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.     

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.     

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。     

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。     

Effect of sodium silicate pretreatment on phosphate layer: Morphology and corrosion resistance behavior

Phosphating is a widely adopted treatment in industry for many purposes. In this paper, carbon steel was pretreated with sodium silicate before phosphating. X‐ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical measurements were used to evaluate the pretreatment effect by sodium silicate on the phosphating layer. The results demonstrate that the phosphate layer pretreated by sodium silicate has a better corrosion resistance as compared with the un‐pretreated ones. More compact and uniform coatings composed of finer crystals were obtained with the pretreatment of sodium silicate.     

Growth and corrosion resistance of molybdate modified zinc phosphate conversion coatings on hot-dip galvanized steel

The modified zinc phosphate conversion coatings（ZPC） were formed on hot-dip galvanized（HDG） steel when 1.0 g/L sodium molybdate were added in a traditional zinc phosphate solution. The growth performance and corrosion resistance of the modified ZPC were investigated by SEM, open circuit potential（OCP）, mass gain, potentiodynamic polarization and electrochemical impedance spectroscopy（EIS） measurements and compared with those of the traditional ZPC. The results show that if sodium molybdate is added in a traditional zinc phosphate solution, the nucleation of zinc phosphate crystals is increased obviously; zinc phosphate crystals are changed from bulky acicular to fine flake and a more compact ZPC is obtained. Moreover, the mass gain and coverage of the modified ZPC are also boosted. The corrosion resistance of ZPC is increased with an increase in coverage, and thus the corrosion protection ability of the modified ZPC for HDG steel is more outstanding than that of the traditional ZPC.     

几种改进磷化膜耐蚀性对比和自修复性初探

研制了钼酸钠添加剂改进磷化膜及钼酸钠、硝酸铈、硅酸钠溶胶封闭后处理改进磷化复合膜,拟替代高毒性铬酸盐钝化膜。采用中性盐雾试验、Tafel极化和电化学阻抗测试对比分析了这4种改进磷化膜与几种传统无铬转化膜、铬酸盐钝化膜耐蚀性的差异;用SEM和EDS研究带划痕试样经盐雾腐蚀后划痕表面的组织形貌和化学成分,初步探讨了改进磷化复合膜的自修复性。结果表明:3种改进磷化复合膜的耐蚀性优于铬酸盐钝化膜,具有自修复作用,有望成为铬酸盐钝化膜的替代品;硅酸钠溶胶封闭后处理改进磷化复合膜的耐蚀性最优。     

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 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.     

The EIS investigation of powder polyester coatings on phosphated low carbon steel: The effect of NaNO2 in the phosphating bath

The effect of different type of iron-phosphate coatings on corrosion stability and adhesion characteristic of top powder polyester coating on steel was investigated. Iron-phosphate coatings were deposited on steel in the novel phosphating bath with or without NaNO₂ as an accelerator. The corrosion stability of the powder polyester coating was evaluated by electrochemical impedance spectroscopy (EIS), adhesion by pull-off and NMP test, while surface morphology of phosphate coatings were investigated by atomic force microscopy (AFM).The adhesion and corrosion stability of powder polyester coatings were improved with pretreatment based on iron-phosphate coating deposited from NaNO₂-free bath.     

高效无公害钢铁表面亮化液研究简

研制了一种用于钢铁构件涂层制备的预处理综合亮化液,集除油、除锈、磷化、钝化为一体,具有高效环保、成本低廉等特点,可在常温下擦拭或浸渍钢铁表面。实验通过单因素和正交实验方案确定了亮化液组分,其中不含有F-,NO2-和Cr3+等毒性离子。通过光学显微镜观察了磷化膜形貌,并测试了亮化液总酸度点、游离酸度点、耐蚀性等。结果表明:用该亮化液处理试样后表面形成的磷化膜薄而致密均匀,耐蚀性好,可直接用于涂层的制备。     

Effect of silicate anion distribution in sodium silicate solution on silicate conversion coatings of hot-dip galvanized steels

Silicate conversion coatings are prepared by immersing hot-dip galvanized (HDG) steel sheets in sodium silicate solutions with 5 wt.% SiO₂ and SiO₂:Na₂O molar ratio in the range of 1.00 to 4.00. The coating with better corrosion resistance is usually obtained in silicate solution with higher molar ratio (3.00-4.00). In this article, the distribution of types of silicate anion in solutions is investigated by transmission infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (²⁹Si NMR), and the surface of the silicate coating is analyzed using reflection infrared spectroscopy (RA-IR). Results indicate that the anion distribution is mainly monomer, linear and less cyclic anions at low molar ratios in very alkaline solutions. With increase in the molar ratio, small anions decrease, two- and three-dimensional anions increase. Accordingly, the silicate coating prepared in the solution with high molar ratio (≥ 3.00) contains a higher number of large silicate anions, and Si-O-Zn and Si-O-Si bonds of the coating increase, leading to the formation of more dense silicate coating and better corrosion resistance of the coating. Based on the above results and the potential-pH diagram of zinc, probable causes for differences in structure and compactness of silicate coatings, prepared by immersing HDG steels in sodium silicate solutions with different SiO₂:Na₂O molar ratio, are discussed.     

铝合金无铬磷化处理

    研制一种不含铬的低温快速磷化液并用X射线衍射及能谱、扫描电镜、电化学等方法研究了游离酸度、温度和所含物质对其磷化效果的影响及磷化膜的晶相、形貌、耐蚀性.结果表明,该磷化液在35℃～45℃、5 min～8 min时,能在6061铝合金上形成一层致密均匀的磷化膜,膜重4 g/m²～6g/m²,作为油漆底层具有良好的应用前景.     

