镁合金稀土镧化学转化工艺研究

镁合金稀土转化膜技术是近年来发展起来的一种环保型镁合金表面处理新技术。通过正交试验对压铸镁合金AZ91D稀土镧化学转化处理工艺进行了研究。利用扫描电子显微镜(SEM)、能量色散谱(EDS)和X射线光电子能谱(XPS)研究了膜层的表面形貌及其组成,并通过容量法对膜层在5%NaCl(pH=6.8~7.0)溶液中的耐腐蚀性能进行了研究。结果表明:La转化处理工艺能够在压铸镁合金AZ91D表面形成均匀、完整的转化膜;膜层主要由La2O3和MgO以及少量的Al2O3组成;La转化膜在浸泡初期的10 h内耐腐蚀性能与铬酸盐转化膜相当。     

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.     

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 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.     

XPS characterization and corrosion resistance of cerium-treated magnesium coatings

Cerium conversion treatment was applied on magnesium coatings in a solution containing CeCl3.The composition of the cerium conversion layer on magnesium was investigated using X-ray photoelectron spectroscopy(XPS).It was revealed that the composition predominately consisted of a three-valent state cerium compound with a relative abundance around 90%.Some of Ce3+ was oxidized to Ce4+.Electrochemical impedance spectroscopy results revealed that the total impedance of cerium-treated samples increased for a sho...     

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.     

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。     

磷酸钠在NaCl溶液中对AZ31镁合金的缓蚀作用

采用电化学阻抗法、动电位极化曲线法、全浸泡失重法和扫描电镜,研究了在3.5%(质量分数)Na Cl溶液中磷酸钠(Na3PO4)对AZ31镁合金腐蚀的抑制作用。结果表明:Na3PO4对3.5%Na Cl溶液中的AZ31镁合金具有缓蚀作用,其缓蚀率随着Na3PO4含量增大逐渐提高,当Na3PO4质量浓度为1.0 g/L时,缓蚀率达到81.5%。结合扫描电镜分析表明,Na3PO4在镁合金表面形成含有Mg(OH)2和Mg3(PO4)2的保护层,这层致密的膜减少了基体与Cl-接触,抑制了镁合金的阳极反应。     

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.     

AZ31B镁合金表面电镀铝锰合金的耐蚀性

在镁合金AZ31B表面通过预镀锌处理后采用无机熔盐电沉积铝锰合金。使用SEM、EDX和XRD分析镀层的表面形貌、成分和组织,采用动电位极化曲线及表面显微硬度测量考察了镀层对镁合金耐蚀耐磨性的影响。结果表明,熔盐成分、电流密度和熔体温度等典型工艺参数对铝锰合金镀层的形貌、成分和组织都具有重要的影响,进而影响了镀层的耐蚀性。镁合金电镀铝锰合金后,腐蚀电位有很大的提高, 而腐蚀电流密度大幅度的下降;同时铝锰合金镀层表现出很高的硬度,显著的提高了镁合金的耐蚀耐磨性。     

AZ31镁合金表面含纳米羟基磷灰石微弧氧化涂层的制备及性能研究

目的改善AZ31镁合金的耐腐蚀性能及生物活性。方法使用微弧氧化技术,分别在以六偏磷酸钠为主盐的电解液和以六偏磷酸钠为主盐、以纳米羟基磷灰石(HA)为添加剂的电解液中,在AZ31镁合金表面制备了微弧氧化涂层。通过扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)表征了涂层的微观形貌、元素特征和相组成。通过电化学方法和浸泡实验考察了涂层的耐蚀性。通过细胞实验评价了两种涂层的细胞相容性。结果电解液中的HA可以进入到微弧氧化涂层中,含HA的微弧氧化涂层较不含HA的更致密,且有封孔现象。电化学方法及浸泡实验结果表明,含HA的微弧氧化涂层的耐腐蚀性能更好。细胞表面粘附实验和细胞增殖实验也表明,经表面纳米HA微弧氧化处理后的AZ31镁合金生物相容性更好,且对MC3T3-E1细胞的增殖有促进作用。结论六偏磷酸钠电解液中添加纳米HA,可以在AZ31镁合金表面制备出含HA的微弧氧化涂层,且其耐腐蚀性能和生物活性均优于不含HA的微弧氧化膜。     

Influence of substrate composition on the formation of phytic acid conversion coatings

In this paper, the formation and corrosion resistance of the phytic acid conversion coatings on Mg, Al, and AZ91D magnesium alloy were contrastively investigated using scanning electronic microscopy (SEM), Auger electron spectroscopy (AES), Fourier transform infrared spectroscopy (FTIR), electronic probe microscopic analyzer (EPMA), electronic balance, and electrochemical methods. The influence of phytic acid conversion coating as a middle layer on the properties of the paint on magnesium alloys was also investigated. The results show that the formation process of the conversion coatings is evidently influenced by the compositions of the substrate. The coating on pure aluminum is thinner and compacter than that on pure magnesium and the coating formed on α phase in AZ91D magnesium alloy is thinner but denser than that on β phase. The phytic acid conversion coatings formed on Mg, Al, and AZ91D magnesium alloy can all increase their corrosion resistance. The active functional groups of hydroxyl and phosphate radical are rich in the conversion coatings, which can improve the bonding between the organic paint and magnesium alloy and then improve their corrosion resistance.     

