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。     

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。     

Study of Cerium and Lanthanum Conversion Coatings on AZ63 Magnesium Alloy Surface

采用扫描电子显微镜,X射线能谱,Tafel极化曲线和电化学阻抗谱法研究了铈镧转化膜对AZ63镁合金耐蚀性能的影响。结果表明,铈和镧的复合转化膜比单一稀土膜的表面更加均匀致密,对镁合金的耐蚀性有明显改善。双稀土转化膜的缓蚀效果随着浸泡成膜时间的增长而增加。延长时效时间有助于铈和镧的进一步氧化,耐蚀性能先增后减,时效48 h膜层的耐蚀效果最好。     

Corrosion electrochemical behaviors of silane coating coated magnesium alloy in NaCl solution containing cerium nitrate

Sol–gel coatings cannot provide adequate corrosion protection for metal/alloys in the corrosive environments due to their high crack‐forming potential. This paper demonstrates the possibility to employ cerium nitrate as inhibitor to decrease the corrosion development of sol–gel‐based silane coating on the magnesium alloy in NaCl solution. Cerium nitrate was added into the NaCl solution where the silane coating coated magnesium alloy was immersed. Scanning electron microcopy (SEM) was used to examine surface morphology of the silane coating coated magnesium alloy immersed in NaCl solutions doped and undoped with cerium nitrate. The corrosion electrochemical behaviors were investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) tests. The results showed that the introduction of cerium nitrate into NaCl solution could effectively inhibit the corrosion of the silane coating coated magnesium alloy. Moreover, the influence of concentration of cerium nitrate on the corrosion inhibition and the possible inhibiting mechanism were also discussed in detail.     

Microstructural characteristics and corrosion property of non‐chromate surface treatments on AZ91D magnesium alloy

Chromate conversion coatings can be successfully used for corrosion protection of magnesium alloys. However, the environmental laws have imposed severe restrictions on chromate use in many countries. In this study, a novel protective environmental‐functionally gradient coating was formed on AZ91D magnesium alloy by non‐chromate surface treatments, which consisted of pre‐etching followed by cerium‐based chemical conversion before applying the sol–gel CeO₂ film. It was determined by the analysis of X‐ray diffraction that the gradient coating was mainly composed of CeO₂. The calculation, based on the Scherrer formula, further revealed the formation of nanocrystalline structure in the coating. Scanning electron microscopy (SEM) observations showed that the coating was homogeneous and compact, no obvious cracked structure occurred. According to the immersion tests, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) tests, the corrosion resistance of AZ91D magnesium alloy was found to be greatly improved by means of this novel environmental‐functionally gradient coating.     

A room temperature cured sol–gel anticorrosion pre-treatment for Al 2024-T3 alloys

The inherent reactivity of the Al–Cu alloys is such that their use for structural, marine, and aerospace components and structures would not be possible without prior application of a corrosion protection system. Historically these corrosion protection systems have been based upon the use of chemicals containing Cr(VI) compounds. Organic–inorganic hybrid silane coatings are of increasing interest in industry due to their potential application for the replacement of current toxic hexavalent chromate based treatments. In the present study, a hybrid epoxy–silica–alumina coating with or without doped cerium nitrate has been prepared using a sol–gel method. The hybrid coatings were applied by a dip-technique to an Al–Cu alloy, Al 2024-T3, and subsequently cured at room temperature. The anticorrosion properties of the coatings within 3.5% NaCl were studied using electrochemical impedance spectroscopy (EIS), and conventional DC polarisation. An exfoliation test method involving immersion in a solution of 4 M NaCl, 0.5 M KNO₃ and 0.1 M HNO₃ was also used. The cerium nitrate doped sol–gel coating exhibited excellent anticorrosion properties providing an adherent protection film on the Al 2024-T3 substrate. The resistance to corrosion of the sol–gel coating was also evaluated by analysing the morphology of the coating before and after corrosion testing using scanning electron microscopy.     

