热镀锌板钼酸盐转化膜制备及耐腐蚀性能研究

以镍盐为促进剂,以有机酸为添加剂,在钼酸盐溶液体系中,在热浸镀锌钢板表面制备出黑色钼酸盐化学转化膜。用电化学技术评价了转化膜的耐化学腐蚀性能,确定了最佳制备工艺条件。结果表明:在3.5%NaCl溶液中,转化膜动电位极化曲线阳极分支呈现钝化状态,电化学阻抗谱为单一容抗弧。扫描电镜观察表明,钝化膜均匀致密。EDS分析显示,钝化膜主要由Mo、P、O、Zn、Al等元素组成。     

添加剂用量对钼酸盐失效转化液再生的影响

热镀锌钢板广泛应用于建筑、汽车和家电领域。化学转化处理能够提高镀锌钢板的耐腐蚀性能。钼酸盐钝化被认为是取代传统铬酸盐钝化工艺的有效途径,成为镀锌钢板环境友好型钝化技术的发展方向。研究了添加剂用量对热浸镀锌钢板钼酸盐失效处理液再生的影响。采用电化学技术评价了转化膜的耐腐蚀性能,极化曲线结果表明,少量添加剂的加入能够使失效的转化液恢复钝化能力,累计处理面积能达到240 cm2;加入适量添加剂后,累计处理面积可达840cm2,明显提高有效处理面积;加入过量添加剂后得到的转化膜耐蚀性降低。SEM观察表明,加入适量添加剂后形成的转化膜表面平整、均匀。     

镀锌钢上钼酸盐/硅烷复合膜的结构与耐蚀性

将热镀锌钢板用二步法（先后浸入钼酸盐钝化液和硅烷溶液）和一步法（一次浸入加有钼酸盐钝化剂的硅烷溶液）获得钼酸盐/硅烷复合膜,用XPS和AES对 2种复合膜的化学成分进行表面分析和剥层分析,用Tafel极化曲线测量和盐雾腐蚀试验（NSS）对膜层的耐蚀性能进行了研究,并将它们与单独的钼酸盐转化膜、硅烷膜对比。结果表明,由一步法制备的复合膜与二步法制备的复合膜具有相似的双层结构,内层以钼酸盐转化膜（含O、Mo、Zn、P）为主而外层以硅烷膜（含C、O、Si）为主,内外层之间及膜与锌基体之间的化学成分呈梯度变化;和单独的钼酸盐膜、硅烷膜相比,2种复合膜对腐蚀的阴极过程的抑制明显增加,自腐蚀电流减小至单层膜的1/5以下,耐蚀性显著提高,接近常规铬酸盐钝化膜。     

磷化/钼酸盐后处理的热镀锌钢板的电化学行为

将热镀锌钢板先磷化再用钼酸盐溶液进行封闭后处理,通过塔菲尔极化和电化学阻抗测量研究其在5%NaCl水溶液中的腐蚀电化学行为,并与单磷化的热镀锌钢板进行了对比.结果表明:磷化的热镀锌钢板再经钼酸盐封闭处理后,阳极极化和阴极极化均明显增强,腐蚀保护效率显著提高,发挥了单磷化膜和单钼酸盐膜耐蚀性能的协同效应,电化学阻抗值提高了一个数量级以上;在5%NaCl水溶液中浸泡的初期,低频扩散阻抗值随浸泡时间延长而增大,表明复合膜具有一定的自修复能力.     

