用仿生涂层控制金属镁的降解速率

在纯镁试样表面形成硅钙凝胶涂层,然后采用仿生法在纯镁试样及具有凝胶涂层试样表面形成羟基磷灰石涂层.利用X射线、能谱分析及扫描电子显微镜对形成的涂层进行表征.通过将试样浸入人体模拟液(SBF)中的腐蚀实验研究涂层对镁耐蚀性的影响.实验结果表明:采用仿生涂层技术,24h后在纯镁和具有凝胶涂层试样表面均可形成HA涂层,涂层降低了金属镁在人体模拟液中的腐蚀速率,通过控制涂层的成分及形貌,试样降解速率可控.     

Cl^-浓度和pH值对AZ31镁合金腐蚀行为的影响

研究了AZ31镬合金在不同Cl-浓度和pH值的NaCl溶液中的腐蚀行为,从腐蚀形貌和腐蚀速率等方面对其进行了定性和定量描述,并对其腐蚀机理进行了探讨.经NaCl溶液腐蚀的AZ31镁合金呈现出明显的点蚀特征.随着Cl-浓度的增大,金属的阳极溶解和局部腐蚀加剧,AZ31镁合金的腐蚀速率也急剧增加,腐蚀程度加重.同时,溶液pH值的增大有利于AZ31镬合金表面形成更稳定的Mg(OH)2钝化膜.于是,随着溶液pH值从7增大到12,AZ31镁合金的腐蚀速率减小,耐腐蚀性能增强.     

仿生涂层控制Mg-Zn-Sr合金的降解速率

镁合金作为生物医用材料面临最大的问题是降解速率过快,不能与骨愈合的速率配合.通过仿生法在Mg-Zn-Sr合金表面形成涂层,利用X射线衍射和扫描电子显微镜对涂层结构和形貌进行分析与观察;采用电化学和浸泡腐蚀实验,研究涂层对Mg-Zn-Sr合金在人体模拟液中降解速率的影响.实验结果表明:仿生法在合金表面形成的涂层为羟基磷灰石涂层;羟基磷灰石涂层提高了Mg-Zn-Sr合金在人体模拟溶液中的耐腐蚀性能.     

植酸改性对AZ31镁合金表面细胞黏附性能的影响

用浸没法在AZ31镁合金表面制备植酸涂层,用携带能谱仪的扫描电子显微镜研究了表面涂层的化学组成和形貌,并用直接法和间接法分别在植酸改性前后的镁合金表面培养细胞,检测细胞存活率,考查人骨肉瘤细胞在植酸改性前后镁合金表面的黏附能力。结果表明：在镁合金表面形成均匀的植酸涂层,植酸改性前后镁合金对细胞存活率影响相近,但细胞在植酸改性前后镁合金表面的黏附能力存在显著差异,植酸改性可有效改善AZ31镁合金的细胞黏附性能。     

采用开尔文扫描探针技术研究镁合金偶接铜合金的电偶腐蚀规律

采用开尔文探针技术(SKP)测量AZ91D镁合金与H62铜合金偶接试样在盐雾加速实验中的电偶腐蚀规律. 研究表明:AZ91D镁合金的电偶腐蚀效应受到阳极与阴极的电位差的影响,AZ91D镁合金与H62铜合金偶接试样之间的伏打电位差约为-1.22V, AZ91D镁合金存在显著的电偶腐蚀效应. 由于存在较大的伏打电位差,在盐雾实验初始阶段,电偶腐蚀主要发生在偶接界面AZ91D镁合金一侧附近区域,而H62黄铜没有发生明显腐蚀. 由于AZ91D镁合金在盐雾中生成的腐蚀产物对基体具有一定的保护作用, AZ91D镁合金表面腐蚀产物与基体间存在显著的伏打电位差,导致AZ91D镁合金基体形成新的腐蚀产物. 因此,随着盐雾实验时间延长,AZ91D镁合金电偶腐蚀效应降低,H62铜合金腐蚀加快.     

真空度对消失模铸造表面陶瓷层形成过程影响

研究了消失模镁合金表面陶瓷层的制备工艺,选用AZ91D作为基体合金,低熔点的玻璃粉作为陶瓷化材料,分析了真空度对表面陶瓷层微观形貌的影响和陶瓷层与基体之间结合界面的状况.结果表明:在其他参数固定的条件下,真空度的大小对涂层和界面结合质量影响很大;当真空度从-0.02MPa变化到-0.06MPa时,基体表面形成的陶瓷涂层变得更加致密、均匀,当真空度为-0.08MPa时,涂层和基体的界面变得凹凸不平.通过对铸件表面消失模涂料以及在浇注过程中泡沫模样状态的分析,建立了消失模镁合金表面陶瓷涂层形成过程模型.     

