β-TCP/HAP复合生物陶瓷工艺研究
摘要
本课题目的是研究一种新型的可降解生物陶瓷骨替代材料,利用β-TCP和HAP的降解速度不同,使材料实现原位成孔,并通过不同途径来提高材料的力学性能。
用化学共沉淀法制备纯β-TCP粉末。参考了各种相关数据和相图,设计并用熔融法制备了用做β-TCP小球烧结助剂的CaO-MgO-Na2O-P2O5四元生物玻璃。采用液相分相成球法制备粒径分布集中在0.6mm-0.8mm的β-TCP/明胶凝胶小球,并将诸多影响成球效果的工艺参数具体化,确定了具有可重复性的小球粒径分布集中的成球方法。
利用相似工艺条件下制得的柱状试样来表征在不同因素的影响下,小球的各项性能的变化趋势。对粉胶比,烧结温度,生物玻璃的添加量等影响因素进行分析。在粉胶比为0.625g/ml,生物玻璃相含量15%,烧结温度1000°C条件下制得的β-TCP柱状试样,含有固溶体Ca9MgNa(PO4)7和少量Ca2P2O7,具有较高的烧结致密度。
在柱状试样的工艺参数指导下,制备了不同因素影响下的小球密堆柱状试样,并对试样进行了烧结致密度,抗压强度和SEM表面形貌分析。证明除上述因素以外,粒径分布对试样的力学性能有很大的影响。粒径分布在0.6-0.8mm的试样其最大抗压强度可以达到27.6MPa。
用真空浸渍溶胶的方法将HAP与小球密堆柱状坯体进行复合。复合的试样保持了未复合时的受生物玻璃相含量和粒径分布影响下的抗压强度的变化规律,并在此基础上有所提高,最大抗压强度达到了27.7MPa。
使用TRIS氯化氢溶液作为模拟体液对小球密堆柱状试样和复合试样进行了降解。生物玻璃相的加入对试样的降解性能影响不大,其降解速率与纯β-TCP试样近似。复合试样的降解特点表明本实验所制备的材料符合课题设计的骨修复材料的特点。
The research focuses on designing a novel biodegradable bioceramics which can be used as bone substitute. This kind of material can form pores in situ owing to the different degrading speed ofβ-TCP and HAP. The mechanical property of the new material is trying to be improved in different ways.
β-tricalcium phosphate(β-TCP) is synthesized by wet precipitation. CaO-MgO-Na2O-P2O5 bioglass is designed and fabricated based on related data and phase graphs by melting method, which will be used as a sintering additive. The method to produce sphericalβ-TCP granules is based on liquids immiscibility and sol-gel effect. The diameter of the spheres centralizes between 0.6mm-0.8mm. The process is repeatable and its working conditions are confirmed.
Column samples are prepared to represent the property diversification of the packed-sphere samples on different process factors, such as powder content, bioglass content and sintering temperature. The column samples produced under the conditions of powder content 0.625g/ml, bioglass content 15% and sintering temperature 1000°C have high density. The XRD research shows that the material contents solid solution Ca9MgNa(PO4)7 and a little of Ca2P2O7 phase. Packed-sphere samples are prepared and analyzed by measuring their density, mechanical property, and SEM photos. The diameter range is also found having great influences on it. The samples that the spheres centralized between 0.6mm-0.8mm have high compressive strength values of 27.6MPa.
The composite is made by vacuum soaking packed-sphere samples in HAP sol. The property of composite samples has the same trend as before. The compressive strength values also reach 27.7MPa.
The in vitro biodegradation ofβ-TCP/HAP composite samples in TRIS/HCl shows that the degradation speed of the material within bioglass is very closed to pureβ-TCP. So it can be concluded that the addition of bioglass improves the mechanical property of the new material and have no affections on its biodegrading speed.
