口腔疾病防治 ›› 2021, Vol. 29 ›› Issue (11): 733-739.doi: 10.12016/j.issn.2096-1456.2021.11.002

• 基础研究 • 上一篇    下一篇

钛表面微弧氧化-微波水热法铜铌涂层的制备及抗菌性研究

王天琦1(),杜青2,谢伟丽1()   

  1. 1.哈尔滨医科大学口腔医学院修复科,黑龙江 哈尔滨(150001)
    2.哈尔滨工业大学材料科学与工程学院,黑龙江 哈尔滨(150001)
  • 收稿日期:2021-03-04 修回日期:2021-04-28 出版日期:2021-11-20 发布日期:2021-07-20
  • 通讯作者: 谢伟丽 E-mail:349530444@qq.com;xwl811@126.com
  • 作者简介:王天琦,医师,硕士,Email: 349530444@qq.com
  • 基金资助:
    黑龙江省科技攻关项目(GC12C305-3)

Preparation and antibacterial properties of a copper-niobium coating on a titanium surface by a microarc oxidation-microwave hydrothermal method

WANG Tianqi1(),DU Qing2,XIE Weili1()   

  1. 1. Department of Prosthodontics, College of Stomatology, Harbin Medical University, Harbin 150001, China
    2. School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
  • Received:2021-03-04 Revised:2021-04-28 Online:2021-11-20 Published:2021-07-20
  • Contact: Weili XIE E-mail:349530444@qq.com;xwl811@126.com
  • Supported by:
    Science and Technology Key Projects of Heilongjiang Province(GC12C305-3)

摘要:

目的 在钛表面通过微弧氧化-微波水热两步法制备铜铌抗菌涂层,对其表面结构和抗菌性能进行探究。方法 以包覆微弧氧化涂层(MAO组)的钛为基体,通过微波水热法分别在低(MHL-Cu组)、中(MHM-Cu组)、高(MHH-Cu组)浓度的氯化铜溶液及草酸铌(MH-Nb组)溶液中引入铜、铌元素。通过能谱分析确定引入铜最多的组分,与草酸铌混合微波水热制备铜铌复合涂层(MH-Cu/Nb组)。通过扫描电子显微镜、X射线能谱仪及X射线衍射仪对各组试件微观结构、元素分布和物相成分进行表征;贴膜法测定涂层对大肠杆菌和金黄色葡萄球菌的抑菌效果。结果 X射线能谱仪显示MHL-Cu、MHM-Cu、MHH-Cu组表面均引入了Cu元素,各组铜元素原子比例依次为(0.68 ± 0.04)%、(1.17 ± 0.06)%、(1.64 ± 0.03)%,组间差异有统计学意义( P< 0.01)。扫描电子显微镜显示MAO组表面呈火山口状多孔结构,MHL-Cu、MHM-Cu、MHH-Cu、MH-Nb、MH-Cu/Nb组均保持微孔形貌,随Cu2+浓度增加,粗糙度增加;其中MH-Nb、MH-Cu/Nb组同时出现沟壑状结构。X射线衍射仪显示MAO组涂层主要由钛和锐钛矿相TiO2组成,MHL-Cu、MHM-Cu、MHH-Cu、MH-Nb、MH-Cu/Nb组涂层主要由锐钛矿和金红石相TiO2组成。与MAO组菌落相比,MHH-Cu、MH-Nb、MH-Cu/Nb组大肠杆菌和金黄色葡萄球菌均有不同程度减少,差异具有统计学意义(P< 0.001);MHH-Cu组与MH-Cu/Nb组相比,菌落数差异无统计学意义(P> 0.05)。结论 微弧氧化-微波水热两步法制备的含铜铌粗糙多孔的涂层可有效抑制大肠杆菌和金黄色葡萄球菌生长。

关键词: 钛; 涂层; 表面处理; 微弧氧化; 微波水热; 铜; 铌; 抗菌; 大肠杆菌; 金黄色葡萄球菌

Abstract:

Objective To prepare a copper-nobium antibacterial coating on a titanium surface by a microarc oxidation-microwave hydrothermal two-step method and to study its surface structure and antibacterial properties. Methods Using titanium coated with a microarc oxidation coating (MAO group) as the substrate, copper and niobium were introduced by a microwave hydrothermal method in low (MHL-Cu group), medium (MHM-Cu group) and high (MHH-Cu group) copper chloride solutions and niobium oxalate (MH-Nb group) solutions, respectively. The component with the highest copper content was determined by energy spectrum analysis, and the copper-niobium composite coating (MH-Cu/Nb group) was prepared by microwave hydrothermal mixing with niobium oxalate. The microstructure, element distribution and phase composition of the specimens were characterized by scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction, and the bacteriostatic effect of the coating onEscherichia coliand Staphylococcus aureus was determined by the film method. Results Energy dispersive spectrometry showed that Cu was introduced onto the surface of the MHL-Cu, MHM-Cu, and MHH-Cu groups, and the atomic ratios of copper in each group were (0.68 ± 0.04)%,(1.17 ± 0.06)%, and (1.64 ± 0.03)%. The difference between groups was statistically significant (P< 0.01). Scanning electron microscopy showed a crater-like porous structure on the surface of the MAO group, and the MHL-Cu, MHM-Cu, MHH-Cu, MH-Nb, MH-Cu/Nb groups maintained micropore morphology. The roughness increased with increasing Cu2+ concentration, in which the MH-Nb and MH-Cu/Nb groups showed gully like structures simultaneously. X-ray diffraction showed that the coating of the MAO group was mainly composed of titanium and anatase phase TiO2, and the coatings of the MHL-Cu, MHM-Cu, MHH-Cu, MH-Nb, MH-Cu/Nb groups were mainly composed of anatase and rutile phase TiO2. Compared with the MAO group, Escherichia coli and Staphylococcus aureus in the MHH-Cu, MH-Nb, MH-Cu/Nb groups decreased to varying degrees, with significant differences (P< 0.001); compared with the MH-Cu/Nb group, the colony number difference had statistical significance (P> 0.05).Conclusion The rough, porous coating containing copper and niobium prepared by the microarc oxidation-microwave hydrothermal two-step method can effectively inhibit the growth ofEscherichia coli and Staphylococcus aureus.

Key words: titanium; coating; surface treatment; microarc oxidation; microwave hydrothermal; copper; niobium; antibacterial; Escherichia coli; Staphylococcus aureus

中图分类号: 

  • R78