摘要
羟基磷灰石(Hydroxyapatite,简称HAp或HA)是一种典型的生物活性材料,具有优良的生物相容性和生物活性。人体的骨骼和牙齿是纳米羟基磷灰石针晶(nano-hydroxyapatite,n-HA)有序排列于胶原纤维而组成的天然复合材料,具有天然的纳米组装结构和优良的力学性能。而这种三维有序的纳米自组装结构与无机液晶态极其相似。
本文采用化学沉淀法制备高长径比的羟基磷灰石纳米颗粒,通过控制反应条件(温度、pH值、反应物浓度、Ca/P比值)和有机物或分散剂种类与添加量变化,调控n-HA的形状和尺寸,然后将其制备成分散性很高的溶胶态,通过溶胶中羟基磷灰石含量的控制,研究实现羟基磷灰石无机液晶态的条件,并对液晶现象进行了初步的观察。结果表明:
以浓度为0.2mol/L的硝酸钙和磷酸铵溶液为原料,控制反应pH为8,温度为90℃,可制备出长200nm-500nm,直径20nm-30nm,长径比为15-20的n-HA。在常压化学沉淀条件下,纳米羟基磷灰石的生长规律为:随反应温度升高n-HA颗粒形状相似、尺寸增大,结晶度提高,而其它因素的影响不明显。
分别采用明胶、低分子量聚丙烯酸钠、柠檬酸钠和六偏磷酸钠复合体系作为纳米羟基磷灰石颗粒的分散剂,通过对n-HA水溶胶对比显示:明胶对n-HA有独特的表面包覆作用而使其保持在水溶液有中一定的悬浮稳定作用;低分子量聚丙烯酸钠通过表面吸附也对n-HA产生一定的稳定作用;柠檬酸钠和六偏磷酸钠复合体系的分散效果最好,可制备出高度稳定n-HA溶胶体系。
对柠檬酸钠和六偏磷酸钠为复合分散剂的n-HA溶胶浓缩后的体系进行了初步的液晶观察,当溶胶浓度为5%时没有双折射现象,达到10%时,双折射现象较弱,而其浓度达到20%,体系出现了比较显著的双折射现象,此时溶胶的凝胶化临界浓度为8%.
Hydroxyapatite, (HAp or HA in short) a typical biomaterial, has excellent biocompatibility and bioactivity, and the bone and the teeth of we human being are natural composites composed of nano-hydoxyapatite, which is systematically organized in collagen fiber with excellent physical property. As we can see, this self-assembled three-dimension nano-structure is similar to that of inorganic liquid crystal.
In this paper, HA particles (n-HA) with high aspect ratio were prepared by chemical deposition. The reacting temperature, pH, the concentration and Ca/P molar ratio of the materials, and the amountof diffierent dispensants determine the shape and size of n-HA and the quality of n-HA aqueous colloids;The conditions for prepartion of n-HA sol and its liquid crystal were studied by controlling the proportion of n-HA in sol. The results are as follows:
HA nano particles, 200nm in length, 20-30nm in diameter, 15-20 in aspect ratio could be obtained by the reacting between Ca(NO3)2 and (NH4)PO4 solutions in 0.2mol/L concentration at 90℃, pH 8. As the reaction temperature goes, it was discovered that as the reaction temperature went high, the sizes of n-HA were enlarged and crystallinity is improved while the shapes were still very simillar to the original.
Found out the proper dispersant such as Gelatin, low molecular weight Polyacrylate sodium, sodium citrate and sodium hexame taphospha for preparation of n-HA colloid. Compared with these dispersants for their stability and dispensilility, it is obvious that gelatin has a particular function of the coating n-HA and it has a certain function on the stability of HAp in aqueous solution; low molecular weight polyacrylate sodium, by chemical absorption on the surface, is also functional for the dispense of n-HA in solution; sol with good quality could be prepared by using sodium citrate and sodium hexame taphospha as multiplex dispersant.
Inspection on liquid crystal state was carried out in the solution that was prepared by using sodium citrate and sodium hexame taphospha as multiplex dispersant, Gelatin respectively. It was found that the birefringence would be obvious when the non-volatile matter content of the sol was over 20%, when it was over 10% the birefringence would become less obvious, while below 5%, there would be no such phenomenon. It was also figured out that the concentration of gelatin is 8%, that is to say; the sol should be concentrated into gel state if there should be obvious phenomena of birefringence.
