富氧氣氛下鈦合金加工表面氧化膜形成及其生物相容性研究
本文選題:綠色切削 切入點(diǎn):鈦合金植入體 出處:《山東大學(xué)》2016年博士論文
【摘要】:醫(yī)用鈦合金因具有良好的力學(xué)、物理、化學(xué)性能及出色的生物相容性,成為了人造關(guān)節(jié),牙植入體及骨創(chuàng)傷產(chǎn)品等硬組織替代物及修復(fù)物的首選材料。鈦及鈦合金植入體在植入之前需要進(jìn)行表面改性,以提高其耐腐蝕性及生物活性。目前國內(nèi)外鈦合金植入體的表面改性方法均是在機(jī)械加工成形之后,其缺點(diǎn)是工藝鏈長、工藝設(shè)備復(fù)雜、效率低、成本高。鑒于此,本研究提出了一種切削加工成形與表面改性于一體的鈦合金植入體制備新方法;利用切削加工產(chǎn)生的切削熱進(jìn)行表面氧化改性,提高其耐腐蝕性;利用切削加工形成的特定表面形貌提高其生物活性。從可持續(xù)發(fā)展的角度開發(fā)出一種針對鈦合金植入體的新型綠色切削加工制備方法,對縮短工藝鏈、提高效率、降低成本、保護(hù)環(huán)境、提高鈦合金植入體制造技術(shù)水平和產(chǎn)品競爭力有重要作用。主要研究工作如下:首先,基于氧化熱力學(xué)研究鈦合金氧化膜產(chǎn)生的機(jī)理,確定形成致密二氧化鈦膜的條件;谖锢砘瘜W(xué)理論,分析鈦合金氧化過程中鈦離子和氧離子的運(yùn)動規(guī)律,揭示鈦合金氧化速度的主要控制因素。研究結(jié)果表明:形成致密二氧化鈦氧化膜的最佳溫度范圍為600-900℃,此溫度范圍內(nèi)鈦合金氧化速度的主要控制因素為氧離子通過氧化膜的擴(kuò)散速度。其次,基于菲克第一定律及阿列紐斯公式建立鈦合金氧化動力學(xué)模型,研究影響氧化速度的主要因素。采用MATLAB對鈦合金氧化動力學(xué)模型進(jìn)行計算,分析各因素對氧化速度的影響規(guī)律。研究結(jié)果表明:影響鈦合金氧化速度的主要因素為氧化溫度、富氧濃度及富氧壓力、晶粒細(xì)化程度及氧化膜厚度;提高氧化溫度、富氧濃度及富氧壓力、晶粒細(xì)化程度可加速鈦合金的氧化,但氧化膜厚度的增加會降低鈦合金氧化速度。然后,搭建富氧氣氛下切削加工工藝試驗平臺,采用Deform 3D有限元仿真軟件對切削參數(shù)進(jìn)行優(yōu)化,將切削溫度控制在最佳氧化溫度范圍。進(jìn)行不同切削參數(shù)及不同富氧氣氛下切削加工試驗,對鈦合金加工表面氧化膜成分和厚度,表面形貌及表層晶粒進(jìn)行表征,分析切削溫度,富氧濃度和晶粒細(xì)化程度等因素對氧化速度的影響規(guī)律。將試驗結(jié)果與理論結(jié)果對比,富氧氣氛下切削加工能夠顯著提高鈦合金加工表面氧化膜的厚度及致密性,驗證了氧化動力學(xué)模型的正確性。最后,對富氧氣氛下切削加工表面進(jìn)行耐腐蝕性及生物活性評價。通過模擬體液浸泡試驗及電化學(xué)腐蝕試驗,研究富氧氣氛下切削鈦合金表面的腐蝕機(jī)理和主要影響因素。通過體外細(xì)胞培養(yǎng),觀測細(xì)胞的黏附、鋪展、增殖、分化及礦化等細(xì)胞行為,研究加工表面的生物活性,分析加工表面對細(xì)胞行為的調(diào)控機(jī)理。研究結(jié)果表明:富氧氣氛下切削加工生成的氧化膜能夠顯著提高鈦合金的耐腐蝕性,而且表面形成的微/納復(fù)合結(jié)構(gòu)面形貌有利于蛋白質(zhì)的吸附,對細(xì)胞的黏附,鋪展,增殖等細(xì)胞行為有較好的調(diào)控作用,顯著提高了鈦合金的生物活性。
[Abstract]:Medical titanium alloy has good mechanical, physical and chemical properties, biocompatibility and excellent biological, has become the preferred material for artificial joints, dental implants and bone trauma products hard tissue substitute and prosthesis. Titanium and titanium alloy implants require surface modification before implantation, in order to improve its resistance biological activity and corrosion. The surface of titanium alloy at home and abroad of the implant modification methods are after mechanical forming, its disadvantage is the process of chain length, complex process equipment, low efficiency and high cost. In view of this, this study proposes a new method of machining and forming titanium alloy implant surface preparation modified in one of the heat generated by cutting; cutting the surface oxidation modification, improve its corrosion resistance; specific surface morphology formed by cutting to improve its bioactivity. The development from the perspective of sustainable development A new type of green machining system for titanium alloy implant preparation method, to shorten the process chain, improve efficiency, reduce costs, protect the environment, improve the titanium alloy implant manufacturing technology level and product competitiveness has an important role. The main research work is as follows: firstly, based on the mechanism of oxidation of titanium oxide film produced by thermodynamics, to determine the formation of dense titania film. The physical and chemical conditions based on the