成膜时间对镁合金镧盐转化膜耐蚀性的影响

稀土盐转化膜是一种绿色环保的金属表面处理技术,为探究硝酸镧成膜时间对镁合金耐蚀性的影响,在镁合金表面成功制备出不同成膜时间下的镧盐转化膜。 试验采用扫描电镜(SEM)、能谱仪(EDS)以及 X 射线衍射仪(XRD) 对膜层的表面形貌及组成进行了表征,采用点滴试验、电化学方法(EIS / Tafel)对不同成膜时间下膜层的耐蚀性进行了测试,并使用软件对结果进行拟合。 试验结果表明,镁合金表面生成了一层微米级的稀土转化膜,转化膜表面存在裂纹,其中 30 min 成膜时间的裂纹最小;点滴试验及电化学测试结果表明镧盐转化膜能够大幅度地提高镁合金耐蚀性, 30 min 成膜时间获得的膜层耐蚀性最佳,相对于空白镁合金,其自腐蚀电流密度下降了 4 个数量级,自腐蚀电位正移了 943 mV;EDS 结果表明,膜层主要由 La 和 O 元素组成,XRD 结果进一步表明 La(OH)₃ 是膜层的主要成分。     

AZ31B镁合金氧化石墨烯掺杂钇盐转化膜耐蚀性研究

目的研究一种绿色环保的表面处理方法,以提高镁合金的耐蚀性。方法采用化学浸泡法,以硝酸钇为成膜物质,在AZ31B镁合金表面成功制备一种新型稀土盐转化膜,并以氧化石墨烯为阻隔剂对该转化膜进行复合掺杂。采用扫描电镜(SEM)对膜层的表面形貌进行观察,采用析氢实验和电化学测试对不同试样在3.5%Na Cl溶液中的耐蚀性进行了研究。结果镁合金钇盐转化膜表面平整均一,覆盖良好。氧化石墨烯掺杂后的钇盐膜层表面出现了大小不均一的瘤状物质,膜层完整,未出现裂痕。析氢实验结果显示,经过处理的转化膜试样可以极大地抑制腐蚀反应的发生。由极化曲线可知,钇盐转化膜的存在使镁合金的腐蚀电位发生了明显正移,正移了150 m V;而氧化石墨烯掺杂的钇盐膜层的腐蚀电位相对于掺杂前变化不大,但其腐蚀电流密度是掺杂前的1/28。电化学交流阻抗谱的测试结果显示,氧化石墨烯掺杂钇盐转化膜的电荷转移电阻最大,Rct为2485?·cm2;钇盐转化膜的电荷转移电阻次之,Rct为1224?·cm2。两者的电荷转移电阻相对于未经处理的镁合金都有明显提升。结论钇盐转化膜可以明显提高AZ31B镁合金的耐蚀性,氧化石墨烯的加入可以进一步提高转化膜层的耐蚀性。     

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.     

Electrodeposition of zinc on AZ91D magnesium alloy pre‐treated by stannate conversion coatings

A stannate chemical conversion process followed by an activation procedure was employed as the pre‐treatment process for AZ91D magnesium alloy substrate. Zn was electroplated onto the pre‐treated AZ91D magnesium alloy surface from pyrophosphate bath to improve the corrosion resistance and the solderability. The surface morphologies of conversion coating and zinc coating were examined with scanning electron microscope (SEM). The phase composition of conversion coating was investigated by X‐ray diffraction (XRD). The electrochemical corrosion behavior of the coatings in the corrosive solution was investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). The experimental results showed that the activated stannate chemical conversion coating provided a suitable interface between zinc coating and the AZ91D magnesium alloy substrate. The corrosion resistance of the AZ91D substrate was improved by the zinc coating.     

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.     

镁合金铈基转化膜研究

采用了单因素实验对镁合金表面硝酸亚铈转化膜制备的实验条件进行了研究,发现在一定条件下硝酸亚铈能在镁合金表面生成宏观上较致密的转化膜.对镁合金表面硝酸亚铈转化膜在3.5%(质量分数,后同)NaCl溶液中浸泡析氢,用极化曲线(Tafel)以及扫描电镜(SEM),对转化膜进行了测试,结果表明:在pH=3,双氧水体积分数为4 mL/L时,转化膜的效果较好.     

化学沉积铈转化膜的工艺优化及其耐蚀性

采用化学沉积法在铝阳极氧化膜上制备铈转化膜。通过SEM和EDS表征了阳极氧化膜、化学沉积铈转化膜形貌和组成成分;用极化曲线法、EIS交流阻抗法和酸、碱点滴试验对膜耐蚀性进行了评估。结果表明,在铝阳极氧化膜上经过化学沉积可制备铈转化膜,其耐蚀性优于铝阳极氧化膜的耐蚀性。优化的铈转化膜工艺为:3 g/LCe2(SO4)3,20 ml/L H2O2,温度50℃,时间60 min。     

Enhanced corrosion performance of magnesium phosphate conversion coating on AZ31 magnesium alloy

Magnesium phosphate conversion coating (MPCC) was fabricated on AZ31 magnesium alloy for corrosion protection by immersion treatment in a simple MPCC solution containing Mg²⁺ and PO^3?₄ ions. The MPCC on AZ31 Mg alloy showed micro-cracks structure and a uniform thickness with the thickness of about 2.5 µm after 20 min of phosphating treatment. The composition analyzed by energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that the coating consisted of magnesium phosphate and magnesium hydroxide/oxide compounds. The MPCC showed a significant protective effect on AZ31 Mg alloy. The corrosion current of MPCC was reduced to about 3% of that of the uncoated surface and the time for the deterioration process during immersion in 0.5 mol/L NaCl solution improved from about 10 min to about 24 h.