基于碳骨架的多孔医用金属材料制备与性能表征

发布时间：2018-04-28 03:04

本文选题：生物材料 + 多孔碳骨架　；参考：《哈尔滨工程大学》2013年博士论文

【摘要】：医用多孔金属材料，由于独特的孔隙结构可以在避免应力遮挡效应的同时，实现生物固定，近年来受到人们的关注，并取得了较好的临床结果，，但是它们具有一些与生俱来的局限，比如低的孔隙度和相对高的弹性模量。金属钯和金属银具有优异的耐蚀性和良好生物相容性，在医学领域的应用越来越受到重视。银还有独特的抑菌性能，被作为抗菌剂广泛应用于医疗保健和疾病治疗。但是，目前尚未见多孔钯和多孔银的研究报导。本文设计了具有三维贯通孔隙结构的多孔碳骨架，通过化学镀、电镀的方法在其上制备金属钯（银）层，通过对化学镀和电镀工艺参数的优化和调整，最终获得孔隙结构可调的多孔钯（银）的新型多孔金属材料，并对多孔钯（银）的孔隙结构、物相组成、压缩行为和生物相容性进行表征，此外还研究了多孔银的抗菌性能。研究结果表明，以不同孔径的聚氨酯海绵为基体，经过酚醛树脂处理及固化，制得的固化泡沫在1100oC真空条件下热解，成功制备了类似泡沫状结构，孔径尺寸287~2020μm的多孔碳骨架，制得的多孔碳骨架是一种典型的短程有序的非石墨化玻璃炭材料。1100oC热解使固化泡沫在轴向和径向尺寸产生14~15%的收缩，两个方向上的收缩是同步的，总体收缩量基本保持相等。孔径55ppi的聚氨酯海绵经酚醛树脂处理固化后1100oC真空热解，所得的多孔碳骨架孔隙率高达95%，孔隙贯通，平均孔径为602±93μm，可作为后期化学镀、电镀的多孔基体材料。制得的多孔碳骨架具有较低的细胞毒性，显示了优良的生物安全性能。以多孔碳骨架为基体，通过化学镀钯、电镀钯工艺成功制得多孔钯。通过对各工艺参数的研究，确定优化制备工艺为：化学镀钯PdCl22g/L，N2H_410ml/L，EDTA60g/L，NH_4OH340ml/L，pH11，Ce添加剂1.5g/L；电镀钯电流密度1.5A/g，pH值9.0，温度50oC、糖精添加剂2.5g/L。使用优化制备工艺通过调整电镀时间制得了孔隙度82.9%~63.5%，表观密度91.7~319.6mg/cm~3，孔径尺寸500~600μm的高度贯通类似松质骨的多孔钯，制备的钯镀层为面心立方钯单质。多孔钯的孔隙度、表观密度和平均孔径尺寸，均与天然松质骨接近。多孔钯的弹性模量为11.5~67.6MPa，与股骨和脊柱部位的松质骨的弹性模量相匹配。多孔钯在模拟体液条件下离子溶出量较低，显示了较低的细胞毒性。制备的多孔钯可作为潜在的植入器械表面多孔涂层应用于齿科种植体或人工关节植入器械中。以多孔碳骨架为基体，通过化学镀银、电镀银工艺成功制得多孔银。通过对各工艺参数的研究，确定优化制备工艺为：化学镀银AgNO316g/L，NH3H2O80ml/L，NaOH12g/L，C_6H_(12)O_621g/L，C2H5OH75ml/L；电镀银4A/g，pH值9.0，温度25oC。使用优化制备工艺，通过不同的电镀时间，成功获得孔隙度68%~81%，表观密度13.1~97mg/cm~3，平均孔径387~575μm的多孔银。制备的多孔银为面心立方银单质，具有高度贯通类似松质骨的孔隙结构；孔隙度、表观密度和平均孔径尺寸，均与天然松质骨接近。不同孔隙度多孔银的弹性模量为1.94~49.3MPa，股骨部位的松质骨的弹性模量相近，并且多孔银的压缩行为可以用Gibson-Ashby提出的松质骨力学模型解释。此外，多孔银在模拟体液条件下离子溶出率较低，显示了可以接受的细胞毒性，和优异的抑菌性能。热处理使电镀多孔银镀层致密，提高了多孔银的力学性能，但是影响了多孔银在SBF中的离子溶出行为，降低了生物安全性。
[Abstract]:Medical porous metal materials have been paid more attention in recent years because of their unique pore structure, which can avoid stress shielding effect, and have obtained good clinical results in recent years. But they have some inherent limitations, such as low porosity and relatively high modulus of elasticity. Metal palladium and metal silver. Excellent corrosion resistance and good biocompatibility have been paid more and more attention in the medical field. Silver has unique antibacterial properties and has been widely used as an antibacterial agent in medical care and disease treatment. However, no porous palladium and porous silver have been reported yet.
The porous carbon skeleton with three-dimensional perforated pore structure was designed. By electroless plating and electroplating, the metal palladium (silver) layer was prepared on it. By optimizing and adjusting the parameters of electroless plating and electroplating, the porous palladium (silver) porous metal material with adjustable pore structure was finally obtained, and the pore structure of porous palladium (silver) was obtained. The phase composition, compression behavior and biocompatibility were characterized, and the antibacterial properties of porous silver were also studied.
The results show that the porous carbon skeleton with a foam like structure and an aperture size of 287~2020 m is successfully prepared by the pyrolysis of the polyurethane foam with different pore sizes and phenolic resin treatment and curing under the vacuum condition of 1100oC. The porous carbon skeleton is a typical short range non graphitized glass. The.1100oC pyrolysis of the glass carbon material causes the curing foam to shrink in the axial and radial dimensions. The contraction in the two directions is synchronous, and the overall shrinkage is basically equal. The polyurethane sponge with the