镁合金表面防腐层的研究现状

本文综述了镁合金防腐层的研究现状,介绍了包括金属及其合金涂层、陶瓷涂层、化学转化膜以及有机膜在内的四种典型表面防护层特点和研究应用现状,并展望镁合金表面防腐层的发展前景。     

微弧氧化对镁合金摩擦及胶接性能的影响

为解决镁合金表面耐摩擦和胶接性能较差的问题,采用微弧氧化法在MB15镁合金原位生长微弧氧化膜层.利用X射线衍射、扫描电镜、摩擦磨损试验机和万能拉伸实验机对膜层的结构组成、表面形貌、摩擦性能和胶接性能进行了研究.结果表明：MB15镁合金表面微弧氧化后可以形成均匀多孔的陶瓷涂层,膜层由MgO和MgAl2O4组成,经微弧氧化...     

生物医用AZ31B镁合金表面氧化锰转化涂层制备及性能研究

采用转化处理的方式,在AZ31B镁合金表面成功制备一层氧化锰转化涂层,以提高合金表面耐蚀性能。SEM研究表明,氧化锰转化涂层均匀分布在AZ31B镁合金表面,涂层中无规分布着微裂纹,涂层厚度为10~12μm。XRD研究表明,氧化锰转化涂层的主要成分包括MgO、MnO和Mn2O3。电化学和腐蚀浸泡实验结果表明,氧化锰转化涂层能够有效改善AZ31B镁合金的体外耐蚀性能。     

AZ91D镁合金表面无铬转化膜/杂化复合涂层的耐蚀性能

溶胶凝胶法制备的涂层性能优良,采用溶胶凝胶法、以正硅酸乙酯为主制备性能优良的涂层技术已很成熟,但用于镁合金的防护鲜有报道。为了提高AZ91D镁合金的耐蚀性能,先在其表面制备了无铬钼酸盐转化膜,然后采用有机/无机杂化溶胶凝胶的方法在转化膜表面制备杂化涂层,从而得到转化膜/杂化复合涂层。对复合涂层进行了红外光谱分析,并用扫描电镜(SEM)观察了其微观形貌,同时也对其进行了极化曲线和电化学阻抗谱分析。结果表明:二氧化硅和有机硅氧键通过溶胶凝胶反应,无机和有机间呈网络结构穿插在一起;复合涂层表面平整均匀,无开裂现象;转化膜层和转化膜/杂化复合涂层都可提高镁合金的耐蚀性,但后者的效果更加明显。     

物理气相沉积在镁合金表面防护领域的研究现状

镁合金表面耐腐蚀性能、耐磨性能较差,物理气相沉积(PVD)镀膜技术是一种提高镁合金表面性能的有效方法。总结了PVD镀膜防腐蚀层和耐磨层的特性,分析了涂层耐腐蚀耐磨的机理和存在的不足。综述了镁合金表面PVD膜层的研究进展,阐述了物理气相沉积技术对镁合金的表面改性的应用现状,并对该技术在镁合金上的发展进行了概括,指出了目前PVD技术在镁合金表面防护领域的新前景,为今后PVD技术对镁合金表面防护的研究与发展提供了相关参考。     

镁合金表面处理的发展现状

综述了镁合金的表面处理方法的现状，主要有化学转化膜，化学氧化，阳极氧化，表面渗层处理，金属涂层，激光表面处理，有机物涂层等，还展望了今后的发展趋势。     

镁稀土合金表面氧化铈-氧化钇稳定氧化锆涂层的耐高温及抗腐蚀性能

为提高镁稀土合金Mg-Gd-Y-Zr的耐高温和抗腐蚀能力,采用溶胶-凝胶法在该合金板表面制备了氧化铈掺杂氧化钇稳定氧化锆(CYSZ)的耐蚀涂层.X射线衍射和红外光谱等分析结果显示该涂层主要由CeO2-Y2O3-ZrO2等氧化物组成.析氢法和交流阻抗等电化学测试表明CYSZ涂层在5%NaCl溶液中比铬酸盐转化膜耐蚀性能更好,溶胶-凝胶膜贮藏和缓慢释放缓蚀剂显著增强了耐蚀涂层对基体镁合金板的耐盐水腐蚀能力.高温氧化动力学行为表明,在623 K时该膜对基体镁合金能够进行长时间保护.     

