电流密度对镁合金微弧氧化膜层性能的影响

微弧氧化技术是近年来备受关注的一种新颖的表面处理技术。在镁合金的应用技术与开发研究受到了发达国家和政府部门的高度重视的时候，将做弧氧化技术应用于镁合金的表面处理以增强其耐蚀、耐磨性能，止引起人们的广泛关注。本文采用不同的电流密度在AZ91D铸造镁合金上制得氧化膜层．主要研究了电流密度对微弧氧化膜层厚度、硬度的影响规律；分析了膜层的相组成；并且对膜层的耐腐蚀性能进行了评价。     

AZ91D微弧氧化的初步研究

镁合金与钢铁、铝合金、工程塑料等材料相比，具有轻质、高比强度和比刚度、高阻尼性和易于回收等优越的性能优势。因此镁合金的应用技术与开发受到了各界的广泛关注。镁的化学性质活泼、稳定性低，即使在室温下也会在空气中发生氧化，形成一层疏松的氧化膜。因此，必须对其进行表面处理，才能使镁合金在工业生产中发挥其优良的性能。其常用的表面处理方法有微弧氧化、离子注入、化学转化膜、激光表面处理等方法。     

强脉冲激光在AZ31B镁合金中诱导冲击波的实验研究

为了研究强脉冲激光在镁合金中诱导冲击波的衰减,采用Nd:Glass脉冲激光(1054 nm,23 ns)对AZ31B变形镁合金试样表面进行冲击,并利用响应快、测量范围大的PVDF压电膜传感器以及示波器实时测量了强脉冲激光在镁合金靶中诱导激光冲击波的相对压力.根据冲击波每次在靶材背面反射时,所经过距离的不同得到激光冲击波在镁合金中的衰减规律.结果表明,在激光能量为5J的强脉冲激光作用下,镁合金中冲击波衰减的平均速度为5.83×10³ m/s,与镁合金中应力波纵波的传播速度相符;强脉冲激光诱导冲击波在镁合金中是以指数规律衰减的.试验所得分析结果对激光冲击强化镁合金的应用具有重要意义. 关键词： 激光 镁合金 压电膜传感器 衰减规律     

氧化态石墨烯/铋膜修饰玻碳电极测定水中铅离子

制备了氧化态石墨烯修饰玻碳电极,并预镀铋膜,采用了示差脉冲溶出伏安法对水中的铅离子含量进行测定,考察了缓冲溶液pH值、沉积电位、沉积时间对铅离子测定的影响.通过实验条件优化,对浓度在0-3.00×10-7mol/L范围内的铅离子进行测定,铅离子浓度与溶出峰面积线性关系良好,检出限是1.00×10-8mol/L.结果表明,方法检测灵敏度高、重现性好,可实现水样中铅离子的快速测定.     

镁合金阳极氧化膜腐蚀特性的红外显微成像分析

采用显微红外成像技术对镁合金阳极氧化膜表面的腐蚀特性进行了研究。镁合金在7.3 Wt% Na₂SO₄溶液中浸泡后,表面氧化层中的部分MgO逐渐转化为Mg(OH)₂,进而发生溶解和脱落,使得镁合金失去保护作用。当浸泡时间达到2 h时,显微红外成像结果表明阳极氧化膜中Mg(OH)₂的红外吸收信号最强,Mg(OH)₂的含量最多。而4 h后Mg(OH)₂的红外吸收信号开始减弱,Mg(OH)₂开始减少,镁合金不断被腐蚀。氧化膜中另一成分Al₂O₃随浸泡时间的显微红外成像信息与Mg(OH)₂的变化规律相同。采用电化学阻抗谱技术对阳极氧化膜的阻抗进行测试,其阻抗随时间的变化特点基本符合氧化膜腐蚀规律。本研究对于镁合金阳极氧化膜的表征具有很好的指导作用和推广应用价值。     

飞秒激光冲击AZ31B镁合金过程的数值模拟

采用有限元分析法对飞秒激光冲击AZ31B镁合金进行数值模拟,研究了激光冲击处理对镁合金变形过程的影响,分析了单脉冲激光冲击下材料内部的位移、动能、应力和应变的分布情况,得到了材料的瞬态速度和应变率变化过程.仿真结果表明,单脉冲飞秒激光冲击镁合金产生的塑性变形,可在材料表面形成微米级凹坑,中心点处最大位移为34μm,最大变形速度390m/s;在冲击初期,材料表面的应力和应变主要分布在冲击区域中心节点和边缘附近,并且得到镁合金的最大应力和最大应变率分别为955 MPa和1.8×106 s-1.研究结果能够为深入分析飞秒激光与镁合金作用时材料变形参量的变化规律提供数值理论依据.     