镀锌钢上钼酸盐/硅烷复合膜的组成与耐蚀性

分别采用一步法和两步法在热镀锌钢板表面获得钼酸盐/硅烷复合膜,通过X射线光电子能谱分析(XPS)、俄歇电子能谱剥层分析(AES)、盐雾腐蚀试验(NSS)及Tafel极化曲线等对两种复合膜的化学成分和耐蚀性能进行了研究,并将它们与单独的钼酸盐转化膜、硅烷膜进行对比.结果表明:一步法和两步法制备的复合膜具有相似的双层结构,内层以钼酸盐转化膜(含O、Mo、Zn、P)为主,外层以硅烷膜(含C、O、Si)为主,内外层之间及膜与锌基体之间的化学成分呈梯度变化;与单独的钼酸盐膜、硅烷膜相比,两种复合膜对腐蚀的阴极过程的抑制明显增强,自腐蚀电流减小至单层膜的1/5以下,耐蚀性显著提高;两步法制备的复合膜耐蚀性超过常规铬酸盐钝化膜,而一步法制备的复合膜的耐蚀性比由两步法制备的稍差,但仍接近常规铬酸盐钝化膜.     

锌铝合金镀层表面低铬钝化膜的研究

探索了低浓度铬酸盐钝化处理在热浸镀锌铝合金镀层上的应用·采用盐雾试验、电化学腐蚀试验和人造海水浸泡试验对锌铝合金镀层表面低浓度铬酸盐钝化膜的耐蚀性进行了测试,并借助ＸＰＳ和ＡＥＳ对钝化膜的组成进行了分析·结果表明,锌铝合金镀层经低铬酸盐钝化处理后耐蚀性得到了显著提高,钝化膜的元素组成(原子数分数,％)为:Ｓ５－５,Ｎａ３－４,Ｃ１１－８,Ｔｉ７－９,Ｏ４１－６,Ｃｒ１３－７,Ｚｎ１６－０·     

电镀锌板上复合硅烷膜的制备及性能

在镀锌钢板表面制备了γ-APT和γ-GPT复合硅烷膜.用扫描电子显微镜观察了处理前后膜层的微观形貌,用中性盐雾试验、电化学测试了耐蚀性,并测试了附着力、弯曲性能.结果表明:复合硅烷膜致密平整,中性盐雾试验72 h无腐蚀;阻抗值和极化电阻均增大证明复合硅烷膜能有效抑制腐蚀反应;划痕浸泡试验证明复合硅烷膜具有自修复性能;复合硅烷膜的附着力为一级、弯曲性能为1 T.     

镀锌层三价铬与六价铬钝化膜的性能

为了以三价铬替代镀锌层钝化溶液中的六价铬,实现镀锌工艺的清洁生产,利用中性盐雾实验(NSS)、Tafel曲线和扫描电镜对镀锌层三价铬和六价铬钝化膜的耐腐蚀性能、电化学行为、耐高温性能和表面结构进行了比较研究.NSS实验结果表明,三价铬钝化膜的耐腐蚀性能高于六价铬钝化膜,NSS时间可达84 h;Tafel曲线表明,三价铬钝化膜的腐蚀速率低于六价铬钝化膜,耐高温性能则高于六价铬钝化膜;SEM照片显示,三价铬钝化膜的表面形貌为致密结构,高温处理后膜层变化不大,而六价铬钝化膜表面为疏松的网状结构.     

苯并三氮唑（BTA）钝化膜对铜的缓蚀作用探讨

通过单一BTA钝化处理和BTA与辅助添加剂复配对比试验,正交法安排BTA钼酸盐复配液钝化试验,表面活性剂对钝化效果的影响试验来探讨BTA钝化膜对铜的缓蚀作用。     

用循环伏安法研究钼酸盐对软钢的缓蚀作用

把软钢加工成旋转圆盘电极,用循环伏安法,研究软钢在去空气和空气饱和的中性低硬度水中钼酸盐的缓蚀性能,以及钼酸盐与亚硝酸盐的协同效应。通过测定点蚀电位再钝化电位和点蚀临界氯离子浓度等参数来评定体系的抗点蚀性能。实验结果表明:钼酸盐比亚硝酸盐对软钢有更好的抗点蚀性能。亚硝酸盐有利于钝化;而钼酸盐有利于再钝化。当它们结合使用时,由于性能的相互补偿,产生很好的协同效应。旋转环盘电极的研究表明,钼酸盐改善再钝化性能是由于形成铁的不溶性钼酸盐化合物所致。     

