CORROSION BEHAVIOR OF A ZIRCONIUM-TITANIUM BASED PHOSPHONIC ACID CONVERSION COATING ON AA6061 ALUMINIUM ALLOY

The conversion coating was formed by dipping AA6061 in a fluorotitanate/zirconate acid and amino trimethylene phosphonic acid （ATMP） solution at room temperature. The formation process and the anti-corrosion performance of the conversion coating were investigated using electrochemical test and salt spray test （SST）, respectively. The electrochemical test shows that the Zr/Ti and ATMP coating improves the corrosion resistance of AA6061 as good as the chromate （VI） coating. But the results of SST show that the corrosion resistance of Zr/Ti and ATMP coating is not as good as the chromate （VI） coating. The corrosion area is less than 2% after 72 h.     

酸根离子对镨盐化学转化膜的组成及性能的影响

为探究转化液主盐酸根在成膜过程中的重要作用,采用扫描电子显微镜、能谱仪、x射线光电子谱仪结合电化学测试对两种常见酸根对应镨盐在镁合金表面形成转化膜后的形貌、成分、元素化学状态以及耐腐蚀性能进行比较,并基于酸根离子在水溶液中的反应过程分析其对转化膜成分及性能的作用机制.结果表明,以PrCl3作为主盐比以Pr(NO3)3作为主盐形成的化学转化膜更加致密;且前者受基体成分的影响较小,形成膜层的Pr、O含量(质量分数)明显高于后者;前者的耐腐蚀性能优于后者.酸根离子对转化膜成分及性能的影响主要体现在镨盐电离后在转化液中形成的相应稀酸与基体合金的作用机制及其对转化膜形成过程的影响.     

氟硅酸钾封闭对钢铁表面氟铁酸钾转化膜耐蚀性能的影响

采用扫描电镜(SEM)、能谱分析(EDS)、电化学测试和中性盐雾试验对经过氟硅酸钾溶液封闭处理后的氟铁酸钾转化膜的表面形貌、元素组成和耐蚀性进行了分析测试。结果表明,氟硅酸钾水解产生的SiO2胶体对钢铁表面氟铁酸钾转化膜的封闭作用使得钢铁样品的腐蚀电流密度降低,防腐性能增强。     

Corrosion protection of magnesium alloys by cerium, zirconium and niobium-based conversion coatings

A new Ce, Zr and Nb-based conversion coating was designed for AZ91 and AM50 magnesium alloys. The corrosion protection provided by this coating was evaluated by electrochemical measurements (polarization curves, electrochemical impedance spectroscopy) in Na₂SO₄ electrolyte, and accelerated atmospheric corrosion tests (humid, SO₂ polluted air, and salt spray). Its chemical composition was characterized by X-ray photoelectron spectroscopy (XPS). Electrochemical measurements showed that Mg alloys treated during 24 h in the Ce-Zr-Nb conversion bath exhibit: (i) increased corrosion potential, (ii) decreased corrosion and anodic dissolution current densities, and (iii) increased polarization and charge transfer resistances. The accelerated corrosion tests revealed excellent atmospheric corrosion resistance for all Ce-Zr-Nb-treated samples, with or without an additional layer of epoxy-polyamide resin lacquer or paint. XPS analysis showed that the coating includes CeO₂, Ce₂O₃, ZrO₂, Nb₂O₅, MgO, and MgF₂ as main components. No significant modification of the chemical composition was observed after cathodic and anodic polarization in Na₂SO₄. This new coating provides improved corrosion resistance, and excellent paint adhesion. It offers an alternative to the chromate conversion coating for magnesium alloys.     

Synthesis and evaluation of corrosion resistance of molybdate-based conversion coatings on electroplated zinc

Three molybdate-based conversion coatings on electroplated zinc have been prepared and the composition, morphology, and structure of these coatings are measured by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and X-ray diffraction (XRD), respectively. It was found that these coatings with ‘meshwork’ surface were complex coatings composed of multiple compounds. Molybdenum species were present in the conversion coating as Mo (VI) and Mo (IV) compounds. The results of neutral salt spray test showed that molybdate-based conversion coatings with the addition of H₃PO₄, SiO₂ and TiOSO₄ in the passivation baths possess higher corrosion resistance compared with chromate conversion coatings, which was due to the compactness and anti-corrosion essence of the conversion coating.     

