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鈦表面多級微鈉米結(jié)構(gòu)及其磷酸鈣涂層制備與表征

發(fā)布時間:2019-03-24 11:01
【摘要】:鈦及其合金因其高的比強度,耐腐蝕性能強及良好的生物相容性等優(yōu)點,而被廣泛用作人工骨、血管支架等生物植入金屬材料。但是鈦及鈦合金植入體內(nèi)后不易于骨組織發(fā)生有效地化學鍵合,故植入體易發(fā)生松動脫落,造成植入失敗。研究表明,鈦合金表面形貌,特別是表面微納米結(jié)構(gòu)可以有效模擬體內(nèi)微納米環(huán)境,促進蛋白質(zhì)吸附與細胞的增殖粘附、分化等。所以,將鈦表面改性,構(gòu)建表面微納米結(jié)構(gòu)可以有效地提高鈦合金與骨組織愈合速度,提高骨整合能力,促進新骨生成。磷灰石作為人體骨組織的主要無機成分,對骨組織的修復愈合有良好的促進作用,但是其力學性能較差。將二者有機結(jié)合起來,在鈦合金表面沉積磷酸鈣涂層,構(gòu)建表面微納米結(jié)構(gòu),不僅可以提高植入體的生物活性,增強骨組織與植入體之間的鍵合,而且彌補了生物陶瓷在力學方面的缺陷。首先,采用水熱植酸處理,通過選取不同濃度植酸,在金屬鈦表面構(gòu)建了多級微納米結(jié)構(gòu),然后采用仿生礦化法在鈦表面沉積了磷酸鈣晶體,運用SEM、EDX、XRD等分析設備對其物相進行表征。結(jié)果顯示:(1)不同濃度植酸水熱處理得到的金屬鈦表面形貌,成分均有差異,當植酸濃度為5 v/v%時,表面生成了1-3μm的Ti02金紅石結(jié)構(gòu),當植酸濃度為7.5 v/v%時,表面形成了微米/納米相結(jié)合的溝槽狀結(jié)構(gòu),當植酸濃度為10 v/v%時,表面形成了由片層狀結(jié)構(gòu)自組裝形成的花瓣狀結(jié)構(gòu),成分為Ti(HPO4)2與Ti(HPO4)2·H2O;(2)將三種不同的水熱植酸處理賦予的微納米結(jié)構(gòu)表面采用浸漬法預鈣化后,浸泡入過飽和鈣磷溶液中,在其表面制備了磷酸鈣涂層。其次,采用水熱堿處理的方法,在鈦表面制備鈦納米線狀結(jié)構(gòu),然后通過二次水熱處理在原有鈦納米線狀結(jié)構(gòu)表面原位沉積磷酸鈣,且不改變原有鈦納米線結(jié)構(gòu)。通過對其分析發(fā)現(xiàn):(1)通過水熱堿處理得到了均勻無裂紋,長度約為4-8μm,寬度約為50-200 nm的鈦納米線狀結(jié)構(gòu);(2)通過二次水熱處理,小分子模板劑H6L調(diào)控磷酸鈣生長,在鈦納米線上原位沉積了磷酸鈣,構(gòu)建了具有多級微納米結(jié)構(gòu)的鈦表面。最后將堿熱處理鈦表面納米線結(jié)構(gòu)樣品與二次水熱原位沉積磷酸鈣樣品進行蛋白吸附與成骨細胞實驗。結(jié)果顯示,鈦表面微納米結(jié)構(gòu)樣品均有利于牛血清蛋白的吸附;鈦納米線二次水熱沉積磷酸鈣構(gòu)建的多級微納結(jié)構(gòu)表面更有利于成骨細胞增殖生長。
[Abstract]:Because of its high specific strength, corrosion resistance and good biocompatibility, titanium and its alloys have been widely used as biomaterials such as artificial bone, vascular scaffolds and so on. However, titanium and titanium alloy are not easy to be effectively chemically bonded in bone tissue after implantation, so the implant is easy to loose and fall off, resulting in the failure of implantation. The results show that the surface morphology of titanium alloy, especially the surface microstructure, can effectively simulate the in vivo micro / nano environment and promote the protein adsorption and cell proliferation, adhesion, differentiation and so on. Therefore, the titanium surface modification and the construction of the surface microstructure can effectively improve the healing rate of titanium alloy and bone tissue, improve the ability of bone integration, and promote the formation of new bone. Apatite, as the main inorganic component of human bone tissue, has a good effect on the healing of bone tissue, but its mechanical properties are poor. Combining them organically, depositing calcium phosphate coating on the surface of titanium alloy to construct the surface microstructure can not only enhance the bioactivity of the implant, but also enhance the bonding between bone tissue and implant. It also makes up for the mechanical defects of bioceramic. First of all, hydrothermal phytic acid treatment was used to construct multistage microstructure on titanium surface by selecting different concentration phytic acid. Then calcium phosphate crystal was deposited on titanium surface by biomimetic mineralization method, and SEM,EDX, was used to deposit calcium phosphate crystal on titanium surface. Its phase was characterized by XRD and other analytical equipment. The results show that: (1) the surface morphology and composition of titanium obtained by hydrothermal treatment with different concentration of phytic acid are different. When the concentration of phytic acid is 5 v / v%, the Ti02 rutile structure of 1-3 渭 m is formed on the surface. When the concentration of phytic acid was 7.5 v%, the surface formed a groove-like structure combined with micron / nano-meter. When the concentration of phytic acid was 10 v / v%, the surface formed a petal-like structure formed by lamellar self-assembly, and when the concentration of phytic acid was 10 v / v%, the surface formed a petal-like structure. The constituents were Ti (HPO4) 2 and Ti (HPO4) 2 路H2O; (2) calcium phosphate coating was prepared on the surface of three kinds of hydrothermal phytic acid treated micro-nanostructures by impregnation precalcification and immersion in supersaturated calcium-phosphorus solution. Secondly, titanium nanowires were prepared on the surface of titanium by hydrothermal alkali treatment, and then calcium phosphate was deposited on the surface of titanium nanowires by secondary hydrothermal treatment without changing the structure of titanium nanowires. It was found that: (1) Ti nanowires with a length of 4-8 渭 m and a width of 50 渭 nm were obtained by hydrothermal alkali treatment. (2) by secondary hydrothermal treatment, the growth of calcium phosphate was regulated by small molecular template H6L, calcium phosphate was deposited on titanium nanowires in situ, and the titanium surface with multi-stage micro-nano-structure was constructed. Finally, protein adsorption and osteoblast experiments were carried out between alkaline-heat-treated titanium nanowires and in-situ secondary hydrothermal deposition of calcium phosphate. The results showed that all the microstructure samples on titanium surface were favorable to the adsorption of bovine serum protein, and the multi-stage nano-nano structure surface constructed by secondary hydrothermal deposition of calcium phosphate on titanium nanowires was more favorable to the proliferation and growth of osteoblasts.
【學位授予單位】:西南交通大學
【學位級別】:碩士
【學位授予年份】:2015
【分類號】:TG174.4

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