铟与4,5-二羟基-1,3-苯二磺酸配合显色反应热力学摩尔吸光系数

用分光光度法测定了在20.0±0.1℃温度下,以NaClO4为支持电解质的水溶液中,Tiron与高价铟离子形成配合物1∶1显色反应的热力学摩尔吸光系数,考察了a值对摩尔吸光系数与溶液离子强度效应的线性关系的影响,测得a＝6.5时的热力学摩尔吸光系数,其logε°＝3.69.     

离子注钇对镍900℃高温氧化行为及氧化膜性能的影响研究

采用热重分析对纯镍及其表面离子注钇样品在900℃空气中的恒温氧化动力学规律进行了研究.用扫描电子显微镜和透射电子显微镜对含钇和不含钇氧化膜的微观形貌及结构进行了观测.用声发射方法对氧化膜在恒温生长阶段和空冷阶段的开裂与剥落进行了实时监测，根据相应的氧化膜开裂模型，对声发射信号在时域和数域上的分布情况进行了分析.结果表明离子注钇显著降低了镍的恒温氧化速率，提高了表面NiO膜的抗开裂和抗剥落性能.离子注钇提高镍抗氧化性能的原因主要是钇细化了表面NiO膜的晶粒、提高了氧化膜的高温塑性和蠕变能力，并显著降低了Ni/NiO界面缺陷的数量和大小. 关键词： 高温氧化 应力 声发射 离子注入     

电学参数对胶体中工业纯钛微弧氧化膜特性的影响

利用自制多功能微弧氧化(MAO)电源对处在胶体中的工业纯钛表面进行了MAO处理,比较系统地研究了电压脉冲的峰值(U)和占空比(d)对膜层的生长特性、微观结构、相结构和处理后试样耐腐蚀性能的影响.结果表明,随着U的增加或d的加大,膜厚几乎呈线性增加,膜表面微孔尺寸和粗糙度逐渐增大,微孔密度逐渐减小.膜层主要由致密层组成,除U=450V,d=10%时制备试样的膜层中含有少量锐钛矿相TiO2外,其他试样的膜层全由金红石相TiO2组成;在30%硫酸溶液中的耐腐蚀测试表明,MAO处理后试样的耐腐蚀性能与U和d密切相关,随着U的增加或d的加大,试样的耐腐蚀能力逐渐增强.     

铝合金薄壁件的点焊及表面处理

某铝合金薄壁件的连接最好采用焊接，在焊接方法中以电阻点焊为宜，而铝合金电阻率ρ小，而热导率λ大，焊接性指数Q值较低，焊接性较差。而目工件要求具备足够的耐腐蚀性能，若在点焊后进行表面处理，将会有表面处理的液体难以彻底清除，在使用和存储过程中会有局部腐蚀，不能满足要求。为此需先进行表面处理，针对LF21防锈铝薄壁件，选择合适的表面处理工艺方法、工艺规范，使表面处理后的膜层耐腐蚀性能满足要求、表面电阳特性适应后续的点焊要求；点焊试验后检测焊点表面质量、焊点熔核金属的直径，分析熔核金属的显微金相组织，测试单个焊点的抗静剪切载荷。     

Chemical nature of phytic acid conversion coating on AZ61 magnesium alloy

Phytic acid (PA) conversion coating on AZ61 magnesium alloy was prepared by the method of deposition. The influences of pH, time and PA concentration on the formation process, microstructure and properties of the conversion coating were investigated. Scanning electron microscopy (SEM) was used to observe the microstructure. The chemical nature of conversion coating was investigated by energy dispersive X-ray spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) techniques. The corrosion resistance was examined by means of potentiodynamic polarization method. The adhesive ability was tested by score experiments. The results showed that the growth and microstructure of the conversion coatings were all obviously affected by pH, time and PA concentration. In 0.5 mg/ml PA solution with a pH of 5, an optimization conversion coating formed after 20 min immersion time by deposition of PA on AZ61 magnesium alloy surface through chelating with Al³⁺. It made the corrosion potential E_corr of sample shifted positively about 171 mV than that of the untreated sample, and the adhesive ability reached to Grade 1 (in accordance with GB/T 9286).     

In vitro corrosion and biocompatibility study of phytic acid modified WE43 magnesium alloy

Phytic acid (PA) conversion coating on WE43 magnesium alloy was prepared by the method of immersion. The influences of phytic acid solution with different pH on the microstructure, properties of the conversion coating and the corrosion resistance were investigated by SEM, FTIR and potentiodynamic polarization method. Furthermore, the biocompatibility of different pH phytic acid solution modified WE43 magnesium alloys was evaluated by MTT and hemolysis test. The results show that PA can enhance the corrosion resistance of WE43 magnesium especially when the pH value of modified solution is 5 and the cytotoxicity of the PA coated WE43 magnesium alloy is much better than that of the bare WE43 magnesium alloy. Moreover, all the hemolysis rates of the PA coated WE43 Mg alloy were lower than 5%, indicating that the modified Mg alloy met the hemolysis standard of biomaterials. Therefore, PA coating is a good candidate to improve the biocompatibility of WE43 magnesium alloy.     