镀锌钢板钛盐/硅烷复合膜的耐蚀性研究

研究了镀锌钢板上钛盐钝化膜、硅烷转化膜、钛盐/硅烷复合转化膜的表面形貌和化学成分,并对比了这3种转化膜与普通铬酸盐转化膜的电化学行为和耐盐雾腐蚀性能。结果表明:镀锌钢板钝化后,腐蚀电流密度降低,极化电阻及交流阻抗得到极大提高;钛盐/硅烷复合膜的耐蚀性已经接近普通铬酸盐钝化。SEM和EIS分析表明,硅烷膜是一层物理遮盖膜。     

Electrophoretic painting on AZ31 Mg alloy pretreated in cerium conversion coating solutions prepared in ethanol-water mixtures

Electrophoretic painting (E-paint) was prepared on AZ31 Mg alloy samples pretreated in cerium conversion coating (CeCC) solutions with various ratios of ethanol and water mixture and its characteristics, adhesion and corrosion resistance were investigated. It was found that CeCC formed on AZ31 Mg alloy in a CeCC solution without ethanol was partly cracked structure and mainly consisted of Mg(OH)₂/MgO, which exhibited weak adhesion with E-painting layer after water immersion test, and low corrosion resistance, as indicated by rapid formation of blisters and paint delamination during salt spray test. The addition of ethanol promoted the growth of a fine nano-crystalline CeO₂ layer over the entire substrate surface. The E-paint on AZ31 pretreated in the CeCC solutions with addition of ethanol showed also improved corrosion resistance, as represented by the delayed time for paint delamination and blister formation. The E-paint layers on the CeCC layers formed in solutions containing 50–80 vol% ethanol showed stronger adhesion and better corrosion resistance than those formed on the samples treated in a non-ethanol containing CeCC solution.     

Corrosion protection properties of vanadium films formed on zinc surfaces

Vanadium films were prepared on zinc surfaces by using a solution containing vanadate. Corrosion protection properties of vanadium-treated (V-treated), chromium-treated (Cr-treated), and untreated zinc surfaces in contact with a 3.5 wt.% NaCl solution were studied using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and neutral salt spray (NSS) tests. According to these results, the V-treated layer significantly improved the corrosion resistance of zinc surfaces. In comparison with the Cr-treated layer, the V-treated layer exhibited a better corrosion resistance. The composition of the V-treated layer was studied using X-ray photoelectron spectroscopy (XPS). XPS measurements indicated that the vanadium layer formed on zinc surfaces and the vanadium-rich coating was a hydrated oxide with a composition of V₂O₅, VO₂, and its hydrates such as V₂O_5·nH₂O and VO(OH)₂.     

Electrochemical properties and structure of vanadium-based conversion coatings on electro-galvanised steel

The corrosion resistance of vanadium-based conversion coatings on electro-galvanised steel (EG) was examined in terms of the different valence species V⁵⁺ and V⁴⁺ as the raw material in the treatment solution. The effects of mixing phosphoric acid with the vanadium-based conversion coating have also been investigated. Corrosion performance was tested by neutral salt spray test and the mechanism of corrosion resistance was analysed by electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy. It was found that conversion coatings formed from V⁵⁺ or V⁴⁺ did not clearly show different corrosion behaviour, but that the addition of phosphoric acid to the solution including V⁵⁺ improved corrosion protection. These results indicate that mixing phosphoric acid lowers the pH of the solution and improves corrosion resistance. The role of phosphoric acid is also explained by the formation of hydrogen bonds at the interface between the vanadium species and EG substrate.     

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.     

