摘要
[目的]1、制作出犬非骨水泥型人工股骨柄假体,建立犬人工关节置换的动物模型；2、探讨真空下在犬钛合金人工股骨柄上等离子喷涂纯钛后复合HA-Ti阶梯式涂层的结构特点,力学强度和固定人工关节假体的可行性,并寻找该复合阶梯式涂层的最佳工艺流程；3、观察骨-涂层-假体间界面的组织结构和功能变化。
[方法]1、制作犬非骨水泥型人工股骨柄假体,进行犬人工假体置换,检测关节功能、X线片、骨-涂层界面的结合强度以及观察涂层界面的结构；2、制作采用不同等离子喷涂功率、距离制备的纯HA涂层并检测其剪切强度；基于真空和大气下制备假体的纯Ti基层,HA涂层和复合Ti-HA阶梯式梯度涂层,分别检测和比较各假体涂层的剪切强度、显微组织和结构；3、硬组织骨切片组织学检测和骨界面显微观察。
[结果]1、人工股骨柄置换后位置和关节功能良好,无松动表现；HA+Ti+A组剪切强度为16.04±0.95MPa,HA+Ti+V组为20.08±1.95MPa,Ti+HAG+Ti+V组23.43±0.37MPa,显著统计学差异(P<0.05)；SEM示Ti+HAG+Ti+V组涂层-骨之间结合紧密,优于HA+Ti+V和HA+Ti+A组；Ti+HAG+Ti+V组骨结合率显著高于HA+Ti+V组和HA+Ti+A组(P<0.05)；2、选择喷涂功率为35kW、喷涂距离为80mm可以兼顾涂层的结构完整和结合强度的提高；真空下钛涂层的剪切强度为46.52±3.43MPa,大气下钛涂层的剪切强度为35.15±2.43MPa,两组比较有显著统计学差异(P<0.05)；Ti+HAG+Ti+V组涂层压剪强度平均为23.36±1.61MPa,高于HA+Ti+V组的18.52±1.63MPa,HA+Ti+A组的15.52±1.58MPa,具有显著性统计学差异(P<0.05)；涂层的显微组织与结构：(1)真空下钛涂层具有连续层状结构和低的气孔率,未见明显裂纹；Ti+HAG+Ti+V组涂层有连续层状结构,梯度涂层上的HA表面层中颗粒间结合致密,未见裂纹,气孔率低,从基体到涂层表面组织分布具有阶梯性；(2)钛涂层的XRD示真空下喷钛的晶体结晶完整,结构致密；Ti+HAG+Ti+V组的XRD显示HA与Ti基材的结合程度相对较高；(3)涂层的红外光谱示真空等离子喷涂的Ti基层适宜HA层的附着,Ti+HAG+Ti+V组涂层结晶度高；3、组织学观察：(1)股骨大结节下无骨质缺损现象,股骨柄固定牢固；(2)光镜下涂层与骨界面上的新生小梁骨已大部矿化与股骨通过板层骨连接；四环素标记荧光显示骨组织与涂层界面内均有新骨长入；Ti+HAG+Ti+V组每单位高倍视野下成骨细胞数和骨细胞数平均为28.9±3.5,高于HA+Ti+V组(19.4±2.4)和HA+Ti+A组(14.9±2.1),差异有显著性统计学意义(P<0.05)。(3)髓腔界面SEM显示：Ti+HAG+Ti+V组界面之间结合良好,拔出后断裂的层面位于骨组织内,Ti+HA+A和HA+Ti+V组拔出后界面断裂位于涂层内。
[结论]1、基于真空下等离子喷涂纯Ti基层及HA-Ti阶梯式梯度涂层能提高骨-假体的结合能力、增强假体的稳定性；2、真空下采用Ti基层喷涂,HA-Ti粉末按比例梯度以及35kw喷涂功率、80mm喷涂距离的等离子喷涂的涂层具有致密度较大、孔隙率适中、与HA的结合强度和HA结晶度高的特征；3、基于真空下等离子喷涂纯Ti基层及HA-Ti阶梯式梯度涂层通过较好的骨长入来提高人工股骨柄的固定效果。
[Objective] 1. To make artificial femoral stem of the no-cement prostheses and animal models of artificial joint replacement; 2. To plasma spray pure Ti on the artificial femoral stem prostheses under vacuum, then graded coat HA-Ti compound in order to understand the structural properties of these compound coating materials, their mechanical strengths and feasibility of artificial joint prostheses and to find the best technological process of graded coating this compound material; 3. To implant artificial femoral stem prostheses in dogs to observe the biological structures and property changes of bone, coating and prostheses.
