镁合金表面铈盐掺杂硅烷膜的腐蚀电化学行为

目的为进一步提升镁合金表面常规硅烷膜的耐蚀性能。方法在γ-氨丙基三乙氧基硅烷溶液中掺杂0.50 g/L硝酸铈,采用简单化学浸渍处理,在AZ91D镁合金基体表面制备了铈盐掺杂硅烷膜。借助扫描电子显微镜(SEM)观察了铈盐掺杂前后硅烷膜的表面微观形貌,通过开路电位-时间曲线、电化学交流阻抗谱(EIS)和中性盐雾试验(NSS)研究了铈盐掺杂对5%Na Cl溶液中硅烷膜耐蚀性能的影响。结果铈盐掺杂硅烷膜比普通硅烷膜更厚且平整,其致密性、均匀一致性较好,完全覆盖了镁合金基体,已看不到磨痕。铈盐掺杂硅烷膜的稳定电位约为-1.31 V,且需要的稳定时间最长。铈盐掺杂硅烷膜具有更大的低频阻抗数值,有效遏制了侵蚀性粒子向镁合金基体的迁移和扩散,避免了镁合金基体发生阳极溶解反应。结论采用向硅烷溶液中添加硝酸铈的方法,能够在AZ91D镁合金表面制备出铈盐掺杂硅烷膜。由于铈离子在某种程度上修复了硅烷膜层中的微裂纹和缺陷,显著提升了硅烷膜的耐蚀能力。     

Application of CeH–V/ sol–gel composite coating for corrosion protection of AM60B magnesium alloy

Application of a composite coating on AM60B magnesium alloy consisting of cerium–vanadium conversion coating and a hybrid sol–gel layer was investigated. Scanning electron microscopy and energy dispersive X-ray spectroscopy analyses revealed a cracked nodular structure for the cerium–vanadium conversion coating which was mainly composed of O, Ce, V, and Mg atoms. All the cracks in the conversion coating were completely sealed by a thin, compact and defect-free hybrid sol–gel film. Potentiodynamic polarization and electrochemical impedance spectroscopy experiments in Harrison's solution showed that the cerium–vanadium conversion coating provides minimal protection against corrosion while the composite coating significantly increases the corrosion resistance of the magnesium alloy. Sol–gel film provides protection against corrosion by sealing cracks in the cerium–vanadium conversion coating and acting as a barrier. Scanning electron microscopy analyses after polarization tests confirmed the results obtained by the electrochemical tests.     

Analytical characterisation and corrosion behaviour of bis-aminosilane coatings modified with carbon nanotubes activated with rare-earth salts applied on AZ31 Magnesium alloy

The present work investigates the corrosion behaviour of AZ31 Magnesium alloy (Mg AZ31) substrates pre-treated with a water soluble bis-aminosilane modified with multiwall carbon nanotubes (CNTs). Prior addition to the silane solution, the CNTs were submitted to a treatment in an aqueous solution containing cerium nitrate or lanthanum nitrate. The chemical composition of the treated CNTs and of the modified silane coatings was assessed by X-ray Photoelectron spectroscopy (XPS). The thickness and the morphology of the silane coatings were investigated by scanning electron microscopy (FEG/SEM).The pre-treatment of the Mg AZ31 was performed by dipping the metallic coupons in the silane solution modified with the CNTs. The electrochemical behaviour of the silane coated coupons was studied during immersion in 0.05 M NaCl solutions, using the scanning vibrating electrode technique.The electrochemical investigation showed that the activation of the CNTs with the rare-earth salt delays the corrosion activity of the Mg AZ31 substrates. The analytical and microscopic study suggested that the CNTs are homogeneously dispersed in the silane coating and that the CNTs act as support for inhibitor storage.     

