目的 为拓宽轻量化镁金属材料的应用范围,在纯镁表面复合超声微弧氧化技术和硅烷偶联法制备复合涂层,研究陶瓷颗粒和绿原酸对复合涂层功能性的影响。方法 实验借助超声辅助微弧氧化（UMAO）工艺,在镁材表面制备UMAO底层,然后采用硅烷偶联（SCA）法在UMAO层上负载陶瓷颗粒（BCP）和绿原酸（CA）,制备SCA-CA-BCP顶层。采用X射线衍射仪、扫描电子显微镜和能谱仪,对涂层的物相结构、元素构成进行表征;采用接触角测量仪测定涂层表面润湿性能;采用销-盘式摩擦磨损试验机和附着力自动划痕仪分析涂层耐磨性和结合性;通过体外浸泡实验和动电位极化测试方法评估涂层生物活性、耐腐蚀性能。结果 UMAO/SCA-CA-BCP涂层由Ca10(PO4)6(OH)2、Ca3(PO4)2、Mg2SiO4及MgO相组成,经模拟体液（SBF）浸泡后,UMAO/SCA-CA-BCP涂层表面对模拟体液中钙、磷离子亲和力较高,负载陶瓷颗粒和绿原酸后更易于诱导磷灰石沉积。UMAO/SCA-CA-BCP涂层接触角为78.14°,纯镁表面经复合改性处理后,更接近疏水性涂层。UMAO/SCA-CA-BCP涂层的临界载荷为12.0 N,涂层为化学结合,结合力增强。动电位极化测试数据表明：UMAO/SCA-CA-BCP涂层的腐蚀电流密度为2.427×10-6 A/cm2,负载陶瓷颗粒和绿原酸后UMAO/SCA-CA-BCP涂层的耐蚀性更好。结论 镁基UMAO/SCA-CA-BCP复合涂层的耐蚀性、结合性和生物活性均优于镁基UMAO涂层,负载陶瓷颗粒和绿原酸后有效提升了复合涂层的功能性。
Abstract
Magnesium metal material is recognized as a lightweight structural material, and is known as "green material" because of its unique properties. It is widely used in construction, aerospace, automobile manufacturing, ship manufacturing, electrical and electronic and biomedical industries. However, magnesium metal is chemically active and prone to corrosion in humid and acidic environments. It can remain stable only in dry environments, kerosene and sodium hydroxide solutions, which limits its wide application. The effective method to improve the surface functionality of the magnesium alloy is the surface treatment technology, which forms a protective film on the magnesium alloy surface. Composites can be combined by selecting materials with different complementary advantages, which can avoid the performance limitations of a single material and improve the performance of the material. Micro-arc oxidation technology has attracted wide attention in surface treatment of magnesium alloy due to its simple preparation process, green environmental protection characteristics, and high applicability to metals such as magnesium, aluminum and titanium. Although the rough porous structure of micro-arc oxidation is conducive to cell adhesion, the porous outer layer of the micro-arc oxidation coating is easy to accumulate corrosive medium and become an erosion channel. Therefore, in practical research, the micro-arc oxidation coating is mostly sealed. At present, there are few studies on the function of the magnesium-based micro-arc oxidation coating reinforced by ceramic particles and traditional Chinese medicine extracts on the magnesium alloy surface. Therefore, in this paper, an UMAO/SCA-CA-BCP coating is prepared by sealing the micro-arc oxidation coating through silane coupling. The UMAO/SCA-CA-BCP coating has corrosion resistance, biological activity, wear resistance and other functions. Firstly, the ultrasonic micro-arc oxidation (UMAO) layer was prepared on the surface of pure magnesium by ultrasonic micro-arc oxidation technology, and then the UMAO/SCA-CA-BCP coating was prepared by loading ceramic particles (BCP) and chlorogenic acid (CA) on the UMAO layer through silane coupling (SCA). The functional coating element composition and phase structure were characterized by scanning electron microscope and X-ray diffractometer, and the surface morphology of the coating was observed. The coating wettability was measured by contact angle measuring instrument. The effects of loading ceramic particles and chlorogenic acid on the wear resistance and adhesion of the coating were analyzed by pin-on-disk friction and wear tester and adhesion automatic scratch tester. The coating biological activity was evaluated by immersion test, and the coating corrosion resistance in a simulated environment was systematically analyzed by potentiodynamic polarization test. The UMAO/SCA-CA-BCP coating is composed of Ca10(PO4)6(OH)2, Ca3(PO4)2, Mg2SiO4 and MgO phases. After immersion in simulated body fluid (SBF), the surface of the UMAO/SCA-CA-BCP coating has a high affinity for calcium and phosphorus ions in SBF, and it is easier to induce apatite deposition after loading ceramic particles and chlorogenic acid. The contact angle of the UMAO/SCA-CA-BCP coating is 78.14°. After the surface of pure magnesium is modified by composite modification, the contact angle of the coating surface increases, which is closer to the hydrophobic coating. The critical load of the UMAO/SCA-CA-BCP coating is 12.0 N. The coating is chemically bonded and the bonding force is enhanced. Potentiodynamic polarization experiments show that the corrosion current density of the UMAO/SCA-CA-BCP coating (2.427×10-6 A/cm2) is much lower than that of the pure Mg substrate (1.756 9×10-5 A/cm2), and the corrosion resistance of the UMAO/SCA-CA-BCP coating is improved. The corrosion resistance, adhesion and bioactivity of the Mg-based UMAO/SCA-CA-BCP composite coating are better than those of the Mg-based UMAO coating. The loading of ceramic particles and chlorogenic acid effectively improves the functionality of the composite coating.
关键词
镁 /
硅烷偶联剂 /
双相磷酸钙 /
绿原酸 /
超声微弧氧化 /
功能性 /
耐蚀性 /
生物活性
Key words
magnesium /
silane coupling agent /
biphasic calcium phosphate /
chlorogenic acid /
ultrasonic micro-arc oxidation /
functionality /
corrosion resistance /
biological activity
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基金
哈尔滨学院青年博士科研启动基金项目（HUDF2023102）
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