热镀锌钢板在青岛不同海水区带的腐蚀行为

开展了热镀锌钢板在青岛不同海水区带的实海腐蚀测试,并利用电化学测试、失重腐蚀测试和扫描电镜研究了镀层的海水腐蚀行为.结果表明,由于镀锌层腐蚀电流密度大,在全浸区流动海水中快速溶解而又难以形成稳定的保护性腐蚀产物膜,耐蚀性最差;镀层在潮差区出现不同程度的生物污损,这可能给镀层带来部分保护,其腐蚀速度比全浸区明显降低;镀层在飞溅区未发生生物污损,但腐蚀速度在三个海水区带中最低,可能与其表面良好的充气条件和腐蚀产物层的阻挡作用有关.与全浸区相比,镀锌层在飞溅区和潮差区的耐蚀性分别提高了94%和37%.     

钢表面热浸镀AlZnSi合金镀层防腐蚀技术研究

创新性地采用了热浸镀二次助镀工艺,对常用型钢试样表面进行防腐蚀处理,如镀Zn,镀Al-Zn-Si合金,镀Zn-Re及镀Al-Zn-Si-Re合金.对热浸镀处理后的型钢试样进行拉伸试验,对其组织形貌进行观察,对其力学性能进行测试.另外,在实验室条件下进行模拟酸雨试验和盐雾试验,对各类镀层的耐腐蚀性能进行研究,并与工业镀Zn件的耐蚀性进行对比研究,进而对其使用寿命进行预测.结果表明：热浸镀工艺对型钢的力学性能无不利影响,两种镀层防腐蚀性能优秀,Al-Zn-Si合金镀层对钢材表面的防腐蚀性能卓越,而Al-Zn-Si-Re合金的防腐蚀性能更佳.     

Corrosion behavior and mechanism of the automotive hot-dip galvanized steel with alkaline mud adhesion

The corrosion behavior and mechanism of hot-dip galvanized steel and interstitial-free (IF) substrate with alkaline mud adhesion were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and linear polarization. The results show that non-uniform corrosion occurs on the galvanized steel and IF substrate during 250 h with the mud adhesion. The corrosion products on the galvanized steel are very loose and porous, which are mainly ZnO, Zn₅(OH)₈C₁₂·H₂O and Zn(OH)₂, and Fe-Zn alloy layer with a lower corrosion rate is exposed on the galvanized steel surface; however, the corrosion products on IF substrate are considerably harder and denser, whose compositions of rust are mainly FeOOH and Fe₃O₄, and several pits appear on their surface. The results of continuous EIS and linear polarization measurements exhibit a corrosion mechanism, that is, under activation control, the charge transfer resistances present different tendencies between the galvanized steel and IF substrate; in addition, the evolution of linear polarization resistances is similar to that of charge transfer resistances. The higher contents of dissolved oxygen and Cl- ions in the mud play an important role in accelerating the corrosion.     

Effect of hot-dip galvanizing processes on the microstructure and mechanical properties of 600-MPa hot-dip galvanized dual-phase steel

A C-Mn dual-phase steel was soaked at 800℃ for 90 s and then either rapidly cooled to 450℃ and held for 30 s (process A) or rapidly cooled to 350℃ and then reheated to 450℃ (process B) to simulate the hot-dip galvanizing process. The influence of the hot-dip galvanizing process on the microstructure and mechanical properties of 600-MPa hot-dip galvanized dual-phase steel (DP600) was investigated using optical microscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and tensile tests. The results showed that, in the case of process A, the microstructure of DP600 was composed of ferrite, martensite, and a small amount of bainite. The granular bainite was formed in the hot-dip galvanizing stage, and martensite islands were formed in the final cooling stage after hot-dip galvanizing. By contrast, in the case of process B, the microstructure of the DP600 was composed of ferrite, martensite, bainite, and cementite. In addition, compared with the yield strength (YS) of the DP600 annealed by process A, that for the DP600 annealed by process B increased by approximately 50 MPa because of the tempering of the martensite formed during rapid cooling. The work-hardening coefficient (n value) of the DP600 steel annealed by process B clearly decreased because the increase of the YS affected the computation result for the n value. However, the ultimate tensile strength (UTS) and elongation (A₈₀) of the DP600 annealed by process B exhibited less variation compared with those of the DP600 annealed by process A. Therefore, DP600 with excellent comprehensive mechanical properties (YS=362 MPa, UTS=638 MPa, A₈₀=24.3%, n=0.17) was obtained via process A.     

