热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气环境中的腐蚀行为研究

目的 为详细研究热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气下的腐蚀行为及作用机理,同时为热浸镀Zn-Al-Mg镀层在湿热海洋大气环境中服役提供数据参考。方法 采用腐蚀失重、XRD、SEM、电化学等测试方法对热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气环境下的腐蚀行为进行研究。结果 腐蚀产物主要由Zn₅(OH)₈Cl₂·H₂O组成,腐蚀一段时间后,发现少量ZnO、Zn₅(OH)₆CO₃,腐蚀产物具有与锌腐蚀类似的层状结构,1 848 h呈“三明治”型,相比于上下两层暗色物质,中层亮色腐蚀产物富集更多的Cl元素。热浸镀Zn-Al-Mg镀层腐蚀速率大体随时间延长呈上升趋势,只在672～840 h腐蚀速率下降,对比镀锌在模拟环境和锌在湿热大气环境中的腐蚀,热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气中表现出较好的耐蚀性。结论热浸镀Zn-Al-Mg镀层在模拟湿热海洋大气下腐蚀产物演变与腐蚀过程中Mg的参与有关。腐蚀672～840h阶段腐蚀速率...     

模拟酸雨大气环境镀锌钢的室内加速腐蚀行为和机理

目的 采用室内加速试验方法研究热浸镀锌钢在模拟酸雨大气环境中的腐蚀行为和机理。方法 主要采用失重法对试样的腐蚀动力学进行研究,采用EDS、XRD和XPS对试样进行腐蚀产物成分分析,通过SEM和共聚焦显微镜观测试样表面形貌,采用EIS对试样表面涂层的保护性能进行检测。结果 在模拟酸雨大气环境中,厚度损失与时间呈幂函数关系,腐蚀大致是一个减速过程但在104 d后加速,在120 d后试样表面出现红锈和密集、深而窄的点蚀坑。主要腐蚀产物有ZnO、Zn4SO4(OH)6及可溶性产物ZnSO4.xH2O和Na2ZnSO4.4H2O,并且由截面形貌可知,镀层在酸雨环境中易被破坏。结论 在模拟酸雨大气环境中,热浸镀锌本身的耐蚀性很快失效,腐蚀速度加快直至生成的腐蚀产物在缺陷处形成较为完整的产物膜,对镀层的腐蚀具有一定抑制作用。但是酸雨环境中腐蚀产物膜较薄,易被破坏,这种溶解会使镀层失去保护,进一步腐蚀。     

镀锌钢在模拟海洋大气环境下的腐蚀行为

通过盐雾/干燥循环加速腐蚀实验模拟海洋大气腐蚀过程,采用宏观形貌观察、电化学测试、X射线衍射(XRD)、扫描电镜(SEM)和能谱(EDAX)等分析手段,研究镀锌钢在模拟海洋大气环境下的腐蚀行为和机理。结果表明:随着腐蚀时间的延长,镀锌钢的耐蚀性先降低后升高,最后再降低;当黄锈刚出现时,试样的耐蚀性有所提升,同时在腐蚀过程中出现双锈层,但最后又消失。     

镀锌钢在东莞大气及模拟大气中的腐蚀行为

采用失重法、金相检验、扫描电镜法(SEM)、X射线衍射法(XRD)、能量色散谱法(EDS)以及电化学阻抗谱法(EIS)研究了镀锌钢在东莞大气环境和模拟大气环境中暴露不同时间后的腐蚀行为。结果显示:在东莞大气中,镀锌钢在暴露早期发生了局部腐蚀,随着暴露时间的延长,腐蚀速率先迅速降低然后逐步稳定,耐蚀性先降低后增强;腐蚀12个月后,主要腐蚀产物为ZnO和Zn4SO4(OH)6;在模拟大气环境中,镀锌钢的腐蚀速率和耐蚀性随时间的变化规律和东莞实地大气暴露试验的结果具有良好相关性。     

高耐蚀热浸镀锌合金镀层

采用正交试验设计了不同Mg、Ni、Al和V元素含量的锌合金镀层,并通过中性盐雾腐蚀试验和电化学试验研究了各元素含量对锌合金镀层可镀性和耐蚀性的影响。正交试验结果表明:Mg对于镀层耐蚀性的影响最为显著,Ni的影响次之,而Al对可镀性的影响最为显著,Mg次之。中性盐雾腐蚀试验和电化学试验结果表明:Mg元素能有效提高镀层的耐蚀性,当Mg含量超过0.3%时,镀层的耐蚀性是传统镀锌层的2倍以上;而Al在本文研究的含量范围内对镀层耐蚀性的影响不显著。     

高频脉冲电镀Ni-Co合金在3.5%NaCl溶液中的耐蚀性

    用电化学方法研究了高频脉冲电镀Ni-Co复合镀层在NaCl溶液中的耐蚀性,结果表明,随着频率的增加,沉积层表面更加致密、均匀,在3.5％NaCl溶液中Ni-Co镀层的腐蚀失重明显减小,腐蚀失重速率变慢;高频和直流电铸Ni-Co复合镀层的阳极极化曲线形状相似,随频率增加,自腐蚀电位正移,自腐蚀电流降低.可见,高频率对沉积层的细化有重要影响,并使镀层的耐蚀性提高.     