引文
[1] Suchanek W., Yoshimura M.. Processing and properties of hydroxyapatite-based biomaterials for use as hard tissue replacement implants[J]. J. Mater. Res., 1998, 13(2):94-117
[2]崔福斋.生物材料学[M].第2版.北京:清华大学出版社. 2004
[3]俞耀庭.生物医用材料[M].天津:天津大学出版社,2000
[4]韩颖超,王欣宇,李世普.自燃烧法合成纳米HA粉末[J].硅酸盐学报,2002,30(3):387-389
[5] Ito A., Nakamura S., Aoki H., et al. Hydrothermal growth of carbonate-containing hydroxyapatite single crystals[J]. J Crystal Growth, 1996, 163:311-317
[6]黄志良,刘羽,王大伟,等.氟羟磷灰石固溶体比较晶体化学FT-IR研究[J].武汉化工学院学报,2003 25 (1): 55-60
[7]Kay M. L, Young R. A., Posner A. S. Crystal structure of hydroxyapatite[J]. Nature, 1964, 204:1050-1052
[8] Arends J., Christoffersen J., Christoffersen M.R., et al. A calcium hydroxyapatite precipitated from an aqueous solution. Journal of Crystal Growth[J], 1987, 84:515-532
[9] Boskey A.L., Posner A.S. Formation of hydroxyapatite at low supersaturation[J]. J Phys. Chem., 1976, 80:40-44
[10]Osaka A., Miura Y, Takeuchi K., et al.. Calcium apatite prepared from calcium hydroxide and orthophosphoric acid[J]. J. Mater. Sci., 1991, 2:51-55
[11]Suzuki S.. Preparation of needle-like hydroxyapatite[J]. J. Mater. Sci. Let., 1998, 17:381-383
[12] Barralet J.E., Best S.M., Bonfield W. Effects of sintering parameters on the density and microstructure of carbonate hydroxyapatite [J]. J. Mater. Sci., 2000, 11:150-158
[13]Akao M., Aoki H., Kato K. Mechanical properties of sintered hydroxyapatite for prosthetic application[J]. J. Mater. Sci., 1981, 16: 809-812
[14]Slavica Lazic, Slavica Zec, Nada Miljevic, et al. The effect of temperature on the properties of hydroxyapatite precipitated from calcium hydroxide and phosphoric acid[J]. Thenmochimica Acta, 2001, 374:13-22
[15]Wantae Kim, Fumio Saito. Sonochemical synthesis of hydroxyapatite from H3PO4 solution with Ca(OH)2[J]. Ultrasonics sonochemistry, 2001, 8:85-88
[16]Bouyer E., Gtzhofer F., Boulos M.I.Morphological study of hydroxy-apatite nanocrystal suspension[J]. J. Mater. Sci.: Mater. Med., 2000, 11:523-531
[17]Changsheng Liu, Yue Huang, Wei Shen, et al. Kinetics of hydroxyapatite precipitation at pH 10 to 11 [J]. Biomaterials, 2001, 22:301-306
[18]kemi Yasukawa, Tomonori Matsuura, Manami Nakajima, et al. Preparation of nonstoichiometric calcium hydroxyapatite using formamide[J]. Mater.Res. Bull., 1999, 34(4):589-601
[19]Kumar R,Prakash K.H., Cheang P., et al. Temperrature driven morpho-logical changes of chemically precipitated hydroxyapatite nanoparticles[J].Langmuir, 2004,20:5196-5200
[20]Anna S., Ewa S., Zofia P., et al. Calcium phosphate materials prepared from precipitates with various Ca/P molar ratios[J]. J. Am. Ceram. Soc., 1996, 79(10): 2539-2544
[21]宋云京.羟基磷灰石粉体的制备工艺优化与合成机理研究[D],山东大学博士论文,2002
[22]郭连峰,张文光,王成熹.纳米羟基磷灰石的制备及结晶尺寸的控制[J].无机化学学报, 2004, 20 (3):291-296
[23] Bernache-Assonant, Ababou A., Champion E., et al. Sintering of calcium phosphate hydroxyapatite: Calcination and particle growth[J]. J. Euro.Ceram. Soc., 2003, 23:229-241
[24]Yun-Mo Sung, Jung-Chul Lee, Jae-Woong Yang. Crystallization and sintering characteristics of chemically precipitated hydroxyapatite nanopowder[J]. J. Crystal Growth, 2004, 262:467-472
[25]Jingbing Liu, Xiaoyue Ye, Hao Wang, et al. The influence of pH and temperature on the morphology of hydroxyapatite synthesized by hydrothermal method [J]. Ceramics international, 2003, 29:629-633
[26]Wei-Jen Shih, Yung-Feng Chen, Moo-Chin Wang, et al. Crystal growth and morphology of the nano-size hydroxyapatite powders synthesized from CaHPO4.2H2O and CaCO3 by hydrolysis method[J]. J. Crystal Growth, 2004, 270:211-218
[27]Kazuhilo Kandori, Akemi Yazukawa, Tatsuo Ishikawa. Preparation and characterization of spherical calcium hydroxyapatite[J]. Chem. Mater., 1995, 7:26-32
[28]Nancollas G.H. Biomineralization. In: Mann S., Webb J., Williams R.J.P., editors. Chemical and biochemical perspectives[J]. V.C.H.; 1989, 157-159.
