本文選題：純鈦 + 微弧氧化��； 參考：《哈爾濱工業(yè)大學》2015年博士論文

【摘要】：本文采用微弧氧化技術(shù)在純鈦表面制備了含鈣、磷、硅和鈉元素的非晶相陶瓷涂層。通過多步微弧氧化處理、熱處理、水熱和水汽處理在所制備微弧氧化涂層表面構(gòu)建了不同尺度的結(jié)構(gòu),同時對涂層的元素化合態(tài)進行了調(diào)控。采用X射線衍射(XRD)、掃描電子顯微鏡(SEM)、透射電子顯微鏡(TEM)、傅立葉變化紅外光譜(FT-IR)、拉曼光譜(Raman)、X-射線光電子譜(XPS)、氮氣吸附、壓汞孔隙測試儀、納米壓痕儀和力學萬能試驗機等分析手段研究了表面調(diào)控前后微弧氧化涂層的組織結(jié)構(gòu)、力學性能和涂層在模擬體液中誘導磷灰石的能力。通過種植體兔脛骨體內(nèi)植入的實驗方法,采用X射線影像、Micro-CT、硬組織切片染色、生物力學測試等分析手段研究了具有不同表面結(jié)構(gòu)和元素化合態(tài)的鈦種植體與骨組織的體內(nèi)相容性、骨整合能力和力學行為。以EDTA-2Na、Ca(CH_3COO)_2·H_2O、Ca(H_2PO_4)_2·H_2O、Na_2SiO_3·9H_2O和NaOH的水溶液為電解液,在純鈦表面制備了含鈣、磷、硅和鈉元素的微弧氧化涂層(MAO涂層)。MAO涂層由非晶相和少量銳鈦礦相組成,含有Ca、P、Si、Na、Ti和O元素。300V下制備的MAO涂層表面具有均勻的微觀多孔結(jié)構(gòu)。隨電壓升高,涂層厚度增加,涂層表面微孔孔徑增大,微孔密度降低,涂層表面Ca、P、Si和Na元素的含量增加,Ti元素含量降低。Ti、O、Ca、P和Si元素在涂層內(nèi)部存在梯度分布。以EDTA-2Na、Ca(CH_3COO)_2·H_2O、Ca(H_2PO_4)_2·H_2O、Na_2SiO_3·9H_2O、NaNO_3和NaOH的水溶液為二步微弧氧化電解液對試樣進行處理,可在MAO涂層表面構(gòu)建亞毫米宏孔結(jié)構(gòu),宏孔內(nèi)生成了致密的Ti_3O_5氧化層。隨NaOH濃度增大,宏孔密度升高,宏孔孔徑減小,宏孔內(nèi)氧化層增厚并引入微量的Ca、P、Si和Na元素。以EDTA-2Na、Ca(CH_3COO)_2·H_2O、Ca(H_2PO_4)_2·H_2O、Na_2SiO_3·9H_2O和NaOH的水溶液為三步微弧氧化電解液對試樣進行處理,在鈦表面形成了完整且具有亞毫米和微米雙級孔隙結(jié)構(gòu)的微弧氧化涂層。宏孔區(qū)域的涂層的微孔密度小于平坦區(qū)域,且宏孔區(qū)域涂層表面生成了Ti-OH和Si-OH官能團。熱處理可調(diào)控MAO涂層表面的微米結(jié)構(gòu)。MAO涂層經(jīng)過800℃空氣氣氛熱處理后,生成銳鈦礦、金紅石和Ca Ti_4(PO_4)_6,涂層表面形貌不變,涂層厚度增加,涂層中C元素幾乎消失。經(jīng)過800℃氬氣保護熱處理后涂層由金紅石和銳鈦礦組成,表面微孔結(jié)構(gòu)消失,生成大量顆粒狀晶體,涂層厚度增加,且在涂層與基體界面處生成β-Ti相變層。水熱和水汽處理均可在MAO涂層表面構(gòu)建納米結(jié)構(gòu)。水熱處理過程中,涂層中Ca、P、Si和Na元素溶入溶液中。隨NaOH濃度增大,HA晶體的生成量先增多后減少,OH-離子對涂層的腐蝕作用增強,涂層表面微孔結(jié)構(gòu)消失,生成排布密集的H_2Ti5O11·H_2O納米棒。水汽處理過程中,涂層表面Ca、P、Si和Na元素含量基本不變。隨NaOH濃度增大,涂層厚度減小,HA晶體生成量增多但長徑比減小,表面生成Ti-OH官能團。當水汽處理的NaOH濃度為1mol/L時,涂層表面出現(xiàn)大量(NaOH)_2(H_2O)7沉積物。在SBF浸泡過程中,MAO涂層中的Na+離子能夠和SBF中的H_3O+離子發(fā)生離子交換形成Si-OH,增加磷灰石的形核。多步微弧氧化處理后試樣表面宏孔區(qū)域的磷灰石誘導能力優(yōu)于平坦區(qū)域的MAO涂層,原因是宏孔結(jié)構(gòu)增大了試樣的比表面積,有利于Si-OH的生成,且三步微弧氧化涂層宏孔區(qū)域內(nèi)含有Ti-OH和Si-OH官能團,增強了磷灰石的形核能力。800℃氬氣保護熱處理后涂層的磷灰石誘導能力增強,原因是涂層表面形成了金紅石,而金紅石(101)晶面與HA(0001)晶面具有良好的晶體學匹配,可為磷灰石的形核提供良好的形核位點。NaOH溶液水汽處理后的涂層表面形成HA和Ti-OH官能團,磷灰石誘導能力明顯增強。所有涂層誘導的磷灰石都含有HPO_42-和CO_32-等官能團,且表面具有納米網(wǎng)狀多孔結(jié)構(gòu)。多步微弧氧化處理試樣表面的宏孔結(jié)構(gòu)可與樹脂膠嚙合,涂層的破壞強度明顯提高。NaOH溶液水汽處理后,涂層的硬度和彈性模量基本不變,涂層內(nèi)部缺陷減少,涂層的結(jié)合強度明顯增大。800℃熱處理后的涂層中生成脆性相,涂層的結(jié)合強度明顯降低。三步微弧氧化制備的表面改性鈦種植體植入兔脛骨內(nèi),體內(nèi)相容性優(yōu)良,在植入期間無排斥感染現(xiàn)象。種植體周圍骨組織吸收良好,骨組織生長入種植體表面亞毫米宏孔中。種植體與骨組織的結(jié)合強度明顯增強,壓出種植體的表面宏孔中可觀察到殘留的嚙合骨組織。水汽處理改性的微弧氧化鈦種植體植入兔脛骨內(nèi),表現(xiàn)出優(yōu)異的骨-種植體界面結(jié)合,骨組織沿種植體表面緊密生長。種植體與骨組織的結(jié)合強度明顯增強,壓出種植體表面可觀察到殘留骨組織。綜上所述,多步微弧氧化處理、熱處理、水熱和水汽處理可在MAO涂層表面構(gòu)建不同尺度的結(jié)構(gòu),有利于磷灰石的形成。采用三步微弧氧化處理和水汽處理的微弧氧化鈦種植體展現(xiàn)出優(yōu)異的力學性能和骨整合能力。
[Abstract]:In this paper, the amorphous ceramic coatings containing calcium, phosphorus, silicon and sodium are prepared by micro arc oxidation on the surface of pure titanium. By multistep micro arc oxidation treatment, heat treatment, water heat and water vapor treatment, the structure of different scales on the surface of the prepared micro arc oxidation coating is constructed. At the same time, the composition of the elements in the coating is regulated by X ray diffraction. Radiation (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fu Liye change infrared spectroscopy (FT-IR), Raman spectroscopy (Raman), X- ray photoelectron spectroscopy (XPS), nitrogen adsorption, mercury porograph test instrument, nano indentation instrument and mechanical universal testing machine were used to study the microstructure and force of the micro arc oxidation coating before and after the surface control. The ability to induce apatite in simulated body fluids. Through the experimental method of implantation in the rabbit tibia, X ray images, Micro-CT, hard tissue section staining, biomechanical test and other analytical methods were used to study the compatibility of titanium implants with different surface structures and elements in the body and bone tissue. With EDTA-2Na, Ca (CH_3COO) _2. H_2O, Ca (H_2PO_4) _2, H_2O, Na_2SiO_3. 