钛材表面耐腐蚀涂层的构建及其生物响应
发布时间：2018-08-12 14:19
【摘要】：钛及钛合金是目前临床上最常用的医用金属材料。因其具有优异的机械性能和良好的生物相容性,钛材植入体被广泛地用于骨、关节和牙齿等硬组织的修复与替换。尽管钛材能在空气中自发氧化形成二氧化钛保护层从而具有良好的抗腐蚀性能,但在人体复杂的生理侵蚀环境中,仅有几纳米厚的氧化层极易受力脱落,而人体内的低氧环境限制了受损氧化层的重新形成。上述问题在植入体细菌感染或炎症反应的情况下尤其严重,这是由于细菌感染以及炎症反应会引起植入体表面的局部酸化,加剧腐蚀过程。因而,对钛材表面改性提升其耐腐蚀性能具有重大研究意义。适宜的表面改性不仅可保留钛材优良的机械性能,还可根据实际应用需求赋予其相应的表面特性,如耐腐蚀性、耐磨性、生物相容性以及抗菌性等。本论文利用聚合物辅助沉积技术(PAD)以及微弧氧化技术(MAO)在钛材表面构建了一系列具有促成骨、抗菌以及抗磨损的耐腐蚀涂层,并在体外对其生物学性能进行初步评价。主要内容和结论如下:1.基于聚合物辅助沉积技术构建具有良好耐腐蚀性和生物相容性的氧化钽涂层为了提高钛材表面耐腐蚀性能,利用聚合物辅助沉积技术(PAD)在钛材表面构建了具有良好耐腐蚀性能的氧化钽涂层。通过扫描电子显微镜(SEM)、原子力显微镜(AFM)、X射线光电子谱(XPS)以及接触角测试等对涂层的理化性质进行表征。利用电化学工作站和划痕仪测量了涂层的动电位极化曲线和结合力,结果表明,该涂层具有良好的耐腐蚀性能和较高的结合强度。此外体外细胞实验显示,与纯钛相比,该氧化钽涂层更有利于成骨细胞的粘附与增殖。本研究提供了一种构建具有耐腐性和良好生物相容性钛基材的新方法。2.基于微弧氧化技术构建具有良好耐腐蚀性和生物相容性的氧化钽/氧化钛复合涂层为了提高氧化钽涂层的构建效率并降低其构建成本。利用微弧氧化技术在钛材表面构建了氧化钽/氧化钛复合涂层。采用原子力显微镜、扫描电子显微镜、X射线衍射(XRD)、X射线能谱仪(EDS)、X射线光电子谱、接触角测试以及电化学工作站等技术对涂层的表面形貌、化学成分、晶体结构和耐腐蚀性能进行检测。结果显示,该涂层主要由氧化钽和氧化钛构成,且涂层能封堵微弧氧化产生的微孔结构,从而具有优异的耐腐蚀性能。此外,细胞活性(CCK-8)、碱性磷酸酶(ALP)、矿化、PCR等体外细胞实验表明,与纯钛相比,具有氧化钽/氧化钛复合涂层的钛材能促进成骨细胞的增殖与分化。本研究为高效构建具有良好生物相容性的耐腐蚀涂层提供新途径。3.基于微弧氧化技术构建具有良好耐腐蚀性能和抗菌性能的介孔硅复合涂层植入体的细菌感染是临床最严重的术后并发症之一,也是导致植入失败的主要原因。而假体植入后的4-6 h通常被认为是细菌感染的关键时期,鉴于此,本章将介孔硅纳米颗粒通过微弧氧化技术沉积到钛材表面与二氧化钛氧化物一起形成复合涂层,并以此为载体加载阳离子抗菌药物奥替尼啶,最终构建出具有良好耐腐蚀能力的抗菌性涂层。通过透射电子显微镜(TEM)、扫描电子显微镜、原子力显微镜、X射线光电子谱、X射线能谱仪、电化学工作站以及接触角测试等对复合涂层的理化性质进行表征。结果显示,介孔硅颗粒被均匀地沉积到钛材表面,大部分介孔硅颗粒形态完整。电化学研究表明,与纯钛相比,该复合涂层具有更高的耐腐蚀潜能。利用大肠杆菌和金黄色葡萄球菌作为模式细菌研究钛基材的抗菌性能,同时通过CCK-8、ALP、矿化等体外细胞实验考察材料对细胞增殖和分化的影响。结果表明,载有奥替尼啶的介孔硅复合涂层表现出较强的早期抗菌能力以及良好的生物相容性。本研究为构建具有抗菌性能的耐腐蚀涂层提供新技术。4.基于微弧氧化技术构建具有良好耐腐蚀和耐磨性能的实心二氧化硅纳米颗粒复合涂层植入体在体内的磨损在所难免,而磨损产生的磨屑会沉积在周围组织之中,进而诱发组织慢性炎症和植入体周围骨溶,甚至可能导致植入体无菌性松动。因此,为了提高钛材的耐磨性能,本章利用微弧氧化技术将实心二氧化硅纳米颗粒掺入到钛材表面氧化层中,构建了二氧化硅纳米颗粒复合涂层。通过透射电子显微镜、扫描电子显微镜、原子力显微镜、X射线光电子谱以及接触角检测对样品进行表征。结果表明实心二氧化硅纳米颗粒被均匀地掺入、包裹在钛材的氧化层中。电化学研究和摩擦磨损测试表明:掺入的实心二氧化硅纳米颗粒能显著地提高钛材的耐腐蚀和耐磨损性能。细胞实验表明二氧化硅纳米颗粒复合涂层具有与纯钛相近的生物相容性。本研究为提高钛材的耐磨性提供了一种新思路。
[Abstract]:Titanium and titanium alloys are currently the most commonly used medical metal materials in clinic. Because of their excellent mechanical properties and good biocompatibility, titanium implants are widely used in the repair and replacement of hard tissues such as bones, joints and teeth. Corrosive properties, but only a few nanometers thick oxide layer is liable to fall off under stress in a complex physiological environment, and hypoxia in the human body limits the formation of the damaged oxide layer. Local acidification of the implant surface aggravates the corrosion process. Therefore, it is of great significance to study the surface modification of titanium to improve its corrosion resistance. In this paper, a series of anti-corrosion coatings were prepared on titanium by PAD and MAO, and their biological properties were evaluated in vitro. The main contents and conclusions are as follows: 1. Tantalum oxide coatings with good corrosion resistance and biocompatibility were prepared on the surface of titanium by polymer assisted deposition (PAD) in order to improve the corrosion resistance of titanium. The tantalum oxide coatings with good corrosion resistance were prepared by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and joining. The electrochemical workstation and scratch tester were used to measure the potentiodynamic polarization curves and adhesion of the coatings. The results showed that the coatings had good corrosion resistance and high bonding strength. In addition, in vitro cell experiments showed that the tantalum oxide coating was more favorable to the formation of the coatings than pure titanium. Bone cell adhesion and proliferation.This study provides a new method to construct titanium substrate with good corrosion resistance and biocompatibility.2.TaO/TiO composite coating with good