用化学共沉淀法制备纯β-TCP粉末。参考了各种相关数据和相图,设计并用熔融法制备了用做β-TCP小球烧结助剂的CaO-MgO-Na2O-P2O5四元生物玻璃。采用液相分相成球法制备粒径分布集中在0.6mm-0.8mm的β-TCP/明胶凝胶小球,并将诸多影响成球效果的工艺参数具体化,确定了具有可重复性的小球粒径分布集中的成球方法。
利用相似工艺条件下制得的柱状试样来表征在不同因素的影响下,小球的各项性能的变化趋势。对粉胶比,烧结温度,生物玻璃的添加量等影响因素进行分析。在粉胶比为0.625g/ml,生物玻璃相含量15%,烧结温度1000°C条件下制得的β-TCP柱状试样,含有固溶体Ca9MgNa(PO4)7和少量Ca2P2O7,具有较高的烧结致密度。
在柱状试样的工艺参数指导下,制备了不同因素影响下的小球密堆柱状试样,并对试样进行了烧结致密度,抗压强度和SEM表面形貌分析。证明除上述因素以外,粒径分布对试样的力学性能有很大的影响。粒径分布在0.6-0.8mm的试样其最大抗压强度可以达到27.6MPa。
用真空浸渍溶胶的方法将HAP与小球密堆柱状坯体进行复合。复合的试样保持了未复合时的受生物玻璃相含量和粒径分布影响下的抗压强度的变化规律,并在此基础上有所提高,最大抗压强度达到了27.7MPa。
使用TRIS氯化氢溶液作为模拟体液对小球密堆柱状试样和复合试样进行了降解。生物玻璃相的加入对试样的降解性能影响不大,其降解速率与纯β-TCP试样近似。复合试样的降解特点表明本实验所制备的材料符合课题设计的骨修复材料的特点。
The research focuses on designing a novel biodegradable bioceramics which can be used as bone substitute. This kind of material can form pores in situ owing to the different degrading speed ofβ-TCP and HAP. The mechanical property of the new material is trying to be improved in different ways.
β-tricalcium phosphate(β-TCP) is synthesized by wet precipitation. CaO-MgO-Na2O-P2O5 bioglass is designed and fabricated based on related data and phase graphs by melting method, which will be used as a sintering additive. The method to produce sphericalβ-TCP granules is based on liquids immiscibility and sol-gel effect. The diameter of the spheres centralizes between 0.6mm-0.8mm. The process is repeatable and its working conditions are confirmed.
Column samples are prepared to represent the property diversification of the packed-sphere samples on different process factors, such as powder content, bioglass content and sintering temperature. The column samples produced under the conditions of powder content 0.625g/ml, bioglass content 15% and sintering temperature 1000°C have high density. The XRD research shows that the material contents solid solution Ca9MgNa(PO4)7 and a little of Ca2P2O7 phase. Packed-sphere samples are prepared and analyzed by measuring their density, mechanical property, and SEM photos. The diameter range is also found having great influences on it. The samples that the spheres centralized between 0.6mm-0.8mm have high compressive strength values of 27.6MPa.
The composite is made by vacuum soaking packed-sphere samples in HAP sol. The property of composite samples has the same trend as before. The compressive strength values also reach 27.7MPa.
The in vitro biodegradation ofβ-TCP/HAP composite samples in TRIS/HCl shows that the degradation speed of the material within bioglass is very closed to pureβ-TCP. So it can be concluded that the addition of bioglass improves the mechanical property of the new material and have no affections on its biodegrading speed.
引文
[1]Vladimir S. Komlev, Serguei M. Barinov, Elena V. Koplik, A method to fabricate porous spherical hydroxyapatite granules intended for time-controlled drug release, Biomaterials. 2002, 23: 3449~3454
[2]王欣宇,韩颖超,李世普,磷酸盐生物玻璃粘接剂对HA植入体烧结的影响,功能材料,2003,2(34),232~233.
[3] L. L. Hench, Bioceramics, J. Am. ceram., 1998, 81(7): 1705~1728
[4]张兴栋,诸培南,生物陶瓷,高新技术要览,北京,中国科学技术出版社,1993,287~289
[5]龚森蔚,江东亮,谭寿洪,孔径可控羟基磷灰石复相陶瓷中玻璃相的作用,材料导报,1998,12(4):31~34.
[6]Kokubo T, Kim HM, Kawashita M. Novel bioactive materials with different mechanical properties, Biomaterials.2003, 24(13): 2161~2175.
[7]Klawitter J,Hulber S, Application of porous ceramics for the attchment of load bearing orthopaedic application, J Matter Res. 1971, 2 (2): 161~167 [8Charlene M, Flahiff Angela S, et al. Analysis of A Biodegradable Composite for Bone Healing. J. Biomed. Mater. Res. 1996, 32: 419~424
[9]张文莉,生物材料及其应用,医药工程设计杂志,2003,24(3):7~10
[10]黄占杰,磷酸钙陶瓷生物降解研究的进展,功能材料,1997,28(1):1~4
[11]李晓溪,闫玉华,可降解磷酸钙生物陶瓷的研究进展,现代技术陶瓷,2002,2:24~27
[12]Kotani S, Fujita Y, Kitsugi T, et al, Bone bonding mechanism ofβ-tricalcium phosphate, J Bio-med Mater Rcs.1991, 25(10): 1303~1315
[13]王士斌,翁连进,郑昌琼等,多孔β-磷酸三钙修复材料的制备,华侨大学学报,1999,20(3):287~290
[14]王士斌,可诱导成骨和生物降解的复合人工骨的研究, [博士学位论文],成都:四川大学高新技术研究院,1996
[15]Martin R B, Chapman M W, Sharkey N A, Zissimos S L, Bay B and Shors E C. Bone ingrowth and mechanical properties of coralline hydroxyapatite 1 yr after implanttion. Biomaterials.1993, 14:341-348.