9H_2O and NaOH as the electrolyte, the microarc oxidation coatings containing calcium, phosphorus, silicon and sodium are prepared on the surface of pure titanium with the amorphous and a small amount of anatase. The surface of the prepared MAO coating has a homogeneous microporous structure. With the increase of the voltage, the thickness of the coating increases, the pore size of the coating increases, the density of micropores is reduced, the content of Ca, P, Si and Na on the coating surface increases, the content of Ti elements decreases.Ti, O, Ca, P and Si elements exist in the gradient distribution of the coating. EDTA-2Na H_2PO_4) _2. H_2O, Na_2SiO_3. 9H_2O, NaNO_3 and NaOH solution are treated by two step micro arc oxidation electrolyte. The submillimeter macroporous structure can be constructed on the surface of MAO coating, and the dense Ti_3O_5 oxidation layer is formed in the macro hole. With the increase of the NaOH concentration, the macropore density is increased, the pore diameter is reduced, the oxidation layer in the macro hole is thickened and introduced into the micropore. The amount of Ca, P, Si and Na elements. The samples were treated with EDTA-2Na, Ca (CH_3COO) _2, H_2O, Ca (H_2PO_4) _2. Aqueous solution as three step micro arc oxidation electrolyte, and formed a complete micro arc oxidation coating with submillimeter and micron two-stage pore structure on the titanium surface. The micropore density of the coating in the macroporous area was small. In the flat area, Ti-OH and Si-OH functional groups are formed on the coating surface of the macroporous region. The microstructural.MAO coating on the surface of the MAO coating can be treated by heat treatment at 800 C air atmosphere. After the heat treatment, the anatase, rutile and Ca Ti_4 (PO_4) _6 are formed, the surface morphology of the coating is unchanged, the coating thickness increases, and the C element in the coating almost vanishes. After 800 degrees centigrade, the coating is almost disappeared. After heat treatment, the coating is composed of rutile and anatase, and the surface microporous structure disappears and produces a large number of granular crystals. The thickness of the coating increases, and the phase transition layer of the coating is formed at the interface between the coating and the matrix. The surface of the coating can be constructed on the surface of the MAO coating. During the hydrothermal treatment, the Ca, P, Si and Na elements in the coating are in the process of hydrothermal treatment. When the concentration of NaOH increases, the formation of HA crystal increases first and then decreases, the corrosion of the coating is enhanced by the OH- ion, the microporous structure of the coating is disappearing and the H_2Ti5O11 H_2O nanorods are formed to be dispersed. In the process of water vapor treatment, the content of Ca, P, Si and Na element in the coating surface is basically unchanged. With