Fluoride treatment and in vitro corrosion behavior of an AZ31B magnesium alloy

As a new class of biodegradable material, magnesium alloys have attracted much attention in recent years. In order to improve the corrosion resistance, a fluoride coating was prepared on the surface of AZ31B magnesium alloy. The surface characterization analysis showed a dense coating with some irregular pores was formed. The TF-XRD analysis indicated that the coating was mainly composed of MgO and MgF₂. Electrochemical and immersion tests proved that the fluoride conversion coating significantly improved the corrosion resistance of AZ31B. Three-point bending test revealed that the degradation behavior of the fluoride treated AZ31B could meet the requirement as a biodegradable material.     

AZ31B镁合金铈基-植酸复合转化膜研究

为了进一步提高镁合金转化膜防腐性能的影响,将铈基转化复合于在AZ31B镁合金植酸转化膜表面,制备了一种铈基一植酸复合转化膜,应用析氢实验、Tafel分析方法及SEM、EDS对AZ31B镁合金不同转化膜的防腐性能及表面微观结构及成份进行了研究。结果表明复合转化膜表面主要由C、O、P、Ce、Mg及Al元素所组成,复合转化膜相比于植酸转化膜及铈基转化膜具有更好的致密性,从而复合转化膜相比于植酸转化膜及铈基转化膜具有更好的防腐性能。     

Protective coating for magnesium alloy

A phosphate–permanganate conversion coating was applied as the pretreatment process for AZ91D magnesium alloy substrate. Zn–Ni alloys were electrodeposited onto the treated AZ91D magnesium alloy from sulfate bath. The morphology and phase composition of the coatings were determined with X-ray diffraction (XRD) and Scanning Electron Microscope (SEM). The results reveal that the conversion rate depends on pH of solution and treatment time. Salt spray and the electrochemical polarization testing were applied to evaluate the corrosion performance of phosphate–permanganate and Zn–Ni coated alloys. It was found that Ni content in deposit is a function of current density and bath composition. Zn–13 wt.% Ni coating provides very good corrosion protective function to inner AZ91D magnesium alloy. Phosphate–permanganate treatment enhances the corrosion resistance of Zn–Ni coatings.     

Growth and corrosion of aluminum PVD-coating on AZ31 magnesium alloy

Magnetron sputtering was applied to prepare aluminum coating on a mechanically polished AZ31 magnesium alloy. A loose oxide film was spontaneously formed on the surface of AZ31 magnesium alloy during polishing process. The aluminum coating, which was subsequently deposited on this oxide layer, presented a developed columnar microstructure. Attributed to the barrier effect of Al coating, the Al coated AZ31 showed a higher corrosion resistance than bare AZ31 in corrosion tests. Generally, Al coating is cathodically protected by magnesium alloy substrate. But it is interesting in this study that Al coating still suffered from severe corrosion due to the occurrence of the alkalization effect.     

Fluoride Conversion Coating on Biodegradable AZ31B Magnesium Alloy

A fluoride conversion coating was successfully prepared on AZ31B magnesium alloy by chemical reaction in hydrofluoric acid. Morphologies, composition, bonding strength, corrosion properties, in vitro cytotoxicity and antibacterial properties of the coating were investigated, respectively. The scanning electron microscopy observations revealed a dense coating with some irregular pores. The thin-film X-ray diffraction analysis indicated that the coating was mainly composed of MgO and MgF2. The electrochemical impedance spectroscopy results showed that the fluoride conversion coating significantly improved the corrosion resistance of AZ31B. The hydroxyapatite formed on the surface of the fluoride coated AZ31 B after being immersed in the simulated blood plasma indicated the good bioactivity of the material. The in vitro cytotoxicity test showed that the fluoride coated AZ31B alloy was not toxic to BMMSCs （human bone marrow-derived mesenchymal stem cells）. It was also found that the fluoride coated AZ31 B alloy had antibacterial capability.     

