医用镁合金等离子喷涂羟基磷灰石涂层研究

为了提高医用镁合金的表面耐蚀性和生物相容性,采用等离子喷涂技术在镁合金表面制备羟基磷灰石(HA)涂层.研究结果表明,镁合金表面所制备的HA涂层与基体结合牢固,界面无裂纹、气孔等缺陷.相组成为生物相容性较好的HA和少量的Ca3(PO4)2(TCP),显微组织具有层状特征,涂层表面存在一些有利于骨长人的孔隙.涂层的弹性模量约为19.825 GPa,接近骨的弹性模量,涂层表面硬度为300～350 HV.腐蚀试验和钙磷沉积试验结果表明HA涂层具有较好的耐蚀性和骨诱导性.     

医用镁合金表面激光重熔羟基磷灰石涂层

为提高医用镁合金的表面耐蚀性和生物相容性,采用等离子喷涂和激光重熔复合技术在镁合金表面制备羟基磷灰石(HA)生物涂层。研究结果表明,所制备的羟基磷灰石涂层为短杆状堆积结构,主要由HA和β-TCP相组成;涂层的弹性模量约为50 GPa,较已临床应用的医用金属材料显著降低,显微硬度约为455 HV,具有较好的耐磨性。涂层在模拟体液中具有很好的耐蚀性,在腐蚀12 d后涂层表面形貌仍然较完整,无腐蚀孔洞出现。钙磷沉积实验结果表明,涂层表面形成一层新的生物磷灰石层,表明涂层具有较好的骨诱导性。     

pH值对镁合金表面水热磷酸钙涂层微观形貌和生物腐蚀性能的影响研究

为改善镁合金的耐蚀性和生物相容性,在不同pH条件下采用水热法在镁合金AZ31表面制备了磷酸钙（Ca-P）涂层。利用XRD、SEM 和 EDS分析了不同pH值下涂层的物相组成、微观形貌和化学成分;采用Hank’s仿生溶液中电化学测试和浸泡的方法研究了涂层在的生物腐蚀行为。结果表明：水热处理的pH值影响涂层的相组成和微观形貌,涂层的微观形貌影响涂层的防护性能。当pH为6时,Ca-P 涂层由Mg3(PO4)2 和OCP组成,当pH增加到8和10时,Ca-P 涂层为羟基磷灰石（HA）。pH值为8时,HA 涂层呈蜂窝状;pH值为10时,HA 涂层由纳米尺度的棒状晶体构成,该涂层在Hank’s溶液中能有效阻止溶液的渗透而保护基体。     

水热处理对电化学沉积HA涂层物相的影响

采用电化学沉积在碱处理Ti6Al4V钛合金基体上生成羟基磷灰石（HA）涂层,研究了水热处理对该涂层物相的影响。结果表明,电化学沉积HA涂层结晶度低、晶粒尺寸较小,经120 ℃和160 ℃水热处理后,HA结晶度和晶粒尺寸显著增大,且随水热处理温度的增加,结晶度和晶粒尺寸增加。     

电泳沉积法制备羟基磷灰石涂层

羟基磷灰石是一种最有发展前途的生物材料之一.采用电泳沉积方法分别在Ti6Al4V基体和电泳沉积的HA/TiO2复合涂层上制备了HA生物陶瓷涂层.将HA粉体分散到正丁醇溶液中,通过测量zeta电位确定了悬浮体系中三乙醇胺和HA的含量.研究发现:HA沉积量随沉积温度和沉积电压的增加而增加,随沉积时间延长呈线性增长.对沉积量与电泳沉积工艺参数的关系进行了理论探讨.SEM结果表明,采用二次电泳沉积在HA/TiO2涂层表面制备的HA涂层更加致密、平整.     

医用镁合金激光熔覆羟基磷灰石涂层初探

为改善医用镁合金表面耐蚀性和生物相容性,采用激光熔覆技术在AZ91D镁合金表面制备具有生物活性的羟基磷灰石涂层.结果表明,所制备的涂层和镁合金基体达到了良好的冶金结合,涂层显微结构为致密的胞状晶,主要由Mg、HA、CaH2P2O7和CaH4(PO3)2·H2O组成,其中Ca和P的摩尔比为1.73, 接近理论值1.67,从而大大提高了涂层的生物活性.另外,控制Mg对涂层的稀释对涂层制备起关键作用.     