[16]Hench L. L. 10th Inter Conk On Glass, 1976, 9: 30
[17]强伯勤,杨国忠,全国第二届纳米材料和技术应用会议论文集,北京:2001,45
[18]苑金生,中国建材,1998,1:39
[19]严建华,冯乃谦等,玻璃与搪瓷,2000,(4):28
[20]Larry L Hench, Zhong Jipin, Proceedings of the Frist Internanonal Conference on Biomaterials. Beijing, China, 2001. 50
[21]Larry L Hench. Journal of Biomedical Material Research, 1998, 41:511
[22]Hamadouche M, Meumer A, Greenspan D C, et al. Sixth World Biomaterials Congress, Hawaii, 2000. 1388
[23]Wilson J, Stanley H R, Hench L L. Clinical Density, Clark J, ed. 4, Chapter 50, 1981
[24]黄占杰等,中国生物医学工程学报,2000,19(1):66
[25]刘贵志,Si-Na2O-CaO-P2O5-B2O3系统生物玻璃在体内的特性[ J],特种玻璃,1990,( 7):6～14
[26]李世普,陈晓明,生物陶瓷,武汉:武汉工业大学出版社,1989
[27]张大海,翁文剑,醇化合物合成磷酸钙盐,硅酸盐通报,1998,6:9~12
[28]张德正,王保修,纪元玉等,医用羟基磷灰石的制备与应用,中国陶瓷,1998,34(6):24~26
[29]刘羽,仲康年,胡文云,溶胶-凝胶法合成条件与羟基磷灰石特征的关系,材料科学与工程,1997,15(1):62~65
[30]C. M. Lopatin, V. Pizzicon, T. L. Alford, et al, Hydroxyapatite powers and thin films prepared by a sol-gel technique, Thin Solid Film. 1998, 326: 227~232
[31]Dean-Mo Liu, Quanzu Yang, Tom Troczynski, et al, Structural evolution of sol-gel-derived hydroxyapatite, Biomaterials. 2002, 23: 1679~1687
[32]L.L.Hench,I.Xynos,A.Edgar,L.Buttery,激活基因的玻璃[J].无机材料学报,2002,(17):897~909.
[33]Hyun-Seung Ryu, Kug Sun Hong, Jung-Kun Lee, et al, Magenesia-doped HA/β-TCP ceramics and evaluation of their biocompatibility, Biomaterials, 2004, 25: 394~401.
[34]L. V. Fateeva, Yu. I. Golovkov, S. V. Tumanov, et al, Effect of sodium phosphate on sintering of hydroxyapatite ceramics, Refrarence and Industrial Ceramics, 2001, 42: 3~8
[35]S. Raynaud, E. Champion, J. P. Lafon, et al, Calcium phosphate apatites with variable Ca/P atomic ratioⅢ, Mechanical properties and degradation in solution of hot pressed ceramics, Biomaterials, 2002, 23: 1081~1085
[36]Jung Shick Lee, Jai Koo Park. Processing of porous ceramic spheres by pseudo-double-emulsion method, ceramic international 2003, 29: 271~278
[2]王欣宇,韩颖超,李世普,磷酸盐生物玻璃粘接剂对HA植入体烧结的影响,功能材料,2003,2(34),232~233.
[3] L. L. Hench, Bioceramics, J. Am. ceram., 1998, 81(7): 1705~1728
[4]张兴栋,诸培南,生物陶瓷,高新技术要览,北京,中国科学技术出版社,1993,287~289
[5]龚森蔚,江东亮,谭寿洪,孔径可控羟基磷灰石复相陶瓷中玻璃相的作用,材料导报,1998,12(4):31~34.
[6]Kokubo T, Kim HM, Kawashita M. Novel bioactive materials with different mechanical properties, Biomaterials.2003, 24(13): 2161~2175.