Mechanical and corrosion properties of Al/Ti film on magnesium alloy AZ31B

Preparation of titanium film on magnesium substrate faces a challenge due to non-Fickian inter-diffusion between titanium and magnesium. Aluminum can build a bridge between titanium and magnesium. Al/Ti duplex coatings were deposited on magnesium alloy AZ31B using magnetron sputtering (MS). The low temperature diffusion bonding behavior of the Mg/Al/Ti coating was investigated through SEM and its affiliated EDS. The phase structure and critical load of the coatings were examined by means of XRD and scratch tests, respectively. The results demonstrated that the bonding strength was significantly improved after a post heat treatment (HT) at a temperature of 210°C. The diffusion mechanism of the interfaces of Mg/Al and Al/Ti in the coating was discussed based on the analysis of formation energy of vacancies and diffusion rates. The Al/Ti dual layer enhanced the corrosion resistance of the alloy. And the HT process further increased the corrosion resistance of the coated alloy. This result implies that a post HT at a lower temperature after MS is an effective approach to enhance the bonding strength and corrosion resistance of the Al/Ti film on Mg alloys.     

Galvanisches Verzinken von Magnesiumlegierungen

Zinc‐Plating of Magnesium Alloys Magnesium alloys are highly susceptible to corrosion that limits their application when exposure to corrosive service conditions is needed. One of the ways to prevent corrosion is to coat the magnesium‐based substrate to avoid a contact with an aggressive environment. Results concerning corrosion behaviour of wrought AZ31 magnesium alloy with electrolytic zinc coatings deposited from different electrolyte solutions are described. Evaluation of corrosion processes in chlorides containing solutions was performed by electrochemical measurements. It was found that thick and dense electrolytic zinc coatings formed on AZ31 significantly improve the corrosion behaviour of magnesium alloy after one hour immersion of zinc coated magnesium alloys in corrosive media. Further increase of immersion time leads to relatively fast decrease of corrosion properties. Electrolytic zinc coatings obtained in consecutive alkaline / acidic process demonstrate an improvement of corrosion resistance of coated AZ31. The time to coating degradation strongly increases.     

镁合金磷化工艺及磷化膜性能的研究

为了有效提高镁合金表面涂层的防护能力,研制了特定的配方体系对AZ31D镁合金基体进行磷化处理,并进行涂装和性能检测试验.结果表明,该配方体系能制备出表观均匀、细致的磷化膜,金相显示其晶粒均匀.该磷化膜与有机涂层的结合力牢固,用划格法测定膜与环氧涂层甚至与丙烯酸涂层的附着力均能达到1级,而没有磷化膜的金属基体与丙烯酸涂层的附着力仅能达到2级.通过48 h中性盐雾试验表明,有磷化膜的涂层比没有磷化膜的涂层的耐腐蚀性能有所提高.     

退火处理对AZ31镁合金表面Ni-Mo-P镀层组织与耐腐蚀性能的影响

为了进一步提高镁合金表面Ni-Mo-P镀层的耐蚀性,采用0M、XRD和浸泡试验等方法,研究了退火处理对AZ31镁合金表面Ni-Mo-P镀层组织与腐蚀性能的影响。结果表明:AZ31镁合金阳极氧化-化学镀Ni-Mo-P镀层表面为“胞状”组织,随着退火温度的升高或退火时间的延长,AZ31镁合金阳极氧化-化学镀Ni-Mo-P镀层的胞状组织逐渐细化,但镀层厚度降低,同时,非晶态Ni-Mo-P镀层组织逐渐向晶态转变,350℃退火1.0h具有较高的非晶化程度,退火处理后的Ni-Mo-P镀层由Mg、MgO、Mg2SiO4、Ni和Ni3P组成;退火使AZ31镁合金阳极氧化-化学镀Ni-Mo-P镀层耐蚀性降低,350℃退火1.0 h镀层具有相对较好的耐蚀性,这与镀层的厚度和非晶化程度有关。     