the increase of NaOH concentration, the thickness of the coating is reduced. Small, HA crystal production increased but the length diameter ratio decreased, and the surface generated Ti-OH functional groups. When the NaOH concentration of the water vapor treatment was 1mol/L, a large number of (NaOH) _2 (H_2O) 7 sediments appeared on the coating surface. During SBF immersion, the Na+ ions in the MAO coating could be exchanged with the H_3O+ ions in SBF and increased the nucleation of the apatite. The apatite induction ability of the macroporous area on the surface of the sample surface after micro arc oxidation is superior to the MAO coating in the flat area. The reason is that the macro pore structure increases the specific surface area of the specimen and is beneficial to the formation of Si-OH, and the three step micro arc oxidation coating contains Ti-OH and Si-OH functional groups in the macro pore region, and the apatite nucleation capacity is enhanced at.800 C argon protection. The apatite induction ability of the coating is enhanced after heat treatment, due to the formation of rutile on the surface of the coating, and the rutile (101) crystal face has a good crystallographic match with the HA (0001) crystal mask, which can provide a good nucleation site for apatite nucleation site.NaOH solution on the surface of the coating to form HA and Ti-OH functional groups, and the apatite induction ability. All coating induced apatite contains the functional groups such as HPO_42- and CO_32-, and the surface has a nano mesh porous structure. The macroporous structure of the surface of the sample surface can be meshed with the resin adhesive. The damage strength of the coating is obviously improved by the water vapor treatment of.NaOH solution, and the hardness and modulus of elasticity of the coating are basically unchanged. The internal defects of the coating decreased and the bonding strength of the coating increased obviously at.800 C. The bonding strength of the coating decreased obviously. The surface modified titanium implants prepared by three step micro arc oxidation were implanted in the tibia of the rabbit tibia, with good compatibility in the body and no rejection during the implantation. Well, the bone tissue grows into the submillimeter macroporous surface of the implant. The bonding strength of the implant and bone tissue is enhanced obviously. The residual meshing bone can be observed in the macroporous surface of the implant. The modified microarc titanium oxide implant in the water vapor treatment is implanted into the rabbit tibia, showing excellent bone implant interface and bone tissue along the implant. The bonding strength of the implant surface is close. The bond strength of the implant and bone tissue is enhanced obviously, and the residual bone can be observed on the surface of the implant. In summary, the multi step micro arc oxidation treatment, heat treatment, water heat and water vapor treatment can construct different scales on the surface of the MAO coating, which is beneficial to the formation of apatite. The three step micro arc oxidation place is used. Microarc titanium oxide implant treated with water and steam showed excellent mechanical properties and osseointegration ability.

【學位授予單位】：哈爾濱工業(yè)大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：TG174.4;R318.08
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本文編號：1825314