鈦材表面耐腐蝕涂層的構(gòu)建及其生物響應(yīng)
發(fā)布時(shí)間：2018-08-12 14:19
【摘要】：鈦及鈦合金是目前臨床上最常用的醫(yī)用金屬材料。因其具有優(yōu)異的機(jī)械性能和良好的生物相容性,鈦材植入體被廣泛地用于骨、關(guān)節(jié)和牙齒等硬組織的修復(fù)與替換。盡管鈦材能在空氣中自發(fā)氧化形成二氧化鈦保護(hù)層從而具有良好的抗腐蝕性能,但在人體復(fù)雜的生理侵蝕環(huán)境中,僅有幾納米厚的氧化層極易受力脫落,而人體內(nèi)的低氧環(huán)境限制了受損氧化層的重新形成。上述問(wèn)題在植入體細(xì)菌感染或炎癥反應(yīng)的情況下尤其嚴(yán)重,這是由于細(xì)菌感染以及炎癥反應(yīng)會(huì)引起植入體表面的局部酸化,加劇腐蝕過(guò)程。因而,對(duì)鈦材表面改性提升其耐腐蝕性能具有重大研究意義。適宜的表面改性不僅可保留鈦材優(yōu)良的機(jī)械性能,還可根據(jù)實(shí)際應(yīng)用需求賦予其相應(yīng)的表面特性,如耐腐蝕性、耐磨性、生物相容性以及抗菌性等。本論文利用聚合物輔助沉積技術(shù)(PAD)以及微弧氧化技術(shù)(MAO)在鈦材表面構(gòu)建了一系列具有促成骨、抗菌以及抗磨損的耐腐蝕涂層,并在體外對(duì)其生物學(xué)性能進(jìn)行初步評(píng)價(jià)。主要內(nèi)容和結(jié)論如下:1.基于聚合物輔助沉積技術(shù)構(gòu)建具有良好耐腐蝕性和生物相容性的氧化鉭涂層為了提高鈦材表面耐腐蝕性能,利用聚合物輔助沉積技術(shù)(PAD)在鈦材表面構(gòu)建了具有良好耐腐蝕性能的氧化鉭涂層。通過(guò)掃描電子顯微鏡(SEM)、原子力顯微鏡(AFM)、X射線光電子譜(XPS)以及接觸角測(cè)試等對(duì)涂層的理化性質(zhì)進(jìn)行表征。利用電化學(xué)工作站和劃痕儀測(cè)量了涂層的動(dòng)電位極化曲線和結(jié)合力,結(jié)果表明,該涂層具有良好的耐腐蝕性能和較高的結(jié)合強(qiáng)度。此外體外細(xì)胞實(shí)驗(yàn)顯示,與純鈦相比,該氧化鉭涂層更有利于成骨細(xì)胞的粘附與增殖。本研究提供了一種構(gòu)建具有耐腐性和良好生物相容性鈦基材的新方法。2.基于微弧氧化技術(shù)構(gòu)建具有良好耐腐蝕性和生物相容性的氧化鉭/氧化鈦復(fù)合涂層為了提高氧化鉭涂層的構(gòu)建效率并降低其構(gòu)建成本。利用微弧氧化技術(shù)在鈦材表面構(gòu)建了氧化鉭/氧化鈦復(fù)合涂層。采用原子力顯微鏡、掃描電子顯微鏡、X射線衍射(XRD)、X射線能譜儀(EDS)、X射線光電子譜、接觸角測(cè)試以及電化學(xué)工作站等技術(shù)對(duì)涂層的表面形貌、化學(xué)成分、晶體結(jié)構(gòu)和耐腐蝕性能進(jìn)行檢測(cè)。結(jié)果顯示,該涂層主要由氧化鉭和氧化鈦構(gòu)成,且涂層能封堵微弧氧化產(chǎn)生的微孔結(jié)構(gòu),從而具有優(yōu)異的耐腐蝕性能。此外,細(xì)胞活性(CCK-8)、堿性磷酸酶(ALP)、礦化、PCR等體外細(xì)胞實(shí)驗(yàn)表明,與純鈦相比,具有氧化鉭/氧化鈦復(fù)合涂層的鈦材能促進(jìn)成骨細(xì)胞的增殖與分化。本研究為高效構(gòu)建具有良好生物相容性的耐腐蝕涂層提供新途徑。3.基于微弧氧化技術(shù)構(gòu)建具有良好耐腐蝕性能和抗菌性能的介孔硅復(fù)合涂層植入體的細(xì)菌感染是臨床最嚴(yán)重的術(shù)后并發(fā)癥之一,也是導(dǎo)致植入失敗的主要原因。