本文選題：工業(yè)純鈦 + 陽極氧化��； 參考：《昆明理工大學(xué)》2017年博士論文

【摘要】：陽極氧化制備的Ti表面氧化膜具有出色的耐蝕性能、良好的生物相容性和優(yōu)異的光催化性等優(yōu)點(diǎn),其制備過程簡單、成本低、污染小,因此被廣泛地應(yīng)用于腐蝕防護(hù)、生物醫(yī)學(xué)、新能源材料、光水解制氫等諸多領(lǐng)域。本論文以工業(yè)純鈦(TA2)為基體材料,對其陽極氧化過程開展研究。通過對TA2表面氧化膜形貌、結(jié)構(gòu)、結(jié)晶行為和電化學(xué)特性的表征和計(jì)算,分析氧化膜結(jié)構(gòu)特征和相構(gòu)成,研究氧化膜的微觀結(jié)構(gòu)、成膜過程和結(jié)晶機(jī)理。為此,本論文在0.5 MH2SO4電解液中,系統(tǒng)研究陽極氧化電位,陽極氧化次數(shù)以及機(jī)械研磨對氧化膜結(jié)構(gòu)和性能的影響。采用XPS深度濺射法,定量分析陽極氧化膜不同深度下Ti氧化物的結(jié)構(gòu)、價(jià)態(tài)和含量;建立氧化膜中,各種氧化物以及氫氧化物的含量與氧化膜深度的關(guān)系;研究了氧化膜的結(jié)構(gòu)特性、電化學(xué)特性和缺陷的擴(kuò)散系數(shù)特性,構(gòu)建氧化膜形成的點(diǎn)陣缺陷模型,研究形成機(jī)理和影響因素。結(jié)果表明,隨著電位的提高,氧化膜厚度增大,結(jié)晶率提高,耐蝕性能增強(qiáng)。高電位促進(jìn)氧化膜中Ti4+化合物的形成和銳鈦礦形核。氧化膜由Ti02、Ti(OH)4、TiO2H2O、Ti203和TiO等組成,含量隨深度呈連續(xù)變化。氧化膜的生成與O空位和Ti陽離子間隙物在氧化膜中的擴(kuò)散有關(guān)。在Ti/氧化膜界面發(fā)生氧空位的生成,氧化膜/溶液界面發(fā)生氧空位的湮滅,Ti陽離子間隙物在氧化膜/溶液界面生成,Ti/氧化膜界面上湮滅,氧化膜同時(shí)向基體和溶液方向生長。在上述研究基礎(chǔ)上,針對陽極氧化膜孔隙率較高的情況,對TA2進(jìn)行二次陽極氧化處理。采用二次氧化陽極氧化處理,可以提高氧化膜的厚度,降低孔隙率。首次加壓為30 V,終電位為40 V時(shí),氧化膜厚度提高了約17.3%,表面微孔基本消失。首次加壓處理形成了較為致密的初始氧化膜,在二次加壓處理時(shí),降低了析氧反應(yīng)的密度,從而使二次氧化形成的氧化膜孔隙率明顯降低。二次氧化處理有助于氧化膜向基體一側(cè)生長,導(dǎo)致氧化膜厚度增加。同時(shí),二次氧化處理增強(qiáng)了 TA2的耐蝕性,二次陽極氧化首次加壓30 V,二次加壓40 V處理后樣品的自腐蝕電位和自腐蝕電流密度,比直接加壓40 V樣品的自腐蝕電位和自腐蝕電流密度分別提高了 0.16 VSCE,下降了約一個(gè)數(shù)量級,可以減少腐蝕傾向,降低腐蝕速率。由于表面形貌對氧化膜的形成過程有顯著影響,對TA2進(jìn)行機(jī)械研磨處理,細(xì)化表面晶粒、增加壓應(yīng)力、缺陷和表面電子能密度,提高表面活性。機(jī)械研磨處理可以明顯增加氧化膜厚度,提高其耐蝕性。研究發(fā)現(xiàn)表面機(jī)械研磨處理可以改變氧化膜的形核方式,由于TA2表面能的提高降低了不同Ti化合物的形核功,形核過程由連續(xù)形核轉(zhuǎn)變?yōu)樗矔r(shí)形核,形核率顯著提高;同時(shí)高的表面能為氧化膜的生長提供足夠的能量,加速了空位和離子的擴(kuò)散過程,導(dǎo)致O空位和Ti陽離子間隙物在氧化膜中的擴(kuò)散速率,比未經(jīng)過表面機(jī)械研磨處理樣品提高了 2個(gè)數(shù)量級。最后形成的氧化膜和直接陽極氧化的氧化膜相比,自腐蝕電位提高了0.462 VSCE,自腐蝕電流密度下降約0.005 A.cm-2%。陽極氧化TA2氧化膜在NaCl溶液中,氧化膜孔洞內(nèi)外易形成"氧濃差電池",使Cl-向孔洞處移動(dòng),孔洞內(nèi)部形成了無氧、低pH和高Cl-濃度的腐蝕環(huán)境,造成孔內(nèi)氧化膜的破裂,使Ti基體暴露在腐蝕介質(zhì)中,平衡電位迅速下降,和孔外部構(gòu)成"接觸腐蝕電偶"。"腐蝕電偶"對腐蝕加速效果的影響和孔隙率有關(guān),孔隙率較低時(shí),腐蝕速率明顯降低。二次陽極氧化處理可以明顯改善表面結(jié)構(gòu),降低氧化膜孔隙率,減小孔洞對氧化膜耐蝕性的影響。當(dāng)表面孔洞幾乎消失時(shí),氧化膜中的缺陷密度成為影響氧化膜耐蝕性的主要因素,NaCl溶液中的Cl-可以吸附在氧化膜中的點(diǎn)缺陷上,擾亂了 Mott-Schottkypair反應(yīng),在Ti基體/氧化膜界面上產(chǎn)生空隙,造成氧化膜和Ti基底分離,進(jìn)而在內(nèi)部壓應(yīng)力的作用下,導(dǎo)致了氧化膜破裂。機(jī)械研磨處理通過改變氧化膜形核模式和促進(jìn)O空位和Ti陽離子間隙物的擴(kuò)散等方式,明顯降低了氧化膜的缺陷密度,有效抑制了 Cl-在氧化膜表面的吸附,最終提高了氧化膜的耐蝕性。
[Abstract]:The Ti surface oxide film prepared by anodic oxidation has excellent corrosion resistance, good biocompatibility and excellent photocatalytic activity. Its preparation process is simple, low cost and low pollution. Therefore, it is widely used in many fields such as corrosion protection, biomedicine, new energy materials, and light hydrolytic hydrogen production. This paper is based on industrial pure titanium (TA2). The anodic oxidation process of the matrix was studied. By characterizing and calculating the morphology, structure, crystallization behavior and electrochemical properties of the TA2 surface oxide film, the structure characteristics and phase composition of the oxide film were analyzed. The microstructure, the film forming process and the crystallization mechanism