阴极极化法制备AZ91D表面铈转化膜的研究

应用阴极极化技术在AZ91D镁合金表面形成铈盐转化膜,研究了转化膜的腐蚀防护作用.腐蚀行为的测试是将阴极极化成膜试样、浸泡转化成膜试样和基体在3.5%NaCl溶液中进行动电位极化测试,结果表明:阴极极化铈盐转化成膜处理可使合金的腐蚀电位正移,出现钝化现象,自腐蚀电流密度明显降低,阴极转化成膜可以对AZ91D镁合金起到理想的防护作用.     

大应变轧制技术制备细晶AZ31镁合金板材

晶粒细化可以改善镁合金的强度和延性,通过控制轧制工艺可以控制变形组织.文中研究了不同轧制道次变形量对AZ31镁合金组织和性能的影响.实验结果表明:随着轧制道次变形量的增加,轧制应变速率增加,镁合金发生了动态再结晶,获得细小的晶粒组织,板材的硬度增加;但是,当轧制道次变形量增加到一定值之后,板材的表面出现宏观裂纹;采用大的道次轧制应变技术,可以减少轧制道次,制备晶粒尺寸为2～5μm的细晶镁合金板材.     

基于三点支撑法镁合金刚度特性的实验研究

镁合金的弯曲刚度是其工程应用的重要考核指标之一.通过三点支撑法分别研究了厚度为2.16mm与3.66mm的AZ31和AZ31B镁合金板的杨氏模量及弯曲刚度.结果表明,AZ31和AZ31B镁合金的杨氏模量和弯曲刚度相差不大.杨氏模量的值介于41.74~45.1GPa之间,弯曲刚度的值介于28.4~30.8GPa之间.对与3.66mm厚镁合金试件具有相同面密度的铝合金和钢质试件做了相同的研究,结果表明,镁合金板具有更高的抗弯系数.同时AZ31镁合金的比刚度为钢板比刚度的93.2%,比铝合金板高20.6%,AZ31B的比刚度比AZ31的略低.因此,镁合金是最合适的轻量化设计材料.     

镁合金表面氩弧熔覆Al-Si基SiC复合涂层组织及耐磨性

采用氩弧熔覆方法作为镁合金材料表面强化,是一项全新技术,在AZ31B镁合金基体表面制备10%Si C粉末+Al-Si合金粉末的复合涂层,利用X射线衍射仪、光学显微镜和扫描电子显微镜分析涂层的物相组成和显微组织;利用显微维氏硬度计和干滑动摩擦磨损实验机测试复合涂层在室温下的显微硬度和摩擦磨损性能。结果表明:氩弧熔覆涂层与基体界面具有良好的结合,无气孔、夹杂、裂纹等缺陷;熔覆层主要由Mg2Si、Mg2C3、Mg17Al12、Al3.21Si0.47等物相组成;熔覆层内部主要由黑色块状组织组成,尺寸为2~5μm;由于在氩弧熔覆过程中生成了新的物相使得涂层的显微硬度提高,涂层平均硬度可达2.5 GPa,是AZ31镁合金基体的4倍;基体的平均摩擦系数约为0.7,10%Si C氩弧熔覆层摩擦系数约为0.57,摩擦系数明显降低;熔覆涂层的相对耐磨性较基体提高近5倍。     

Mg-Zn-Ca合金的性能及降解速率控制

以经过铸造和热挤压的Mg-Zn-Ca合金为研究对象，利用光学显微镜、万能试验机对合金的微观组织以及机械性能进行了分析测试.采用仿生法在该合金表面形成了羟基磷灰石(HA)涂层.利用X射线衍射仪和扫描电子显微镜对涂层结构和形貌进行分析与观察，并对有、无涂层试样进行腐蚀实验研究.结果表明:采用铸造和热挤压技术制备的Mg-Zn-Ca合金抗拉强度和抗压强度与人骨接近，分别为365MPa和338MPa；屈服强度为360MPa，延伸率为1025%，弹性模量为4169GPa.HA涂层能一定程度上降低合金试样的降解速率.     