Ce元素对低碳钢热浸镀锌镀层耐蚀性的影响

采用热浸镀法在低碳钢表面制备含Ce元素的镀锌层,利用光学显微镜(OM)、扫描电镜(SEM)、X射线衍射仪(XRD)、中性盐雾试验(NSS)以及电化学测试方法,揭示不同Ce元素添加量对镀层微观组织结构及耐蚀性能的影响规律。结果表明:在镀液中添加适量的Ce元素可在细化镀锌层晶粒和减薄镀锌层厚度的同时有效地提高镀锌层的耐蚀性。与纯锌镀层相比,镀液中添加0.012%和0.2%Ce(质量分数)后镀层的腐蚀速率分别降低24%和27%。Ce元素提高镀锌层耐蚀性的机理为:一方面,Ce的添加提高了腐蚀产物中Zn_5(OH)_8Cl_2?H_2O占比,从而提高了腐蚀产物的致密性与粘附性;另一方面,腐蚀过程所形成的Ce(OH)_3沉淀吸附在阴极相,阻碍氧的扩散,抑制了阴极吸氧反应。当镀液中添加超过0.012%Ce后(过饱和),阴极反应已被充分抑制,因而继续提高Ce添加量对镀锌层耐蚀性的提高有限。     

锌铝镁镀层中合金相与耐蚀性关系的研究进展

随着材料服役环境的恶化,Zn-Al-Mg (ZAM)镀层因其具有优良的耐蚀性而受到广泛关注。本文从合金元素入手,探讨了其对ZAM中合金相的形成乃至镀层耐蚀性能的影响及作用机制;同时通过对ZAM在大气环境中的腐蚀行为特征的归纳,从腐蚀产物的角度阐述了镀层的腐蚀机理。一般认为,MgZn₂作为阳极优先被腐蚀,从而产生Mg²⁺和Zn²⁺。Mg²⁺可以抑制腐蚀环境pH值的升高,从而防止在高pH值条件下保护性腐蚀产物Zn₅(OH)₈Cl₂·H₂O向非保护性腐蚀产物ZnO转变。Zn²⁺的产生更有利于形成保护性腐蚀产物LDH(双层氢氧化物)。但目前的研究仍存在不足,特别是对高铝含量的ZAM镀层中复杂的相结构所带来的腐蚀机理仍不明晰。这些都是未来ZAM镀层的研究重点。     

锌层对镀锌钢板力学性能指标的影响

通过对热镀纯锌、电镀纯锌、预磷化电镀纯锌和热镀锌铁4种钢板去锌前后力学性能的对比研究，定量分析了锌层对镀锌钢板力学性能指标的影响规律。在此基础上探讨了镀锌钢板冲压成形的变形机理，结果显示：与电镀纯锌、预磷化电镀纯锌和热镀纯锌镀层相比，锌铁合金镀层的延展性较差，变形过程中镀层和基板之间的不协调显著降低了钢板的整体成形性能。     

合金元素对耐候钢在海洋大气环境下耐蚀性的影响

介绍了不同合金元素对耐候钢在海洋大气环境下耐蚀性的影响,并对国内耐海洋大气腐蚀耐候钢的发展趋势进行了展望。     

Effect of porosity of phosphate coating on corrosion resistance of galvanized and phosphated steels Part II: Evaluation of corrosion resistance

The effect of porosity of phosphate coatings on the corrosion resistance of ungalvanized (UG), electrogalvanized, and hot dip galvanized steels is evaluated in this study. The corrosion resistance of phosphatized and painted steel is related to the integrity and continuity of phosphate and paint layers, and pores in the phosphate layer affect the corrosion resistance of material. The porosity of the phosphate coating was evaluated by using the cathodic polarization electrochemical test. To evaluate the corrosion resistance of the phosphatized and painted steels, they were submitted to accelerated corrosion tests. As was expected, the creepback from the scribe increased with the increase in porosity. This behavior was evident for UG steel, but less evident for galvanized steels due to cathodic protection and/or barrier effect of the zinc coating.     

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。     

Evaluation of the corrosion resistance of different galvanized steels treated in a cerium salt solution

Analysis of polarization curves and impedance spectra has shown that the surface chemistry of galvanized steels plays an important role in determining their corrosion behavior. Zn‐Ni samples that were untreated or had been treated in a 10 mM Ce(NO₃)₃ solution had the lowest corrosion rates in 0.5 N NaCl. The efficiency of the surface modification process was the highest for electrogalvanized steel. Surface analysis showed that the protective layers on Zn‐Ni and electrogalvanized steel contained mainly cerium oxides/hydroxides, while the layer on hot‐dipped steel consisted mainly of zinc hydroxide.     