溶胶-凝胶涂层在镁合金腐蚀防护应用中的研究进展

镁合金是21世纪最富开发和应用潜力的优异绿色工程材料之一,但耐蚀性差成为制约其广泛应用的瓶颈。选择和开发合适的表面防护涂层可以有效提高镁合金表面的耐蚀性能。溶胶-凝胶涂层技术凭借其工艺简单、膜层成分结构可控、耐蚀性能优良等优点近年来在镁合金表面的腐蚀防护应用中得到重视。将用溶胶-凝胶技术在镁合金表面制备防腐蚀涂层的研究成果按照有机/无机杂化涂层、缓蚀因子/杂化涂层、电化学氧化/杂化涂层、化学转化/杂化涂层的分类方法进行了分析总结。这些涂层体系各具特色,其中含缓蚀因子的杂化涂层具备自修复能力,化学转化和电化学氧化杂化涂层的附着力突出,而单一涂层更容易破坏。在未来,镁合金表面溶胶-凝胶防护涂层的研究工作仍以有效结合现有的表面处理技术开发长效高耐蚀复合涂层为重心。     

AM60镁合金Cr涂层制备及其耐腐蚀性研究

为了提高AM60镁合金的耐腐蚀性能,采用机械涂覆的方法在合金表面制备Cr涂层。通过XRD、视频显微镜、SEM、显微硬度分析等方法对表面涂层的物相、截面形貌、涂层的显微硬度等进行表征,利用电化学工作站对涂覆Cr前后的AM60镁合金的耐蚀性能进行分析。结果表明:AM60镁合金表面成功涂覆了Cr涂层,所制备涂层与基体结合致密,涂覆效果较好;同时,涂层的显微硬度高达到1 132 HV,较基体提高了1.96倍;球料比为10∶1和20∶1时,球磨时间为20 h和15 h时所制备的膜层耐腐蚀性能较好,和基体相比,所制备样品的自腐蚀电流密度均降低了3个数量级,自腐蚀电位均大幅提高,阻抗谱半径也均增加,在模拟海水中的耐腐蚀性能都得到明显改善。因此,在该实验条件下,Cr涂层的最佳制备工艺为:球料比为10∶1,球磨时间为20 h。      

锆合金表面Cr基涂层的耐高温氧化性能

用磁控溅射法在锆合金基体表面制备Cr和CrAl层,并使其在1200℃/1 h水蒸汽中氧化,用扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)等手段表征氧化前后涂层和Zr合金基体的微观结构,研究了两种涂层在(反应堆失水(LOCA)事故情况下的)高温蒸汽环境中的抗氧化性能。结果表明：在1200℃/1 h水蒸汽中氧化后没有涂层的锆合金基体表面生成厚度约为100 μm的氧化膜;而在Cr涂层表面生成的致密Cr₂O₃层其厚度约为4 μm,表明氧化速率显著降低。CrAl涂层氧化后表面生成致密的Cr₂O₃和Al₂O₃混合氧化层,其厚度只有0.8 μm,表明氧化速率进一步降低。这些结果表明: 用磁控溅射法在锆合金表面制备的Cr和CrAl涂层,在1200℃水蒸气环境中均表现出良好的耐氧化性能。在Cr涂层表面生成的氧化膜厚度约为未涂层锆合金氧化层的1/25,CrAl涂层氧化膜厚度低于锆合金表面氧化层的1/100。     

Coatings on Mg alloys and their mechanical properties: A review

Poor corrosion resistance is a serious drawback of Mg alloys, restricting their practical applications. Coating is one of the effective techniques for improvement in the poor corrosion resistance. In this paper, the coating processes for Mg alloys so far developed are reviewed. Among several processes, the coating processes based on mechanical energy, including metal forming, are attractive because the corrosion resistance and formability of Mg alloys are simultaneously improved.     

镁合金Ni-Ce-P/纳米TiO_2化学复合镀工艺及性能

为了改善镁合金表面的耐磨、耐蚀及抗茵性能,在Ni-ce-P化学镀的基础上加入了纳米TiO2,在镁合金上获得了Ni-ce-P/纳米TiO2化学复合镀层,对复合镀层组织进行了分析.最佳工艺参数:25.0 g/L.NiSO4·6H2O,2.0 g/L TiO2,20.0 g/L柠檬酸,25.0 g/L NaH2PO2·H2O,10.0 g/L NH4HF2,0.1 g/LCe(N03)3,0.2 g/L硫脲,2.0 g/L十二烷基硫酸钠,时间1 h,磁力搅拌.结果表明:Ni-Ce-P/纳米Ti02化学复合镀层使镁合金的耐磨性提高了1倍,耐蚀性优异,光催化性及抗茵性能良好.     