Organic-magnesium complex conversion coating on AZ91D magnesium alloy

An organic-magnesium complex conversion (OMCC) coating on AZ91D magnesium alloy was obtained by treating in a solution containing organic compounds. SEM, FESEM and XPS were used to examine the surface morphology, thickness and structure of the conversion coatings. The results show that the continuous and uniform conversion coating is deposited on AZ91D alloy and the main component of the coatings is organic compound containing benzene ring, which forms a chemical bond with magnesium. The polarization measurement and salt spray test show that the corrosion resistance of the conversion coating is much higher than that of traditional chromate conversion coating.     

化学镀Ni-P和Ni-Cu-P合金耐蚀性研究

研究了硫酸铜加入量对化学镀Ni-Cu-P合金的镀层成分、组织及热稳定性影响,用中性盐雾实验和在20%H2SO4+20 g/LAl2O3溶液中的冲刷腐蚀实验研究了Ni-P与Ni-Cu-P合金的耐蚀性和耐冲刷腐蚀性能.结果表明,Ni-Cu-P合金镀层具有比Ni-P合金镀层更好的热稳定性、耐蚀性和耐冲刷腐蚀性能.     

紫外辐射对2024铝合金表面钛盐转化膜形成的影响

采用由硫酸氧钛、氟化钠为主盐的转化液,在60℃,pH 5～5.5及紫外光照射条件下处理5min,在2024铝合金表面制备了一种钛盐转化膜,中性盐雾时间超过96h。EDS和XPS分析结果表明,转化膜主要由O,Ti,Al,F,Mg及Cu等元素组成,转化膜中的Ti主要以TiO2的形式存在。电化学测试结果表明,紫外照射条件下,转化反应处理的2024铝合金腐蚀电位正移和阳极钝化区形成,使得2024铝合金惰性、防腐性能显著增强。     

Effect of surfactant on the alumina dispersion and corrosion behavior of electroless Ni?P?Al2O3 composite coatings

Electroless Ni? P? Al₂O₃ composite coatings have been synthesized on mild steel shafts using surfactant cetyltrimethyle ammonium bromide (CTAB) as dispersant. The effects of the surfactant on the alumina dispersion, weight fraction in coatings, and corrosion resistance of the composite coatings under salt spray test were investigated. Results showed that alumina dispersion was improved, whereas weight fraction was decreased, with the increasing concentration of the dispersant CTAB. The corrosion resistance of the composite coatings was found to increase with the increase in CTAB concentration up to a certain optimum of 20 mg/L, beyond which a decreasing trend of corrosion resistance was observed under salt spray test. Compared with Ni? P coating, all the Ni? P? Al₂O₃ composite coatings showed improved corrosion‐resistant properties.     

Corrosion behaviour of AIP NiCoCrAlYSiB coating in salt spray tests

NiCoCrAlYSiB coatings were deposited by arc ion plating (AIP) and annealed/pre-oxidised under various conditions. The corrosion behaviour of as-deposited and annealed/pre-oxidised coatings was studied by salt spray testing in a neutral mist of 5 wt% NaCl at 35 °C for 200 h. The results showed that the as-deposited NiCoCrAlYSiB coating behaved poorly while the annealed and pre-oxidised ones performed much better in salt spray tests. The dense microstructure in annealed coatings and formation of α-Al₂O₃ scales on the surface during pre-oxidation improved the corrosion resistance in salt spray test. The corrosion process was investigated from the aspects of corrosion products, and its electrochemical mechanism was proposed as well.     

