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。     

热镀锌板三价铬钝化剂的制备及其钝化膜耐蚀性能

目的制备钝化膜耐蚀性良好的热镀锌板三价铬钝化剂。方法以铬酸酐、酒石酸盐、无机混酸、纳米硅溶胶为原料,制备三价铬钝化剂。采用该钝化剂对热镀锌板进行钝化处理,通过中性盐雾试验、Tafel极化曲线和交流阻抗谱分析钝化膜的耐蚀性能,并表征钝化膜的表面形貌和元素组成。结果钝化镀锌板经120 h中性盐雾试验后,腐蚀面积仅为5%。与未钝化镀锌板相比,钝化试样的自腐蚀电位有所正移,自腐蚀电流密度降低了约2个数量级。钝化膜表面较为平整,有少量白色颗粒沉积,膜中主要含有C,O,Si,Cr,Zn等元素,且Cr主要以三价和六价存在,Zn以二价存在。结论该三价铬钝化剂可提高镀锌板的耐蚀性能,具有较好的工业使用推广价值。     

锌铝镁镀层不同表面处理体系成分分析及耐蚀性研究

目的 分析锌铝镁镀层不同表面处理体系的成分,考察表面处理膜层的耐蚀性,明晰不同表面处理方式的防腐机制。方法 通过白光干涉仪和扫描电镜(SEM)对3种表面处理方式下锌铝镁钢板不同表面微观形貌进行观察,通过辉光光谱(GDS)、X射线衍射(XRD)、X射线光电子能谱(XPS)以及傅里叶变换红外反射吸收光谱(FTIR)对表面处理膜膜层厚度及成分结构等进行表征,并结合家电板实际使用条件,考察不同钝化膜层的耐蚀性。结果 涂油样品表面存在约10 nm厚、以烃类基础油和钙盐缓蚀剂等成分为主的油膜。三价铬钝化膜为厚度约50 nm,以Cr2O3、Cr(OH)3及ZnO为主的致密不溶性氧化物膜层,无铬钝化膜为厚度约3 μm、以氨基硅烷-树脂为主成膜物质的有机钝化膜。XPS及FTIR结果表明,硅烷-树脂在钢板表面发生了交联反应,形成了三维立体网状结构,同时钝化膜与镀层Zn之间形成了强化学键作用。电化学试验结果表明,三价铬钝化以及无铬钝化样品具有更小的自腐蚀电流密度及更大的电化学阻抗。在中性盐雾环境中,三价铬钝化膜具有更好的平面耐蚀性。无铬钝化膜具有更优异的划叉耐蚀性。结论 三价铬钝化处理以及无铬钝化处理锌铝镁板的腐蚀倾向均小于涂油处理锌铝镁板的,相关研究可为锌铝镁镀层材料在家电板市场的推广应用提供理论支撑。     

铝管表面掺杂改性杂化膜的制备及性能表征

采用溶胶-凝胶法,以正硅酸乙酯(TEOS)和乙烯基三乙氧基硅烷(KH151)作为水解前驱体制备杂化溶胶,掺杂1.5×10-3mol/L Ce(NO3)3,通过浸渍法在蒸发器铝管表面制备了耐蚀性膜层。CuSO4点滴实验、中性盐雾实验和电化学测试结果表明,掺杂改性杂化膜的耐蚀性能优于铬酸盐钝化膜。红外光谱分析表明,膜层中存在不同类型的Si—O—Si共价键,有机官能团C=C共价键增强了膜层的疏水性。从SEM像可看出,杂化膜均匀、致密、平整。     