工艺参数对镁合金植酸转化膜的影响

传统铬酸盐化学转化处理能提高镁合金的耐腐蚀性能,但因处理液有剧毒而受到限制.采用环保型金属处理剂植酸对AZ31B镁合金进行化学转化处理,通过正交试验初步确定了工艺参数(植酸浓度、处理液pH值、处理时间、处理温度)对植酸转化膜耐蚀性影响的主次顺序,并优化了工艺参数.采用扫描电子显微镜(SEM)、电子能谱仪(EDS)、光学金相显微镜对植酸转化膜腐蚀前后的形貌、成分和厚度进行了分析;通过电化学测试技术和化学浸泡法测试了其耐蚀性能.结果表明:与传统的铬酸盐和磷酸盐体系相比,经植酸处理后,AZ31B镁合金在3.5%NaCl溶液中的腐蚀电位分别提高了0.06 V和0.09 V,且在相同的电位下,阳极电流密度最小,电化学性能得到显著改善,腐蚀速度降低.     

Corrosion behavior of friction stir welded AZ31B magnesium alloy with plasma electrolytic oxidation coating formed in silicate electrolyte

A protective ceramic coating of about 50 μm thick on a friction stir welded (FSW) joint of AZ31B magnesium alloy was prepared by plasma electrolytic oxidation (PEO) in silicate electrolyte. Electrochemical corrosion behavior of uncoated and coated FSW joints was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The equivalent circuits of EIS plots for uncoated and coated FSW magnesium alloy were suggested. The corrosion resistance of FSW magnesium alloy depended on microstructure of the FSW joint. The heat-affected zone with severe grain growth was more susceptible to corrosion than the stir zone and base metal. The PEO coating consisted of a porous outer layer and a dense inner layer. The inner layer of PEO coating played a key role on corrosion protection of the FSW joint of magnesium alloy. Meanwhile, corrosion potential, corrosion current density and impedance at different zones of coated FSW joint were almost the same. The PEO surface treatment significantly improved the corrosion resistance of FSW joints of AZ31B magnesium alloy.     

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.     

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...     

AZ31镁合金的SiO2（Mg）涂层的组织及性能研究

采用机械合金化的方法在AZ31镁合金表面涂覆SiO₂（Mg）涂层。通过XRD、显微硬度计、扫描电镜等测试手段对表面涂层的微观形貌结构、涂层的显微硬度进行分析,利用电化学工作站对涂覆前后的AZ31镁合金的耐蚀性能进行检测。结果表明:SiO₂涂层被成功地涂覆到AZ31镁合金表面;同时,随着球磨时间的增加,涂层的显微硬度呈增加趋势,且随着球料比的增加,显微硬度亦增加,最高达到370.6HV,较基体提高了15.2%;涂层的厚度也呈现先增加后趋于稳定的趋势,但球磨时间过长,涂层内部出现裂纹;当球料比为15:1、球磨时间为15 h时,所制备涂层厚度为148μm,涂层致密且与基体结合较好;所对应的自腐蚀电流密度较基体降低了一个数量级,对应的腐蚀电压提高了6.5%,耐腐蚀性能得到明显改善。      

The surface chemistry of 3-mercaptopropyltrimethoxysilane films deposited on magnesium alloy AZ91

Magnesium and its alloys have desirable physical and mechanical properties for a number of applications. Unfortunately, these materials are highly susceptible to corrosion, particularly in the presence of aqueous solutions. The purpose of this study is to develop a uniform, non-toxic surface treatment to enhance the corrosion resistance of magnesium alloys. This paper reports the influence of the coating bath parameters and alloy microstructure on the deposition of 3-mercaptopropyltrimethoxysilane (MPTS) coatings on magnesium alloy AZ91. The surface chemistry at the magnesium/MPTS interface has also been explored. The results indicate that the deposition of MPTS onto AZ91 was influenced by both the pH and MPTS concentration in the coating bath. Furthermore, scanning electron microscopy results showed that the MPTS film deposited uniformly on all phases of the magnesium alloy surface. X-ray photoelectron spectroscopy studies revealed that at the magnesium/MPTS interface, the molecules bond to the surface through the thiol group in an acid-base interaction with the Mg(OH)₂ layer, whereas in the bulk of the film, the molecules are randomly oriented.     

