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.     

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。     

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.     

热镀锌层上磷酸锌转化膜的生长与耐蚀性

热镀锌钢板在pH3.0、45℃的磷酸锌溶液中磷化2～600s,用扫描电镜、能谱仪和X射线衍射仪分析磷化膜的组织形貌和成分,并探讨膜层的生长行为。结果表明:磷酸锌晶体在锌晶粒内及晶界处均可成核,开始是以接近平行的片状生长,并逐渐向多方向生长成扇骨状的晶片。随着磷酸锌晶体的成核和生长,磷化膜的覆盖率增加,但晶体之间的孔隙难以完全消除;长大的磷酸锌晶片容易折断脱落,导致磷化后期膜层的质量增量减小;磷化膜主要由Zn3(PO4)2.4H2O组成。热镀锌钢板经磷化处理后,耐蚀性显著提高,磷化膜的耐蚀性随磷化时间和膜层覆盖率的增加而提高。     

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.     

热浸镀锌层上钼酸盐转化膜的腐蚀电化学性能

    将热镀锌钢在含10 g/L Na₂MoO₄·2H₂O、pH为5的溶液中60℃下处理10~300秒,获得了钼酸盐转化膜试样.应用极化曲线和电化学交流阻抗谱(EIS)研究了转化膜层在5% NaCl水溶液的耐蚀性能.结果表明,经钼酸盐转化处理后的镀锌钢板,其腐蚀电流密度下降,极化电阻升高,阴极极化作用明显增强,腐蚀保护效率显著提高,电化学阻抗值提高了一个数量级;低频扩散阻抗值随处理时间的增加先增大后减小,表明腐蚀电解质在转化膜层孔隙中扩散的难易程度先增加后下降.     

Zn(NO3 ) 2 ·6H2O,Na2MoO4 ·2H2O 与 Na5P3O10对 1Cr18Ni9Ti 的协同缓蚀作用

目的研究硝酸锌、钼酸钠及三聚磷酸钠之间的协同缓蚀作用机理,使其在性能上实现互补。方法以酸性高锰酸钾溶液为基础,通过极化曲线和失重法实验,研究3种缓蚀剂对1Cr18Ni9Ti奥氏体不锈钢的协同缓蚀作用。结果硝酸锌和三聚磷酸钠以抑制不锈钢的阴极反应为主,钼酸钠则主要抑制不锈钢的阳极反应。硝酸锌与钼酸钠表现出明显的拮抗作用,导致缓蚀效果变差。只有当三聚磷酸钠加入后,三者之间才表现出了良好的协同作用,使总的缓蚀性能达到最优,复配后的缓蚀效率可以达到90%以上。结论硝酸锌、钼酸钠及三聚磷酸钠之间存在良好的协同缓蚀作用,可以明显降低1Cr18Ni9Ti不锈钢在酸性高锰酸钾溶液中腐蚀速率,从而延长设备的使用寿命。     

Corrosion control of galvanized steel using a phosphate/calcium ion inhibitor mixture

The corrosion inhibition of galvanized steel was studied in artificial acid rain solution using extracts of pigments normally used in organic coatings for corrosion control. It was established that a combination of zinc phosphate/molybdate and calcium ion exchange silica has a significant synergetic anticorrosion effect in the acid rain solution compared to the pigments used alone. Further, the charge transfer resistance of galvanized steel in acid rain solution saturated by the above pigment blend approaches that of strontium chromate in artificial acid rain solution. Use of the pigment blend was found to lead to development of a protective film, which is thought to be a complex mixture of calcium phosphates and zinc phosphate.     

钢铁新型复合缓蚀剂

由钼酸盐,三乙醇胺磷酸盐,磷酸二氢锌,磷酸氢二争和碳酰胺组成的复合缓蚀剂,对抑制钢铁在氯化钠溶液中的腐蚀效果良好,当浓度为１０００ｍｇ／Ｌ时,缓蚀率可高达９６．８％。     

Effect of SiO2:Na2O molar ratio of sodium silicate on the corrosion resistance of silicate conversion coatings

