本文選題：生物材料 + 多孔碳骨架��； 參考：《哈爾濱工程大學(xué)》2013年博士論文

【摘要】：醫(yī)用多孔金屬材料，由于獨特的孔隙結(jié)構(gòu)可以在避免應(yīng)力遮擋效應(yīng)的同時，實現(xiàn)生物固定，近年來受到人們的關(guān)注，并取得了較好的臨床結(jié)果，，但是它們具有一些與生俱來的局限，比如低的孔隙度和相對高的彈性模量。金屬鈀和金屬銀具有優(yōu)異的耐蝕性和良好生物相容性，在醫(yī)學(xué)領(lǐng)域的應(yīng)用越來越受到重視。銀還有獨特的抑菌性能，被作為抗菌劑廣泛應(yīng)用于醫(yī)療保健和疾病治療。但是，目前尚未見多孔鈀和多孔銀的研究報導(dǎo)。 本文設(shè)計了具有三維貫通孔隙結(jié)構(gòu)的多孔碳骨架，通過化學(xué)鍍、電鍍的方法在其上制備金屬鈀（銀）層，通過對化學(xué)鍍和電鍍工藝參數(shù)的優(yōu)化和調(diào)整，最終獲得孔隙結(jié)構(gòu)可調(diào)的多孔鈀（銀）的新型多孔金屬材料，并對多孔鈀（銀）的孔隙結(jié)構(gòu)、物相組成、壓縮行為和生物相容性進行表征，此外還研究了多孔銀的抗菌性能。 研究結(jié)果表明，以不同孔徑的聚氨酯海綿為基體，經(jīng)過酚醛樹脂處理及固化，制得的固化泡沫在1100oC真空條件下熱解，成功制備了類似泡沫狀結(jié)構(gòu)，孔徑尺寸287~2020μm的多孔碳骨架，制得的多孔碳骨架是一種典型的短程有序的非石墨化玻璃炭材料。1100oC熱解使固化泡沫在軸向和徑向尺寸產(chǎn)生14~15%的收縮，兩個方向上的收縮是同步的，總體收縮量基本保持相等。孔徑55ppi的聚氨酯海綿經(jīng)酚醛樹脂處理固化后1100oC真空熱解，所得的多孔碳骨架孔隙率高達95%，孔隙貫通，平均孔徑為602±93μm，可作為后期化學(xué)鍍、電鍍的多孔基體材料。制得的多孔碳骨架具有較低的細胞毒性，顯示了優(yōu)良的生物安全性能。 以多孔碳骨架為基體，通過化學(xué)鍍鈀、電鍍鈀工藝成功制得多孔鈀。通過對各工藝參數(shù)的研究，確定優(yōu)化制備工藝為：化學(xué)鍍鈀PdCl22g/L，N2H_410ml/L，EDTA60g/L，NH_4OH340ml/L，pH11，Ce添加劑1.5g/L；電鍍鈀電流密度1.5A/g，pH值9.0，溫度50oC、糖精添加劑2.5g/L。使用優(yōu)化制備工藝通過調(diào)整電鍍時間制得了孔隙度82.9%~63.5%，表觀密度91.7~319.6mg/cm~3，孔徑尺寸500~600μm的高度貫通類似松質(zhì)骨的多孔鈀，制備的鈀鍍層為面心立方鈀單質(zhì)。多孔鈀的孔隙度、表觀密度和平均孔徑尺寸，均與天然松質(zhì)骨接近。多孔鈀的彈性模量為11.5~67.6MPa，與股骨和脊柱部位的松質(zhì)骨的彈性模量相匹配。多孔鈀在模擬體液條件下離子溶出量較低，顯示了較低的細胞毒性。制備的多孔鈀可作為潛在的植入器械表面多孔涂層應(yīng)用于齒科種植體或人工關(guān)節(jié)植入器械中。 以多孔碳骨架為基體，通過化學(xué)鍍銀、電鍍銀工藝成功制得多孔銀。通過對各工藝參數(shù)的研究，確定優(yōu)化制備工藝為：化學(xué)鍍銀AgNO316g/L，NH3H2O80ml/L，NaOH12g/L，C_6H_(12)O_621g/L，C2H5OH75ml/L；電鍍銀4A/g，pH值9.0，溫度25oC。使用優(yōu)化制備工藝，通過不同的電鍍時間，成功獲得孔隙度68%~81%，表觀密度13.1~97mg/cm~3，平均孔徑387~575μm的多孔銀。制備的多孔銀為面心立方銀單質(zhì)，具有高度貫通類似松質(zhì)骨的孔隙結(jié)構(gòu)；孔隙度、表觀密度和平均孔徑尺寸，均與天然松質(zhì)骨接近。不同孔隙度多孔銀的彈性模量為1.94~49.3MPa，股骨部位的松質(zhì)骨的彈性模量相近，并且多孔銀的壓縮行為可以用Gibson-Ashby提出的松質(zhì)骨力學(xué)模型解釋。此外，多孔銀在模擬體液條件下離子溶出率較低，顯示了可以接受的細胞毒性，和優(yōu)異的抑菌性能。熱處理使電鍍多孔銀鍍層致密，提高了多孔銀的力學(xué)性能，但是影響了多孔銀在SBF中的離子溶出行為，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.

【學(xué)位授予單位】：哈爾濱工程大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2013
【分類號】：R318.08

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