【摘要】：生物材料的化學(xué)組成及其表面拓?fù)浣Y(jié)構(gòu)在調(diào)整蛋白質(zhì)吸附、細(xì)胞粘附、鋪展、遷移、增殖和分化等生物學(xué)行為中起著關(guān)鍵的作用。由于鈦及鈦合金具有優(yōu)越的理化性能,其已被廣泛應(yīng)用于各種植入體,例如骨科、牙科及心血管支架等。然而,鈦基材表面具有生物惰性,其與周邊骨組織形成骨整合的能力較弱,延緩了組織愈合的時(shí)間。因此,改善鈦植入體表面生物性能具有重要的臨床意義。鈦基材表面羥基磷灰石(HAP)復(fù)合涂層的制備成為了一種重要的表面生物活性改良手段。本課題在鈦表面制備了FHAP/ZrO2、Sr FHAP、Sr-Ca-P/明膠、MnHAP和HAP/Ca SiO3復(fù)合涂層。采用掃描電子顯微鏡(SEM)、X-射線衍射儀(XRD)、傅立葉變換紅外光譜儀(FTIR)、X-射線光電子能譜儀(EDS)等分析設(shè)備,研究了HAP復(fù)合涂層的相結(jié)構(gòu)、形貌和膜層成分等特性。對復(fù)合涂層的耐生理液腐蝕性、力學(xué)性能和細(xì)胞相容性進(jìn)行了評價(jià)。主要研究內(nèi)容和結(jié)論如下:采用恒電流沉積法在鈦表面制備出摻氟羥基磷灰石/氧化鋯(FHAP/Zr O2)復(fù)合涂層。氟離子摻雜進(jìn)入HAP晶體結(jié)構(gòu),磷灰石的晶粒變小,結(jié)晶度增加,涂層為納米級針狀形貌。涂層致密且分布均勻,厚度約為10μm。ZrO2作為緩沖層,很好地緩解了FHAP與Ti之間熱膨脹系數(shù)的差異,拉力測試結(jié)果表明,即便是在生理溶液中浸泡2w以后,FHAP/ZrO2復(fù)合涂層仍然具有較好的結(jié)合強(qiáng)度。體外溶解實(shí)驗(yàn)表明,FHAP/ZrO2復(fù)合涂層具有較單相HAP涂層更低的溶解度,即更好的穩(wěn)定性。極化測試表明FHAP/ZrO2復(fù)合涂層具有較HAP強(qiáng)的耐生理液腐蝕性。細(xì)胞粘附實(shí)驗(yàn)結(jié)果表明FHAP/ZrO2復(fù)合涂層具有良好的細(xì)胞相容性,成骨細(xì)胞大量、緊密地粘附其上,形態(tài)良好。為了考察氟離子和鍶離子的摻雜對涂層特性的影響,采用電沉積法在鈦表面制備出鍶和氟共摻雜羥基磷灰石(Sr FHAP)復(fù)合涂層。復(fù)合涂層分布均勻且致密,為納米級的針狀形貌。氟離子和鍶離子共摻雜進(jìn)入HAP晶體結(jié)構(gòu),氟作為抗溶解元素以維持涂層的長期穩(wěn)定性,鍶作為溶解元素以促進(jìn)涂層生物活性和細(xì)胞相容性。鈣離子溶解實(shí)驗(yàn)表明,SrFHAP復(fù)合涂層在2w內(nèi)具有良好的生理穩(wěn)定性。在模擬體液中,SrFHAP復(fù)合涂層表現(xiàn)出較純HAP更強(qiáng)的耐腐蝕性。體外細(xì)胞檢測中,復(fù)合涂層對成骨細(xì)胞粘附與增殖的促進(jìn)效果最好,表明其具有良好細(xì)胞相容性。為了考察鍶離子和明膠的摻雜對涂層特性的影響,采用電沉積法在鈦表面制備了摻鍶磷酸鈣/明膠(Sr-Ca-P/明膠)復(fù)合涂層。鍶離子摻雜進(jìn)入Ca-P晶體結(jié)構(gòu),明膠與Sr-Ca-P雜化為Sr-Ca-P/明膠復(fù)合涂層,涂層整體為多孔狀形貌,涂層表面粗糙而不均勻,多孔結(jié)構(gòu)對于成骨細(xì)胞的粘附非常有利。Sr2+離子和明膠均勻地?fù)诫s和分散在Ca-P涂層中。涂層的厚度約為10μm,涂層與基材之間無剝離和/或界面處開裂的現(xiàn)象。拉力測試實(shí)驗(yàn)表明Sr-Ca-P/明膠復(fù)合涂層與基底的結(jié)合強(qiáng)度為5.6MPa±1.8MPa,其結(jié)合強(qiáng)度較弱。極化測試表明Sr-Ca-P/明膠復(fù)合涂層具有較強(qiáng)的耐腐蝕性。成骨細(xì)胞在復(fù)合涂層表面粘附性良好,MTT實(shí)驗(yàn)表明成骨細(xì)胞在復(fù)合涂層表面的增殖能力較好,則Sr-Ca-P/明膠復(fù)合涂層具有較好的細(xì)胞相容性。采用電沉積法在鈦表面制備出摻錳羥基磷灰石(MnHAP)復(fù)合涂層。Ti表面經(jīng)過熱堿浸泡后形成了Na2TiO3薄膜,該膜的存在可以增加MnHAP復(fù)合涂層與鈦基材之間的結(jié)合強(qiáng)度。復(fù)合涂層分布均勻且致密,其由針狀晶體聚集而成,厚度約為10μm。拉力測試結(jié)果表明MnHAP復(fù)合涂層與基底的結(jié)合強(qiáng)度約為純HAP涂層的2倍,基本滿足國際標(biāo)準(zhǔn)的要求。極化曲線的分析得知,MnHAP復(fù)合涂層使得Ti的耐腐蝕性得到較大增強(qiáng)。Mn HAP涂層在模擬體液中能迅速誘導(dǎo)類骨磷灰石成核和生長,表明涂層具有良好的生物活性。細(xì)胞在MnHAP復(fù)合涂層表面呈現(xiàn)出典型的成骨細(xì)胞粘附表型,錳元素的摻雜使得細(xì)胞在MnHAP復(fù)合涂層表面的增殖活力表現(xiàn)良好,涂層的細(xì)胞相容性良好。采用電沉積法在由納米SiO2、Ca(NO3)2和NH4H2PO4組成的電解液中,在鈦表面制備出了HAP/CaSiO3復(fù)合涂層。HAP/CaSiO3復(fù)合涂層表面由內(nèi)部致密的納米級針須狀晶體和外表微米級的孔狀結(jié)構(gòu)組成,這種多孔結(jié)構(gòu)對于新骨的形成非常有利。X-射線衍射結(jié)果表明復(fù)合涂層主要包括HAP相和Ca Si O3相。拉力測試結(jié)果表明HAP/CaSiO3復(fù)合涂層與Ti基底的結(jié)合強(qiáng)度為19.1±4.7MPa,這個(gè)值已經(jīng)基本滿足了國際標(biāo)準(zhǔn)的要求。極化測試表明HAP/CaSiO3復(fù)合涂層具有較強(qiáng)的耐腐蝕性。MC3T3-E1成骨細(xì)胞在HAP/Ca SiO3復(fù)合涂層表面的增殖能力顯著地高于在HAP表面,表明HAP/CaSiO3復(fù)合涂層具有較好的細(xì)胞相容性。綜上所述,本研究采用電沉積法進(jìn)行多種離子摻雜磷酸鈣活性涂層的構(gòu)建,對磷酸鈣復(fù)合涂層的電沉積制備技術(shù)進(jìn)行了理論和實(shí)驗(yàn)研究。本研究著重考察氟離子,鍶離子,錳離子,硅離子和明膠的存在對復(fù)合涂層物理性能、化學(xué)性能以及生物活性的影響。成骨所需的多種微量元素(如氟、鍶、錳、硅等)被成功地引入到Ca-P涂層中,為進(jìn)一步研究磷酸鈣復(fù)合涂層在骨缺損修復(fù)中的臨床應(yīng)用提供初步的實(shí)驗(yàn)依據(jù)。
[Abstract]:The chemical composition of biological material and its surface topological structure play a key role in adjusting the biological behavior of protein adsorption, cell adhesion, spreading, migration, proliferation and differentiation. Titanium and titanium alloys have superior physical and chemical properties, which have been widely used in various implants, such as orthopedic, dental, and cardiovascular stents. However, that surface of the titanium base material has a biological inertia, which is weak in the ability of the peripheral bone tissue to form a bone, which delay the time of tissue healing. Therefore, it is of great clinical significance to