Effect of extrusion ratio on mechanical and corrosion properties of AZ31B alloys prepared by a solid recycling process

Some AZ31B magnesium alloy bars were prepared by a solid recycling process with different extrusion ratios. A reference specimen was processed by extruding an as-received AZ31 ingot. The microstructures, mechanical and corrosion properties of AZ31B magnesium recycled specimens were investigated. With increasing extrusion ratio, the yield strength, tensile strength and yield ratio increases. The reliability of the recycled alloy is poorer than the reference specimen. The corrosion rates of recycled AZ31B magnesium specimens increase immersed in both alkaline and neutral 4% NaCl solution with a decrease extrusion ratio. The corrosion resistance of recycled AZ31B magnesium specimens is improved with increasing pH of immersed solution. The recycled specimens show superior corrosion resistance than reference specimen.     

单宁酸对镁合金锆酸盐转化膜耐蚀性能的影响

在钒锆体系基础上添加单宁酸可提高AZ91D镁合金表面锆酸盐转化膜的耐蚀性能,目前研究较少。采用单因素试验的方法,研究单宁酸浓度对转化膜的影响;通过盐雾试验、电化学测试来检测膜层的耐蚀性能;利用扫描电镜(SEM)以及能谱(EDS)分析转化膜的微观形貌和成分变化。结果表明:单宁酸的浓度在0.3~0.5 g/L之间时,膜层晶粒较为细致,膜层均匀,阻抗值弧明显大于其他浓度时的阻抗弧,腐蚀电流密度达2.256×10-5A/cm~2,耐盐雾时间达600 min;在锆酸盐里添加单宁酸后形成的转化膜可以提高AZ91D镁合金表面的耐蚀性能。     

Corrosion resistance of in-situ growth of nano-sized Mg(OH)2 on micro-arc oxidized magnesium alloy AZ31—Influence of EDTA

One of the major obstacles for the clinical use of biodegradable magnesium (Mg)-based materials is their high corrosion rate. Micro-arc oxidation (MAO) coatings on Mg alloys provide mild corrosion protection owing to their porous structure. Hence, in this study a dense Mg(OH)₂ film was fabricated on MAO-coated Mg alloy AZ31 in an alkaline electrolyte containing ethylenediamine tetraacetic acid disodium (EDTA-2Na) to reinforce the protection. Surface morphology, chemical composition and growth process of the MAO/Mg(OH)₂ hybrid coating were examined using field-emission scanning electron microscopy, energy dispersive X-ray spectrometer, X-ray diffraction, X-ray photoelectron spectroscopy and Fourier transform infrared spectrophotometer. Corrosion resistance of the coatings was evaluated via potentiodynamic polarization curves and hydrogen evolution tests. Results manifested that the Mg(OH)₂ coating possesses a porous nano-sized structure and completely seals the micro-pores and micro-cracks of the MAO coating. The intermetallic compound of AlMn phase in the substrate plays a key role in the growth of Mg(OH)₂ film. The current density of Mg(OH)₂-MAO composite coating decreases three orders of magnitude in comparison with that of bare substrate, indicating excellent corrosion resistance. The Mg(OH)₂-MAO composite coating is beneficial to the formation of calcium phosphate corrosion products on the surface of Mg alloy AZ31, demonstrating a great promise for orthopaedic applications.     

温度对AZ31B镁合金植酸转化膜性能的影响

为了探讨转化温度对镁合金防腐蚀性能的影响,应用析氢试验、Tafel分析法及SEM,EDS,FTIR研究了不同植酸液温度所形成的转化膜的防腐蚀性能及表面微观形貌、元素组成及官能团构成。结果表明转化温度对镁合金植酸转化膜的防腐蚀性能有较大的影响：在较低范围内,转化膜的防腐蚀性能随着温度的升高而增加,转化温度为40℃时,转化...     

镁合金铈化学转化工艺及性能研究

镁合金稀土转化膜技术是一种环保型镁合金表面处理新技术.通过正交实验对压铸镁合金AZ91D铈化学转化处理工艺进行了研究,并对膜层性能进行了测试.结果表明,铈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Ce2O3、CeO2和MgO以及少量的Al2O3组成;铈转化处理提高了镁合金的耐腐蚀性能.