无铬复合钝化膜的微观组织结构及耐腐蚀性能

目的解决热镀锌钢板表面六价铬钝化工艺所产生的环境污染问题。方法以钼酸铵、纳米硅溶胶、单宁酸、硅烷偶联剂KH151和KH792为主要原料配制新型环保的无铬复合钝化液,在镀锌板表面制备钝化膜。采用扫描电子显微镜(SEM)、能谱仪(EDS)和X射线光电子能谱仪(XPS)分析无铬复合钝化膜表面的微观形貌、元素组成和化学成分,用电化学工作站测试Mo元素对镀锌板耐蚀性的影响,使用中性盐雾实验研究不同皮模量时膜层的耐蚀性。结果无铬复合钝化膜中的Mo元素可以抑制微裂纹的产生和发展,阻挡腐蚀性介质向金属基体扩散,提高复合硅烷膜的电阻。复合钝化膜的电化学交流阻抗比硅烷钝化膜提高了1.6倍,与六价铬钝化膜接近,可以有效抑制腐蚀电化学反应的发生,降低反应速度,提高膜层的耐蚀性。皮膜量为892 mg/m2时,膜层的腐蚀面积为0,耐蚀性达到六价铬钝化膜水平;皮膜量为1252 mg/m2时,耐蚀性能优异。结论制备的无铬复合钝化膜结合了硅烷钝化膜和钼酸盐钝化膜两方面的优点,提高了膜层的致密性和结合性,膜层耐腐蚀性接近/达到了六价铬钝化的效果。     

热镀锌钢表面铈盐与硅烷处理后的耐蚀性能

将热镀锌(HDG)钢板经20g/L的Ce(NO3)3·6H2O溶液处理后浸涂5%(体积比)硅烷,研究膜层的耐蚀性能。5%NaCl溶液中的电化学极化曲线测试结果和中性盐雾试验(NSS)结果表明,单独的铈盐处理或浸涂硅烷膜都能够提高热镀锌层的耐蚀性,而经过该铈盐处理后再浸涂硅烷形成双层膜后能够明显地抑制腐蚀过程中的阴极和阳极反应,极化电阻Rp较HDG试样增加40多倍,也是单一膜层处理试样的5~9倍,膜层的耐蚀性能明显提高。俄歇电子谱(AES)分析表明,热镀锌试样经过两步处理后,在表面形成了双层膜,外层是富含C、Si、O的均匀硅烷膜层,里层是富含Ce的稀土转化膜层。     

纳米 SiO2的改性及其对水性聚氨酯树脂复合涂层性能的影响

在乙醇水溶液中,用硅烷偶联剂KH560对纳米SiO2进行表面改性处理,通过测定粒径,探讨了纳米SiO2含量、乙醇水溶液配比以及改性剂含量对分散性的影响。将改性后的纳米SiO2分散液、水性聚氨酯树脂及无机组分等复配成无铬钝化液,在热镀锌板上制备钝化膜,通过电化学Tafel极化曲线、交流阻抗以及中性盐雾试验对比纳米SiO2改性聚氨酯复合钝化膜和未改性聚氨酯复合钝化膜的耐蚀性,结果表明,与后者相比,前者的耐腐蚀性能有了较大的提升。     

建筑用镀锌钢板的表面处理及耐蚀性能研究

对比分析了建筑用镀锌基材、铬酸盐钝化膜和无铬复合膜在中性盐雾试验、醋酸铅点滴试验和电化学腐蚀试验中的腐蚀行为,并观察了镀锌基材钝化前后的表面形貌和元素变化。结果表明,无铬复合膜的耐腐蚀性能得到显著提高,与铬酸盐钝化效果较为接近。     

氟钛酸改性复合有机硅烷钝化膜及膜层性能研究

通过氟钛酸改性KH858+KH580混合硅烷,配制出无铬钝化液,将其涂覆在热镀锌板上,经烘干、固化,形成无铬钝化膜。测定了钝化膜的厚度、附着力和硬度;通过中性盐雾试验,研究了钝化膜的耐化学腐蚀性能;通过Tafel极化曲线和EIS图谱,表征了钝化膜的耐电化学腐蚀性能。结果表明:钝化膜的平均厚度为5.2μm,附着力测试的被剥离面积为3%,硬度为3H,均满足国家标准,符合工业生产要求;此外,钝化膜的耐化学腐蚀和耐电化学腐蚀性能优良,相比于改性前,其性能有较大提高。     

锌铝铬膜的防腐性能与机理

通过SEM ,XRD ,EDS ,盐腐蚀试验 ,热腐蚀试验和电化学测试等研究了锌铝铬膜的防腐蚀性能与机理。结果表明 ,该膜层耐中性盐腐蚀性能至少优于镀锌钝化层 4倍。至于锌铝铬膜层的抗腐蚀机理可能在于锌和铝粒子的电化学保护、铬的表面钝化和锌铝铬化合物保护层的屏蔽等作用 ,3者的协同作用结果赋予该膜层优异的耐腐蚀性能     