improve the biological performance of the surface of the titanium implant. The preparation of the hydroxyapatite (HAP) composite coating on the surface of the titanium substrate has become an important means to improve the surface biological activity. FHAP/ ZrO2, Sr FHAP, Sr-Ca-P/ gelatin, MnHAP and HAP/ Ca-SiO3 composite coatings were prepared on the surface of titanium. The phase structure, morphology and composition of the HAP composite coating were studied by means of scanning electron microscope (SEM), X-ray diffractometer (XRD), Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (EDS). The corrosion resistance, mechanical property and cell compatibility of the composite coating were evaluated. The main research contents and conclusions are as follows: a compound coating of a fluorine-doped hydroxyapatite/ oxide-oxide (FHAP/ Zr O2) is prepared on the surface of the titanium by a constant current deposition method. And the crystal grains of the apatite are smaller and the crystallinity is increased, and the coating is a nano-scale needle-like shape. The results show that the FHAP/ ZrO2 composite coating still has good bonding strength even after soaking for 2w in the physiological solution. In vitro dissolution experiments show that the FHAP/ ZrO2 composite coating has lower solubility, that is, better stability, than that of the single-phase HAP coating. The polarization tests show that the FHAP/ ZrO2 composite coating has high corrosion resistance to the HAP. The results of cell adhesion show that the FHAP/ ZrO2 composite coating has good cell compatibility, and the osteoblast is large and closely adhered to it with good morphology. In order to investigate the influence of the doping of fluoride ion and fluoride ion on the properties of the coating, a composite coating of codoped hydroxyapatite (Sr FHAP) was prepared on the surface of titanium by electrodeposition. The composite coating is uniform and dense, and is a nanometer-scale needle-like shape. The fluoride ion and the ionization ions are co-doped into the HAP crystal structure, and fluorine is used as an anti-dissolution element to maintain the long-term stability of the coating, and is used as a dissolution element to promote the bioactivity and the cell compatibility of the coating. The calcium ion dissolution test shows that the SrFHAP composite coating has good physiological stability in 2w. In the simulated body fluid, the SrFHAP composite coating shows stronger corrosion resistance than the pure HAP. In vitro cell detection, the effect of the composite coating on the adhesion and proliferation of the osteoblast is the best, indicating that it has good cell compatibility. In order to investigate the effect of doping on the properties of the coating, a composite coating of calcium-doped calcium phosphate/ gelatin (Sr-Ca-P/ gelatin) was prepared on the surface of titanium by electrodeposition. The Ca-P crystal structure, the gelatin and the Sr-Ca-P are mixed into the Sr-Ca-P/ gelatin composite coating, the whole of the coating is a porous shape, the surface of the coating is rough and uneven, and the adhesion of the porous structure to the osteoblast is very favorable. Sr2 + ions and gelatin are uniformly doped and dispersed in the Ca-P coating. The coating has a thickness of about 10. m u.m, and there is no peeling and/ or cracking at the interface between the coating and the substrate. The tensile test shows that the bonding strength between the Sr-Ca-P/ gelatin composite coating and the substrate is 5.6 MPa and 1.8 MPa, and the bonding strength is weak. The polarization tests show