镁合金表面覆盖层形成方法及相关国家标准

镁合金具有优异的比强度,但耐蚀性较差,很少在铸态下直接使用,需要进行表面处理以形成防护性覆盖层.本文对现有的镁合金表面覆盖层形成方法,如电化学镀、化学转化、阳极氧化、气相沉积、激光表面改性和有机涂层等,进行了评述.国家标准对相关技术等具有极强的指导意义,而目前系统介绍有关我国国家标准中涉及表面处理方面的资料很少,所以本文也针对目前国家标准中表面处理工艺、检测方法等进行简单的介绍.     

Surface treatments for controlling corrosion rate of biodegradable Mg and Mg-based alloy implants

Due to their excellent biodegradability characteristics, Mg and Mg-based alloys have become an emerging material in biomedical implants, notably for repair of bone as well as coronary arterial stents. However, the main problem with Mg-based alloys is their rapid corrosion in aggressive environments such as human bodily fluids. Previously, many approaches such as control of alloying materials, composition and surface treatments, have been attempted to regulate the corrosion rate. This article presents a comprehensive review of recent research focusing on surface treatment techniques utilised to control the corrosion rate and surface integrity of Mg-based alloys in both in vitro and in vivo environments. Surface treatments generally involve the controlled deposition of thin film coatings using various coating processes, and mechanical surfacing such as machining, deep rolling or low plasticity burnishing. The aim is to either make a protective thin layer of a material or to change the micro-structure and mechanical properties at the surface and sub-surface levels, which will prevent rapid corrosion and thus delay the degradation of the alloys. We have organised the review of past works on coatings by categorising the coatings into two classes—conversion and deposition coatings—while works on mechanical treatments are reviewed based on the tool-based processes which affect the sub-surface microstructure and mechanical properties of the material. Various types of coatings and their processing techniques under two classes of coating and mechanical treatment approaches have been analysed and discussed to investigate their impact on the corrosion performance, biomechanical integrity, biocompatibility and cell viability. Potential challenges and future directions in designing and developing the improved biodegradable Mg/Mg-based alloy implants were addressed and discussed. The literature reveals that no solutions are yet complete and hence new and innovative approaches are required to leverage the benefit of Mg-based alloys. Hybrid treatments combining innovative biomimetic coating and mechanical processing would be regarded as a potentially promising way to tackle the corrosion problem. Synergetic cutting-burnishing integrated with cryogenic cooling may be another encouraging approach in this regard. More studies focusing on rigorous testing, evaluation and characterisation are needed to assess the efficacy of the methods.     

Surface treatments for controlling corrosion rate of biodegradable Mg and Mg-based alloy implants

Abstract

Due to their excellent biodegradability characteristics, Mg and Mg-based alloys have become an emerging material in biomedical implants, notably for repair of bone as well as coronary arterial stents. However, the main problem with Mg-based alloys is their rapid corrosion in aggressive environments such as human bodily fluids. Previously, many approaches such as control of alloying materials, composition and surface treatments, have been attempted to regulate the corrosion rate. This article presents a comprehensive review of recent research focusing on surface treatment techniques utilised to control the corrosion rate and surface integrity of Mg-based alloys in both in vitro and in vivo environments. Surface treatments generally involve the controlled deposition of thin film coatings using various coating processes, and mechanical surfacing such as machining, deep rolling or low plasticity burnishing. The aim is to either make a protective thin layer of a material or to change the micro-structure and mechanical properties at the surface and sub-surface levels, which will prevent rapid corrosion and thus delay the degradation of the alloys. We have organised the review of past works on coatings by categorising the coatings into two classes—conversion and deposition coatings—while works on mechanical treatments are reviewed based on the tool-based processes which affect the sub-surface microstructure and mechanical properties of the material. Various types of coatings and their processing techniques under two classes of coating and mechanical treatment approaches have been analysed and discussed to investigate their impact on the corrosion performance, biomechanical integrity, biocompatibility and cell viability. Potential challenges and future directions in designing and developing the improved biodegradable Mg/Mg-based alloy implants were addressed and discussed. The literature reveals that no solutions are yet complete and hence new and innovative approaches are required to leverage the benefit of Mg-based alloys. Hybrid treatments combining innovative biomimetic coating and mechanical processing would be regarded as a potentially promising way to tackle the corrosion problem. Synergetic cutting-burnishing integrated with cryogenic cooling may be another encouraging approach in this regard. More studies focusing on rigorous testing, evaluation and characterisation are needed to assess the efficacy of the methods.     