Preparation and characterization of inorganic and organic coatings on AZ91D magnesium alloy with electroless plating pretreatment

In this paper, a protective coating scheme was applied for the corrosion protection of AZ91D magnesium alloy. Electroless Ni coating (EN coating) as bottom layer, electrodeposited Ni coating (ENN coating), and silane‐based coating (ENS coating) as top layer, respectively, were successfully prepared on AZ91D magnesium alloy by combination techniques. Scanning electron microscopy and X‐ray diffraction were employed to investigate the surface and phase structure of coatings, respectively. The electrochemical corrosion behaviors of coatings in neutral 3.5 wt% NaCl solution were evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The corrosion testing showed that the three kinds of coatings all could provide corrosion protection for AZ91D magnesium alloy to a certain extent, and the corrosion resistance of ENN and ENS was superior to EN. In order to further study the corrosion protection properties of ENN and ENS, a comparative investigation on the evolution of EIS of ENN and ENS was carried out by dint of immersion test in neutral 3.5 wt% NaCl solution. The results indicated that, compared with ENN, the ENS could provide longer corrosion protection for AZ91D magnesium alloy. It is significant to determine the barrier effect of each coating, which could provide reference for industry applications.     

Composite cerium oxide/titanium oxide thin films for corrosion protection of AZ91D magnesium alloy via sol–gel process

Anti‐corrosive composite cerium oxide/titanium oxide (CeO₂/TiO₂) thin films were successfully prepared on an AZ91D magnesium alloy substrate by applying cerium oxide (CeO₂) thin films as the inner layer with a sol–gel process. Composition and surface morphology of the thin films were analyzed using X‐ray diffraction (XRD) and scanning electron microscope (SEM). XRD showed that the composite films consisted of cerianite and anatase phases. The wettability of the thin films was evaluated by water contact angles measurements. Potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) tests were used to evaluate the corrosion behavior of the bare substrate and coated samples in 3.5 wt% sodium chloride solution (3.5 wt% NaCl). The results demonstrated that titanium oxide (TiO₂) thin film mainly dominated the corrosion resistance of samples and the composite films with excellent hydrophilicity could significantly improve the corrosion resistance of AZ91D magnesium alloy.     

Comparative study on corrosion protection properties of electroless Ni‐P‐ZrO2 and Ni‐P coatings on AZ91D magnesium alloy

Electroless Ni‐P‐ZrO₂ and Ni‐P coatings on AZ91D magnesium alloy were prepared, and their corrosion protection properties were compared in this paper. The potentiodynamic curves and electrochemical impedance spectroscopy (EIS) of the coated magnesium alloy in 3.5% NaCl solution showed that the corrosion performance of Ni‐P‐ZrO₂ composite coating was superior to that of Ni‐P coating. The same conclusion was obtained with salt spray and immersion tests. The corrosion morphologies of two kinds of coatings with various immersion time intervals in 3.5% NaCl solution indicated that most corrosion products concentrated on the nodules boundaries of Ni‐P coating and blocked corrosion pit was the main corrosion form. For the Ni‐P‐ZrO₂ coating, tortuous nodules boundaries were not the weak sites of the coating and corrosion initiated from the nickel phosphor alloy around the nanometer powders. Open corrosion pits occurred on the composite coating surface, and the coating was corroded gradually. Thus, the Ni‐P‐ZrO₂ coating exhibited better corrosion protection property to magnesium alloy substrate than Ni‐P coating.     

Q235钢表面铈盐掺杂乙烯基三乙氧基硅烷膜制备及耐蚀性能

在Q235钢表面制备铈盐掺杂乙烯基三乙氧基硅烷膜。利用电化学阻抗谱(EIS)确定了最佳铈盐添加量,利用EIS和动电位极化法研究了涂覆掺杂硅烷膜的Q235钢在3.5% NaCl水溶液中的耐蚀性能,利用扫描电镜(SEM)观察了掺杂硅烷膜的表面形貌。结果表明,铈盐最佳添加量为1×10^-3 mol/L,经涂镀掺杂硅烷的Q235钢在腐蚀过程中的阳极反应和阴极反应受到抑制,与空白Q235钢相比其腐蚀电流密度减小近3个数量级,极化电阻提高3个数量级,低频阻抗值提高至少4个数量级。     

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.     

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.     