Passivation treatment by sodium silicate solution is considered as an alternative to chromium chemical conversion treatment to improve the corrosion resistance of hot-dip galvanized (HDG) steels. In this paper, a transparent silicate coating was formed on the surface of HDG steel by immersing in sodium silicate solution with SiO₂:Na₂O molar ratio in the range from 1.00 to 4.00. The parameter about the SiO₂:Na₂O molar ratio of silicate solution has been discussed using corrosion resistance and surface morphology. Tafel polarization, electrochemical impedance spectroscopy (EIS) measurements and neutral salt spray (NSS) test show that silicate coatings increase the corrosion resistance of HDG steels. From the results obtained, it is deduced that the optimum SiO₂:Na₂O molar ratio is 3.50. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction analysis (XRD), and reflectance absorption infrared spectroscopy (RA-IR) show that there are no obvious differences of the chemical composition and structure in various silicate coatings. The silicate coatings mainly consist of zinc oxides/hydroxides, zinc silicate and SiO₂. However, atomic force microscopy (AFM) images reveal that the surface of silicate coatings with a molar ratio of 3.50 is more compact and uniform than other silicate coatings.     

Growth and corrosion behavior of rare earth film on hot-dip galvanized steel

1Introduction For a long time,chromate compounds Cr(VI)have been used as effective and inexpensive corrosion inhibitors for zinc and zinc coating.However,with the advent of increasing environmental awareness,the toxicity and carcinogenic nature of Cr(VI)b…     

Growth and corrosion behavior of molybdate passivation film on hot dip galvanized steel

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Corrosion and wear of zinc in various aqueous based environments

The corrosion and corrosive wear resistance of zinc sliding against 440C martensitic stainless steel counterface, were studied in aqueous based solutions having different NaCl and sodium molybdate dihydrate concentrations respectively. The main objective was to investigate the effect of aqueous based environments and corrosion inhibitors on the interface and tribological characteristics of this tribosystem, as in several cases the formation of a thin corrosion product layer can act as a lubricating film. The experimental results indicated that sodium molybdate dihydrate acted as a corrosion inhibitor, decreasing significantly the corrosion susceptibility of zinc. However, during the corrosive wear of zinc under free corrosion conditions, the addition of sodium molybdate dihydrate inhibitor did not improve the tribological properties of zinc, as higher friction coefficients of the tribosystem were recorded. This observation indicates that aqueous lubrication cannot be applied in this tribosystem, even though an inhibitor was used to minimize the effect of Cl⁻ halide ions. In addition, the observed wear mechanisms of zinc were mainly plastic deformation and abrasion. These wear mechanisms coexisted with pitting and dissolution–precipitation corrosion phenomena on the surface of this material.     

Effect of surface condition on the initial corrosion of galvanized reinforcing steel embedded in concrete

The present work was aimed at determining the effect of coating surface condition on the initial corrosion of hot-dip galvanized reinforcing steel bar (HDG rebar) in ordinary Portland cement (OPC) concrete. During zinc corrosion in OPC concrete, calcium hydroxyzincate (CHZ) formed on untreated HDG steel provided sufficient protection against corrosion. Therefore, it is concluded that treating HDG rebar with dilute chromic acid is unnecessary as a method of passivating zinc. A layer of zinc oxide and zinc carbonate formed, through weathering, on HDG bars increased the initial corrosion rate and passivation time compared with the non-weathered rebar exposed to concrete. HDG steel with an alloyed coating, i.e. containing only of Fe-Zn intermetallic phases, required a longer time to passivate than those with a pure zinc surface layer. The lower zinc content of the surface limited the rate of CHZ formation; hence, delayed passivation. Regardless of the surface condition, the coating depth loss after two days of embedment in ordinary Portland cement concrete was insignificant.     

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。     

Corrosion performance of Zn–Al–Mg coatings in open and confined zones in conditions simulating automotive applications