镀锌板硅烷-硝酸锆复合转化膜的性能与表征

目的获得一种防腐性能优越的转化膜。方法将KH560和KH791两种硅烷复合后水解,添加硝酸锆,得到KH560-KH791-硝酸锆复合钝化液,采用该钝化液对镀锌钢板进行钝化处理,通过盐水浸泡实验、中性盐雾试验和附着力测试,与添加硝酸锆前的转化膜进行性能对比。结果盐水浸泡和中性盐雾腐蚀72 h的实验中,添加硝酸锆后的转化膜性能都明显优于添加前,二者的附着力测试均能达到一级。结论加入的硝酸锆填充了膜层空隙,更加有效地阻挡了腐蚀介质的渗透,使得钝化膜的防腐性能提高。     

DTAB 和甘氨酸对钢铁表面氟铁酸盐转化膜耐蚀性的影响

目的提高氟铁酸钾转化膜的耐蚀性。方法通过扫描电子显微镜分析、中性盐雾实验和极化曲线测试,研究氟铁酸盐转化液中加入十二烷基三甲基溴化铵和甘氨酸对钢铁表面转化膜耐蚀性的影响。结果转化液中加入两种物质使转化膜的厚度增加,自腐蚀电位正移了大约42 mV,自腐蚀电流降低了大约1/3,耐中性盐雾时间延长了2倍以上。结论钢铁表面转化膜的耐蚀性获得显著提高。     

纳米CeO2掺杂对烧结钕铁硼磁体表面Zn-Al涂层性能的影响

采用喷涂工艺在烧结钕铁硼磁体表面制备了不同纳米 CeO₂ 掺杂量的 CeO₂ / Zn-Al 复合涂层。 利用扫描电子显微镜、显微硬度仪、盐雾试验箱和电化学工作站对 CeO₂ / Zn-Al 复合涂层的微观结构、力学性能及耐腐蚀性能进行表征分析。 结果表明:CeO₂ 纳米颗粒较均匀弥散分布于 Zn-Al 涂层中,不仅能够增加 Zn-Al 涂层的硬度,而且可以提高 Zn-Al 涂层的屏蔽性能,CeO₂ / Zn-Al 复合涂层耐中性盐雾试验能力高达 720 h。 添加的 CeO₂ 颗粒能够隔绝 Zn-Al 涂层中的锌铝薄片之间的直接接触,起到绝缘作用,延长了腐蚀介质渗入钕铁硼基体的腐蚀通道。     

添加剂对镁合金磷酸盐-高锰酸盐化学转化膜耐蚀性的影响

在磷酸二氢铵和高锰酸钾组成的化学转化处理基础液中,添加单一添加剂和复合添加剂,在AZ31镁合金表面上制备出了耐蚀性良好的化学转化膜。采用扫描电镜(SEM)、能谱分析仪(EDS)、电化学方法、全浸蚀试验和中性盐雾试验分别对化学转化膜的微观形貌、成分和耐蚀性进行了检测和评价。结果表明,化学转化处理提高了镁合金的耐蚀性,且不同的添加剂对化学转化膜耐蚀性的提高效果不一样。其中,复合添加剂对镁合金的耐蚀性的提高效果更为显著。     

Study of the formation and growth of tannic acid based conversion coating on AZ91D magnesium alloy

A tannic acid based conversion coating was formed on AZ91D magnesium alloy through a solution containing C₇₆H₅₂O₄₆ (tannic acid), NH₄VO₃, K₂ZrF₆ and H₃PO₄. The growth process and corrosion resistance of the conversion coating were investigated by SEM, FESEM, XPS, IR, potentiodynamic polarization and EIS test. The results showed that the main components of the coatings were penta-hydroxy benzamide–magnesium complex, Al₂O₃ and MgF₂. Zr(HPO₄)₂·H₂O(α-ZrP) was first formed in the time interval of 70 s–120 s, which acted as catalyst to activate the main reaction of gallic acid being oxidized into the penta-hydroxy benzamide–magnesium complex, as well as the formation of MgF₂ and Al₂O₃, which took place in the time interval of 120 s to 600 s. The thickness of coating treated for 300 s and 600 s was 1.1 μm and 1.6 μm, respectively. Polarization measurement and EIS test in 3 wt.% NaCl solution indicated that the conversion coating treated for about 300–600 s shows good corrosion resistance while an excess time treatment (720 s) induces the coating surface coarse and uneven, leading to the reduction of corrosion resistance of the conversion coating.