of the oxide film were studied. In this paper, the anode was systematically studied in the 0.5 MH2SO4 electrolyte. The effect of oxidation potential, anodic oxidation number and mechanical grinding on the structure and properties of the oxide film. The structure, valence and content of Ti oxide under different depths of anodic oxide film were quantitatively analyzed by XPS depth sputtering; the relationship between the content of various oxides and hydroxides in the oxide film and the depth of the oxide film was established; and the oxide film was studied. The structure characteristics, electrochemical properties and the diffusion coefficient characteristics of the defects are used to construct a lattice defect model formed by the oxide film and study the formation mechanism and influencing factors. The results show that the thickness of the oxide film increases with the increase of the potential, the crystallization rate increases, and the corrosion resistance is enhanced. The high potential promotes the formation of Ti4+ compounds in the oxide film and the anatase nucleation. The oxide film consists of Ti02, Ti (OH) 4, TiO2H2O, Ti203 and TiO. The content of the oxide film is continuously changed with the depth. The formation of the oxide film is related to the diffusion of the O vacancy and the Ti cation gap in the oxide film. The formation of oxygen vacancies in the Ti/ oxide film interface, the annihilation of oxygen vacancies in the oxide film / solution interface, and the Ti cation gap in the oxide film / solution. The interface is formed, the Ti/ oxide film is annihilated at the interface, and the oxide film grows to the direction of the matrix and the solution. On the basis of the above study, two anodized TA2 treatments are carried out for the anode oxidation film with high porosity. The thickness of the oxide film can be increased and the porosity can be reduced by the two oxidation anodizing treatment. It is first pressurized to 30 V, When the final potential is 40 V, the thickness of the oxide film increases about 17.3% and the surface micropores basically disappear. The initial pressure treatment forms a more compact initial oxide film, which reduces the density of the oxygen evolution reaction at the two times of pressure treatment, thus reducing the porosity of the oxide film formed by the two oxidation. The two oxidation treatment helps the oxide film to the matrix. The growth of the oxide film increases the thickness of the oxide film. At the same time, the corrosion resistance of TA2 is enhanced by the two oxidation treatment. The self corrosion potential and the self corrosion current density of the samples after the two anodization for the first time are 30 V and the two times pressurized 40 V. The self corrosion potential and the self corrosion current density of the samples with direct pressure 40 V are increased by 0.16 VSCE, respectively. The corrosion tendency and corrosion rate can be reduced by about one order of magnitude. The surface morphology has a significant influence on