[29]Ohta K., Kikuchi M., Tanaka J., et al. Synthesis of c axes oriented hydroxyapatite aggregate[J]. Chem. Lett., 2002, 9:894-895
[30]Skinner H.C. W. Studies in the basic mineralizing system CaO-P2O5-H2O [J]. Calcif tissue Res., 1974, 14:3-14
[31]Biggar G M.. Experimental studies of apatite crystallization in parts of the system CaO-P2O5-H2O at 1000 bar [J]. Min. Mag., 1966, 35:1110-1122
[32]刘榕芳,肖秀峰,倪军,等.羟基磷灰石粉末的水热合成及动力学研究[J].无机化学学报,2003 19(10): 1079-1084
[33]Li Yan, Yadong Li, Zhao-Xiang Deng, et al. Surfactant-assisted hydrothermal synthesis of hydroxyapatite nanorods[J]. International Journal of Inorganic Materials, 2001, 3:633-637
[34]王友法,闫玉华,梁飞,等.水热条件下针状羟基磷灰石单晶体的均相合成[J].硅酸盐通报,2001,2:30-33
[35]王德平,黄文山,周蔡.纳米羟基磷灰石球状晶体的合成及其吸附特性的研究[J].功能材料,2003, 34(4):476-478
[36]Liu Dean-Mo, Yang Quanzu, Troczynski Tom, et al. Structural evolution of sol-gel-derived hydroxyapatite[J]. Biomaterials, 2002, 23:1679-1687
[37]邬鸿彦,朱明刚,孔令宜,等.纳米级羟基磷灰石生物陶瓷粉末的制备新方法[J].硅酸盐通报,2002, 3:27-29
[38]Weng Wenjian, Han Gaorong, Du Piyi, et al. The effect of citric acid addition on the formation of sol-gel derived hydroxyapatite[J]. Materials Chemistry and Physics, 2002, 74:92-97
[39]Eided-Aβmann S., Viertelhaus M., Heip A., et al. The influence of aminoacids on the biomineralization of hydroxyapatite in gelatin[J]. J. Inorganic Biochemistry, 2002, 91:481-486
[40]Cameron S. Chai, Karlis A.Gross, Besim Ben-Nissan. Critical ageing of hydroxyapatite sol-gel solutions[J]. Biomaterials, 1998, 19:2291-2296
[41]Ming-Fa Hsieh, Li-Hsiang Perng, Tsung-Shune Chin, et al. Phase purity of sol-gel-dreived hydroxyapatite ceramic[J]. Biomaterials, 2001,22:2601-2607
[42]Wang Feng, Li Mu-sen, Lu Yu-peng, et al. A simple sol-gel technique for preparing hydroxyapatite nanopowders[J]. Materials Letters, 2005, 69:916-919
[43]Bezzi G, Celotti Cz, Landi E., et al. A novel sol-gel technique for hydroxyapatite preparation[J]. Materials Chemistry and Physical, 2003, 78:816-824
[44]Hwang K., Lim Y. Chemical and structure changes of hydroxyapatite films by using a sot-gel method [J]. Surface and Coatings Technology, 1999, 115:172-175
[45]刘羽,钟康年,胡文云.溶胶一凝胶法合成条件与羟基磷灰石特征的关系[J].材料科学与工程,1997 15(1): 63-65
[46]Prince L.M. Microemulsions Theory and Practice [M]. Academic Press, New York, 1977
[47]陈宗淇,王光信,徐桂英.胶体与界面化学[M].北京:高等教育出版社,2001
[48]崔正刚,殷福珊.微乳液技术及应用[M].北京:中国轻工业出版社,1999
[49]Cao Minhua, Wang Yonghui, Guo Caixin, et al. Preparation of ultrahigh-aspect-ratio hydroxyapatite nanofibers in reverse micelles under hydrothermal conditions [J]. Langmuir, 2004, 20:4784-4786