corrosion resistance and biocompatibility was constructed based on micro-arc oxidation technology to improve the construction efficiency and reduce the construction cost of TaO coating. Tantalum oxide/titanium oxide composite coatings were fabricated on titanium surface by micro-arc oxidation. The surface morphology, chemical composition, crystal structure and corrosion resistance of the coatings were characterized by atomic force microscopy, scanning electron microscopy, X-ray diffraction (XRD), X-ray energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy, contact angle measurement and electrochemical workstation. The results show that the coating is mainly composed of tantalum oxide and titanium oxide, and the coating can block the micro-porous structure produced by micro-arc oxidation, so it has excellent corrosion resistance. In addition, cell activity (CCK-8), alkaline phosphatase (ALP), mineralization, PCR and other in vitro cell experiments show that compared with pure titanium, the coating has tantalum oxide / titanium oxide composite. Titanium coated materials can promote the proliferation and differentiation of osteoblasts. This study provides a new way to construct highly effective corrosion-resistant coatings with good biocompatibility. 3. Bacterial infection of mesoporous silicon composite coated implants with good corrosion resistance and antibacterial properties is the most serious postoperative complication in clinic. In this chapter, mesoporous silica nanoparticles were deposited on the surface of titanium by micro-arc oxidation to form composite coatings with titanium dioxide, and then loaded with cationic antimicrobial agents. Otenidine was used to construct antibacterial coatings with good corrosion resistance. The physical and chemical properties of the coatings were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray energy spectrometry (XES), electrochemical workstation and contact angle test. Most of the mesoporous silicon particles were uniformly deposited on the surface of titanium. Electrochemical studies showed that the composite coatings had higher corrosion resistance than pure titanium. The antibacterial properties of titanium substrate were studied by using E. coli and Staphylococcus aureus as model bacteria. Cell experiments such as CCK-8, ALP and mineralization were carried out in vitro. The results showed that the composite coatings containing otinidine exhibited strong early antibacterial activity and good biocompatibility. This study provides a new technology for the construction of corrosion resistant coatings with antibacterial properties. 4. The composite coatings based on micro-arc oxidation technology have good corrosion resistance and wear resistance. The wear of solid silica nanoparticles coated implants is unavoidable in vivo, and the wear debris deposits in the surrounding tissues, which induces chronic inflammation and osteolysis around the implants, and may even lead to aseptic loosening of the implants. The solid silica nanoparticles were incorporated into the oxide layer on the surface of titanium material by micro-arc oxidation technology, and the composite coating was constructed. The samples were characterized by transmission electron microscopy, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy and contact angle measurement. The results of electrochemical study and friction and wear tests show that the solid silica nanoparticles can significantly improve the corrosion resistance and wear resistance of titanium. Cell experiments show that the silica nanoparticles composite coating has similar biocompatibility with pure titanium. It provides a new idea for improving wear resistance of titanium materials.