Panels coated by hot dipping with zinc (HDG), Zn–5Al (Galfan) and Zn–1.5Al–1.5Mg coatings at different thicknesses were phosphated and painted on an industrial line. Crevice panels with non‐painted bare parts modelling conditions in hem flanges, reference panels with open surfaces and formed non‐painted panels were exposed to a cyclic accelerated automotive test. Zn–Al–Mg coatings with the thickness of 10 µm provided similar or even better protection than HDG and Galfan at 20 µm in both confined and open configurations. In comparison to 10‐µm HDG, the Zn–Al–Mg coating delayed red rust appearance in crevices by a factor of 2 and the maximal depth of corrosion in the steel substrate was by 42% lower. Confined areas were more corroded than open surfaces. For HDG, the time to red rust appearance dropped by 50–75%, corrosion attack in steel was from 3.5 to 7 times deeper and mass gain was about 2.3 times higher in crevices than on open surfaces. Corrosion of Zn–Al–Mg may be more affected by local environmental conditions created by the crevice configuration than for HDG. Red rust appearance on formed panels of 20‐µm Galfan, 7‐, 10‐ and 14‐µm Zn–Al–Mg was delayed to 10‐µm HDG by a factor of 2.8, 3.5, 3.8 and >4.5, respectively. No adverse effect of forming was noticed. The results indicate that 2‐ to 3‐fold reduction of the coating thickness for Zn–Al–Mg alloy coatings in comparison to traditional HDG may be possible without compromising the corrosion performance.     

化学镀镍层缓蚀工艺研究

目的提高化学镀Ni-P镀层的耐蚀性能。方法在钢铁基体表面化学镀Ni-P镀层,采用植酸、硅酸钠、钼酸铵和双氧水中的一种或多种复配对镀层进行钝化处理。通过硝酸点滴法、贴滤纸法分析镀层耐蚀性的变化,并通过正交实验确定四种物质复配的最佳浓度。结果以植酸、硅酸钠、钼酸铵和双氧水为主要成分配制的复合缓蚀剂能使镀层耐硝酸效果良好,电化学实验表明,复合钝化膜的腐蚀电流密度降低和阻抗值增加都超过1个数量级。结论所研究的复合缓蚀剂各组分间存在协同效应,最佳配方为:6 g/L植酸,6 g/L硅酸钠,4 g/L钼酸铵,30 mL/L双氧水。     

Study of role of phosphate coating properties on electrophoretic paint performance by EIS and simulated corrosion tests

The influence of phosphate bath chemistry on phosphate coating properties and, eventually, on corrosion resistance properties of electrophoretic (ED) painted steel samples was examined. Two types of zinc phosphate bath chemistry with different concentration of zinc and nickel ions, and different values of total acid, free acid, and accelerator content were studied. The phosphate bath with higher value of acid ratio (total acid/free acid), nickel ion concentration, and accelerator point produced the best phosphate coating on steel surface with globular microstructure, small crystal size, high P ratio, and uniform coverage. Phosphate coated and only alkali cleaned samples were cathodic ED painted. Their corrosion resistance properties were evaluated by salt spray test, cyclic corrosion test and electrochemical impedance spectroscopy. The relative increase in corrosion resistance of painted sample due to best phosphate coating was 1·4 to 1·8×. Paint adhesion of samples significantly deteriorated when painted without phosphate pretreatment.     

钼酸盐复合缓蚀剂对海水中碳钢的缓蚀作用

采用失重法、极化曲线法和表面分析技术对钼酸盐复合缓蚀剂的缓蚀性能进行了研究,并通过试验确定了与钼酸盐有较好协同缓蚀效应的缓蚀剂配方。结果表明,单一钼酸盐对海水中碳钢的缓蚀率随着钼酸盐浓度的增加而增加,但钼酸盐浓度低于30 mg/L时存在加速碳钢腐蚀的情况。当钼酸盐为40 mg/L、有机膦酸盐(HEDP)为10 mg/L、Zn2 为4 mg/L、葡萄糖酸盐为50 mg/L时,该缓蚀剂对海水中碳钢的缓蚀率超过90%。钼酸盐复合缓蚀剂为阳极型缓蚀剂,海水中添加了缓蚀剂后碳钢试片表面形成了以氧化铁为主要成分,同时含有钼和磷的混合型沉淀膜。     

Corrosion testing of phosphatized steel samples

A method for corrosion testing of phosphatized steel samples has been described. The specimens, treated with different phosphatizing, solutions and covered by a chemically inert paint film, have been exposed in a sulphur-dioxide-polluted atmosphere with 90% relative humidity at 22.0°C. The corrosion rate has been measured as an increase in weight. The corrosion resistance shows a good correlation with the crystal coverage of the zinc phosphate layers. Filiform corrosion can be inhibited by zinc phosphate as well as iron phosphate coatings. However, underfilm corrosion is more frequent on the iron phosphatized samples.