[Method] 1 Making artificial femoral stem prostheses made in no-cement, replacing artificial femoral stem prostheses in dogs, Joint function tests, X ray films, bone-coating interface bond strength were tested and interface structure of the coatings were observed; 2 Pure HA coatings were plasma sprayed under different power and distances. Shear strengths and structural properties were tested; 3. primary pure Ti, HA coating and graded Ti-HA coating were made under vacuum and air, their shear strength, microstructure and structure were tested and compared, histologic studies of bone biopsy and observe the structure between bone and coatings under microscopy.
[Results] 1. Position and function of artificial prostheses in 3 groups were all good after replacement. No loose prostheses were found; Shear strength in pull-out testing was 16.04±0.95MPa in HA+Ti+A group,20.08±1.95MPa in HA+Ti+V group, and 23.43±0.37MPa in Ti+HAG+Ti+V group. Statistic differences were significant(p<0.05); SEM illustrated that bones bonded tightly with interfaces in Ti+HAG+Ti+V group, which was better than those in HA+Ti+V group and HA+Ti+A group. Bone bond rate in Ti+HAG+Ti+V group was much higher than that in HA+Ti+V group and HA+Ti+A group. 35kW spraying power and 80mm spraying distance can make both the structures of coating intact and bond strength strong.; The shear strengths between Ti coatings and substrates were 46.52±3.43MPa in Vacuum group, while they were 35.15±2.43 Mpa in air group. There were significant differences in these two groups; Average shear strength was 23.36±1.61 Mpa in Ti+HAG+Ti+V group,18.52±1.63MPa in HA+Ti+V group, and 15.52±1.58MPa in HA+Ti+A group; Statistic differences were significant(p<0.05); Regarding the analysis results of microstruction and structure:(1) In Vacuum group, there were continuous layer structure and low porosity on coatings, no big cracks were found under scanning electron microscope; In Ti+HAG+Ti+V group, there were continuous layer structure on the coatings, there were dense bond within the particles in HA surface layers of graded coatings, no big cracks were found. There were low porosity on coatings, even layer, no deep cracks, purely ladder like tissue distributors from the substrate to coating surface. (2) XRD results of Ti-coating showed that spraying Ti under vacuum had more intact crystallizations and denser structure; pure Ti substrate bond with HA was better in Ti+HAG+Ti+V group; (3) Analysis of the FTIR results showed that plasma spraying primary Ti was adapt to HA coating attachment. Crystallizations in Ti+HAG+Ti+V group were better; 3 In the respect of histological results:(1) there were no bone defects under the Large tuberosities, The femoral stems were fixed firmly.(2) under microscopy, the majorities of new bones on the coating-bone interfaces had been mineralized, and connected with femurs through Lamellar bones; From the Tetracycline marked bone tissues, we found that new bones had grown into coatings. There were averagely 28.9±3.5 osteoblasts and oesteocytes per view under microscopy in Ti+HAG+Ti+V group, which was more than those in HA+Ti+V group (19.4±2.4), and HA+Ti+A group (14.9±2.1).The statistical difference was significant.(p<0.05). (3) The SEM results of interface in the femoral medullary cavity illustrated good bond between interfaces in Ti+HAG+Ti+V group, broken layers were in the bone tissues after pulling out the prostheses, while broken interfaces were within the coatings in Ti+HA+A group and HA+Ti+V group.
[Conclusion] 1. The technology of plasma spraying pure-Ti on the substrate of artificial femoral stems under vacuum and graded coating HA-Ti can improve bonding strengths between medullary and coatings, enhance stability of prostheses.2. Plasma spraying primary Ti under vacuum and graded coating HA-Ti,35kw spray power and 80mm spray distance in this trial can make density of the substrate high, the porosity appropriate, their bond strength and crystallizations with HA is high 3. The technology in this study can improve fixation ability of joints through better bone growing in.