【学位授予单位】：重庆大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TG174.4
本文编号：2179316
[Abstract]:Titanium and titanium alloys are currently the most commonly used medical metal materials in clinic. Because of their excellent mechanical properties and good biocompatibility, titanium implants are widely used in the repair and replacement of hard tissues such as bones, joints and teeth. Corrosive properties, but only a few nanometers thick oxide layer is liable to fall off under stress in a complex physiological environment, and hypoxia in the human body limits the formation of the damaged oxide layer. Local acidification of the implant surface aggravates the corrosion process. Therefore, it is of great significance to study the surface modification of titanium to improve its corrosion resistance. In this paper, a series of anti-corrosion coatings were prepared on titanium by PAD and MAO, and their biological properties were evaluated in vitro. The main contents and conclusions are as follows: 1. Tantalum oxide coatings with good corrosion resistance and biocompatibility were prepared on the surface of titanium by polymer assisted deposition (PAD) in order to improve the corrosion resistance of titanium. The tantalum oxide coatings with good corrosion resistance were prepared by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and joining. The electrochemical workstation and scratch tester were used to measure the potentiodynamic polarization curves and adhesion of the coatings. The results showed that the coatings had good corrosion resistance and high bonding strength. In addition, in vitro cell experiments showed that the tantalum oxide coating was more favorable to the formation of the coatings than pure titanium. Bone cell adhesion and proliferation.This study provides a new method to construct titanium substrate with good corrosion resistance and biocompatibility.2.TaO/TiO composite coating with good corrosion resistance and biocompatibility was constructed based on micro-arc oxidation technology to improve the construction efficiency and reduce the construction cost of TaO coating. Tantalum oxide/titanium oxide composite coatings were fabricated on titanium surface by micro-arc oxidation. The surface morphology, chemical composition, crystal structure and corrosion resistance of the coatings were characterized by atomic force microscopy, scanning electron microscopy, X-ray diffraction (XRD), X-ray energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy, contact angle measurement and electrochemical workstation. The results show that the coating is mainly composed of tantalum oxide and titanium oxide, and the coating can block the micro-porous structure produced by micro-arc oxidation, so it has excellent corrosion resistance. In addition, cell activity (CCK-8), alkaline phosphatase (ALP), mineralization, PCR and other in vitro cell experiments show that compared with pure titanium, the coating has tantalum oxide / titanium oxide composite. Titanium coated materials can promote the proliferation and differentiation of osteoblasts. This study provides a new way to construct highly effective corrosion-resistant coatings with good biocompatibility. 3. Bacterial infection of mesoporous silicon composite coated implants with good corrosion resistance and antibacterial properties is the most serious postoperative complication in clinic. In this chapter, mesoporous silica nanoparticles were deposited on the surface of titanium by micro-arc oxidation to form composite coatings with titanium dioxide, and then loaded with cationic antimicrobial agents. Otenidine was used to construct antibacterial coatings with good corrosion resistance. The physical and chemical properties of the coatings were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray energy spectrometry (XES), electrochemical workstation and contact angle test. Most of the mesoporous silicon particles were uniformly deposited on the surface of titanium. Electrochemical studies showed that the composite coatings had higher corrosion resistance than pure titanium. The antibacterial properties of titanium substrate were studied by using E. coli and Staphylococcus aureus as model bacteria. Cell experiments such as CCK-8, ALP and mineralization were carried out in vitro. The results showed that the composite coatings containing otinidine exhibited strong early antibacterial activity and good biocompatibility. This study provides a new technology for the construction of corrosion resistant coatings with antibacterial properties. 4. The composite coatings based on micro-arc oxidation technology have good corrosion resistance and wear resistance. The wear of solid silica nanoparticles coated implants is unavoidable in vivo, and the wear debris deposits in the surrounding tissues, which induces chronic inflammation and osteolysis around the implants, and may even lead to aseptic loosening of the implants. The solid silica nanoparticles were incorporated into the oxide layer on the surface of titanium material by micro-arc oxidation technology, and the composite coating was constructed. The samples were characterized by transmission electron microscopy, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy and contact angle measurement. The results of electrochemical study and friction and wear tests show that the solid silica nanoparticles can significantly improve the corrosion resistance and wear resistance of titanium. Cell experiments show that the silica nanoparticles composite coating has similar biocompatibility with pure titanium. It provides a new idea for improving wear resistance of titanium materials.
【学位授予单位】：重庆大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TG174.4
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相关期刊论文 前2条
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2 席晓光;;微弧氧化技术述评[J];表面技术;2007年04期
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