pore size 55ppi is treated by the phenol formaldehyde resin and the 1100oC vacuum pyrolysis. The porosity of the porous carbon skeleton is up to 95%, the porosity is through, the average porosity is through. The average porosity is through, the average porosity is through, the average of the pore is through. The average porosity is through, the average porosity is through, the average is average. The pore size is 602 + 93 mu m, which can be used as a porous matrix material for electroless plating and electroplating in the later period. The porous carbon skeleton has low cytotoxicity and shows excellent biological safety.
Porous palladium was successfully prepared by electroless palladium plating and palladium plating process. Through the study of various technological parameters, the optimum preparation process was as follows: electroless palladium PdCl22g/L, N2H_410ml/L, EDTA60g/L, NH_4OH340ml/L, pH11, Ce additive 1.5g/L, electroplating palladium current density 1.5A/g, pH value 9, temperature 50oC, saccharin additive 2.5g/ L. with the optimized preparation process, the porosity is 82.9%~63.5%, the apparent density is 91.7~319.6mg/cm~3, the pore size 500~600 mu m is high through porous palladium similar to the cancellous bone. The palladium coating is prepared as the face center cubic palladium monomer. The porosity, apparent density and the average pore size of porous palladium are connected with the natural cancellous bone. The elastic modulus of the porous palladium is 11.5~67.6MPa, which matches the elastic modulus of the cancellous bone in the femur and spine. Porous palladium is low in ion dissolution under simulated humoral conditions and shows lower cytotoxicity. The porous palladium prepared can be used as a potential porous coating for implant or artificial joint implant. Enter the instrument.
Multi hole silver was successfully prepared by electroless silver plating and electroplating silver with porous carbon skeleton as matrix. Through the study of various process parameters, the optimum preparation process was determined as: electroless silver plating AgNO316g/L, NH3H2O80ml/L, NaOH12g/L, C_6H_ (12) O_621g/L, C2H5OH75ml/L; electroplating silver 4A/g, pH value 9, temperature 25oC. use optimization preparation process, through the different process, through the different In the plating time, the porosity 68%~81%, the apparent density of 13.1~97mg/cm~3, the pore size of the porous silver with the average pore size 387~575 m are obtained. The porous silver prepared by the porous silver is a face centered cubic silver single substance with a high penetration of the pore structure similar to the cancellous bone, and the porosity, apparent density and the average pore size are all close to the natural cancellous bone. The modulus of elasticity is 1.94~49.3MPa, and the elastic modulus of the cancellous bone of the femur is similar, and the compression behavior of the porous silver can be explained by the mechanical model of the cancellous bone proposed by Gibson-Ashby. In addition, the ion dissolution rate of the porous silver is low under the simulated humoral condition, which shows the cytotoxicity and the excellent bacteriostasis. The electroplated porous silver coating is compact, which improves the mechanical properties of porous silver, but affects the ionic dissolution behavior of porous silver in SBF, and reduces the biological safety.

【学位授予单位】：哈尔滨工程大学
【学位级别】：博士
【学位授予年份】：2013
【分类号】：R318.08

【参考文献】