引文
1. 吕厚山主编.人工关节外科学.第一版.北京.1998,22-36
2. Morrey BF. Reconstructive surgery of the joints. Second edition 1997,979-1003
3. Mont MA,Hungerford DS. Proximally coated porous ingrowth prostheses. Clin Orthop,1997,344:139-149
4. Chandler HP,Reineck FT,Wixon RL,McCarthy JC. Total hip replacement in patients younger than 30 years old.A 5-Year follow-up study. J Bone Joint Surg,1981,63A: 1426-1434
5. Callaghan JJ, Salvati EA, Pellici PM,Wilson PD,Jr, Ranawat CS. Results of revision for mechanical failure after cemented total hip replacement,1979 to 1982. A 2 to 5-year followup. J Bone Joint Surg,1985,67A:1074-1085
6.栾晨光,杨庆铭.羟基磷灰石梯度涂层的生物学研究[J].中国矫形外科杂志,2001,8(8)：378-380
7. D'Lima DD, Oishi CS, Petersilge WJ, etal.100 cemented versus 100 noncemented stems with comparison of 25 matched pairs. Clin Orthop,1998, (348):140-148
8. Bourne RB, Rorabeck CH. Porous coated femoral fixation:the long and short of it! Orthopedics,2003,26:911-912
9. Bourne RB, Rorabeck CH, Burkart BC, Kirk PG:Ingrowth surfaces plasma spray coating to titanium-alloy hip replacements. Clin Orthop.1994. (298):37-46
10. Kim YH, Kim JS, Oh SH, etal. Comparison of porous-coated titanium femoral stems with and without hydroxyapatite coating. J Bone Joint Surg(Am),2003,85: 1682-1688
11. Hamadouche M, Witvoet J, Porcher R, etal:Hydroxyapatite-coated versus grit-blasted femoral stems:A prospective, randomised study using EBRA-FCA. J Bone Joint Surg 83B:979-987,2001
12. Bierbaum BE, Zeegen EN, Dayton MR. Hydroxyapatite coatingon the femoral stem in primary total hip arthroplastv. Orthonedics.2003.26:913-914
13.何智勇,廖威明,李佛保等. 生物活性羟基磷灰石涂层的动物实验观察[J].中华外科杂志,2003,41：153-154
14. Christian S,DorisM, WalterG, etal. The effectof three different calcium phosphate implant coatings on bone deposition and coating resorption:a long-term histological study in sheep[J].ClinicaiOral Implants Research,2005,16:357-373
15. Lopes MA, Knowles JC, Kuru L, etal Flow cytometry for assessing biocompatibility. J Biomed Mater Res,1998,41(4):649-656
16. Chou BY, Chang E Plasma-sprayed zircon is bond coat as an intern ediate layer for hydroxyapatite coating on titanimn alloy substrate.JM ater SciM ater M ed 2002 13(6): 589-595
17. Kim HW. Kim HE Salih V, etal Hydroxyapatite and titaniia solgel composite coatings on titanimn for hard tissue inplants mechanical and in vitro biological performance. J Biomed Mater R B Appl Bio mater 2005,72(1):1-8
18. A.Mortensen and S. Suresh. Functionally Graded Metals and Metal ceramic Composites:Part 1 Processing. International Materials Reviews.1995,40(6):239-265
19. Lee TM, Yang CY, Chan etal Camparison of plasma-sprayed Hydroxyapatite coatings and zirconia-reinforced hydroxyapatite composite coatings in vivo study,J Biomed MaterRes A,200471(4):652-660
1. Schurman DJ, Smith RL:Osteoarthritis-Current treatment and future prospects for surgical, medical, and biologic intervention. Clin Orthop Related Res 2004, 427:S183-S189.
2.崔福斋,冯庆玲.生物材料学[M].2版.北京：清华大学出版社,2004：126-200.
3. Sierra, R.J., Cooney, W.P.4th, Pagnano, M.W., Trousdale, R.T., Rand, J.A. (2004): Reoperations after 3200 revision TKAs:rates, etiology, and lessons learned. Clin Orthop 425,200-206.
4. Kang JD,McKernan DJ,Kruger M etal:Ingrowth and formation of bone in defects in and uncemented fiber-metal total hip replacement model in dogs (Review). J Bone oint Surg,1991,73A:93-99
5. Aamodt A, Lard-Larson J, Eine J. Changes in proxima femoral strain after insertion of uncemented standard and customized femoral stems. An experimental study in humanfumora [J]. J Bone Joint Surg (Br),2001,83 (6):901-909.
6. Huiskes R, Weinans H, Dalstra M. Adaptive bone remodeling in biomechanical design considerations for noncemented total hip arthroplasty. Orthopedics 1989,12:1255-1564
7. Wan Z, Dorr LD, Woodsome T, etal. Effect of stem stiffness and bone stiffness on bone remodeling in cemented total hip replacement. J Arthroplasty,1999,14:149-158.
