改性HAP基多孔生物陶瓷的制备与性能研究

发布时间：2018-05-10 09:28

本文选题：二氧化硅包覆的羟基磷灰石 + 生物玻璃　；参考：《武汉理工大学》2013年博士论文

【摘要】：多孔羟基磷灰石(HAP)基生物陶瓷因为与人体骨骼的无机化合成分相似,具有很好的生物相容性和成骨与诱导骨形成的导向作用,已被广泛用作生物体硬组织修复。目前,有关多孔HAP陶瓷在医学领域的研究已经延伸到将其作为药物载体以及抗肿瘤活性上,且发现将多孔陶瓷作为药物载体有广泛的应用前景和重要的研究价值。本论文以多孔陶瓷作为药物控释缓释载体为研究背景,为制备出满足实际需要的多孔体,对材料的组成进行了设计,研制了以纳米生物玻璃作为增强相、纳米炭粉为成孔剂的工艺,并对多孔材料的结构和性能进行了表征。采用不同溶液对多孔陶瓷进行了渗透与反渗透评估,通过体外RSC96细胞与材料的作用,对其进行生物学评价等。主要内容如下：合成了形貌不同的羟基磷灰石纳米粒子,并分析讨论了影响HAP形貌的主要参数。通过异质凝结机制,利用TEOS水解对经十二烷醇酯化后的HAP纳米粒子进行表面SiO2包覆改性(HAPSi050),研究了不同SiO2含量对产物包覆率及其在水和酸溶液中溶解性能的影响。改性后获得的粒子通过FT-IR、XRD、 SEM-EDS、HR-TEM、TG-DSC和Zeta电位等分析方法表征合成的SiO2改性HAP的结构与性能,并观察了其在水溶液中的悬浮稳定性能。结果表明：SiO2包覆层厚度大约为3nm,表面改性后,Zeta电势均为负值,粒子在水溶液中的悬浮稳定性提高了5倍,抗酸溶解能力增强。通过W/O型微乳液技术合成了SiO2-CaO-P2O5系统生物活性玻璃纳米粒子,探讨了水与表面活性剂的摩尔比ω的变化对合成的纳米粒子结构和性能的影响。并对合成的粒子进行了体外降解和与RSC96细胞联合培养的研究。采用FTIR、 XRD、SEM-EDS、XRF、TEM、BET比表面积分析仪和激光粒度分析仪等手段对合成的和经过降解的纳米玻璃粒子进行表征,结果表明：合成的球形纳米玻璃粒子尺寸在100nnm左右,分布均匀,分散性较好；颗粒之间彼此连接而具有微孔结构,测得的比表面积和孔体积分别为137.9cm3/g和0.37cm3/g。测定降解过程中降解介质pH值、离子溶出行为表明：材料在生理环境中,经过较短的时间即可在玻璃颗粒表面形成类骨HCA,同时有离子溶出现象发生,说明材料具有较高的体外生物活性和良好的降解性能。材料在降解过程中溶液的pH值略呈上升的趋势,基本处于中性。MTT实验测试细胞增殖表明材料能促进细胞的增殖,说明合成的纳米玻璃粒子有良好的细胞亲和性,可作为生物材料使用。以HAPSi050纳米粉体为原料,SiO2-CaO-P2O5系统生物玻璃为增强相,纳米活性炭粉作造孔剂,制备出了孔径彼此贯通、分布均匀、且孔隙率可调的多孔生物陶瓷。利用XRD、SEM等手段测试多孔体的相组成及微观形貌,采用万能试验机、硬度计以及渗透率测试仪测定多孔孔体的力学性能及流体渗透率。并应用ANSYS软件和图像处理技术进一步分析孔形貌对力学性能的影响。结果发现：抗折强度随烧结温度和生物玻璃含量的增加而升高,气孔率和渗透率则随相应因素的升高而降低。气孔率和渗透率随炭粉含量增加呈上升趋势,但是抗弯强度却逐渐降低。图像处理和ANSYS分析表明：试样中孔越圆、近圆形孔的数量越多、孔分布越均匀,多孔体力学性能越高。多孔陶瓷经模拟体液浸泡,测定矿化过程中材料失重率、抗折强度的变化和采用扫描电子显微镜(SEM)观察材料微观结构变化表明：浸泡初期试样表面即有类骨磷灰石形成,预示着材料有较好的生物矿化能力。但同时,试样的质量和抗折强度降低。之后,随着试样表面类骨磷灰石数量的增多,试样的质量和强度又开始回升并逐渐增加。将RSC96细胞与多孔陶瓷体外联合培养,通过细胞增殖、细胞毒性、SEM观察进行生物学评价。噻唑蓝(MTT)比色法表明多孔体材料能促进细胞的增殖；吉姆萨和荧光探针技术测试细胞毒性表明多孔材料与对照组单相HAP一致；SEM观察表明RSC96细胞在多孔材料上铺展良好,证明多孔体具有良好的细胞亲和性和生物活性。
[Abstract]:Porous hydroxyapatite (HAP) based bioceramics have been widely used as hard tissue repair for biological compatibility and osteogenesis and induced bone formation because they are similar to the inorganic compounds of human skeleton, and have been widely used in the medical field as a drug carrier. As well as the anti-tumor activity, porous ceramics as drug carrier have wide application prospects and important research value. In this paper, porous ceramics are used as drug controlled release sustained-release carriers as research background. In order to prepare porous bodies to meet the actual needs, the composition of materials is designed and nano glass is developed. The structure and properties of the porous materials were characterized by the enhancement phase and the nano carbon powder as the pore forming agent. The porous ceramics were evaluated by permeation and reverse osmosis by different solutions. The biological evaluation of the porous ceramics by the effect of RSC96 cells and materials in vitro was carried out. The main contents were as follows:
The hydroxyapatite nanoparticles with different morphologies were synthesized and the main parameters affecting the HAP morphology were analyzed and discussed. The surface SiO2 coating modification (HAPSi050) of the HAP nanoparticles after twelve alkanols was hydrolyzed by TEOS hydrolysis by the heterogeneous condensation mechanism. The coating rate of the products and the solution in water and acid solution were studied with different SiO2 content. The properties of the modified particles were characterized by FT-IR, XRD, SEM-EDS, HR-TEM, TG-DSC and Zeta potential, and the structure and properties of the synthesized SiO2 modified HAP were characterized, and the suspension stability was observed in the aqueous solution. The results showed that the thickness of the SiO2 coating layer was about 3nm, and the Zeta potential was negative after surface modification. The stability of the suspension in aqueous solution increased by 5 times and the ability to resist acid dissolution increased.