the formation process of the oxide film. The surface grain is refined, the surface grain is refined, the pressure stress, the defect and surface electron energy density are increased, and the surface activity is improved because the surface morphology has a significant influence on the formation of the oxide film. The thickness of the oxide film can be obviously increased by mechanical grinding. It is found that the surface mechanical grinding can change the nucleation of the oxide film. Because of the increase of the TA2 surface energy, the nucleation work of different Ti compounds is reduced. The nucleation process is transformed from the continuous nucleation to the instantaneous nucleation, and the nucleation rate is significantly increased. At the same time, the high surface can provide enough energy for the growth of the oxide film and accelerate the growth of the oxide film. The diffusion process of the vacancy and ion causes the diffusion rate of the O vacancy and the Ti cation gap in the oxide film, which is 2 orders of magnitude higher than that without the surface mechanical grinding. In the end, the corrosion potential of the oxide film is 0.462 VSCE higher than that of the oxide film directly anodized, and the corrosion current density decreases by about 0. 05 A.cm-2%. anodized TA2 oxide film in the NaCl solution, the oxygen concentration difference battery is easily formed inside and outside the pores of the oxide film, which causes the Cl- to move to the hole. The corrosion environment of oxygen free, low pH and high Cl- concentration is formed inside the hole, resulting in the rupture of the oxide film in the hole and exposing the Ti matrix to the corrosive medium, the equilibrium potential drops rapidly, and the pore structure is formed outside the hole. "Contact corrosion galvanic". "Corrosion galvanic" affects the effect of corrosion acceleration and porosity, and the corrosion rate decreases obviously when the porosity is low. The two anodized treatment can obviously improve the surface structure, reduce the porosity of the oxide film and reduce the effect of holes on the corrosion resistance of the oxide film. The defect density becomes the main factor affecting the corrosion resistance of the oxide film. The Cl- in the NaCl solution can adsorb on the point defects in the oxide film, disrupt the Mott-Schottkypair reaction, produce the gap in the interface of the Ti matrix / oxide film, and cause the separation of the oxide film and the Ti substrate, which leads to the rupture of the oxide film under the action of internal pressure. By changing the nucleation mode of the oxide film and promoting the diffusion of the O vacancy and the Ti cation gap, the grinding treatment obviously reduced the defect density of the oxide film, effectively inhibited the adsorption of Cl- on the surface of the oxide film, and finally improved the corrosion resistance of the oxide film.

【學(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TG174.451

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