temperature. The adhesive strength of the coating was estimated with the help of the scratch test. The surface chemistry and coating morphologies were studied with scanning electron microscope (SEM). X-Ray diffraction (XRD) was used for qualitative phase analyses of coatings and substrate. The properties of CAPVD titanium nitride coating were compared with electrodeposited multilayer nickel–copper–nickel coating. It was figured out that the CAPVD titanium nitride coating had better adhesion strength and shifted the free corrosion potential (FCP) of the system towards positive potential, providing protection to the NdFeB substrate. However, the corrosion rate of CAPVD titanium nitride coating was more than the electrodeposited multilayer nickel–copper–nickel coating. The magnetic properties remained comparable.     

Corrosion of AZ91D magnesium alloy with a chemical conversion coating and electroless nickel layer

A chemical conversion treatment and an electroless nickel plating were applied to AZ91D alloy to improve its corrosion resistance. By conversion treatment in alkaline stannate solution, the corrosion resistance of the alloy was improved to some extent as verified by immersion test and potentiodynamic polarization test in 3.5 wt.% NaCl solution at pH 7.0. X-ray diffraction patterns of the stannate treated AZ91D alloy showed the presence of MgSnO₃ · H₂O, and SEM images indicated a porous structure, which provided advantage for the adsorption during sensitisation treatment prior to electroless nickel plating. A nickel coating with high phosphorus content was successfully deposited on the chemical conversion coating pre-applied to AZ91D alloy. The presence of the conversion coating between the nickel coating and the substrate reduced the potential difference between them and enhanced the corrosion resistance of the alloy. An obvious passivation occurred for the nickel coating during anodic polarization in 3.5 wt.% NaCl solution.     

纳米结构黑镍薄膜的电沉积制备及其电化学行为

采用电沉积方法制备具有整体纳米结构的黑镍镀层,并通过肉眼观察结合扫描电镜、X射线衍射等测试技术研究电沉积过程中的主要参数(电解液pH、搅拌速度、制备温度及电流密度)对镀层颜色及整体微观结构的影响。进一步采用动电位极化及电化学阻抗等电化学测量技术研究黑镍镀层在中性3.5%NaCl溶液中的腐蚀行为及腐蚀机理。结果表明：黑镍镀层的颜色变化趋势决定于电沉积制备参数的选择;通过优化本工艺制备的黑镍镀层平均粒径约为50 nm。对比了近似条件下制备的光亮镍镀层,发现黑镍镀层在耐蚀性方面具有较大优势。     

镀锌层表面钝化膜在5%NaCl溶液中的腐蚀降解过程和半导体行为

采用扫描电化学显微镜(SECM)分析技术、电化学阻抗谱(EIS)和电容-电位测试研究了镀锌层表面钝化膜在质量分数5%NaCl溶液中的腐蚀降解过程和半导体行为。结果表明:浸泡过程中随着水和离子逐渐侵入钝化膜,钝化膜发生着缓慢的腐蚀降解,钝化膜在浸泡初期保持稳定,能够对基体金属起到较好的保护作用;钝化膜表现出n型半导体特征,随着浸泡时间的延长,Mott-Schottky曲线拟合直线的斜率逐渐减小,钝化膜载流子密度逐渐增大,表明钝化膜在浸泡过程中发生缓慢的腐蚀降解。     

聚吡咯涂层的制备及耐腐蚀性能研究

目的在铜表面制备聚吡咯涂层,研究其在3.5%(质量分数)Na Cl溶液中的耐腐蚀性能。方法采用恒电位法、恒电流法和循环伏安法在铜表面制备聚吡咯薄膜,用扫描电子显微镜观察聚吡咯膜形貌,用动电位极化曲线、长期浸泡实验研究铜表面聚吡咯膜的防腐蚀情况。结果三种方法都可以在铜表面形成结构致密、结合力较好的呈菜花状结构的聚吡咯膜。聚吡咯膜在3.5%(质量分数)Na Cl溶液中的极化曲线与空白铜不同,形成了钝化区。在60 min,0.659 V和60 min,1 m A条件下制备的聚吡咯膜的腐蚀电位与空白铜片相比,分别提高了约50 m V和150 m V,阳极溶解电流密度比空白铜片均降低了1个数量级。在长期浸泡实验中,带有聚吡咯膜的铜片的腐蚀速度低于空白铜片。结论聚吡咯膜可以延缓铜片的腐蚀,恒电位法制备的聚吡咯膜具有更优良的耐蚀性能。     