Biodegradable poly(lactide-co-glycolide) coatings on magnesium alloys for orthopedic applications

Polymeric film coatings were applied by dip coating on two magnesium alloy systems, AZ31 and Mg4Y, in an attempt to slow the degradation of these alloys under in vitro conditions. Poly(lactic-co-glycolic acid) polymer in solution was explored at various concentrations, yielding coatings of varying thicknesses on the alloy substrates. Electrochemical corrosion studies indicate that the coatings initially provide some corrosion protection. Degradation studies showed reduced degradation over 3 days, but beyond this time point however, do not maintain a reduction in corrosion rate. Scanning electron microscopy indicates inhomogeneous coating durability, with gas pocket formation in the polymer coating, resulting in eventual detachment from the alloy surface. In vitro studies of cell viability utilizing mouse osteoblast cells showed improved biocompatibility of polymer coated substrates over the bare AZ31 and Mg4Y substrates. Results demonstrate that while challenges remain for long term degradation control, the developed polymeric coatings nevertheless provide short term corrosion protection and improved biocompatibility of magnesium alloys for possible use in orthopedic applications.     

A novel polymer critical re-melting treatment for improving corrosion resistance of magnesium alloy stent

Polymer coating was widely used as a protective coating on Mg alloy stent due to its excellent deformability. However, the polymer coating with lots of macro- and micro-holes after solvent evaporation during forming process would make corrosion medium permeate easier and decrease the corrosion resistance of Mg alloy stent. In this study, a novel critical re-melting method was adopted to improve the polymer coating densification, which was evaluated by the surface morphology of coating. The corrosion resistance of Mg alloy stent after critical re-melting treatment was examined by the electrochemical and immersion tests. The results indicated that the corrosion resistance of Mg alloy stent with polymer coating was improved significantly by polymer critical re-melting treatment.     

镁合金表面改性与防护研究进展

镁合金是最轻的金属结构材料,具有比强度高、比刚度高、导电导热性好、生物相容性好等优点,在汽车、航空航天、电子、生物医学等领域有着广阔的应用前景。然而,镁自身化学活性极高且其表面的原生氧化膜疏松多孔,无法有效保护基底,往往在各加工工序间就会发生表面腐蚀。严重的腐蚀问题已经成为制约镁及其合金应用与发展的主要短板,因此,对镁合金进行表面防护处理是极为重要的。现阶段,镁合金的表面处理方法虽然种类繁多,但防护效果良莠不齐。重点综述了两种常用的镁合金表面改性技术--化学转化膜技术和微弧氧化技术的新进展,并介绍了一种基于活性CO2处理提高镁合金耐蚀性的新技术,以及仿生超疏水表面在提升镁合金耐蚀性上的应用,最后,对镁合金表面改性与防护的未来发展方向进行了展望。     

Investigation on a Non-cyanide Plating Process of Ni-P Coating on Magnesium Alloy AZ91D

In this research we presented a non-cyanide plating process of Ni-P alloy coating on Mg alloy AZ91D. By applying a new process flow of electroless nickel plating in which zinc coating is used as transition of Ni-P coating on Mg alloy AZ91D, the process of copper transition coating plated in the cyanides bath can be replaced. A new bath composed of NiSO4 was established by orthogonal test. The results show that zinc transition coating can increase the adhesion and pH 4.0 and 95℃, respectively. The present process flow is composed of ultrasonic cleaning→alkaline cleaning→acid pickling→activation→double immersing zinc→electroplating zinc→electroless nickel plating→passivation treatment.The present non-cyanide process of electroless nickel plating is harmless to our surroundings and Ni-P coating on Mg alloy AZ91D produced by present process possesses good adhesion and corrosion resistance.     

镁合金磷化处理对化学镀镍层性能的影响

为了有利于环保,采用磷化工艺对AZ31B镁合金进行化学镀镍前处理.采用直观法、扫描电子显微镜和阴极极化曲线法对磷化膜及其化学镀镍层进行了分析.结果表明:AZ31B镁合金表面经磷化处理后得到了良好的化学镀镍层;AZ31B镁合金化学镀镍层的耐蚀性随磷化时间的延长先增加后减小,当磷化时间为75 s时,化学镀镍层的腐蚀电势比直...