添加剂对铝合金稀土转化膜的影响

目的寻找有效提高稀土转化膜性能的添加剂体系。方法采用电化学手段研究添加剂(硼酸、柠檬酸钠、磷酸钠、硅酸钠、氟化氢铵、氟化钠、草酸铵)对稀土转化膜的影响,对于具有积极作用的添加剂,使用响应面法进行复配,并优化配方。通过扫描电子显微镜(SEM)、能谱仪(EDS)和电化学测试对优化条件下制备的稀土转化膜性能进行表征。结果向基础转化液中加入氟化钠(NaF)、柠檬酸钠(Na_3C_6H_5O_7)和磷酸钠(Na_3PO_4)可以提高稀土转化膜的电化学性能。经过复配并优化配方,得到最优添加剂体系为0.68g/L氟化钠+0.80g/L磷酸钠。该配方可以抑制铝合金在转化液中的溶解,有利于铈元素的沉积,使铈的沉积量由5.01%提高到了9.60%。优化配方下制备出的膜层更加均匀致密,腐蚀电位提高了0.13 V,点滴时间可达122 s。XRD和EDS结果表明,膜层的主要成分为非晶态的铈锰氧化物。结论 0.68 g/L氟化钠+0.80g/L磷酸钠为最优添加剂配方。在优化体系中制得的稀土膜层的电化学性能得到了提升,表面更加均匀致密。     

环氧涂层中锌铬黄颜料对镁合金的防蚀机理

采用电化学阻抗、动电位极化、开路电位监测和X射线光电子能谱(XPS)等手段,研究了环氧涂层中锌铬黄颜料对镁合金的腐蚀防护作用,并分析了其防蚀机理。结果表明,锌铬黄防锈颜料均匀分散在涂层中,增强了涂层的屏蔽性能以及涂层与镁合金基体的结合力;在3%NaCl水溶液中,锌铬黄是一种阳极型缓蚀剂,它依靠铬酸根离子的阳极钝化作用形成钝化膜,阻滞了阳极腐蚀过程,造成涂层试样开路电位正移,使涂层试样的阳极极化增大。     

Exfoliation corrosion of aluminum alloys II. Protection methods, their effectiveness and improvement

Advantages of the aluminum alloys protection against exfoliation, corrosion by conversion (anodic oxide, phosphate, and chromate), as well as polymeric (inhibited and metal-filled), paint coatings are revealed. The potentialilities of the electrochemical protection and application of easily removable coatings, preservation oils, and greases doped with inhibitors and bactericides are considered.     

Evolution of corrosion protection performance of hybrid silica based sol–gel nanocoatings by doping inorganic inhibitor

Silica based hybrid sol–gel coatings were developed to protect AA2024 alloy from corrosion. In order to have an active protection, cerium nitrate corrosion inhibitor was introduced into the coating system. The anti‐corrosion properties of the coatings were evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic scanning (PDS) methods. The structure of the films was studied by scanning electron microscopy (SEM) after corrosion. The results indicate that the improvement of the protection properties of the films occurred with immersion time. This would imply that cerium ions could reach the defects, hindering the corrosion reactions and thus reduces the corrosion rate.     

Electrochemical and In Vitro Behavior of Nanostructure Sol-Gel Coated 316L Stainless Steel Incorporated with Rosemary Extract

The corrosion resistance of AISI 316L stainless steel for biomedical applications, was significantly enhanced by means of hybrid organic-inorganic sol-gel thin films deposited by spin-coating. Thin films of less than 100 nm with different hybrid characters were obtained by incorporating rosemary extract as green corrosion inhibitor. The morphology, composition, and adhesion of hybrid sol-gel coatings have been examined by SEM, EDX, and pull-off test, respectively. Addition of high additive concentrations (0.1%) did not disorganize the sol-gel network. Direct pull-off test recorded a mean coating-substrate bonding strength larger than 21.2 MPa for the hybrid sol-gel coating. The effect of rosemary extract, with various added concentrations from 0.012 to 0.1%, on the anticorrosion properties of sol-gel films have been characterized by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests in simulated body fluid (SBF) solution and has been compared to the bare metal. Rosemary extract additions (0.05%) have significantly increased the corrosion protection of the sol-gel thin film to higher than 90%. The in vitro bioactivity of prepared films indicates that hydroxyapatite nuclei can form and grow on the surface of the doped sol-gel thin films. The present study shows that due to their excellent anticorrosion properties, bioactivity and bonding strength to substrate, doped sol-gel thin films are practical hybrid films in biomedical applications.     