Preparation of Phytic Acid/Silane Hybrid Coating on Magnesium Alloy and Its Corrosion Resistance in Simulated Body Fluid

In order to decrease the corrosion rate and improve the bioactivity of magnesium alloy, phytic acid/saline hybrid coatings were synthesized on AZ31 magnesium alloys by sol–gel dip-coating method. It was found that the mole ratio of phytic acid to γ-APS had a great influence on coating morphology and the corresponding corrosion resistance of the coated magnesium alloys. When the mole ratio of phytic acid to γ-APS was 1:1, the obtained hybrid coating was integral and without cracks, which was ascribed to the strong chelate capability of phytic acid and Si-O-Si network derived from silane. Electrochemical test result indicated that the corrosion resistance of the coated magnesium alloy was about 27 times larger than that of the naked counterpart. In parallel, immersion test showed that the phytic acid/silane hybrid coating could induce CaP-mineralized product deposition, which offered another protection for magnesium alloy.     

AZ91D镁合金微弧氧化膜在不同浓度NaCl溶液中的腐蚀行为(英文)

采用微弧氧化技术(MAO)在镁合金 AZ91D 表面制备微弧氧化陶瓷膜。利用电化学技术和浸泡实验研究该镁合金试样在不同浓度(0.1%,0.5%,1.0%,3.5%和 5.0%,质量分数) NaCl 溶液中的腐蚀行为。结果表明,试样的腐蚀速率随着氯离子浓度的升高而增大。在较高浓度(1.0%,3.5%和 5.0%)的 NaCl 溶液中的主要腐蚀形式是点蚀,而在较低浓度(0.1%和 0.5%)中是全面腐蚀。腐蚀过程可以分为两个阶段:亚稳态蚀点的出现和蚀点的生长。根据腐蚀过程中阻抗谱的特点,对镁合金微弧氧化膜试样在不同浓度 NaCl 溶液中浸泡 120 h 提出了不同的等效电路来模拟其腐蚀行为。     

硅烷处理对 EW75 M 稀土镁合金阴极电泳涂层性能的影响

目的探究硅烷处理对阴极电泳涂层的耐腐蚀性能及其与基体间结合力的影响。方法对稀土镁合金表面进行硅烷前处理,再沉积阴极电泳涂层,评价涂层的耐腐蚀性能、抗溶胀性能,分析涂层的腐蚀微观形貌、组织结构及界面结合。结果硅烷膜层具有一定的防护性能,能够减少阴极电泳涂层针孔、橘皮的出现,增强阴极电泳涂层的致密性。硅烷改性能够提高阴极电泳涂层与基体的结合力,硅烷预处理的电泳试样在NMP溶液中浸泡102 h,依然结合完好;而未经硅烷预处理的电泳试样浸泡7 min后,涂层就完全剥落。此外,硅烷处理能够极大地改善阴极电泳涂层的阻抗性能,使涂层在3.5%(质量分数)NaCl溶液中浸泡227 h的极化电阻Rp仍在108数量级以上。结论硅烷阴极电泳复合涂层具有良好的耐蚀性能和抗溶胀性能,值得推广应用。     

硝酸铈对镁合金在硝酸铵溶液中的缓蚀作用

采用失重法、Tafel极化曲线和电化学阻抗谱法研究了在1 mol/L硝酸铵溶液中,稀土盐硝酸铈对镁合金的缓蚀作用。试验结果表明:在硝酸铵溶液中,硝酸铈能较好地减缓镁合金的腐蚀;硝酸铈对镁合金的缓蚀作用随其添加浓度的增加先增大,以后略有减小,硝酸铈浓度为1×10-3mol/L时,缓蚀率达到最大。     

Corrosion fatigue behavior of epoxy-coated Mg–3Al–1Zn alloy in NaCl solution

The corrosion fatigue behavior of epoxy-coated Mg–3Al–1Zn alloy was investigated in air and 3.5 wt%NaCl solution. Epoxy coating as a new method was used to improve the corrosion fatigue property of the material.Results show that the fatigue limit(FL) of the coated specimens is higher than that of the uncoated specimens in3.5 wt% NaCl solution because of the strengthening and blocking functions of the epoxy coating. The FL of the coated specimens in 3.5 wt% NaCl solution is as high as that in air. It implies that the coated specimens are not as sensitive to the environment as the magnesium alloy. The low tensile strength and the short elongation of the pure epoxy coating lead to that the fatigue crack of the coated specimen is always initiated from the epoxy-coating film Pores and pinholes accelerate the fatigue crack initiation process. Pinholes are caused by the corrosion reactions between the epoxy coating and the NaCl solution.     

