稀土增强型多孔钛的表面活化处理及仿生矿化研究
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摘要
采用粉末冶金法成功制备出孔隙率范围在62%～73%的氟化镧增强型多孔钛,且其力学性能已满足硬组织替代物的要求。多孔钛的表面活性程度直接影响植入后的骨键合情况,而多孔钛属于惰性材料,因此本实验选择碱热处理以提高多孔钛表面活性,然后再进行仿生矿化研究。结果显示,两种钛粉粒径制备所得的多孔钛,无论是否加入氟化镧,碱热处理后都显示出良好的生物活性。并且在仿生矿化条件下可诱导HA(羟基磷灰石)和OCP(磷酸八钙)自发沉积,随着沉积时间的增长,类骨磷灰石呈现不同的形状外貌。由于La3+对Ca2+具有拮抗作用,导致添加氟化镧的多孔钛经碱热处理后的沉积类骨磷灰石的速度较未添加氟化镧的多孔钛要慢些。
The porous titanium enhanced by rare earth lanthanum fluoride( La F3) with porosity of 62% ～73% was successfully prepared by powder metallurgy method,and its mechanical properties have been met with the requirement of hard tissue substitute. The surface active degree of porous titanium directly affect the bone bonding situation after implantation,while the porous titanium is inert material. Therefore,the alkali heat treatment was adapted to improve the surface activity of porous titanium,and then the biomimetic mineralization was studied. It showed that whether or not to add rare earth lanthanum fluoride( La F3),porous titanium prepared by two kinds of titanium powder particle size had good biological activity after alkali treatment. What's more,under the condition of biomimetic mineralization,the HA( hydroxyapatite) and OCP( calcium phosphate eight) could be spontaneously deposited. With the increase of deposition time,the bone-like apatite had different shape and appearance. Due to the antagonistic effect of La3+on Ca2+,the deposition rate of bone-like apatite of porous titanium with La F3 after alkaline heat treatment was slower than porous titanium without La F3.
The porous titanium enhanced by rare earth lanthanum fluoride( La F3) with porosity of 62% ～73% was successfully prepared by powder metallurgy method,and its mechanical properties have been met with the requirement of hard tissue substitute. The surface active degree of porous titanium directly affect the bone bonding situation after implantation,while the porous titanium is inert material. Therefore,the alkali heat treatment was adapted to improve the surface activity of porous titanium,and then the biomimetic mineralization was studied. It showed that whether or not to add rare earth lanthanum fluoride( La F3),porous titanium prepared by two kinds of titanium powder particle size had good biological activity after alkali treatment. What's more,under the condition of biomimetic mineralization,the HA( hydroxyapatite) and OCP( calcium phosphate eight) could be spontaneously deposited. With the increase of deposition time,the bone-like apatite had different shape and appearance. Due to the antagonistic effect of La3+on Ca2+,the deposition rate of bone-like apatite of porous titanium with La F3 after alkaline heat treatment was slower than porous titanium without La F3.
引文
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[2] Fujibayashi S,Neo M,Kim H M,et al. Osteoinduction of porous bioactive titanium metal[J]. Biomaterials,2004,25(3):443-449.
[3] Barrere F,Vander Valk C M,Meijer G,et al. Osteointegration of biomimetic apatite coating applied onto dense and porous metal implants in femur of goat[J]. Journal of Biomedical materials Research,2003,67B(1):655-665.
[4] Long M.(Marc Long,H J Rack),Rack H J. Titanium alloys in total joint replacement—a materials science perspective[J]. Biomaterials,1998,19(18):1621-1639.
[5] Shimko D A,Shimko V F,Sander E A,et al. Effect of porostiy on the fluid flow charateristics and mechanical properties of tatalum scaffolds[J]. Journal of Biomedical Materials Research Part B:Applied Biomaterials,2005,73(2):315-324.
[6] Ryan G,Pandit A,Apatsidis D P. Fabrication methods of porous metals for use in orthopaedic pplications[J].Biomaterials,2006,27:2651-2670.
[7]狄玉丽.梯度多孔钛和稀土La F3增强多孔钛的制备与性能评价[D].成都:西南交通大学,2009:12-32.Di Y L. Fabrication of Gradient Porous Titanium Enhanced by Laf3and its Performance Evaluation.[D].Chengdu:Southwest Jiao Tong University,2009:12-32.
[8]狄玉丽,冯波,范兴平,等.稀土La F3增强型梯度结构多孔钛及其力学性能[J].稀有金属材料与工程,2013,42(4):814-818.Di Y L,Feng B,Fan X P,et al. Gradient structural porous titanium enhanced by La F3and its mechanical properties[J]. Rare Metal Materials and Engineering,2013,42(4):814-818.
[9] Wen H B,Wolke J G C,Wijin J R,et al.Fast precipitation of calcium phosphate layers on titanium induced by simple chemical treatments[J]. Biomaterials,1997,18(22):1471-1478.
[10] Jonasova L,Muller F A,Helebrant A,et al.Biomimetic apatite formation on chemically treated titanium[J].Biomaterials,2004,25(7-8):1187-1194.
[11] Zhao C Y,Zhu X D,Yuan T,et al. Fabrication of biomimetic apatite coating on porous titanium and their osteointegration in femurs of dogs[J]. Materials Science and Engineering C,2010,30(1):98-104.
[12] Kukibo T,Takidama H.How useful is SBF in predicting in vivo bone bioactivity[J]. Biomaterials,2006,27(15):2907-2915.
[13]李萍.浅谈稀土在医学中的应用[J].微量元素与健康研究,1999,16(4):69-70.Li P. Review of the application of rare earth in medicine[J]. Studies of Trace Elements and Health,1999,16(4):69-70.
[14]秦俊法,陈祥友,李增禧.稀土的生物学效应[J].广东微量元素科学,2002,9(3):1-16.Qin J F,Chen X Y,Li Z X. Biological effect of rare earth element[J]. Guangdong Trace Elements Science,2002,9(3):1-16.
[15]郭伯生.稀土在生物领域中应用研究进展[J].稀土,1999,20(1):64-68.Guo B S. Recent research advance of rare earth in the field of biology[J]. Chinese Rare Earths,1999,20(1):64-68.
[16]杨凯,张雪梅,田莉瑛,等.稀土元素及其化合物在生物和医药中的应用研究进展[J].煤炭与化工,2008,31(11):26-29.Yan K,Zhang X M,Tian L Y,et al. Research progress on application of rare earth and related compounds[J].Coal and Chemical Industry,2008,31(11):26-29.
[17]熊炳昆.稀土生物功能化合物的应用研究[J].中国稀土学报,1994,12(4):258-265.Xiong B K. Application of Rare Earth Biological Functional Compounds[J].Journal of The Chinese Society of Rare Earths,1994,12(4):258-265.
[18] Donald T R,Albert H B. The mechanical properties of cortical bone[J]. Journal of Bone&Joint Surgery,1974,56:1001-1022.
[19] Zysset P K,Guo X E,Hoffler C E,et al. Elastic modulus and hardness of cortical and trabecular bone lamellae measured by nanoindentation in the human femur[J].Journal of Biomechanics,1999,32(10):1005-1012.
[20]徐秀林,薜文东,戴克戎.正常人皮质骨压缩力学性能实验研究[J].医用生物力学,1996,11(1):26-29.Xu X L,Xue W D,Dai K R. The study of the mechanical property of the normal young male human cortical bone[J]. Journal of Medical Biomechanics,1996,11(1):26-29.