theory analysis of the motion law of the oxidation process of titanium ions and oxygen ions, the main control reveals the oxidation rate of titanium alloy. The results show that: the optimum temperature range to form a dense oxide film of titanium dioxide is 600-900 DEG C, the main controlling factors of titanium alloy oxidation rate in this temperature range the oxygen ion diffusion through the film speed. Secondly, Fick's first law and Alexyevna Arrhenius formula is set up based on the oxidation of titanium alloy Dynamic model, study main factors affecting the oxidation rate. Using MATLAB to calculate the titanium alloy oxidation kinetics model, analysis of effects of different factors on the oxidation rate. The results show that the main factors affecting the oxidation rate of titanium alloy for the oxidation temperature, oxygen concentration and oxygen pressure, the grain size and film thickness; improve the oxidation temperature, oxygen concentration and oxygen pressure, the degree of grain refinement can accelerate the oxidation of titanium alloy, but the increase of film thickness will reduce the oxidation rate of titanium alloy. Then, the experiment platform in cutting process under oxygen rich atmosphere, the cutting parameters were optimized by using Deform finite element simulation software 3D, the cutting temperature control in the optimal oxidation temperature range cutting test. Different cutting parameters and different oxygen enriched atmosphere, the composition and thickness of oxide film on titanium alloy surface processing, table The grain surface morphology and surface characterization, analysis of influence factors of cutting temperature, oxygen concentration and the degree of grain refinement on the oxidation rate. The experimental results and theoretical results of oxygen enriched atmosphere cutting can increase the thickness and density of the oxide film on the surface of titanium alloy processing, to verify the correctness of the oxidation kinetics model. Finally, to evaluate the corrosion resistance and biological activity of oxygen enriched atmosphere cutting surface. Through the SBF test and electrochemical corrosion test, and the main factors which influence the corrosion mechanism of the surface machining of titanium alloy on the oxygen enriched atmosphere. The cell culture, cell adhesion, observation spreading, proliferation, differentiation and mineralization of cell behavior study on the processing surface, biological activity, analysis of regulation mechanism of machined surface on cell behavior. The results show that: oxygen enriched atmosphere cutting processing The oxide film can significantly improve the corrosion resistance of titanium alloy, and the surface micro / nano composite surface morphology is conducive to protein adsorption, and has a good regulation effect on cell adhesion, spreading, proliferation and other cell behaviors, significantly improving the bioactivity of titanium alloy.
【學(xué)位授予單位】:山東大學(xué)
【學(xué)位級別】:博士
【學(xué)位授予年份】:2016
【分類號】:TG174.4;R318.08
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