SiO2-CaO-P2O5 system bioactive glass nanoparticles were synthesized by W/O microemulsion technology. The influence of the change of molar ratio omega of water and surfactant on the structure and properties of synthesized nanoparticles was investigated. The degradation of synthesized particles in vitro and co culture with RSC96 cells were studied. FTIR, XRD, SEM-EDS, XRF, TE were used. M, BET ratio surface area analyzer and laser particle size analyzer are used to characterize the synthesized and degraded nanoscale glass particles. The results show that the size of the spherical nano glass particles is around 100nnm, the distribution is uniform and the dispersibility is good; the particles are connected to each other with microporous structure, the specific surface area and pore body are measured. The integration of 137.9cm3/g and 0.37cm3/g. to determine the pH value of degradation medium in the degradation process, the dissolution behavior of ion shows that the material can form bone like HCA on the surface of glass particles in a short time in physiological environment, and the phenomenon of ion dissolution occurs, indicating that the material has higher biological activity in vitro and good degradation performance. In the process of degradation, the pH value of the solution is slightly rising, and the proliferation of the cells can be promoted by the neutral.MTT test. It shows that the synthesized nano glass particles have good cell affinity and can be used as biomaterials.
The porous bioceramics with HAPSi050 nano powder as raw material, SiO2-CaO-P2O5 system Bioglass as enhanced phase and nano activated carbon powder as pore making agents, the porous bioceramics with pore penetration, uniform distribution and adjustable porosity were prepared. The phase composition and Micromorphology of the porous body were tested by means of XRD and SEM, and the universal testing machine, hardness meter and seepage were used. The mechanical properties and fluid permeability of porous pores were measured by the permeability test instrument. The effect of pore morphology on the mechanical properties was further analyzed by ANSYS software and image processing technology. The results showed that the flexural strength increased with the increase of sintering temperature and the content of Bioglass, and the porosity and permeability decreased with the increase of the corresponding factors. The porosity and permeability increase with the increase of carbon powder content, but the bending strength decreases gradually. The image processing and ANSYS analysis show that the holes in the specimen are round, the number of near circular holes is more, the distribution of holes is more uniform and the mechanical properties of the porous body are higher.
Porous ceramics were soaked in simulated body fluid to determine the material weight loss rate, the change of fracture strength and the microstructure change of the material observed by scanning electron microscope (SEM). It showed that the surface of the sample was formed at the initial surface of the sample, indicating the better biomineralization ability of the material, but at the same time, the quality and the bending resistance of the specimen were also found. Then, with the increase in the number of apatite on the surface of the specimen, the quality and strength of the sample began to recover and gradually increase. RSC96 cells were co cultured with porous ceramics in vitro, and biological evaluation was carried out through cell proliferation, cytotoxicity, and SEM observation. MTT colorimetric assay showed that porous material could promote cell growth. Proliferation, the test of cytotoxicity by Giemsa and fluorescence probe showed that the porous material was the same as the single phase HAP in the control group, and the SEM observation showed that the RSC96 cells spread well on the porous material, which proved that the porous body had good cell affinity and biological activity.

【学位授予单位】：武汉理工大学
【学位级别】：博士
【学位授予年份】：2013
【分类号】：R318.08

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