碳钢超声磷化及在模拟干热岩地热水中的耐蚀性能

采用环境友好的硫酸羟胺为主要促进剂,避免使用强氧化性物质,并以超声处理来改进磷化工艺。通过动电位极化曲线方法研究了超声、促进剂、pH值和磷化时间对磷化膜耐蚀性能的影响。结果表明,超声处理能够细化磷化颗粒,提高其耐蚀性能。pH值和磷化时间显著影响磷化膜的耐蚀性,需保持在较优的范围。采用电化学阻抗谱研究了优化工艺得到的磷化膜在模拟干热岩地热水中的耐蚀性,发现其电荷转移电阻由碳钢的1.44×10³ Ωcm²增加到3.39×10⁶ Ωcm²。     

提高钢质件黑色磷化耐蚀性能

通过对前处理、装载方式、磷化液的改进,使钢质黑色磷化件的耐蚀性能有了大大提高,也提高了黑色磷化工艺在产品上的运用,从而达到了使用要求.     

Nonmetallic conducting coatings: Properties and behaviour of iron and iron-copper phosphate coatings

Surface conversion of steel by means of conducting iron phosphate coatings protects mechanical parts blanked from steel sheets, even in a very high-humidity environment, and also allows their assembly through electrical resistance welding. Corrosion tests carried out by exposing the materials to alternate humid/dry cycles, in a humidostatic chamber at 40°C, indicate that the welding process gives rise to corrosion phenomena. These can be strongly mitigated by using conversion coatings of mixed iron/copper phosphates. Conditions for obtaining optimum corrosion resistance for the final conversion coatings are therefore defined. Measurements of the related corrosion potentials made at 25 °C in a sodium hydroxide solution (pH 12, saturated in oxygen) indicate the existence of threshold values above which corrosion resistance of the phosphatized specimens is acceptable, and suggest a method for performing an industrial control of phosphating efficiency. The performance of converted steel surface has been related to the porosity of phosphate coatings.     

Effect of surface mechanical attrition treatment (SMAT) on zinc phosphating of steel

The effects of surface mechanical attrition treatment (SMAT) of EN8 steel on the growth of phosphate coatings, morphological features and corrosion resistance of the resultant coatings have been studied. SMAT enabled the formation of a uniform surface profile although the average surface roughness is increased after treatment. SMAT increased the extent of metal dissolution and the rate of growth of phosphate coating. In spite of the similarity in phase composition, the phosphate crystallite size is relatively high for samples treated by SMAT. Compared to the untreated one, a cathodic shift in E_corr with a corresponding decrease in i_corr is observed for SMAT treated EN8 steel after phosphating. For all tested samples, zinc phosphate coatings deposited on EN8 steel after SMAT using 8 mm Ø balls for 30 min offers the highest corrosion resistance. The increase in surface roughness by SMAT is partly compensated by the expected improvement in corrosion resistance.     

锈蚀输电铁塔涂装体系耐蚀性

采用磷化技术处理锈蚀输电铁塔,并在此基础上设计出与磷化液配套的防腐蚀涂装体系。试验结果表明,使用磷化技术处理锈蚀铁塔时,磷化液在锈蚀金属表面形成致密磷酸盐膜,清洗、锈层转化、锌层磷化以及表面调整可以一步完成;配制的涂装体系中,以有机涂料为底漆的涂装体系与磷化液配套使用机械性能与耐蚀性能良好。     

工艺参数对38MnVS钢锰系磷化膜表面形貌和耐蚀性的影响

目的研究磷化温度和时间对38MnVS钢磷化膜表面形貌、膜厚和耐蚀性的影响,获得38MnVS钢锰系磷化的最佳工艺参数。方法通过控制单因素变量,在不同磷化温度和时间下在38MnVS表面制备锰系磷化膜。通过扫描电镜(SEM)、测厚仪和硫酸铜点蚀测试等方法,对38MnVS钢表面磷化膜形貌、膜厚及耐蚀性能进行了分析。结果 38MnVS钢表面磷化膜为非均匀形核,磷化膜晶粒首先形成于划痕和晶界处。随磷化时间延长,磷化膜晶粒迅速覆盖基体表面,磷化膜厚度和耐蚀性不断增加。当磷化时间大于15 min时,磷化膜性能变化不大。当磷化温度小于75℃时,不利于磷化膜的生长,磷化膜不能完全覆盖基体,磷化膜的厚度和耐蚀性较低。随磷化温度的升高,磷化膜晶粒不断长大,磷化膜厚度和耐蚀性迅速增加。当磷化温度超过95℃时,磷化膜性能增速下降。结论 38MnVS钢的最佳磷化工艺为:85℃,15 min。     

Corrosion and protection characteristics of phosphate coatings: effect of yttrium oxide as additive

Abstract

The corrosion and protection characteristics of phosphate coatings formed in a phosphating solution containing mainly ZnO, H₃PO₄ and NaF, using Y₂O₃ as an additive, were investigated through SEM, polarisation curves and EIS diagrams. The results show that the corrosion protection of phosphate coatings has been improved when Y₂O₃ is added to the phosphating solution, making the free corrosion potential shift to the positive direction and causing the corrosion current to decrease. The protection ability of phosphate coatings depends mainly on their barrier performance. The phosphate coatings formed in the phosphating solution with 10 and 20 mg L^–1 Y₂O₃ have finer crystal structures and smaller porosity; therefore, they exhibit better corrosion resistance and adhesion properties than those without Y₂O₃ and with 40 mg L^–1 Y₂O₃.