甘油磷酸钙浓度对钛合金MAO涂层性能的影响  

Effect of Calcium Glycerophosphate Concentration on Properties of MAO Coatings Developed on Titanium Alloys

作　　者：肖水清 秦晋 王学禹 赵融芳 张荣发[1] XIAO Shuiqing;QIN Jin;WANG Xueyu;ZHAO Rongfang;ZHANG Rongfa(Jiangxi Science and Technology Normal University,Nanchang 330038,China)

机构地区：[1]江西科技师范大学,南昌330038

出　　处：《表面技术》2024年第9期56-64,共9页Surface Technology

基　　金：国家自然科学基金(52261017,52061013)。

摘　　要：目的提高医用钛合金的生物活性。方法在含葡萄糖酸钙(CaGlu_(2))、葡萄糖酸镁(MgGlu_(2))、植酸钠(Na12Phy)和磷酸(H3PO_(4))的基本溶液中,分别添加8、10、12 g/L甘油磷酸钙(Ca-GP),采用MAO方法在Ti-6Al-4V表面制备3种涂层。使用SEM、EDS、XRD、XPS和AFM检测涂层表面形貌、化学成分、物相结构、元素存在状态和表面粗糙度,并测试涂层的接触角、结合强度以及体外生物活性。结果经过MAO处理后,钛合金表面可成功生长出多孔陶瓷涂层,Ca-GP参与了MAO涂层形成。当Ca-GP的质量浓度为8g/L时,涂层非常粗糙,Ca和Mg的原子数分数分别为7.56%和1.74%。随着Ca-GP浓度的增加,微孔均匀性变好,表面微裂纹减少,且钙磷原子比(Ca/P)显著提高。在含8、10g/L的Ca-GP溶液中,制备的涂层以Ti、锐钛矿和金红石型TiO_(2)组成为主;在12 g/L的Ca-GP溶液中生成的涂层,Ca/P原子比可达1.77,含有TiP_(2)O_(7)、Mg_(3)(PO_(4))_(2)和少量HA。Ca-GP能显著增加涂层的粗糙度,且稍微增加涂层与基体之间的结合强度。接触角测试结果表明,Ca-GP能明显改善涂层的亲水性。结论随着Ca-GP浓度增加,涂层中钙含量增加,表明钙离子通过扩散进入MAO涂层中。在含12 g/L Ca-GP溶液中制备的涂层,含TiP_(2)O_(7)、Mg_(3)(PO_(4))_(2)和HA,且Ca/P原子比与HA中的Ca/P原子比接近。模拟体液中浸泡试验结果表明,添加12g/L Ca-GP制备的MAO样品,表面形成了大量颗粒状HA,表现出优异的体外生物活性。Titanium alloys have been widely used as implant materials due to their low density and elastic modulus,good biocompatibility and excellent corrosion resistance.However,they belong to bio-inert materials,which prevents the titanium implant from tightly bonding with the bone tissue.As a surface treatment method,micro-arc oxidation(MAO)can effectively improve the property of titanium alloys but may generate industrial wastewater.Therefore,selecting environmental friendly electrolytes to prepare high bioactive MAO coatings on the surface of titanium alloys will become the investigation focus.In this study,the environmentally friendly sodium phytate(Na12Phy)was used as the organic phosphorus-containing electrolyte.In addition,calcium gluconate(CaGlu_(2)),magnesium gluconate(MgGlu_(2))and calcium glycerophosphate(Ca-GP),commonly used in food and pharmaceutical industries,were separately selected as the calcium and magnesium sources in the coatings.Three anodic coatings were prepared by MAO treatment under constant voltage mode in a base solution containing 20.19 g/L CaGlu_(2),6.24 g/L MgGlu_(2),5 g/L Na12Phy and 1.3 g/L phosphoric acid(H3PO_(4))added with 8,10 and 12 g/L Ca-GP.Coating surface morphology,chemical composition,phase structure,elemental existing stage,and roughness were analyzed by scanning electron microscope(SEM),energy dispersive X-sight spectrophotometer(EDS),X-ray diffraction(XRD),X-ray photoelectron spectrophotometer(XPS)and Atomic Force Microscope(AFM).In addition,static contact angle,bond strength and in vitro bioactivity of three MAO coatings were also measured.After MAO treatment,ceramic coatings with porous characteristics were successfully developed on titanium alloys and Ca-GP took part in coating formation.When Ca-GP was 8 g/L,the developed coating was very rough with evident micro cracks and its amounts of Ca and Mg elements were separately 7.56at.%and 1.74at.%.With the increasing Ca-GP concentration,the coating uniformity about surface micro pores became well with less micro cracks.The inc

关 键 词：钛合金 微弧氧化 钙磷比 HA 生物活性 

分 类 号：TG174.4[金属学及工艺—金属表面处理]