环保型镀锌层蓝色钝化膜耐腐蚀性能的研究

采用钛盐溶液替代铬酸盐溶液对镀锌层进行表面钝化处理,获得了色泽光亮、耐腐蚀性能优良的蓝色钝化膜层。探讨了钛盐钝化溶液成分及工艺参数对镀锌层表面钝化膜的耐腐蚀性影响;中性盐雾、电化学测试等腐蚀性能试验结果表明,钛盐钝化溶液所获得的蓝色钝化膜,其耐腐蚀性能更优于铬酸盐钝化膜。     

Impeding corrosion of sintered NdFeB magnets with titanium nitride coating

Sintered NdFeB magnets have poor corrosion resistance that renders them susceptible to corrosion in industrial and marine environments. This paper evaluates the properties of cathodic arc physical vapour deposited (CAPVD) titanium nitride coating for corrosion protection of sintered NdFeB permanent magnets. The performance of titanium nitride coating has been compared to the electrodeposited nickel–copper–nickel multilayer coating. The rates of coatings degradation in simulated marine environment were estimated with electrochemical impedance spectroscopy (EIS). Cyclic polarization was carried out to assess the pitting potential. The surface chemistry and coating morphologies were studied with scanning electron microscope (SEM). X‐ray diffraction (XRD) was used for qualitative phase analyses of coatings and the substrate. It was figured out that the charge transfer resistance of CAPVD titanium nitride coating increased with exposure time. The negative rate of Rp‐degradation for titanium nitride coating compared to the nickel–copper–nickel multilayer for equivalent exposure time is a unique and valuable result. Polarization results showed that ‘pits re‐passivation’ of titanium nitride coating could be responsible for the extended corrosion protection of the NdFeB substrate. The magnetic properties remained comparable for both types of coatings.     

铁基粉末冶金零件电镀前二次水基防锈溶液的封孔技术研究

目的铁基粉末冶金零件具有特殊的疏松和多孔结构,在前处理、电镀、钝化等过程中易造成零件孔隙的酸、碱、盐等残留,镀后零件在使用过程中也易出现耐腐蚀性能下降或镀层脱落的现象。因此,对铁基粉末冶金零件孔隙进行封闭是一种提高镀层防腐蚀性能和结合性能的有效方法。方法采用一种专用的粉末冶金零件水基防锈封闭溶液,对零件孔隙进行前处理前的第一次封闭和前处理后的第二次封闭。其孔隙封闭原理是在镀前处理前,利用水基防锈溶液中的缓蚀剂、钝化剂等成分的扩散、渗透,在孔隙处发生吸附、钝化及沉淀等反应,来减轻或避免前处理过程中接触到的酸、碱等成分在孔隙的残留;再在电镀前处理后,进行第二次防锈水溶液的封闭处理,可进一步强化粉末冶金零件的钝化封闭效果。结果没有经过防锈水溶液封闭处理的白钝化锌镍合金镀层(滚镀零件),在96 h盐雾试验后,表面出现了轻微的腐蚀;经过一次防锈水溶液封闭处理的锌镍合金镀层,在120 h后出现了轻微的腐蚀;经过二次防锈水溶液封闭处理的锌镍合金镀层,在240 h后未出现腐蚀。结论粉末冶金零件经过这二次封闭处理,再进行电镀Zn-Ni合金及镀层钝化处理,可以有效提高零件表面镀层的耐腐蚀性能和结合性能。