[7]Klawitter J,Hulber S, Application of porous ceramics for the attchment of load bearing orthopaedic application, J Matter Res. 1971, 2 (2): 161~167 [8Charlene M, Flahiff Angela S, et al. Analysis of A Biodegradable Composite for Bone Healing. J. Biomed. Mater. Res. 1996, 32: 419~424
[9]张文莉,生物材料及其应用,医药工程设计杂志,2003,24(3):7~10
[10]黄占杰,磷酸钙陶瓷生物降解研究的进展,功能材料,1997,28(1):1~4
[11]李晓溪,闫玉华,可降解磷酸钙生物陶瓷的研究进展,现代技术陶瓷,2002,2:24~27
[12]Kotani S, Fujita Y, Kitsugi T, et al, Bone bonding mechanism ofβ-tricalcium phosphate, J Bio-med Mater Rcs.1991, 25(10): 1303~1315
[13]王士斌,翁连进,郑昌琼等,多孔β-磷酸三钙修复材料的制备,华侨大学学报,1999,20(3):287~290
[14]王士斌,可诱导成骨和生物降解的复合人工骨的研究, [博士学位论文],成都:四川大学高新技术研究院,1996
[15]Martin R B, Chapman M W, Sharkey N A, Zissimos S L, Bay B and Shors E C. Bone ingrowth and mechanical properties of coralline hydroxyapatite 1 yr after implanttion. Biomaterials.1993, 14:341-348.
[16]Hench L. L. 10th Inter Conk On Glass, 1976, 9: 30
[17]强伯勤,杨国忠,全国第二届纳米材料和技术应用会议论文集,北京:2001,45
[18]苑金生,中国建材,1998,1:39
[19]严建华,冯乃谦等,玻璃与搪瓷,2000,(4):28
[20]Larry L Hench, Zhong Jipin, Proceedings of the Frist Internanonal Conference on Biomaterials. Beijing, China, 2001. 50
[21]Larry L Hench. Journal of Biomedical Material Research, 1998, 41:511
[22]Hamadouche M, Meumer A, Greenspan D C, et al. Sixth World Biomaterials Congress, Hawaii, 2000. 1388
[23]Wilson J, Stanley H R, Hench L L. Clinical Density, Clark J, ed. 4, Chapter 50, 1981
[24]黄占杰等,中国生物医学工程学报,2000,19(1):66
[25]刘贵志,Si-Na2O-CaO-P2O5-B2O3系统生物玻璃在体内的特性[ J],特种玻璃,1990,( 7):6～14
[26]李世普,陈晓明,生物陶瓷,武汉:武汉工业大学出版社,1989
[27]张大海,翁文剑,醇化合物合成磷酸钙盐,硅酸盐通报,1998,6:9~12
[28]张德正,王保修,纪元玉等,医用羟基磷灰石的制备与应用,中国陶瓷,1998,34(6):24~26
[29]刘羽,仲康年,胡文云,溶胶-凝胶法合成条件与羟基磷灰石特征的关系,材料科学与工程,1997,15(1):62~65
[30]C. M. Lopatin, V. Pizzicon, T. L. Alford, et al, Hydroxyapatite powers and thin films prepared by a sol-gel technique, Thin Solid Film. 1998, 326: 227~232
[31]Dean-Mo Liu, Quanzu Yang, Tom Troczynski, et al, Structural evolution of sol-gel-derived hydroxyapatite, Biomaterials. 2002, 23: 1679~1687
[32]L.L.Hench,I.Xynos,A.Edgar,L.Buttery,激活基因的玻璃[J].无机材料学报,2002,(17):897~909.
[33]Hyun-Seung Ryu, Kug Sun Hong, Jung-Kun Lee, et al, Magenesia-doped HA/β-TCP ceramics and evaluation of their biocompatibility, Biomaterials, 2004, 25: 394~401.
[34]L. V. Fateeva, Yu. I. Golovkov, S. V. Tumanov, et al, Effect of sodium phosphate on sintering of hydroxyapatite ceramics, Refrarence and Industrial Ceramics, 2001, 42: 3~8
[35]S. Raynaud, E. Champion, J. P. Lafon, et al, Calcium phosphate apatites with variable Ca/P atomic ratioⅢ, Mechanical properties and degradation in solution of hot pressed ceramics, Biomaterials, 2002, 23: 1081~1085
[36]Jung Shick Lee, Jai Koo Park. Processing of porous ceramic spheres by pseudo-double-emulsion method, ceramic international 2003, 29: 271~278