[50]任卫,李世普,王友法,等超细羟基磷灰石颗粒的反相微乳液合成[J].硅酸盐通报,2002, 6: 27-31
[51]Lim G. K., Wang.,Ng S. C., et al. processing of hydroxyapatite via microemulsion and emulsion routes [J]. Biomaterials. 1997, 18(21):1433-1439
[52]Han Y, Li S., Wang X., et al. Synthesis and sintering of nanocrystalline hydroxyapatite powders by citric acid sol-gel combustion method [J]. Mater. Res. Bull., 2004, 39:25-32
[53]韩颖超,王欣宇,李世普,闫玉华.自燃烧法合成纳米HAp粉末[J].硅酸盐学报,2002, 30 (3): 387-389
[54]Kano S, Akao M, Aoki H. Application of Hydroxyapatite2sol as Drug Carrier[J]. Bio-Med Mater Eng, 1994, 4(5): 283-290
[55]Li T, Aoki H. Reaction of Hydroxyapatite-sol in Bone Marrow. Bio-Med Mater Eng, 1995, 5(2):83-92
[56]Shipu Li, Shicheng Zhang, Wenjie Chen, et al. Effects of hydroxyapatite ultrafine powder on colony formation and cytoskeletons of MGC-803 cell[J]. Bioceramics, 1996, 9:225-227
[57]张士成,李世普,袁润章,磷灰石超微粉对骨癌Os-732细胞形态的影响[J].武汉工业大学学报,1996,18(1):12-15,
[58]Lingyun Feng, Shipu Li, Yuhua Yan. Effects of CaCO3 and TiO2 Nanometer Particles on A59 and L929 Cells[J]. Bioceramics, 2000, 13:325-328
[59]闫玉华,刘翠秀,陈闻杰.具有抑癌作用的HAP-so!的稳定性研究[J].武汉工业大学学报,1998, 20(1):45
[60]冯凌云,李世普,陈闻杰.羟基磷灰石溶胶对W-256癌肉瘤细胞和艾氏腹水瘤细胞增殖的影响[J].中国有色金属学报,1999 9(3). 651
[61]张十成,李世普,陈芳.羟基磷灰石超微粉对癌细胞作用的机理初步研究[J],武汉工业大学学报,1996, 18(1):5-8
[62]张士成.羟基磷灰石超微粉对癌细胞作用初探.[D].武汉:武汉工业大学,1996
[63]夏清华,陈道达,闫玉华.HASM对W-256细胞DNA含量及细胞周期的影响[J].武汉工.业大学学报,1999, 21(2):5-6
[64]夏清华,陈道达,林华.HASM对W-256癌肉瘤细胞胞浆Ca2+浓度及超微结构的影响[J].武汉工业大学学报,1999,21(3):17-19
[65]冯凌云,闫玉华等.HAP溶胶对W-256癌肉瘤细胞内钙离子浓度及细胞形态结构的影响[J].中国生物医学工程学报,1996, 17(4):374-377
[66]王友法.生物医用羟基磷灰石粒子的控制合成表征及其溶胶稳定性研究.[D].武汉:武汉工业大学,2005
[67]任卫,曹献英等,纳米羟基磷灰石合成及表面改性的途径和方法[J].硅酸盐通报,2002,1:38-43
[68]Sz-Chian Liou,San-Yuan Chen et al. Synthesis and characterization of needlike apatitic nanocomposite with controlled aspect ratios[J]. Biomaterials, 2003 24:3981-3988
[69]钱人元主编.无规与有序-高分子凝聚态的基本物理问题研究[M].湖南科学技术出版社,2000
[70]吴大诚著.高分子液晶[M].四川教育出版社,1988
[71]周其凤,王新久著.液晶高分子[M].科学出版社,1999
[72]谢毓章著,液晶物理学[M].科学出版社,1998
[73]O. Pelletier, P. Davidson, C. Bourgaux, C. Coulon, S. Regnault and J. Livage. A Detailed Study of the Synthesis of Aqueous vanadium Pentoxide Nematic Gels[J]. Langmuir 2000, 16, 5295-5303
[74]X. Commeinhes, P. Davidson, C. Bourgaux, J. Livage. Alignment of liquid-crystalline V2O5 ribbons suspensions in a magnetic field[J]. Adv. Mater.1997, 9, 900-903
[75]P. A. Buining, H. N. W. Lekkerkerker. Isotropic-nematic phase separation of a dispersion of organophilic boehmite rods[J]. J. Phem. Chem. 1993. 97, 11510-11516