8. Bourne RB, Rorabeck CH. Porous coated femoral fixation:the long and short of it Orthopedics,2003,26:911-912.,
9. Mandell JA, Carter DR, Goodman SB, etal. A conical collared intramedullary stem can improve stress transfer and limit micromotion [J]. Clin Biomech (Bristol, Avon), 2004,19 (7):695-703
10. Whiteside LA, Junichi A, Stephen E, etal. Fixation of the modular total hip femoral componet in cementless total hip arthoplasty [J]. Clin Orthop,1994,298:184-190
11. Meding JB. Comparison of collared and collarless femoral components in primary uncemented total hip arthroplasty. J-Arthroplasty,1997,12:27-41
12. Bloebaum RD, Bachus KN, Momberger NG, etal. Mineral apposition rates of human cancellous bone at the interface of porous coated implants. J Biomed Mater Res,1994, 28:537
13. Goetz DD,Smith EJ,Harris WH. The prevalence of femoral osteolysis associated with components inserted with or without cement in total hip replacements. J Bone Joint Surg,1994,76A:1121-1135.
14. Hagevold HE,Lyberg T,Kierulf P,Reikeras O. Micromotion of cemented and uncemented femoral components. J Bone Joint Surg,1991,73B:33-52
15. Kawasaki T, Niikura M, Kobayashi Y. Fundamental study of hydroxyl-apatite high performance liquid chromatography. Journal of Chrom-atography,1990,515: 125-128
16.沈卫,顾燕芳,刘昌胜等.羟基磷灰石的表面特性.硅酸盐报,1996(1)44-52
17. Hyun-Min Kim, Teruyuki Himeno, Masakazu Kawashita, etal. The mechanism of biomineralization of bone-like apatite on synthetic hydroxyapatite:an in vitro assessment. J R Soc Lond Inter-face,2004,1098(10):1-6
18.顾汉卿,徐国风.生物医学材料学.天津：天津翻译出版公司,1993,455-464
19.郑岳华,侯小妹,杨兆雄.多孔羟基磷灰石生物陶瓷的进展.硅酸盐通报,1995(3)：20-24
20. Soballe K, Overgaard S, Hansen ES, etal. A review of ceramic coatings for implant fixation. J Long Term Eff Med Implants.1999;9:131-151.
21. Capello WN,D'Antonio JA,Manley MT,Feinberg JR. Hydroxyapatite in total hip arthroplasty. Clin Orthop,1998,355:200-211.
22. Poss R,Walker P,Spector M,Reilly DT,Robertson DD,Sledge CB. Strategies for improving fixation of femoral components in total hip arthroplasty. Clin Orthop,1988,235:181-193
23. Mont MA,Hungerford DS. Proximally coated porous ingrowth prostheses. Clin Orthop,1997 344:139-149
24. Kim YH, Kim JS, Cho SH. Strain distribution in the proximal human femur. An in vitro comparison in the intact femur and after insertion of reference and experimental femoral stems[J].J Bone Joint Surg (Br),2001,83 (2):295-301
25. Rahbeck O, Overgaard S, Lind M, etal Sealing effect of hydroxyapatite coating on peri-implant migration of particles an experi-mental study in dogs. J Bone Joint Surg(Br),2001,83:441-447
26. Meijerink HJ, Gardeniers.JW, Buma P, etal. Hydroxyapatite does not improve the outcome of a bipolar hemiarthroplasty. Clin Orthon.2004. (421):143-150
27. Capello WN, D'Antonio JA, Feinberg JR, etal. Ten-year results with hydroxyapatite-coated total hip femoral components in patients less than fifty years old. A concise follow-up of a previous report. J Bone Joint Surg(Am),2003,85:885-889.
28. Geesink RC. Osteoconductive coatings for total joint arthroplasty.Clin Orthop,2002, (395):53-65
29. Spector M, Shortkroff S. Hsu HP, etal. Synovium-like tissue from loose joint replacement prosthesis:comparision of human material with a canine model. Semin Arthritis Rheum.1992; 21 (5);335-344
30. Tanzer M,Maloney W.J.,Jasty M.,etal The progression of femoral cortical osteolysis in association with total hip arthroplasty without cement. J. Bone Joint Surg.,1992,74-A,404-410.
31. Poss R, Walker P, Spector M,Reilly DT,Robertson DD, Sledge CB. Strategies for improving fixation of femoral components in total hip arthroplasty. Clin Orthop,1988,235:181-193
1. William LJ,Scott DF,etal. Total hip arthroplasty with hydroxyapatite coated prostheses. J Bone Joint Surg (Am),1996,8,12:1918·
2. Geesink RG. Osteoconductive coatings for total joint arthroplasty. Clin Orthop, 2002, (395):53-65
3. Capello WN, D'Antonio JA, Feinberg JR, etal Ten-years results with hydroxyapatite-coated total hip femoral components in patients less than fifty years old. A concise follow-up of a previous report J Bone Joint Surg(Am),2003, 85:885-889.