Developments in the continuous galvanizing of steel

The performance history of galvanized steels, particularly in the automotive industry, has heightened demand for both hot-dip galvanized and electrogalvanized products. Such marketability has led to the commissioning of several new galvanizing lines in recent years. Still, for this timehonored coating process to remain competitive, researchers are investigating methods to improve surface appearance, coating uniformity, corrosion resistance and cost effectiveness.     

热镀锌板双硅烷无铬钝化膜性能的研究

目的为进一步提高热镀锌板无铬钝化膜的耐腐蚀性能。方法以偏钒酸铵和氟钛酸作为无机组分,添加主要成膜物质苯丙乳液,通过硅烷偶联剂KH-560和KH-570将两者紧密连接,在热镀锌板表面获得一层耐腐蚀性较强的双硅烷无铬钝化膜。采用中性盐雾试验、电化学试验、扫描电镜(SEM)、傅里叶红外光谱(FTIR)等表征钝化膜的耐腐蚀性能。结果热镀锌板-双硅烷无铬钝化膜经96 h中性盐雾试验,腐蚀面积在2%~4%,腐蚀电流密度比热镀锌板基体降低一个数量等级,这表明双硅烷无铬钝化膜能提供良好的耐腐蚀能力。SEM分析表明在热镀锌板表面生成了一层均匀、连续、致密的钝化薄膜,钝化膜的厚度大约在3μm。FTIR分析表明,双硅烷无铬钝化膜中存在—(CH_2)_n—、C=O、Si—O、Si—O—Si、Si—O—Zn键。结论在热镀锌板表面生成了一层均匀、致密的钝化膜,使热镀锌板呈现良好的耐腐蚀性能,且满足工业应用标准。     

Synergistic corrosion protection for galvanized steel by phosphating and sodium silicate post-sealing

To improve the corrosion resistance of phosphate coatings, the phosphated hot-dip galvanized (HDG) sheets were post-sealed with sodium silicate (water glass) solutions. The morphology and chemical composition of the composite coatings was analyzed using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The effect of sodium silicate post-sealing treatment on the corrosion behaviors of phosphate coatings was investigated by neutral spray salt (NSS) tests and electrochemical measurements. The results show that after the silicate post-treatment the pores among zinc phosphate crystals are sealed with the films containing Si, P, O and Zn, leading to the formation of the continuous composite coatings on the surface of HDG steel. The corrosion resistance of the composite coatings depending on concentration of sodium silicate and post-sealing time is greatly improved by the silicate post-treatment. The optimum concentration of silicate and post-sealing time are 5 g/L and 10 min, respectively. Both the anodic and cathodic processes of zinc corrosion on the samples are suppressed conspicuously, and the synergistic protection effect of the single phosphate coatings and the single silicate films is evident. Moreover, the low frequency inductive loop in electrochemical impedance spectroscopy (EIS) is disappeared and the electrochemical impedance values are increased for more than one order of magnitude. The corrosion protection of the composite coatings is comparable to that provided by the chromic acid post-treatment.     

钼酸盐后处理提高热镀锌上磷化膜耐蚀性的探讨

将磷化后的热镀锌钢板用钼酸盐后处理,以提高磷化膜的耐蚀性。用SEM、EDS、电化学极化测量和盐雾试验研究了钼酸盐后处理对磷化膜组成和耐蚀性的影响。结果表明,经钼酸盐处理后,磷化膜上磷酸锌晶体间的孔隙被钼酸盐膜填补,从而在锌层表面形成了由磷化膜和钼酸盐膜构成的连续完整致密的复合膜;复合膜的极化电阻Rp显著增大,腐蚀电流密度显著减小,耐蚀性大大增强。磷化300s、后处理50s时复合膜的耐蚀性最优,Rp比单磷化膜的增加了一个数量级。     

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 the metallic substrate and zinc layer on the atmospheric corrosion resistance of phosphatized and painted electrogalvanized steels

In this work, the influence of the metallic substrate and zinc layer on the atmospheric corrosion resistance of phosphatized and painted electrogalvanized steels was evaluated. For this purpose two types of electrogalvanized steels were used, one with drawing quality carbon steel as metallic substrate, and the other one with a substrate of Ni–Cu–Cr added carbon steel. The corrosion resistance was determined by accelerated and non‐accelerated corrosion tests, using cyclic test chambers and field tests in industrial and marine atmosphere. The mean corrosion advance and the maximum corrosion penetration of samples were measured using image analysis techniques. The study showed that the substrate and zinc layer mass play a decisive role on the atmospheric corrosion resistance of the phosphatized and painted electrogalvanized steels. It was also verified that it is possible to use smaller zinc layer masses without compromising the corrosion resistance of the material, provided that the metallic substrate has characteristics of atmospheric corrosion resistance, thus contributing to the improvement of the zinc coated steels.     

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.