[76]P. A. Buining, A. P. Philipes, H. N. W. Lekkerkerker. Phase Behavior of Aqueous Dispersions ofColloidal Boehmite Rods[J]. Langmuir 1994, 10, 2106-2114
[77]J. Buttenhuis, L. N. Donselaar, P. A. Buining, A. Stroobants, H. N. W. Lekkerkerker. Phase Separation of Mixtures of Colloidal Boehmite Rods and Flexible Polymers[J]. J. Colloid Interface Sci. 1995, 175, 46-56
[78]M P B van Bruggen, F M van der Kooij and H N W Lekkerkerker. Liquid crystal phase transitions in dispersions of rod-like colloidal particles[J]. J. Phys.: Condens. Matter 1996, 8,9451-9456
[79]M. P. B. van Bruggen, M. Donker, H. N. W. Lekkerkerker, T. L. Hughes. Anomalous stability of aqueous boehmite dispersions induced by hydrolyzed aluminum poly-cations[J]. Colloids and Surfaces, A: Physicochemical and Engineering Aspects 1999, 150, 115-128
[80]M. P. B, van Bruggen, J. K. G Dhont and H. N. W. Lekkerkerker. Morphology and Kinetics of the Isotropic-Nematic Phase Transition in Dispersions of Hard Rods[J]. Macromolecules 1999, 32, 2256-2264
[81]M. P. B. van Bruggen, H. N. W. Lekkerkerker. Tunable Attractions Directing Noneguilibrium States in Dispersions of Hard Rods[J]. Macromolecules 2000. 33. 5532-5535
[82]Randall W. Hicks and Thomas J. Pinnavaia. Nanoparticle Assembly of Mesoporous AlOOH(Boehmite) [J]. Chem. Mater. 2003, 15, 78-82
[83]Langmuir, I. The role of attractive and repulsive forces in the formation of tactoids, thixotropic gels, protein crystals and coacervates[J]. J. Chem. Phys. 1938, 6, 873-896
[84]Jean-Christophe P. Gabriel, Patrick Davidson. New Trends in Colloidal Liquid Crystals Based on Mineral Moieties[J]. Adv. Mater. 2000, 12, 9-20
[85]P. Gabriel, C. Sanchez and P. Davidson Observation of Nematic Liquid-Crystal Textures in Aqueous Gels of Smectite Clays[J]. J Phys. Chem.1996, 100, 11139-11143
[86]Felix M. van der Kooij, Katerina Kassapidou, Henk N. W. Lekkerkerker. Liquid crystal phase transitions in suspensions of polydisperse plate-like particles[J]. Nature 2000, 406, 868-871
[87]F. M. van der Kooij, D. van der Beek, H. N. W. Lekkerkerker. Isotropic-Nematic Phase Separation in Suspensions of Polydisperse Colloidal Platelets[J]. J. Phys. Chem. B 2001,105, 1696-1700
[88]Felix M. van der Kooij, Henk N. W. Lekkerkerker. Formation of Nematic Liquid Crystals in Suspensions of Hard Colloidal Platelets[J]. J. Phys. Chem. B 1998, 102, 7829-7832
[89]D. van der Beek, H. N. W. Lekkerkerker. Nematic ordering vs. gelation in suspensions of charged platelets[J]. Europhys. Lett. 2003, 61(5), 702-707.