Preparing Ca-P coating on biodegradable magnesium alloy by hydrothermal method: In vitro degradation behavior

Magnesium alloys are potentially attractive biodegradable materials.However,their rapid corrosion rate limits their biomedical application.To slow down the rate of biodegradation,a protective calcium-phosphate coating was formed on a magnesium alloy substrate by a hydrothermal method.Scanning electron microscope results showed that the coating consisted of two layers with different crystalline characteristics.The loose outer layer showed a prism-like crystal structure,while the compact inner layer is a dense ultra-fine regular di-pyramid-like structure with an average grain dimension of ～200 nm.The compositions of the inner layer and outer layer were calcium-deficient hydroxyapatite (Ca-def HA) and dicalcium phosphate (DCPa),respectively.The coating adhered well to the substrate with a thickness of about 15 m.Immersion in Hank’s solution indicated that the coating could significantly improve the degradation properties of magnesium alloy.The pH of the solution containing the coated samples increased much more slowly than the untreated control.After 8 d immersion,the uncoated sample had corroded seriously while the coated sample was much less corroded.The Ca/P atom ratio in both the layers of the coating increased and the coating was still protecting the substrate.The two layers of the coating corroded differently because of differences in solubility.The outer layer was more severely attacked and many holes were formed on the surface,the inner layer suffered less attack.In addition,a growth of precipitate on the inner layer was observed,indicating that surface bioactivity was improved by the coating.Thus,magnesium alloys coated with a Ca-P coating prepared by a hydrothermal method are promising candidate biodegradable biomaterials,and further investigation of in vivo degradation behavior is suggested.     

镁合金表面复合膜的制备及其耐蚀性

利用溶胶凝胶技术在镁合金微弧氧化膜表面制备SiO2溶胶凝胶膜形成复合膜层.通过扫描电镜和能谱测试,分析膜层的表面形貌和成分.采用动电位极化曲线测试研究不同条件下复合膜的电化学性能.研究结果表明:SiO2溶胶凝胶膜的最佳沉积条件为浸涂次数3次,浸泡时间1 min,干燥温度80～100℃,干燥时间8h,固化温度170℃,固化时间1h.溶胶凝胶膜能够有效地封闭镁合金表面微弧氧化膜的微孔,形成均匀且较为致密的复合膜层.动电位极化曲线结果表明:复合膜比微弧氧化膜和镁合金基体具有更正的腐蚀电位(Ecorr)、更低的腐蚀电流密度(icorr)和更大的线性极化电阻(Rp),说明微弧氧化镁合金沉积溶胶凝胶膜后耐腐蚀性能有显著地提高,复合膜对AZ91D镁合金具有良好的防腐蚀作用.     

铝及铝镁合金的室温电沉积制备

采用氯化铝-氢化铝锂-四氢呋喃-苯的有机体系电沉积铝,并在此基础上,研究n（氯化铝）∶n（氯化镁）=10∶1时电沉积铝镁合金的工艺条件.结果表明,采用该法在室温下能够成功制备铝及铝镁合金,电沉积铝比沉积铝镁合金条件容易控制,沉积效果也优于铝镁合金.当电流密度为0.010A/cm2,苯与四氢呋喃的体积比为8∶7,氢化铝锂的质量为1.27g时,成功获得了灰黑色粉末状的铝镁镀层,但晶粒较大,镀层与铜基体的结合力差.通过SEM和XRD对镀层进行形貌观察和成分检测可知,该铝镁合金成分为Al3Mg2,且随着电沉积时间的加长,镀层厚度随之增加.     

镁合金表面MoS2/树脂杂化涂层的制备及其摩擦磨损和电化学性能研究

以水作为分散介质,制备了含丙烯酸树脂和MoS2颗粒的分散液,以阳极氧化为前处理,采用电化学共沉积法在镁合金表面制备了MoS2/树脂杂化涂层;采用MR 060型多功能摩擦磨损试验机考察涂层的摩擦磨损性能,并分析其磨损机制;采用PARSTAT2273型电化学工作站测试涂层的电化学阻抗谱及极化曲线;利用扫描电子显微镜和能谱仪分析涂层的表面形貌及结构.结果表明：所制备的涂层厚度高达50 μm,在质量分数为3.5%的NaCl溶液中表现出优异的耐腐蚀性能;MoS2的加入,能够有效降低涂层的摩擦系数,提高其耐磨性.     