Al合金表面铬酸盐处理及替代工艺研究进展

综述了Al合金表面化学转化防腐蚀处理技术的研究进 展,分析了铬酸盐表面处理的成膜机理及耐蚀机理.在比较各种处理技术的防护性能及处理 工艺的基础上,探讨了替代Al合金铬酸盐处理工艺的可能性.     

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.     

铝合金稀土转化膜碱性成膜工艺T3/T7的研究

采用正交实验方法得出了最佳成膜工艺T3/T7,利用线性极化、极化曲线测试、中性盐雾实验等对该工艺形成的膜层耐蚀性进行了研究,并对表面膜层的性能进行了一系列测试.结果表明:在NaCl水溶液中的全面腐蚀速度可降低10～20倍,可通过504h的中性盐雾试验;经该工艺处理后铝合金腐蚀的阴阳极过程都受到明显阻滞,且自然腐蚀电位负移,点蚀电位相对于自然腐蚀电位明显正移,T3/T7处理明显的改善了铝合金在氯化物介质中的耐点蚀性能     

Cerium-based conversion coatings on aluminium alloys: a process review

Abstract

Rare earths are among the most promising options for replacing chromate conversion coatings on aluminium. In nearly three decades of research, several hundred papers have been published in the area, the bulk of which has never been reviewed. This paper reviews the literature on rare earth coating processes, with particular emphasis on those based on cerium. It is concluded that several process areas are poorly understood, some of which are critical to further progress in the field. These include the development of industrially suitable pretreatments, technologies for coating non-aerospace alloys and seals to enhance corrosion performance and paint adhesion.     

6061 铝合金表面无铬稀土镧转化膜性能的研究

利用极化曲线方法,研究了以La(NO3)3.6H2O为促进剂的磷酸盐转化膜的耐蚀性,同时与铬磷化膜及无稀土促进的单纯磷酸盐膜的耐蚀性进行了对比;通过划格法和全浸腐蚀试验,研究了这三种转化膜与有机涂层间的结合力。结果发现:与单纯磷酸盐膜相比,稀土促进生成的磷酸盐膜中的传输阻力增加,耐蚀性明显增强,而与铬磷化膜相比,二者在弱极化区的耐蚀性能相近;稀土促进生成的磷酸盐膜与有涂层间的结合力明显优于铬磷化膜。     

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。     

镁合金表面稀土转化膜研究进展

镁合金作为结构材料具有十分突出的性能,但镁的低电位导致其耐蚀性很差,大大限制了镁合金的广泛应用.化学转化膜作为一种简单、有效的防腐蚀表面处理方法得到了迅速发展.相较目前成熟但污染严重的铬酸盐转化膜处理工艺,稀土盐转化处理因其良好的环境友好性和耐蚀性能而备受关注.总结了稀土盐转化膜的成膜工艺及膜的性能、膜的组成及微观形貌、膜的形成机理以及膜的耐腐蚀机理等方面的研究现状,提出了转化膜的一些技术问题,并展望了该技术的发展趋势.     

铝合金表面稀土转化膜研究进展

介绍了铝合金表面稀土转化膜在国内外的研究进展及现状,综述了铝合金表面稀土转化膜工艺研究的发展过程,讨论了稀土转化膜的成膜机理和耐腐蚀机理,提出了稀土转化膜技术目前阶段存在的问题,并对这一技术的发展提出了展望。     

Study of a New Chromium-Free Conversion Coating Formed on ZnAl Alloy

BECAUSE OF A HIGHER CHEMICAL ACTIVITYzinc and zinc alloys(in bulk or in coating form)corrode rapidly in moist atmospheres recovering withwhite corrosion products—white rust and in acidicclimatic conditions becoming grey[l].So passivition orchemical conversion treatments is often needed fortheir corrosion protection.This is generally done bymeans of chromate treatment which offers a goodcorrosion inhibition.However,chromates are highlytoxic and carcinogenic[2]and their use can lead…