海洋工程用结构铝合金无铬化学转化膜耐腐蚀及涂装配套性能

为改善服役于海洋环境下的结构铝合金的耐腐蚀性及其与底漆的配套性能,在两种典型海洋工程用结构铝合金(5083-H116和6061-T6)基体上制备了一种无铬钛/锆基化学转化膜———Alum-nanoceramic coating。采用扫描电子显微镜(SEM)和能谱仪(EDS)对膜层形貌及组成进行了表征,通过动电位极化曲线和电化学阻抗谱研究了膜层的电化学性能,利用中性盐雾试验及胶带剥离试验分别对膜层耐蚀性及其与环氧厚浆底漆的配套性进行了考察。结果表明:5083和6061铝合金Alum-nanoceramic无铬化学转化膜中性盐雾试验白锈面积达到5%所需时间分别为240h和168h;5083铝合金Alum-nanoceramic膜层比后者显示出更好的与环氧厚浆底漆的配套性能。     

Corrosion resistance of the electro-galvanized steel treated in a titanium conversion solution

The conversion coating can be obtained by using a solution containing titanium tetrachloride, fluorosilicate acid and nitric acid. The results of X-ray photoelectron spectroscopy (XPS) showed that the titanium conversion coating consisted of ZnO, TiO₂ and Zn₄Si₂O₇(OH)₂. The formation process of the titanium conversion coating was studied. Effects of the immersion time, pH value and solution temperature on the corrosion resistance and the chemical composition of the titanium conversion coating were investigated by the salt spray test (SST) and XPS, respectively. The results of XPS and SST showed that the titanium conversion coating displayed better corrosion resistance with higher contents of Si and Ti. Results of corrosion tests (the salt spray and electrochemical test) indicate that the corrosion resistance of the conversion coating by titanium solution is better than that of the conversion coating using the traditional chromate solution.     

Structural investigation of the zirconium-titanium based amino trimethylene phosphonate hybrid coating on aluminum alloy

A zirconium-titanium based amino trimethylene phosphonate hybrid coating on AA6061 aluminum alloys was formed by dipping in a fluorotitanate/zirconate acid and amino trimethylene phosphonic acid (ATMP) solution for improving the lacquer adhesion and corrosion resistance as a substitute of chromate coatings. The morphol-ogy and structure of the hybrid coating were studied by means of scanning electror microscopy (SEM) and atomic force microscopy (AFM). The surface compositior and structure characteristics were also investigated by means of X-ray photoelectron spectroscopy (XPS) and Fourier transformation infra-red spectroscopy (FTIR). The results of SEM and AFM show that the hybrid coating present piece particle distrib-ution which is much denser than that of the zirconium-titanium coating. The results of XPS and FTIR indicate that the hybrid coating is a hybrid composite structure composed of both the zirconium-titanium and amino trimethylene phosphonate coat-ings.     

铝合金稀土磷化与铬磷化比较

采用电化学测试、全浸腐蚀试验和结合力测试,研究了6061铝合金铬磷化处理和以稀土为添加剂的磷酸盐处理所形成的化学转化膜的工艺性能。动力学研究表明,两者的成膜过程是不相同的。极化曲线测试结果显示,在弱极化区范围内,两者抗蚀性能相近,而在强极化区,铬磷化转化膜的抗蚀性优于以稀土为添加剂的磷酸盐化学处理所形成的转化膜,全浸腐蚀试验有类似的结果。结合力测试结果则表明,以稀土为添加剂的磷酸盐化学处理所形成的转化膜与有机涂层间的结合力要优于铬磷化转化膜。     

AMINO-TRIS-（METHYLENEPHOSPHONIC ACID） LAYERS ADSORPTION ON AA6061 ALUMINUM ALLOY

The amino-tri-（methylenephosphonic acid） layers were adsorbed on the surface of AA6061 aluminum alloy for improving the lacquer adhesion and corrosion inhibition as a substitute for chromate coatings. The surface structure and characteristic of the amino-tri-（methylenephosphonic acid） layers on AA6061 aluminum alloy were investigated by means of XPS and ATR-FTIR analysis. The analyzed results showed that the amino-tri-（methylenephosphonic acid） adsorption layers adsorb on the surface of aluminium alloy via acid-base interaction in a bi-dentate conformation. After the amino-tri-（methylenephosphonic acid） layers were coated with epoxy resin, the layers showed good adhesive strength and favorable corrosion resistance in contrast to chromate coatings.     

