本文關(guān)鍵詞： 醫(yī)用金屬 鈦合金 陽極氧化 納米多孔結(jié)構(gòu) 抗菌　出處：《北京科技大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：鈦及鈦合金由于其優(yōu)異的力學(xué)性能和良好的生物相容性,在生物醫(yī)用材料領(lǐng)域具有廣泛的應(yīng)用。然而研究者經(jīng)過長期臨床應(yīng)用與研究發(fā)現(xiàn),現(xiàn)有的鈦植入體仍然有許多亟待解決的問題。例如植入體與骨組織之間的彈性模量不匹配造成骨的吸收及植入體的松動,骨組織整合再生能力差,植入后感染等問題。通過對鈦金屬材料進(jìn)行表面改性或采用模量較低的β型合金,可以有效的提高植入體材料的生物力學(xué)匹配性,改善生物相容性及生物活性,降低植入后細(xì)菌感染發(fā)炎的幾率等問題。本論文采用電化學(xué)陽極氧化技術(shù)對鈦進(jìn)行了表面改性,制備得到了具有微納尺度的三維貫通多孔結(jié)構(gòu)的二氧化鈦氧化層,并在此基礎(chǔ)上于氧化層表面進(jìn)一步構(gòu)筑了一層含有納米銀／磷酸八鈣的復(fù)合涂層,對改性后材料表面及涂層的微觀形貌、物相組成、元素組分進(jìn)行了檢測和分析,對不同結(jié)構(gòu)的氧化層生成機(jī)理進(jìn)行了闡明,并對材料進(jìn)行了體外生物學(xué)評價(jià)。同時(shí)采用陽極氧化技術(shù)對具有β相的鈦鈮合金表面改性,制備得到了納米管陣列,并對氧化層的結(jié)構(gòu)及性能進(jìn)行了系統(tǒng)的研究和表征,探索了鈮元素和氧化電壓對表面改性納米管陣列結(jié)構(gòu)和表面性能的影響。本文的研究內(nèi)容及結(jié)果具體包括以下三個(gè)方面：(1)通過陽極氧化法,在鈦金屬表面構(gòu)筑了一層具有三維貫通多孔結(jié)構(gòu)的氧化層,孔徑大小可以通過電流密度等實(shí)驗(yàn)參數(shù)進(jìn)行調(diào)控,孔徑分布為30～200nm。三維多孔氧化層的形成與反應(yīng)時(shí)間、電解質(zhì)組分和電流密度密切相關(guān)。相比于類似實(shí)驗(yàn)條件下制備得到的納米管陣列氧化層,具有三維貫通多孔結(jié)構(gòu)氧化層的材料具有更好的力學(xué)性能如硬度、模量以及更強(qiáng)的界面結(jié)合力,而且具有更好的耐腐蝕性能。此外體外生物學(xué)評價(jià)顯示,該氧化層有利于成骨細(xì)胞的黏附與增值,從而在生物醫(yī)用方面顯示了潛在的應(yīng)用價(jià)值。(2)在金屬鈦表面進(jìn)行三維貫通多孔修飾的基礎(chǔ)上,利用光還原和仿生礦化技術(shù)相結(jié)合的方法進(jìn)一步在材料表面構(gòu)筑了一層納米銀／磷酸八鈣復(fù)合涂層。該涂層中銀以單質(zhì)的形式存在,其含量可控,分布均勻。在表面構(gòu)筑復(fù)合涂層后材料粗糙度進(jìn)一步增加,并顯示出超親水性。此外,實(shí)驗(yàn)結(jié)果顯示,該涂層能夠?qū)崿F(xiàn)銀的持久緩釋,對大腸桿菌和金黃色葡萄球菌均表現(xiàn)出了很好的抗菌活性,其抗菌率可分別達(dá)到93%和87%以上。(3)通過陽極氧化法在不同鈮含量的鈦鈮合金表面制備得到了納米管陣列。并對納米管陣列生長的影響因素進(jìn)行了系統(tǒng)研究。研究發(fā)現(xiàn)合金中的鈮禽量的增加不改變表面納米管陣列形貌。氧化電壓的增大,能夠增大納米管陣列的管徑和長度。在對合金表面納米管陣列修飾后,材料的親水性變得非常優(yōu)異。且這種親水性與表面納米管陣列尺寸的密切相關(guān),管徑越小,親水性越好。對材料進(jìn)行熱處理會使其表面親水性變差。
[Abstract]:Titanium and titanium alloys have been widely used in biomedical materials due to their excellent mechanical properties and good biocompatibility. The existing titanium implants still have many problems to be solved, such as the mismatch of elastic modulus between the implants and bone tissues, resulting in bone resorption and loosening of implants, and poor ability of bone tissue integration and regeneration. Problems such as infection after implantation. Through surface modification of titanium metal materials or the use of 尾-type alloys with lower modulus, the biomechanical matching, biocompatibility and bioactivity of the implants can be improved effectively. In order to reduce the incidence of bacterial infection and inflammation after implantation, the surface modification of titanium was carried out by electrochemical anodization. Three-dimensional porous TIO _ 2 oxide layer with micro-nano scale was prepared, and a composite coating containing nano-silver / octadecalcium phosphate was further constructed on the surface of the oxide layer. The microstructure, phase composition and elemental composition of the modified surface and coating were examined and analyzed, and the formation mechanism of the oxide layer with different structures was clarified. At the same time, the surface of Ti-Niobium alloy with 尾 phase was modified by anodizing technology, and nanotube arrays were prepared. The structure and properties of the oxide layer were systematically studied and characterized. The effects of niobium and oxidation voltage on the structure and surface properties of surface modified nanotube arrays were investigated. An oxide layer with three dimensional perforated porous structure was constructed on the surface of titanium metal. The pore size can be controlled by experimental parameters such as current density. The pore size distribution is 30 ~ 200 nm. The formation of three-dimensional porous oxide layer is closely related to reaction time, electrolyte composition and current density, compared with the prepared nanotube array oxide layer under similar experimental conditions. The materials with three dimensional penetrating porous structure have better mechanical properties such as hardness, modulus and interfacial adhesion, as well as better corrosion resistance. In addition, biological evaluation in vitro shows that the material has better mechanical properties such as hardness, modulus and interfacial adhesion. The oxide layer is conducive to the adhesion and proliferation of osteoblasts, which shows potential application value in biomedical applications. 2) on the basis of three-dimensional porous modification on the surface of titanium metal. A nano-silver / octadecalcium phosphate composite coating was further constructed on the material surface by combining photoreduction and biomimetic mineralization technology. The silver in the coating exists in the form of a single substance and its content is controllable. After the composite coating was constructed on the surface, the roughness was further increased and the superhydrophilicity was shown. In addition, the experimental results showed that the coating could realize the sustained release of silver. It showed good antibacterial activity against Escherichia coli and Staphylococcus aureus. The antimicrobial rate was 93% and 87%, respectively. Nanotube arrays were prepared on the surface of titanium and niobium alloys with different niobium content by anodizing method. The factors affecting the growth of nanotube arrays were systematically studied. It was found that the increase of niobium content in the alloy did not change. Morphology of surface nanotubes array and increase of oxidation voltage. It can increase the diameter and length of nanotube arrays. The hydrophilicity of the materials becomes very good after the modification of nanotube arrays on the alloy surface, and this hydrophilicity is closely related to the size of surface nanotubes arrays. The smaller the diameter, the better the hydrophilicity. Heat treatment of the material will make its surface hydrophilicity worse.
【學(xué)位授予單位】：北京科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TG174.4;R318.08

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