Study of molybdenum/lanthanum-based composite conversion coatings on AZ31 magnesium alloy

The molybdenum/lanthanum-based (Mo/La) composite conversion coating on AZ31 magnesium alloy was investigated and the corrosion resistance was evaluated as well. The morphology, composition and corrosion resistance of the coating were studied by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and potentiodynamic polarization analysis, respectively. The results revealed that the conversion coating consisted of spherical nodular particles, which was mainly composed of Mo, La, O and Mg. After conversion treatment the corrosion potential shifts about 500 mV positively, and the corrosion current density decreases two orders of magnitude. The corrosion resistance of AZ31 alloy is remarkably improved by Mo/La composite conversion coating.     

Electrodeposition of Al-Mn alloy on AZ31B magnesium alloy in molten salts

The Al-Mn alloy coatings were electrodeposited on AZ31B Mg alloy in AlCl₃-NaCl-KCl-MnCl₂ molten salts at 170 °C aiming to improve the corrosion resistance. However, in order to prevent AZ31B Mg alloy from corrosion during electrodeposition in molten salts and to ensure excellent adhesion of coatings to the substrate, AZ31B Mg alloy should be pre-plated with a thin zinc layer as intermediate layer. Then the microstructure, composition and phase constituents of the coatings were investigated by scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDX), and X-ray diffraction (XRD). It was indicated that, by adjusting the MnCl₂ content in the molten salts from 0.5 wt% to 2 wt%, the Mn content in the alloy coating was increased and the phase constituents were changed from f.c.c Al-Mn solid solution to amorphous phase. The corrosion resistance of the coatings was evaluated by potentiodynamic polarization measurements in 3.5% NaCl solution. It was confirmed that the Al-Mn alloy coatings exhibited good corrosion resistance with a chear passive region and significantly reduced corrosion current density at anodic potentiodynamic polarization. The corrosion resistance of the alloy coatings was also related with the microstructure and Mn content of the coatings.     

Composition and corrosion resistance of cerium conversion films on the AZ31 magnesium alloy and its relation to the salt anion

Pre-treatments based on different cerium salts were applied to the AZ31 Mg alloy. The pre-treatments were performed by immersion in solutions of various Ce(III) salts: cerium chloride, cerium nitrate, cerium sulphate and cerium phosphate. The chemical composition of the treated surfaces was investigated by X-ray photoelectron spectroscopy and Auger electron spectroscopy, whereas the corrosion behaviour of the pre-treated AZ31 substrates was investigated in 0.005 M NaCl solutions using potentiodynamic polarisation and open circuit potential monitoring. The surface film contained a mixture of Ce(IV) and Ce(III) salts. The film thickness depends upon the cerium salt used. The electrochemical results show that all the conversion pre-treatments reduced the corrosion activity of the AZ31 Mg alloy substrates in the presence of chloride ions. The corrosion protection efficiency is related with the anion present in the cerium salt.     

Characterization of ceramic PVD thin films on AZ31 magnesium alloys

Ceramic thin films have been widely used to protect the metal substrate as coatings in the past years. In order to improve the poor corrosion resistance of AZ31 magnesium alloy, the study in this paper used the electron beam evaporation method to prepare ceramic PVD films on its surface with TiO₂ and Al₂O₃ as donors, respectively. Atomic force microscopy (AFM), scanning electron microscope (SEM), energy dispersive X-ray spectrometer (EDS), Auger electron spectroscopy (AES) and X-ray diffraction (XRD) were used to investigate the surface morphology, composition and microstructure of the thin films. Both films deposited on AZ31 took on compact top surface morphologies and grew as amorphous structures on substrate. AES test not only showed that films compositions deviated the standard stoichiometric ratios, but also found that element Mg diffused into films and existed as magnesium oxide in the TiO_x film as well as the AlO_x film. In the electrochemical corrosion test, the AlO_x coating on AZ31 exhibited the largest electrochemical impedance in a 3.5% NaCl solution. But it did not show better corrosion resistance than others for the poorer adhesion. Even if its thickness was small, the TiO_x coating on AZ31 exhibited the best corrosion resistance in this study. According to the observation and analysis, the damage of these films on AZ31 in aggressive solutions was mainly due to the existence of pores, microcracks, vacancies and poor adhesion between coating and substrate.     