Effect of cerium chloride on corrosion resistance and adhesion of chromate conversion coatings

The corrosion resistance, adhesion and morphology of the chromate conversion coating (CCCs) formed on AA6061 in a chromate conversion solution containing mainly potassium dichromate (K₂Cr₂O₇), chromic anhydride (CrO₃) and sodium fluoride (NaF), using cerium chloride (CeCl₃) as additive, were investigated by using potentiodynamic polarization curves, EIS, adhesion test and SEM. The corrosion resistance and adhesion of the CCCs are improved greatly by adding a small amount of CeCl₃ (from 20 to 40 mg/L), whereas the excessive CeCl₃ (60 mg/L) deteriorates these properties of the CCCs. The results of polarization curves are in good agreement with those of EIS. SEM photographs show that the precipitation of cerium hydroxide significantly affects the morphologies of CCCs.     

AA6061铝合金表面钛锆膜的结构及性能研究

在AA6061铝合金表面形成了钛锆膜.用SEM/EDX和XPS分析了钛锆膜的表面形貌及成分.采用电化学测试和中性盐雾测试研究了钛锆膜的耐蚀性能.结果表明,钛锆膜是由Zn-Ti-F-O-Al等元素组成的复合物;钛锆膜的耐蚀性能与基体相比有明显的提高,但不及六价铬酸盐膜;经72小时中性盐雾腐蚀,腐蚀面积小于10%.     

壳聚糖对钛锆转化膜组织结构及耐蚀性的影响

目的 研究壳聚糖对铝合金表面天冬氨酸-钛锆转化膜组织结构及耐蚀性能的影响。方法 在5083船用铝合金表面分别制备添加不同含量壳聚糖的天冬氨酸-钛锆转化膜,采用SEM、EDS、FT-IR、XPS等表征手段,对转化膜的组织结构以及成分进行分析。通过电化学工作站对添加不同含量壳聚糖转化膜的开路电位-时间曲线及极化曲线进行分析。结果 成功制备了添加不同含量壳聚糖的天冬氨酸-钛锆转化膜,添加壳聚糖后,转化膜的裂纹减少,并在红外光谱结果中存在较强的氢键,出现与天冬氨酸及壳聚糖相对应的特征峰。XPS结果表明,转化膜中的Zr以ZrO2及Zr的有机络合物形式存在,转化膜中的Ti以TiO2形式存在,同时也存在天冬氨酸自身结构以及壳聚糖自身结构的峰位。腐蚀电流密度由未添加壳聚糖时的3.966×10-6 A/cm2降低至3.274×10-7A/cm2,耐蚀性具有明显提升。结论 添加壳聚糖能够与传统天冬氨酸-钛锆转化膜结合形成络合物转化膜。适量添加壳聚糖能够改善钛锆转化膜的裂纹情况及耐蚀性,当壳聚糖添加量为15 mL/L时,膜层裂纹最少,同时转化膜的耐蚀性最优。     

Titanium-zirconium-phosphonate hybrid film on 6061 aluminum alloy

Three titanium-zirconium-phosphonate hybrid films were formed on AA6061 aluminum alloy by immersing in fluorotitanic acid and fluorozirconic acid based solution containing different phosphonic acids for protective coatings of aluminium alloy.The corrosion resistance of three hybrid films as the substitute for chromate film were evaluated and compared.The neutral salt spray test was explored,the immersion test was conducted and electrochemical test was also executed.The hybrid films exhibited well-pleasing c...     

Preparation and corrosion resistance of titanium–zirconium–cerium based conversion coating on 6061 aluminum alloy

This paper aims to develop a chromium-free chemical conversion coating with good corrosion resistance. A novel chemical conversion coating was prepared on 6061 aluminum alloy by dipping in the treatment solution containing titanium/zirconium based-ions and sodium metaphosphate and cerium nitrate hexahydrate as additives. The morphology and composition of the conversion coatings were observed by scanning electron microscopy and energy dispersive X-ray spectroscopy. The microarea structure of conversion coatings at different formation stages was analyzed by electron probe microanalyzer. The electrochemical polarization curve revealed that the corrosion potential of the conversion coating was −0.577 V and the corrosion current density was 0.1148 μA/cm². The equivalent circuit fitted by AC impedance showed that the film resistance reaches 68,140 Ω. The formation of coating preferentially grows on the Al (Fe) Si intermetallic to form oxides of Ti and Zr; then TiO₂ formed by a higher concentration of Ti⁴⁺ gradually covered ZrO₂. Ce³⁺ could adsorb on the intermetallic compound, the hydrolysis of which causes the local pH of the solution to decrease and promotes the aluminum alloy dissolved.     