电泳沉积法制备HA/Ti0，复合涂层

羟基磷灰石是一种最有发展前途的生物材料之一.采用电泳沉积方法在钛合金基体上制备了HA/TiO2生物陶瓷涂层.将HA和TiO2粉体分散到正丁醇溶液中,再加入三乙醇胺,通过zeta电位确定了稳定的悬浮液中三乙醇胺和HA/TiO2的含量.研究了沉积电压和电泳时间对HA/TiO2涂层形貌和沉积量的影响.制得均匀致密涂层的适宜电压范围为250～350V.研究结果表明:由于电场强度随沉积时间改变,HA/TiO2沉积量随着沉积时间的增加表现出2段沉积速率不同的线性增长.     

镁合金表面MgF_2/HA复合涂层的体外降解性能

为改善镁合金的耐蚀性和生物相容性,利用化学处理和电化学沉积法在镁合金AZ31表面制备MgF_2/HA复合涂层。采用Hank’s仿生溶液中浸泡和电化学阻抗(EIS)的方法,结合浸泡过程中涂层EIS谱和表面形貌成分的变化,研究MgF_2/HA涂层的体外降解行为。结果表明:在Hank’s仿生溶液浸泡过程中,涂层电化学阻抗谱的高频容抗弧明显减小,涂层电阻随浸泡时间而降低。浸泡至5 d时,出现感抗弧,涂层表面区域产生腐蚀孔核。浸泡至8 d时,镁合金基体发生点蚀,点蚀产生的腐蚀产物在孔中堆积形成胞状突起。浸泡至12 d时,Cl-渗透至镁合金基体,涂层表面形成MgCl_2结晶。浸泡过程中,表面涂层未发生脱落和明显的溶解,降解以溶液渗透至基体,然后发生局部点蚀为主。     

脉冲电化学沉积羟基磷灰石涂层改善Mg-Nd-Zn-Zr合金在模拟体液中的耐腐蚀性能

采用脉冲电化学沉积的方法,在新开发的Mg-Nd-Zn-Zr合金(JDBM)表面制备出了羟基磷灰石(HA)涂层,并对其耐蚀性能和血液相容性进行了研究.结果表明,表面改性后的JDBM镁合金具有更好的耐腐蚀性能,腐蚀后涂层保持了良好的完整性,析氢试验也表明涂层对基体在仿生腐蚀环境中有一定的保护作用,且不会引起模拟体液pH值较...     

镁合金表面HA复合涂层的设计研发及应用展望

镁及镁合金具有与骨骼硬组织良好的力学性能适配性、生物相容性和体内可生物降解等优良特性,被认为是一种最具有应用潜力的新型外科金属基植入材料,但其过快的降解速度限制了它的应用和普及推广。羟基磷灰石(HA)具有良好的生物活性,在镁合金表面制备HA涂层,能有效增强镁合金植入体的活性和耐腐蚀性,延缓其降解速率。但纯的HA涂层存在脆性大,强韧性不足,与基体间黏附力较差且功能性单一等问题,因此开发镁合金表面的高品质、多功能HA复合涂层,具有非常重要的科学和实践价值。本文综述了近年来开发的在镁合金基体表面的HA复合涂层及在骨修复上应用的研究进展,并对未来镁合金基体表面HA复合涂层的研究发展趋势进行了展望。     

Preparation and characterization of inorganic and organic coatings on AZ91D magnesium alloy with electroless plating pretreatment

In this paper, a protective coating scheme was applied for the corrosion protection of AZ91D magnesium alloy. Electroless Ni coating (EN coating) as bottom layer, electrodeposited Ni coating (ENN coating), and silane‐based coating (ENS coating) as top layer, respectively, were successfully prepared on AZ91D magnesium alloy by combination techniques. Scanning electron microscopy and X‐ray diffraction were employed to investigate the surface and phase structure of coatings, respectively. The electrochemical corrosion behaviors of coatings in neutral 3.5 wt% NaCl solution were evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The corrosion testing showed that the three kinds of coatings all could provide corrosion protection for AZ91D magnesium alloy to a certain extent, and the corrosion resistance of ENN and ENS was superior to EN. In order to further study the corrosion protection properties of ENN and ENS, a comparative investigation on the evolution of EIS of ENN and ENS was carried out by dint of immersion test in neutral 3.5 wt% NaCl solution. The results indicated that, compared with ENN, the ENS could provide longer corrosion protection for AZ91D magnesium alloy. It is significant to determine the barrier effect of each coating, which could provide reference for industry applications.     