磷化/硅酸盐溶胶封闭复合膜的EIS腐蚀机理

采用电化学阻抗谱EIS测量研究了先磷化再硅酸盐溶胶封闭后处理的热镀锌钢在5%NaCl溶液中浸泡不同时间的腐蚀行为,建立了等效电路模型,分析了相关参数的变化规律,探讨了复合膜的腐蚀机理.结果表明:复合膜的耐蚀性随磷化时间的延长而增强,复合膜高电阻、低电容的特性是抑制基底锌层电极反应的关键;随着浸泡时间的延长,镀锌钢的耐蚀性指标变差,腐蚀初期主要发生复合膜的溶解破坏,腐蚀后期主要发生膜层下基体锌层的腐蚀反应.     

Influence of silane coupling agent on the conversion film forming of galvanized steel treated with cerium salt

The influence of silane coupling agent on the film forming of galvanized steel treated with cerium salt was studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), and the corrosion resistance of conversion films was analyzed by electro interstitial scanning (EIS). The results show that silane coupling agent KH-570 has significant influence on the compactness and homogeneity of cerium conversion films, and the process of film forming is promoted by increasing the content of tervalent and tetravalent cerium oxide. The impedance value of the cerium conversion film, especially modified with KH-570, is greater than that of the base metal, which reveals that it is necessary to add silane coupling agent to the film-forming solution in order to improve the corrosion resistance of the conversion film.     

热镀锌钢卷力学性能GBDT预报模型

针对热镀锌钢卷力学性能预报建模条件属性选取难、预报精度不足的问题,研究了热镀锌钢卷力学性能梯度提升树(gradient boosting decision tree,GBDT)预报模型。利用互信息差算法综合评估工艺参数、化学成分和钢卷尺寸参数等条件属性的相对重要性以及属性之间冗余性,进行模型条件属性筛选;采用同分布原理进行样本划分,结合网格搜索法和交叉验证法优化模型参数,建立力学性能GBDT预报模型。将GBDT模型预报结果与随机森林(random forest,RF)、AdaBoost算法和BP神经网络的预报结果进行比较,比较表明GBDT模型优于其他模型,90%的数据样本预测的绝对误差小于14.24 MPa,94.6%的数据样本相对误差在6%范围内,具有更高的预测精度。     

柠檬酸对镧盐转化膜耐蚀性和自愈性的影响

将热镀锌钢分别浸入添加和不添加柠檬酸的镧盐钝化液中,在镀锌钢表面获得柠檬酸改进型镧盐转化膜和常规镧盐转化膜.用中性盐雾(NSS)试验、塔菲尔极化和电化学阻抗谱研究了这些试样的耐蚀性能,并对带划痕的柠檬酸改进型和常规镧盐膜层试样进行NSS腐蚀,用扫描电子显微镜和能谱仪观察分析了腐蚀过程中划痕表面的组织形貌和化学成分.结果表明:柠檬酸的加入显著提高了镧盐转化膜的耐蚀性能,并使膜层具备自愈性;腐蚀过程中,划痕附近的柠檬酸镧溶解产生La3+和柠檬酸根离子,从膜层中扩散迁移至划痕处,形成新的由Zn、O、La、C元素组成的保护膜,从而抑制了划痕处锌的腐蚀.