6063铝合金着色钛锆转化膜结构和耐蚀性能的研究

为了获得性能优异的有色钛锆转化膜层,利用正交试验确定了组分为六氟钛酸、六氟锆酸、含锰成膜剂和有机酸的6063铝合金转化处理液的较佳配方,并分析了转化膜的表面形貌、成分及耐蚀性能.分析结果表明:生成的转化膜为淡黄色,且均匀、连续;转化膜中含有钛、锆元素,其腐蚀电位和腐蚀电流密度比裸6063铝合金明显降低,说明钛锆转化膜可以更好地抑制铝合金的阴极反应,从而更有效地提高铝合金的耐蚀性能.     

Chromate passivation of hot dipped Zn25Al alloy coatings

Abstract

A low concentration chromate passivation treatment has been successfully applied to a new type of hot dipped Zn2 5Al alloy coating, and the corrosion resistance of the chromate passive film has been assessed using the copper accelerated acetic salt spray (CASS) test, electrochemical measurements, and sea water immersion testing. The results showed that the corrosion resistance of the Zn2 5Al alloy coating was significantly better after the chromate passivation treatment. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) analyses showed that the composition (at.-%) of the low concentration chromate passive film was: 5·5S–3·4Na–11·8C–7·9Ti–41·6O–1 3·7Cr–16·0Zn. Aluminium was not found in the film, which is attributed to the dissolution behaviour of the Zn2 5Al alloy coating in acidic chromate solution.     

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。     

Corrosion behavior of lanthanum-based conversion coating modified with citric acid on hot dip galvanized steel in aerated 1 M NaCl solution

Rare earth conversion coating is one of the most promising substitutes to the toxic chromate coating. The corrosion resistance of lanthanum conversion coating modified with citric acid on hot dip galvanized (HDG) steel was investigated in aerated 1 M NaCl solution by means of electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. Equivalent circuits were subsequently developed from the measurements to elucidate the corrosion behavior of the coating. The surface morphology of the lanthanum conversion coating was observed by scanning electron microscopy (SEM), and the chemical composition of the coating was characterized by energy dispersive spectroscopy (EDS). The results showed that the corrosion process of the modified lanthanum conversion coating consisted of three stages. The overall corrosion resistance of the coating was excellent.     

The electrochemical corrosion behavior of TiN and (Ti,Al)N coatings in acid and salt solution

In this study, the corrosion properties of TiN and (Ti,Al)N coatings fabricated by Hollow Cathode Ionic Plating (HCIP) were studied by electrochemical techniques such as electrochemical impedance spectroscopy (EIS) measurement and potentiodynamic measurement in acid and salt solution. It was found that both coatings showed an excellent corrosion resistance in acid and salt solutions at the beginning of long-term immersing test. The corrosion resistance of TiN coating deteriorated rapidly after nearly 100 h immersion in both acid and salt solutions. In the contrast, the corrosion rate of (Ti,Al)N coating decreased a little and then kept at a stable value. For the TiN coating, the corrosion initiated from pinholes and the underlying corrosion was very similar to pitting corrosion. With the addition of aluminum to the TiN coating, the corrosion resistance was improved, especially in salt solution. The test results demonstrated that the (Ti,Al)N coating seemed to posses certain self-repairing function. The corrosion mechanism took the form of denudation corrosion, owing to deterioration of the adhesion of the coating.     