that the Sr-Ca-P/ gelatin composite coating has strong corrosion resistance. The adhesion of the osteoblast to the surface of the composite coating was good, and the MTT assay showed that the proliferation ability of the osteoblast on the surface of the composite coating was good, and the Sr-Ca-P/ gelatin composite coating had better cell compatibility. The composite coating of Mn-doped hydroxyapatite (MnHAP) was prepared by electrodeposition. And the surface of the Ti is soaked by a hot alkali to form a Na2TiO3 thin film, and the bonding strength between the MnHAP composite coating and the titanium substrate can be increased. The composite coating is uniform and dense, which is formed by the aggregation of needle-like crystals with a thickness of about 10. m u.m. The tensile test results show that the bonding strength between the composite coating of the MnHAP and the substrate is about 2 times that of the pure HAP coating, which basically meets the requirements of the international standard. The analysis of the polarization curve shows that the corrosion resistance of the Ti is greatly enhanced by the composite coating of MnHAP. The Mn-HAP coating can rapidly induce the nucleation and growth of the bone-like apatite in the simulated body fluid, indicating that the coating has good biological activity. The cell has a typical osteoblast adhesion phenotype on the surface of the MnHAP composite coating, and the doping of the manganese element makes the proliferation activity of the cell on the surface of the MnHAP composite coating good, and the cell compatibility of the coating is good. HAP/ CaSiO3 composite coatings were prepared on the surface of titanium by electrodeposition in the electrolyte composed of nano-SiO2, Ca (NO3)2 and NH4H2PO4. The surface of the HAP/ CaSiO3 composite coating is composed of an internal dense nano-scale needle-like crystal and an outer micron-sized porous structure, and the porous structure is very favorable for the formation of the new bone. The X-ray diffraction results show that the composite coating mainly includes the HAP phase and the Ca-Si 3 phase. The tensile test results show that the bonding strength between the HAP/ CaSiO3 composite coating and the Ti substrate is 19.1-4.7 MPa, which has basically met the requirements of international standards. The polarization test shows that the HAP/ CaSiO3 composite coating has strong corrosion resistance. The proliferation ability of MC3T3-E1 osteoblast on the surface of HAP/ Ca SiO3 composite coating was significantly higher than on the surface of HAP, indicating that the HAP/ CaSiO3 composite coating had better cell compatibility. In the light of the above, the present study adopts the electrodeposition method to carry out the construction of a plurality of ion-doped calcium phosphate active coatings, and the electrodeposition preparation technology of the calcium phosphate composite coating is theoretically and experimentally studied. The effects of fluoride ion, iron ion, manganese ion, silicon ion and gelatin on the physical properties, chemical properties and biological activity of the composite coatings were studied. The various trace elements (such as fluorine, iron, manganese, silicon, etc.) required for osteogenesis were successfully introduced into the Ca-P coating to provide a preliminary experimental basis for the further study of the clinical application of the calcium phosphate composite coating in the repair of bone defects.
【學(xué)位授予單位】：電子科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：R318.08

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