Corrosion resistance of Mg−Al LDH/Mg(OH)2/silane−Ce hybrid coating on magnesium alloy AZ31

An environmentally-friendly hybrid coating on AZ31 magnesium alloy substrates was reported. The synergic effect was studied on Mg−Al-layered double hydroxide Mg−Al LDH/Mg(OH)₂-coated AZ31 magnesium alloy via an in-situ steam coating process and a subsequent combined surface modification of bis-[triethoxysilylpropyl]tetrasulfide (BTESPT) silane and Ce(NO₃)₃. The microstructure and composition characteristics of the hybrid coatings were investigated by means of X-ray diffraction (XRD), scanning electronic microscopy (SEM), Fourier transform infrared spectrophotometry (FT-IR) and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the coated samples was evaluated by potentiodynamic polarization (PDP), electrochemical impedance spectrum (EIS) and hydrogen evolution rate during immersion in 3.5 wt.% NaCl solution. The results show an improved corrosion resistance of the alloy in the presence of BTESPT silane and Ce(NO₃)₃. This is most likely due to the synergistic effect of steam coating and silane coating to enhance the barrier properties of hybrid coating. In addition, the formation mechanism and anti-corrosion mechanism of coatings were discussed.     

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。     

铝合金稀土硝酸盐磷化的电化学行为

采用电化学测试和扫描电镜等方法研究了硝酸铈对6061 铝合金磷化过程及磷化膜形貌的影响。结果表明,硝酸铈的加入改变了铝合金基体与磷化液之间液固界面间的初始电位;硝酸铈吸附在铝合金表面上形成凝胶,成为磷酸盐晶体形成的良好晶核,磷化晶粒细化,生成较为致密的磷化膜,膜的耐蚀性得到提高。硝酸铈使铝合金达到最高电位的时间缩短,阴极极化电流密度增大,磷化速度加快。硝酸铈在整个铝合金磷化过程中起到了成核和促进的作用。在本实验条件下,最佳硝酸盐含量为20 mg/L～40 mg/L。     

Improvement in corrosion resistance of magnesium coating with cerium treatment

Corrosion protection afforded by a magnesium coating treated in cerium salt solution on steel substrate was investigated using open circuit potential, polarization curves, and electrochemical impedance spectroscopy (EIS) in 0.005 M sodium chloride solution (NaCl). The morphology of the surface was characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). The cerium treated coating was obtained by immersion in CeCl3 solution. The results showed that the corrosion resistance of the treated magnesium coating was improved. The corrosion potential of the treated coating was found to be nobler than that of the untreated magnesium coating and the corrosion current decreased significantly. Impedance results showed that the cerium treatment increased corrosion protection. The improvement of anti-corrosion properties was ataibuted to the formation of cerium oxides and hydroxides that gave to a physical barrier effect.     

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.     

Corrosion resistance of environment‐friendly sealing layer for Zn‐coated sintered NdFeB magnet

In this paper, a protective sealed Zn coating (SZC) was prepared on sintered NdFeB magnet by the combination of electrodeposition and sol–gel method. The unsealed Zn coating (UZC) was also studied for a comparison. The surface morphology of UZC and the cross‐section morphology of SZC were investigated using scanning election microscope (SEM). The microstructure of Zn coating and structure of sealing layer were studied by X‐ray diffraction (XRD) and Fourier transform infrared (FT‐IR) spectrum, respectively. The corrosion characteristics of SZC and UZC in neutral 3.5 wt% NaCl solution were evaluated using electrochemical measurements including open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization test, indicating that the anticorrosive properties of SZC coated specimens increased 20 times compared with that of UZC coated specimens. In order to further investigate the anticorrosive properties of SZC, a long‐term immersion test was carried out in neutral 3.5 wt% NaCl solution using EIS. The results of long‐term corrosion test showed that the SZC could provide long‐term protection in neutral 3.5 wt% NaCl solution for NdFeB magnet.