AZ91D 镁合金表面 Ni-P / Ni-Sn-P 双镀层的制备与性能研究

目的提高AZ91D镁合金的耐腐蚀性能,扩大其应用范围。方法先在AZ91D镁合金表面化学镀Ni-P镀层,再化学镀Ni-Sn-P镀层,形成Ni-P/Ni-Sn-P双镀层。研究Ni-P/Ni-Sn-P双镀层的表面形貌和耐腐蚀性能,并与Ni-P单镀层进行对比。结果 Ni-P/Ni-Sn-P双镀层表面分布更均匀平整,缺陷较少,孔隙率较低,具有无定形结构。二次Ni-Sn-P镀层的腐蚀电位约为-0.77 V,略低于一次化学镀Ni-P层(约-0.68 V),两镀层间的电位差使得其构成了微腐蚀电偶,Ni-P层作为阴极,Ni-Sn-P层作为阳极,阳极优先被腐蚀。结论 Ni-P/Ni-Sn-P双镀层的Ni-Sn-P外层能为Ni-P内层提供阴极保护,较好地横向分散腐蚀电流,从而增强AZ91D镁合金基底的耐腐蚀性能。     

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.     

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.     

铝基非晶纳米晶复合涂层研究

采用自动化高速电弧喷涂系统,用自行研制的粉芯丝材,在AZ91镁合金基体表面上制备出Al-Ni-Y-Co非晶纳米晶复合涂层.采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、透射电子显微镜(TEM)分析了Al-Ni-Y-Co非晶纳米晶复合涂层的微观形貌和组织结构,结果表明Al-Ni-Y-Co非晶纳米晶复合涂层是由非晶相和纳米晶化相共同组成的,涂层结构致密,孔隙率约为1.8%.Al-Ni-Y-Co非晶纳米晶复合涂层的平均显微Vickers硬度值为311.7 HV0 1,结合强度为26.8 MPa.涂层的抗磨损耐腐蚀性能优于Al涂层和AZ91镁合金基体;其相对耐磨性约为Al涂层的10倍,为AZ91镁合金的6倍;其自腐蚀电位值正于Al涂层及AZ91镁合金,自腐蚀电流密度值约为Al涂层的1/2,AZ91镁合金的1/5;其腐蚀后的表面形貌比Al涂层和AZ91镁合金平整,点蚀较少.Al-Ni-Y-Co非晶纳米晶复合涂层的耐磨防腐综合性能优异.     

镁合金表面电弧喷涂用铝粉芯丝材

为改善镁合金的表面性能，研制了新型铝基粉芯丝材，并采用电弧喷涂的方法在AZ91镁合金表面制备耐蚀涂层。通过盐雾试验和电化学试验对涂层的耐蚀性进行评价。利用光学显微镜和XRD分析技术对涂层的显微组织结构和相组成进行了研究。结果表明，铝基涂层能对镁合金基体起到保护作用，涂层均匀致密；加入Ni和Re能够提高涂层的耐腐蚀性能。     

Statistical Process Control

Abstract

In order to improve the corrosion resistance provided by a micro-arc oxidation (MAO) coating on AZ31 magnesium alloy, a polypropylene film was prepared on its surface. Scanning electron microscopy, energy dispersive X-ray analysis and Fourier transform infrared spectroscopy were used to characterise the surfaces of the coatings. The corrosion protective performance of the coatings was evaluated by potentiodynamic polarisation curves, electrochemical impedance spectroscopy and immersion testing. The results show that the microdefects of the MAO coating can be filled by PP and the corrosion resistance of the AZ31 magnesium alloy is improved greatly.     

镁合金等离子喷涂Al/Al_2O_3涂层的耐腐蚀性能

采用等离子喷涂技术在AZ31镁合金表面制备Al/Al_2O_3复合涂层,测试了镁合金及表面喷涂有Al/Al_2O_3复合涂层的镁合金试样的极化曲线,研究了没有涂层、经封孔处理和未经封孔处理的喷涂有复合涂层的镁合金三种试样在浸泡腐蚀和5%NaCl盐雾腐蚀情况下的耐腐蚀性能及其腐蚀行为.结果表明,经封孔处理的Al/Al_2O_3复合涂层镁合金试样在上述腐蚀条件下的耐腐蚀性均优于镁合金和涂层未封孔处理的试样,在浸泡试验中未封孔处理的涂层试样比镁合金腐蚀更加严重,在盐雾试验中却优于镁合金.     

The corrosion performance of anodised magnesium alloys

The corrosion performance of anodised magnesium and its alloys, such as commercial purity magnesium (CP-Mg) and high-purity magnesium (HP-Mg) ingots, magnesium alloy ingots of MEZ, ZE41, AM60 and AZ91D and diecast AM60 (AM60-DC) and AZ91D (AZ91D-DC) plates, was evaluated by salt spray and salt immersion testing. The corrosion resistance was in the sequential order: AZ91D ≈ AM60 ≈ MEZ ? AZ91D-DC ? AM60-DC > HP-Mg > ZE41 > CP-Mg. It was concluded the corrosion resistance of an anodised magnesium alloy was determined by the corrosion performance of the substrate alloy due to the porous coating formed on the substrate alloy acting as a simple corrosion barrier.