Ra 及 Rpc 对无铬耐指纹热镀锌板表面性能的影响

目的研究热镀锌板表面平均粗糙度Ra和峰值数Rpc对无铬耐指纹热镀锌板表面耐指纹性、耐腐蚀性和涂装性的影响。方法将Ra=0.6~1.1μm和Rpc=55~100的热镀锌板制成耐指纹板,采用X射线光电子能谱仪分析其组成,采用分光光度仪分析其耐指纹性,采用硫酸铜混合溶液滴定和盐雾试验方法检测其耐腐蚀性,采用涂漆和冲击实验检测其涂装性。结果耐指纹膜和锌层表面形成Si—O—Zn金属键,耐指纹膜除了物理结合,还通过化学键合的方式与锌层表面结合。在充分交联固化和化学键合的情况下,无铬耐指纹热镀锌板耐指纹性不受热镀锌板Ra和Rpc的影响;热镀锌板Ra值越低,耐腐蚀性越好;耐指纹膜单位质量为1.1 g/m2,Ra≤1.1μm时,耐指纹板72 h盐雾试验白锈面积不大于5%;热镀锌板Rpc值越高,无铬耐指纹热镀锌板涂装性越好,Rpc≥80时,耐指纹热镀锌板涂漆冲压后,漆膜完好。结论 Ra和Rpc对热镀锌板耐指纹性影响不大,对耐磨蚀性和涂装性影响显著。     

A comparative study of molybdate/silane composite films on galvanized steel with different treatment processes

Two types of molybdate/silane composite films were obtained on the surface of hot-dip galvanized steel sheets by either directly immersing in a solution containing silane and molybdate as additive (single-step process), or firstly immersing in a molybdate solution, then in a silane solution (two-step process). The chemical compositions and microstructures of the films were examined by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and reflection absorption infrared spectroscopy (RAIR). The corrosion resistances were investigated by electrochemical measurements and neutral salt spray (NSS) test. The results showed that the molybdate/silane composite film formed in the single-step process had a similar double-layer structure as that obtained in the two-step process. The inner layer was composed mainly of the elements O, Mo, Zn, and P, similar to the single molybdate film; whereas the outer layer was composed mainly of the elements C, O and Si, similar to the single silane film. Compared with the single molybdate or silane film, the corrosion current of the composite films was reduced and the impedance of the films was increased. Accordingly, the corrosion resistance of the composite films was remarkably enhanced to a level which was comparable to or even surpassing that of the conventional chromate passivation film.     

稀土La对热镀锌层耐蚀性能的影响

向热镀锌（GI）（Zn-0．2％Al）锌池中加入微量单质稀土La,采用热镀锌模拟机制备含La的锌镀层。采用盐雾腐蚀试验、全浸腐蚀失重试验和线性极化试验,研究了单质稀土La元素对镀层耐蚀性能的影响。结果表明,不同的腐蚀试验结果具有很好的一致性;相对Gl镀层而言,含La镀层中的La并未明显抑制白锈的产生,但明显抑制了红锈的...     

Effect of silicate pretreatment, post-sealing and additives on corrosion resistance of phosphated galvanized steel

Sodium silicate （water glass） pretreatment before phosphating, silicate post-sealing after phosphating and adding silicate to a traditional phosphating solution were respectively carried out to obtain the improved phosphate coatings with high corrosion resistance and coverage on hot-dip galvanized（HDG） steel. The corrosion resistance, morphology and chemical composition of the coatings were investigated using neutral salt spray（NSS） tests, scanning electron microscopy（SEM） and energy dispersive spectroscopy（EDS）. The results show that pretreatment HDG steel with silicate solutions, phosphate coatings with finer crystals and higher coverage are formed and the corrosion resistance is enhanced. Adding silicate to a traditional phosphating solution, the surface morphology of the coatings is nearly unchanged. The corrosion resistance of the coatings is mainly dependent on phosphating time. Phosphating for a longer time （such as 5 min）, the corrosion resistance, increasing with concentration of silicate, is improved significantly. Post-sealing the phosphated HDG steel with silicate solutions, the pores among the zinc phosphate crystals are sealed with the films containing Si, P, O and Zn and the continuous composite coatings are formed. The corrosion resistance of the composite coatings, related to the pH value, contents of hydrated gel of silica and Si2O^2- 5 and post-sealing time, is increased markedly. The improved coatings with optimal corrosion resistance are obtained for phosphating 5 min and post-sealing with 5 g/L silicate solution for 10 min.     