[90]H. H. Wensink, G. J. Vroege, H. N. W. Lekkerkerker. Isotropic-Nematic Density Inversion in a Binary Mixture of Thin and Thick Hard Platelets[J]. J. Phys. Chem. B 2001.105, 10610-10618
[91]Weihui Song, lan A. Kinloch, Alan H. Windle, Nematic Liquid Crystallinity of Multiwall Carbon Nanotubes [J]. Science. 2003. 302, 1363
[92]Arnaud Dessombz etal, Design of Liquid-Crystalline Aqueous Suspension of Rutile Nanorods: Evidence of Anisotropic Photocatalytic Properties [J]. J.Am.Chem.Soc. 2007, 129, 5904-5909
[93]Zocher H, Iacobsohn K. [J] Kolloid Beih, 1929. 28, 167-206
[94]Heller W. polymer colloids II. Fitch E (ed) [M] Plenum Press, New York: 1980
[95]Maeda Y. Hachisu S. Schiller layers in beta-ferric oxyhydroxide sol as an ordered-disordered phase separating system[J]. Colloids&Surf. 1983, 6, 1-16.
[96]Maeda H. Maeda Y. Atomic force microscopy studies for investigating the smectic structures of colloidal crystals of beta-FeOOH[J]. Langmuir. 1996, 12:1446-1452
[97]Gabrie J C P, Camerel F, hemaire B J, DesvauY H, Davidson P. Batail P Swollen liquid-crystalline lamellar phase based on extended solid-like sheets[J]. Nature,2001. 413. 504-508
[98]F. Camerel, .J. C. P. Gabriel, P. Batail. P. Panine, P. Damdson. Combined SAXS-Rheological Studied of Liquid-Crystalline Colloidal Dispersions of Mineral Particles[J]. Langmuir, 2003, 19, 10028-10035
[99]Brown A B D, Clarke S M. Rennie A R. Ordered phase of platelike particles in concentrated dispersions[J]. Langmuir. 1998, 14, 3129-3132
[100]Brown A B D, Ferrero C, Narayanan T, Rennie A R. Phase separation and structure in a concentrated colloidal dispersion of uniform plates[J]. Eur Phys J H, 1999, 11.481-489
[101]Brown A B D, Rennie A R. Monodisperse colloidal plates under shear[J]. Phys Rev E, 2000, 62: 851-862
[102]David van der Beek, Henk N. W. Lekkerkerker. Liquid Crystal Phases of Charged Colloidal Platelets[J]. Langmuir 2004, 20, 8682-8586
[103]Marie M. Giraud Guille et al. Bone matrix like assemblies of collagen: From liquid crystals to gels and biomimetic materials[J]. Micron 2005 36:602-608
[104]Salyer K.E., Hall C.D. Porous hydroxyapatite as an only bone graftsubstitute for maxillofocid surgery[J]. Plast Reconstr. Surg., 1989, 84:236-244
[105]李祖兵,黄洪章.骨代用材料及其在牙种植中的应用[J]口腔医学纵横杂志,1995, 11:121-123
[106]吴新荣.国产羟基磷灰石眼座眶内植入的临床探讨[J].眼外伤职业眼病杂志, 2002, 24(6): 697-698
[107]宁聪琴. Ti/HA生物复合材料的力学性能与生物学行为[D],哈尔滨工业大学博士论文,2001
[108]Zhang X., Gubbels GH. M., Terpstra R.A., Metselaar R.. Toughnening of calcium hydroxyapatite with silver particles[J]. J. Mater. Sci., 1997, 32:235-243
[109]Li H., Marquis P M.. Sintering behavior of hydroxyapatite reinforced with 20wt% Al2O3[J]. J. Mater. Sci., 1993, 28:1941-1945
[110]Piconi C., Maccauro G. Zirconia as a ceramic biomaterials[J]. Biomaterials, 1999, 20:1-25
[111]Mashers N.J., Czernuszka J.T. Growth of hydroxyapatite on type collagen[J]. J. Mater. Sci. Lett., 1991, 10:992-993
[112]Groot K., Geesink R., Klein C.P A.T., et al.. Plasma sprayed coatings of hydroxyapatite[J]. Journal of Biomedical Materials Research, 1987, 21:1375-1381
[113]程逢,翁文剑,葛曼珍.生物陶瓷涂层[J].材料科学与工程,1998,16:8-12
[114]Nathalie Arnich. Marie-Claire Lanhers. Franck Laurensot, et al.. In vitroand in vivo studies of lead immobilization by synthetic hydroxyapatite[J].Environmental Pollution 2003, 124:139-143