Electrodeposition of high corrosion resistance Cu/Ni-P coating on AZ91D magnesium alloy

High corrosion resistance Cu/Ni-P coatings were electrodeposited on AZ91D magnesium alloy via suitable pretreatments, such as one-step acid pickling-activation, once zinc immersion and environment-friendly electroplated copper as the protective under-layer, which made Ni-P deposit on AZ91D Mg alloy in acid plating baths successfully. The pH value and current density for Ni-P electrodeposition were optimized to obtain high corrosion resistance. With increasing the phosphorous content of the Ni-P coatings, the deposits were found to gradually transform to amorphous structure and the corrosion resistance increased synchronously. The anticorrosion ability of AZ91D Mg alloy was greatly improved by the amorphous Ni-P deposits, which was investigated by potentiodynamic polarization curve and electrochemical impedance spectroscopy (EIS). The corrosion current density (I_corr) of the coated Mg alloy substrate is about two orders of magnitude less than that of the uncoated.     

Correlation between the surface chemistry and the atmospheric corrosion of AZ31, AZ80 and AZ91D magnesium alloys

X-ray photoelectron spectroscopy (XPS) was used in order to investigate the correlation between the surface chemistry and the atmospheric corrosion of AZ31, AZ80 and AZ91D magnesium alloys exposed to 98% relative humidity at 50 °C. Commercially pure magnesium, used as the reference material, revealed MgO, Mg(OH)₂ and tracers of magnesium carbonate in the air-formed film. For the AZ80 and AZ91D alloys, the amount of magnesium carbonate formed on the surface reached similar values to those of MgO and Mg(OH)₂. A linear relation between the amount of magnesium carbonate formed on the surface and the subsequent corrosion behaviour in the humid environment was found. The AZ80 alloy revealed the highest amount of magnesium carbonate in the air-formed film and the highest atmospheric corrosion resistance, even higher than the AZ91D alloy, indicating that aluminium distribution in the alloy microstructure influenced the amount of magnesium carbonate formed.     

Studies on influence of zinc immersion and fluoride on nickel electroplating on magnesium alloy AZ91D

The effect of zinc immersion and the role of fluoride in nickel plating bath were mainly investigated in nickel electroplating on magnesium alloy AZ91D. The state of zinc immersion, the composition of zinc film and the role of fluoride in nickel plating bath were explored from the curves of open circuit potential (OCP) and potentiodynamic polarization, the images of scanning electron microscopy (SEM) and the patterns of energy dispersive X-ray (EDX). Results show that the optimum zinc film mixing small amount of Mg(OH)₂ and MgF₂ is obtained by zinc immersion for 30-90 s. The corrosion potential of magnesium alloy substrate attached zinc film will be increased in nickel plating bath and the quantity of MgF₂ sandwiched between magnesium alloy substrate and nickel coating will be reduced, which contributed to produce nickel coating with good performance. Fluoride in nickel plating bath serves as an activator of nickel anodic dissolution and corrosion inhibitor of magnesium alloy substrate. 1.0-1.5 mol dm⁻³ of F⁻ is the optimum concentration range for dissolving nickel anode and protecting magnesium alloy substrate from over-corrosion in nickel plating bath. The nickel coating with good adhesion and high corrosion resistance on magnesium alloy AZ91D is obtained by the developed process of nickel electroplating. This nickel layer can be used as the rendering coating for further plating on magnesium alloys.     

Effect of electrodeposition modes on surface characteristics and corrosion properties of fluorine-doped hydroxyapatite coatings on Mg-Zn-Ca alloy

The microstructure, morphology and composition highly determine the corrosion resistance and bioactivity of coating. In traditional cathodic electrodeposition process, because of the unfavorable effects of the polarization of concentration difference and H₂ evolution, fluorine-doped hydroxyapatite coating was loose and porous. This coating could not ensure the long-term stability of the Mg alloy implants. In order to improve the corrosion resistance and bioactivity of coating, pulse electrodeposition and H₂O₂ were introduced into the electrodeposition to deposit fluorine-doped hydroxyapatite coating. As a comparative study, microstructure, corrosion resistance properties and bioactivity of traditional cathodic electrodeposition coating and pulse electrodeposition coating were investigated, respectively. The results revealed that nano fluorine-doped hydroxyapatite coating could be prepared by pulse electrodeposition, and the coating was dense and uniform. The potentiodynamic polarization experiment indicated that the dense and uniform coating could effectively protect Mg alloy substrate from corrosion. Immersion testing was performed in simulated body fluid. It was found that pulse electrodeposition coating could more effectively induce the precipitation of Mg²⁺, Ca²⁺ and PO₄³⁻ in comparison with traditional cathodic electrodeposition coating, because the nano phase had comparatively high specific surface area. Thus magnesium alloy coated with fluorine-doped nano-hydroxyapatite coating may be a promising candidate as biodegradable bone implants, and was worthwhile to further investigate the in vivo degradation behavior.