氟对不锈钢钝化效果的影响

分析了钝化液组分及工艺条件对不锈钢钝化效果的影响,结果表明:在HNO3和H2O2组成的不锈钢钝化液中,高浓度的氟促进高耐蚀性钝化膜的形成,其耐中性盐雾时间达到168h,同时也增强了钝化液中过氧化氢的稳定性。EDS能谱分析结果表明,不锈钢经过这种含高浓度氟的钝化液处理后,表面形成的钝化膜成分均一,无杂质S和Si,且有益组分Cr富集,因而耐蚀性能明显提高。     

热镀锌钢表面硅烷膜耐蚀性能的初步研究

将热镀锌(HDG)钢板经不同的表面处理后涂覆硅烷,研究成膜后的耐蚀性能。中性盐雾腐蚀试验和5%NaCl溶液中的电化学极化曲线测试表明:涂覆硅烷膜后,能够抑制热镀锌钢板产生白锈,涂覆前的碱处理和Ce3 盐处理能进一步提高膜层耐蚀性;硅烷膜能降低腐蚀速度,尤其是在镀锌层上经Ce3 盐处理后再涂覆硅烷成膜能够明显地抑制腐蚀过程中的阴极和阳极反应,耐蚀效果最好。     

镀锌板上丙烯酸树脂复合膜的制备和表征

在镀锌钢板表面制备了丙烯酸树脂复合膜,用扫描电子显微镜观察膜层的微观形貌.用傅里叶变换红外光谱表征膜层的分子结构,用中性盐雾试验和电化学方法测试其耐蚀性,并用划痕浸泡实验测试膜层的自修复性能.结果表明:丙烯酸树脂复合膜表面致密平整;耐中性盐雾腐蚀达72 h;阻抗值和极化电阻值均较大,说明丙烯酸树脂复合膜能有效抑制腐蚀电化学反应;划痕浸泡试验证明丙烯酸树脂复合膜具有自修复功能.成膜过程中碳酸锆铵能够和丙烯酸树脂分子上的羟基和羧基发生交联反应,形成互穿网络结构,提高膜层内部的交联密度,有效地阻挡外界环境的侵蚀,当膜层破损时钼酸盐和磷酸盐与锌反应形成难溶盐吸附在破损处,起到自修复作用.     

硝酸铈处理对磷化膜组织和耐蚀性的影响

为了发挥磷化膜和铈盐膜的优势,采用硝酸铈前处理或硝酸铈后处理对热镀锌层上的磷化膜进行改进,通过SEM,EDS,NSS和Tafel极化研究了硝酸铈改进磷化膜的显微组织和耐蚀性,并与铬酸盐钝化膜进行了比较。结果表明:硝酸铈前处理或后处理改进磷化膜均为含P,O,Ce和Zn化合物的复合膜,基本上克服了单一膜层的缺陷,使得复合膜的耐蚀性明显增强;硝酸铈后处理改进复合膜的耐蚀性优于铬酸盐钝化膜,有望成为高毒性铬酸盐钝化膜的替代品。     

Effect of molybdate post-sealing on the corrosion resistance of zinc phosphate coatings on hot-dip galvanized steel

The technique of post-sealing the phosphated hot-dip galvanized (HDG) steel with molybdate solution was addressed. The composition and corrosion resistance of the improved phosphate coatings were investigated by SEM, EDS, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements, and neutral salt spray (NSS) test. The results showed that molybdate films were formed in the pores of phosphate coatings, and the compact and complete composite coatings composed of phosphate coatings and molybdate films were formed on the zinc surface, resulting in that both the anodic and cathodic processes of zinc corrosion were inhibited remarkably; the corrosion protection efficiency values were increased; and the electrochemical impedance values were enhanced at least one order of magnitude. The low frequency impedance values for the composite coatings were increased at the initial stages of immersion in 5% sodium chloride solution, indicating the self-repairing activity of the composite coatings.