而假體植入后的4-6 h通常被認(rèn)為是細(xì)菌感染的關(guān)鍵時(shí)期,鑒于此,本章將介孔硅納米顆粒通過(guò)微弧氧化技術(shù)沉積到鈦材表面與二氧化鈦氧化物一起形成復(fù)合涂層,并以此為載體加載陽(yáng)離子抗菌藥物奧替尼啶,最終構(gòu)建出具有良好耐腐蝕能力的抗菌性涂層。通過(guò)透射電子顯微鏡(TEM)、掃描電子顯微鏡、原子力顯微鏡、X射線光電子譜、X射線能譜儀、電化學(xué)工作站以及接觸角測(cè)試等對(duì)復(fù)合涂層的理化性質(zhì)進(jìn)行表征。結(jié)果顯示,介孔硅顆粒被均勻地沉積到鈦材表面,大部分介孔硅顆粒形態(tài)完整。電化學(xué)研究表明,與純鈦相比,該復(fù)合涂層具有更高的耐腐蝕潛能。利用大腸桿菌和金黃色葡萄球菌作為模式細(xì)菌研究鈦基材的抗菌性能,同時(shí)通過(guò)CCK-8、ALP、礦化等體外細(xì)胞實(shí)驗(yàn)考察材料對(duì)細(xì)胞增殖和分化的影響。結(jié)果表明,載有奧替尼啶的介孔硅復(fù)合涂層表現(xiàn)出較強(qiáng)的早期抗菌能力以及良好的生物相容性。本研究為構(gòu)建具有抗菌性能的耐腐蝕涂層提供新技術(shù)。4.基于微弧氧化技術(shù)構(gòu)建具有良好耐腐蝕和耐磨性能的實(shí)心二氧化硅納米顆粒復(fù)合涂層植入體在體內(nèi)的磨損在所難免,而磨損產(chǎn)生的磨屑會(huì)沉積在周圍組織之中,進(jìn)而誘發(fā)組織慢性炎癥和植入體周圍骨溶,甚至可能導(dǎo)致植入體無(wú)菌性松動(dòng)。因此,為了提高鈦材的耐磨性能,本章利用微弧氧化技術(shù)將實(shí)心二氧化硅納米顆粒摻入到鈦材表面氧化層中,構(gòu)建了二氧化硅納米顆粒復(fù)合涂層。通過(guò)透射電子顯微鏡、掃描電子顯微鏡、原子力顯微鏡、X射線光電子譜以及接觸角檢測(cè)對(duì)樣品進(jìn)行表征。結(jié)果表明實(shí)心二氧化硅納米顆粒被均勻地?fù)饺搿阝伈牡难趸瘜又�。電化學(xué)研究和摩擦磨損測(cè)試表明:摻入的實(shí)心二氧化硅納米顆粒能顯著地提高鈦材的耐腐蝕和耐磨損性能。細(xì)胞實(shí)驗(yàn)表明二氧化硅納米顆粒復(fù)合涂層具有與純鈦相近的生物相容性。本研究為提高鈦材的耐磨性提供了一種新思路。
[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.
【學(xué)位授予單位】：重慶大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TG174.4
本文編號(hào)：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.
【學(xué)位授予單位】：重慶大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TG174.4
【參考文獻(xiàn)】
相關(guān)期刊論文 前2條
1 曾麗;張勇;楊旭;忻賢貞;魏斌;;含氟人工唾液對(duì)選擇性激光熔積鈷鉻合金耐腐蝕性的影響[J];上海交通大學(xué)學(xué)報(bào)(醫(yī)學(xué)版);2014年03期
2 席曉光;;微弧氧化技術(shù)述評(píng)[J];表面技術(shù);2007年04期
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