镁合金微弧氧化-涂装体系的研究

提出了一种镁合金/微弧氧化膜/有机涂层的镁合金防护体系.在以硅酸钠为主的复合溶液中,利用双向对称脉冲电压在阴、阳极镁合金表面同时微弧电沉积陶瓷膜.利用盐雾实验比较了以镁合金微弧氧化膜为基底并涂覆环氧底漆和聚胺脂丙烯酸面漆的试样与镁合金/微弧氧化膜/有机硅、镁合金/微弧氧化膜/溶胶凝胶涂装试样的耐蚀性,并利用盐雾实验与交流阻抗谱相结合跟踪对比分析了镁合金/有机涂层、镁合金/铬酸盐转化膜/有机涂层、镁合金/微弧氧化膜/有机涂层的屏蔽性能.结果表明:采用溶胶凝胶、有机硅和有机涂层对微弧氧化膜进行涂装的方法均可进一步提高镁合金的耐蚀性,其中镁合金/微弧氧化膜/有机涂层试样可承受480h以上的中性盐雾实验,且其介质屏蔽性能优于镁合金/有机涂层和传统的镁合金/铬酸盐转化膜/有机涂层防护体系.     

Corrosion mechanism of micro-arc oxidation treated biocompatible AZ31 magnesium alloy in simulated body fluid

The rapid degradation of magnesium(Mg) based alloys has prevented their further use in orthopedic trauma fixation and vascular intervention,and therefore it is essential to investigate the corrosion mechanism for improving the corrosion resistance of these alloys. In this work, the effect of applied voltage on the surface morphology and the corrosion behavior of micro-arc oxidation(MAO) with different voltages were carried out to obtain biocompatible ceramic coatings on AZ31 Mg alloy. The effects of applied voltage on the surface morphology and the corrosion behavior of MAO samples in the simulated body fluid(SBF) were studied systematically. Scanning electron microscope(SEM) and X-ray diffractometer(XRD)were employed to characterize the morphologies and phase compositions of coating before and after corrosion. The results showed that corrosion resistance of the MAO coating obtained at 250 V was better than the others in SBF. The dense layer of MAO coating and the corrosion precipitation were the key factors for corrosion behavior. The corrosion of precipitation Mg(OH)2and the calcium phosphate(Ca–P) minerals on the surface of MAO coatings could enhance their corrosion resistance effectively. In addition, the mechanism of MAO coated Mg alloys was proposed.     

High-temperature oxidation resistance of ceramic coatings on titanium alloy by micro-arc oxidation in aluminate solution

Ceramic coatings with aluminum titanuate (Al₂TiO₅) were prepared on Ti–6Al–4V alloy using pulsed bi-polar Micro-arc Oxidation (MAO). The micromorphology and phase composition of the micro-arc-oxidition ceramic coatings on the titanium alloy were characterized by X-ray powder diffraction (XRD), and scanning electron microscopy (SEM) respectively. The results revealed that the distinct discharge channels and pores on the surface of the micro-arc-oxidition coatings appeared, and these channels were connected in the molten state. The electrolyte concentration was inversely proportional to the coating hardness; additionally, the coating prepared with sodium aluminate and sodium hypophosphite concentrations of 4 ?g/L and 0.5 ?g/L, respectively, was the most refined after high-temperature sintering, and it was demonstrated to better prevent oxidation. Increasing the electrolyte concentration coincided with fluctuating coating thermal shock resistance. The thermal shock resistance of the coating respectively prepared with sodium aluminate, and the sodium hypophosphite concentrations of 4 ?g/L and 0.5 ?g/L was the highest. Additionally, the high-concentration coatings performed significantly better than the low-concentration coatings. The oxidation resistance of the coating samples was also significantly higher than that of the TC4 titanium alloy substrate. The adhesion strength between the coatings and the substrate with and without the sealing treatment was measured by tensile tests. Then, the high-temperature oxidation performance of the coating samples with and without the sealing treatment was investigated by conducting a high-temperature oxidation experiment at a calcinating temperature of 500 ?°C. The results indicate that the adhesion strength between the coatings and substrate was high for the as-prepared and sealed micro-arc oxidation samples regardless of whether they were calcined. The high-temperature oxidation mass increase curves for the sealed and unsealed coating samples calcined at 500 ?°C for 500 ?h revealed that the high-temperature-oxidation-induced mass increase of the coating samples sealed with a sodium silicate solution was much lower than that of the titanium alloy substrate. Thus, the sealing treatment significantly improved the high-temperature oxidation resistance of the TC4 titanium alloy. Lastly, the high-temperature oxidation behavior at 500 ?°C was analyzed and discussed.