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Development of self-healing calcium phosphate coating on biodegradable metallic implant materials

机译:可生物降解金属植入物材料上自修复磷酸钙涂层的开发

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In recent years, magnesium and its alloys have received much attention as a new biomaterial in orthopedic applications due to their biodegradability, biocompatibility, and their mechanical properties that are similar to natural bone. The most common problem associated with magnesium as a biomaterial is low corrosion resistance in physiological solutions. This decreases the mechanical integrity of the implants in the early stages of healing and has a negative impact on the overall biocompatibility. Coatings can be used to control the degradation rate and provide optimum biocompatibility of these implant materials. Mesoporous silica materials have been shown to have good bioactivity and the ability to stimulate osteoblast proliferation and differentiation at implant surfaces. Furthermore, they have been shown to be non-toxic and non-inflammatory to mammalian tissues. Materials and Methods: The surfaces of Mg AZ31 alloys were prepared by polishing the samples to one micron surface finish and then cleaning them by sonication in acetone for 20min. alkaline aging was used to promote the formation of hydroxyl grope on the surface which is important for the covalent bond formation between the metal and the coating. Two types of coating were used in this research: silane coating as a protective film and mesoporous silica coating. The silane coating solution was prepared by using methanol as a solvent, deionized water, ammonia, and TEOS in varying v/v ratio and then hydrolysis for 24h and they were deposited for varying of time. The mesoporous silica coating solution was synthesized by using TEOS as a silica precursor and cationic surfactant C12CAT (alkyltrimethylammonium chlorides), deionized water, methanol, and ammonia. The molar ratio of TEOS: C12CAT: deionized water, methanol, and ammonia was 1:0.4:774:1501:72. The solution was hydrolysis for 1h before coated the samples by spin Coating. The samples were dried and curing for 1 h after each coated step. To remove the surfactant, the coated samples were calcined at 350 °C for 3h. These mesoporous silica films will be further modified through deposition of calcium phosphate to produce self-healing. Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and atomic absorption spectrometry (AFM) were used to characterize the surface of coated sample before and after calcination. Disscution: The initial results show that with the right conditions, it is possible to deposit mesoporous silica particles on Mg alloys. However, corrosion due to the presence of surfactant in the coating bath was observed. This problem was addressed by the introduction of a silica-based pre-layer to protect the surface during mesoporous silica film formation. The influence of coating bath concentration and deposition time on the pre-layer thickness and uniformity were investigated. From it is clear that deposition time does not have significant effect on TEOS film. However, the thickness of the TEOS film increases with increase the TEOS concentration. So, the best conditions to deposit TEOS layers were 20 min as the optimum deposition time and the 3.2% as the optimum concentration. IR Spectra for as deposited mesoporous silica at various deposition times (the results are not shown) indicated that short deposition time was the best for the coating so the 20 min was chosen as the best deposition time for the mesoporos silica film. The thickness of the film was increased with increase the number of layers as shown in. Moreover, the AFM images (the results are not shown) indicated the presence of the spherical particles on the film and increase the density of the film with increase the number of layers. Therefore, to get the mesoporous silica film, the surfactant was removed completely after calcination.Calcium phosphate (CaHPO4.2H2O) is successfully deposited on the mesoporous silica film on Mg alloys.
机译:近年来,由于镁及其合金的生物降解性,生物相容性以及类似于天然骨骼的机械性能,在骨科应用中作为一种新型生物材料受到了广泛关注。与镁作为生物材料有关的最常见问题是在生理溶液中的耐腐蚀性低。这在愈合的早期降低了植入物的机械完整性,并且对整体生物相容性具有负面影响。涂层可用于控制降解速率并提供这些植入物材料的最佳生物相容性。已经显示出介孔二氧化硅材料具有良好的生物活性,并具有在植入物表面刺激成骨细胞增殖和分化的能力。此外,它们已经显示出对哺乳动物组织无毒和无炎性。材料和方法:通过将样品抛光至一微米的表面光洁度,然后在丙酮中超声处理20分钟,以清洁Mg AZ31合金的表面。碱性时效被用来促进羟基摸索在表面上的形成,这对于金属与涂层之间的共价键形成很重要。在这项研究中使用了两种类型的涂层:作为保护膜的硅烷涂层和中孔二氧化硅涂层。通过使用甲醇作为溶剂,去离子水,氨水和TEOS以不同的v / v比例制备硅烷涂层溶液,然后水解24小时,然后将它们沉积不同的时间。中孔二氧化硅涂层溶液是通过使用TEOS作为二氧化硅前体和阳离子表面活性剂C12CAT(烷基三甲基氯化铵),去离子水,甲醇和氨水合成的。 TEOS:C12CAT:去离子水,甲醇和氨的摩尔比为1:0.4:774:1501:72。在通过旋涂将样品涂覆之前,将溶液水解1小时。在每个涂覆步骤之后将样品干燥并固化1小时。为了除去表面活性剂,将涂覆的样品在350℃下煅烧3小时。这些中孔二氧化硅膜将通过沉积磷酸钙进行进一步修饰,以产生自愈作用。衰减全反射傅立叶变换红外光谱(ATR-FTIR)和原子吸收光谱(AFM)用于表征涂层样品在煅烧前后的表面。分析:初步结果表明,在合适的条件下,有可能在Mg合金上沉积介孔二氧化硅颗粒。然而,观察到由于涂覆浴中存在表面活性剂而引起的腐蚀。通过引入基于二氧化硅的预层以在介孔二氧化硅膜形成过程中保护表面来解决该问题。研究了镀液浓度和沉积时间对预镀层厚度和均匀度的影响。显然,沉积时间对TEOS膜没有显着影响。然而,TEOS膜的厚度随着TEOS浓度的增加而增加。因此,沉积TEOS层的最佳条件是最佳沉积时间为20分钟,最佳浓度为3.2%。在各种沉积时间下沉积的介孔二氧化硅的红外光谱图(结果未显示)表明,较短的沉积时间对于涂层来说是最佳的,因此选择20分钟作为介孔二氧化硅膜的最佳沉积时间。如图所示,膜的厚度随层数的增加而增加。此外,AFM图像(结果未显示)表明膜上存在球形颗粒,并且随着层数的增加而增加了膜的密度层。因此,要获得介孔二氧化硅膜,需在煅烧后将表面活性剂完全去除。磷酸钙(CaHPO4.2H2O)成功沉积在Mg合金的介孔二氧化硅膜上。

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