Ti-Zr-Be-Cu-Co块体非晶合金形成能力及其耐蚀性的研究

采用磁控溅射法制备Dyx(Co21Cu79)100-x(x=0,4,8,9,12,14)颗粒膜.XRD结果表明:添加稀土元素Dy将促进CoCu过饱和固溶体分解,此外Dy元素还具有细化晶粒的作用.磁电阻测试发现:随着Dy含量的增加,Dyx(Co21Cu79)100-x薄膜的电阻逐渐增大,而薄膜的巨磁电阻(GMR)值先升后降,当退火温度Ta=425℃时,Dy4(Co21Cu79)96薄膜的GMR值达到最大,为-4.68％.薄膜的磁滞回线表明:矫顽力Hc随退火温度的升高逐渐增大,随Dy含量的增加,却单调减小.     

Substitution of hexavalent chromate conversion treatment with a plasma electrolytic oxidation process to improve the corrosion properties of ion vapour deposited AlMg coatings

In this paper plasma electrolytic oxidation (PEO) is examined as a potentially beneficial post-deposition treatment for Al-5 wt.%Mg coatings deposited onto Ti alloy substrates using Ion Vapour Deposition (IVD), with a view to replacing toxic hexavalent chromate conversion treatments and at the same time enhancing the barrier protection properties of such IVD coatings. The aqueous corrosion behaviour of PEO layers formed on IVD coatings was evaluated by means of potentiodynamic polarisation scans, open circuit potential measurements and electrochemical impedance spectroscopy. Normally, IVD aluminium-based coatings require a post-coat shot peening treatment to densify the coating structure; however it was found that PEO layers could be formed successfully on as-deposited IVD coatings deposited onto Ti alloy substrates, providing a cost effective process to improve corrosion behaviour. PEO treatment provides unique improvements in the corrosion resistance of IVD coatings; the PEO layer possesses effective anticorrosion properties in aqueous environments containing Cl⁻ ions. A more positive corrosion potential, lower corrosion current and increased polarisation resistance were recorded for PEO layers, compared to traditional chromate conversion treatments.     

Effect of surface treatments based on self‐assembling molecules and cerium coatings on the AA3003 alloy corrosion resistance

This work presents the effects of a cerium conversion coating, self‐assembling molecules (SAM) treatment, and a combination of these two treatments on the corrosion resistance of the AA3003 alloy. The results were compared to that of a conversion coating treatment with hexavalent chromium (Cr VI). The corrosion resistance of the surface‐treated AA3003 alloy samples was investigated by electrochemical impedance spectroscopy and anodic polarization curves in 0.5 mol/L sodium sulfate solution with pH adjusted to 4.0. The results showed that the SAM treatment offered better corrosion protection for the AA3003 alloy than that provided by cerium conversion coating. The combination of cerium conversion and SAM treatments improved the corrosion resistance of the AA3003 alloy due to SAM adsorption on the alloy substrate exposed at the defects in the cerium conversion layer.     

热浸Zn-Ti合金镀层的耐腐蚀性能

为了抑制热镀锌过程中因含硅活性钢引起的镀层超厚生长,采用在纯锌浴中加Ti的方法,研究了热浸Zn-Ti合金镀层的耐蚀性能.采用浸泡腐蚀、电化学极化、交流阻抗以及X射线光电子能谱等方法,研究了热浸Zn-Ti合金镀层的耐蚀性能.结果表明:Zn-Ti舍金镀层在5%NaCl溶液中的自发腐蚀倾向小于Zn镀层,其极化电阻和交流阻抗增大,腐蚀电流密度减小,耐蚀性能提高.Zn-Ti镀层表面形成的氧化膜由ZnO和TiO2组成.Zn-Ti合金镀层的耐腐蚀性能优于纯锌镀层是由于在镀层表面形成了更加稳定的TiO2膜.     

In vitro corrosion resistance and cytotoxicity of novel TiNbTaZr alloy

A novel β type Ti35Nb2Ta3Zr alloy with low modulus (48 GPa) was fabricated using vacuum consumable arc melting. The corrosion resistance and cytotoxicity of Ti35Nb2Ta3Zr were evaluated. The open circuit potential, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization methods were used to determine the corrosion resistance. In Ringer's solution, Ti35Nb2Ta3Zr alloy exhibits better corrosion resistance, as compared to that of Ti6Al4V and Ti. The cytotoxicity tests indicate that the biocompatibility of Ti35Nb2Ta3Zr is as good as Ti and Ti6Al4V which are widely used in biomedical fields. Based on corrosion resistance and cytotoxicity, the novel β type Ti35Nb2Ta3Zr alloy can be considered as a potential biomaterial.