4. D'Antonio JA, Capello WN, Manley MT,etal. Hydroxyapatite femoral stems for total hip arthroplasty:10 to 13-year followup Clin Orthop Relat Res,2001, Dec (393):101-111
5. Kim YH, Kim JS, Oh SH, etal. Comparison of porous-coated titanium femoral stems with and without hydroxyapatite coating.J Bone Joint Surg(Am),2003, 85:1682-1688.
6. Duffy.P,Sher JL, Partington PF. Premature wear and osteolysis in an HA-coated, uncemented total hip arthroplasty. J Bone Joint Surg(Br),2004,86:34-38
7. 肖秀兰,陈志刚.羟基磷灰石涂层制备技术的可行性研究.材料导报,2003,17(4)：32-34
8. Yuan Huipin, Kurashina, Kenji, Bruijn, Joost etal. A preliminary study on osteoinduction of two kinds of calcium phosphate ceramics. Biomaterials,1999,20: 1799-1806
9. Ripamonti Ugo. Osteoinduction in porous hydroxyapatite implanted in heterotopic sites of different animal models. Biomaterials,1996,17:31-35
10.常程康,朱然怡,毛大立等. 等离子喷涂羟基磷灰石涂层的材料学特征无机材料学报.2000,15(5)：952-956
11. Limin Sun, etal. Surface characteristics and dissolution behavior of plasma sprayed hydroxyapatite coating. J. Bio med.Mater. Res 2002;62:228-236.
12. Michele,Rocca, etal. Osteointegration hydroxyapatite-coated and uncoated titanium screws in long-term ovatiectomized sheep.Biomaterials,2002; 23:1017-1023.
13. Bio 3. de Groot K, etal. Plasma sprayed coating of hydroxyapatite. J.Biomed.Mater.Res.,1987;21:1375-1381.
14. P. G Laing, A. B. Jr Fergosun and E. S. Hodge, Tissue Reaction in Rabbit Muscle Exposed to Metallic Implants. J. of Biomedical Materials Research.1967,1:135-149
15. D. P. Perl and A. R. Brody. Alzeimer's Disease:X-ray Spectrometric Evidence of Aluminum Accumulation in Neurofibrillary Tangle-bearing Neurons. Science.1980. 208:297-299
16. Jinno T,Goldberg VM,Davy D,etal. Osseointegration of surface-blasted implants made of titanium alloy and cobalt-chromium alloy in a rabbit intramedullary model. J Biomed Mater Res,1998,42:20-29
17. Groot K, etal. Plasma sprayed coating of hydroxyapatite. J. Biomed. Mater.Res.,1987;21:1375-1381
18.蔡建平,李波.等离子喷涂羚基磷灰石涂层的结合强度[J].材来保护.2000,33(9)：35-37
19.李宝娥,罗宏杰. 羟基磷灰石涂层与钦基体之间过渡层的研究[J]中国陶瓷.2005,41(1)：28-30
20. Kim C Y, Jee S S. Hydroxyapatite formation on bioactive glazed alumina[J]. Journal of the European Ceramic Society.2003,23:1803-1811
21.南开辉钛基种植体活性表而构建及其仿生矿化性能研究[D].广州华南理工大学,2004
22. Branemark PI, Hansson BO, Adell R, etal. Osseointegrated implants in the treatment of the edentulous jaw. Experience from a 10-year period. Scand J Plast Reconstr Surg,1977,16(Suppl):1-132
23. Hsieh MF,Perng LH,Chin TS. Hydroxyapatite coating on Ti6A14V alloy using a sol-gel derived precursor[J].Mater Chem Physics,2002,74(3):245-250.
24. A. Mortensen and S. Suresh. Functionally Graded Metals and Metal-ceramic Composites:Part 1 Processing. International Materials Reviews.1995, 40(6):239-265
25.郭成,朱维斗,金志浩.梯度功能材料的研究现状与展望.稀有金属材料与工程.1995,24(3)：18-25
26. A. Mortensen and S. Suresh. Functionally Graded Metals and Metal-ceramic Composites:Part 2 Thermome chanical Behaviour.International Materials Reviews. 1997,42(3):85-114
27.王迎军,宁成云,马利泰等.等离子喷涂生物活性梯度涂层的残余应力与结合强度.无机材料学报.1998,13(4)：529-533
28.储成林,尹钟大,朱景川等.HA-Ti生物梯度功能材料微观组织及热应力缓和特性.无机材料学报.1999,14(5)：775-781
29.高荣发.热喷涂.北京,化学工业出版社,1992：60-63
30. L.GEllies, D.GA.Nelson and J.D.B. Featherstone. Crystal lographic changes in Calcium Phosphates During Plasma-spraying. Biomaterials.1992,13 (5):313-316
31.常程康,朱然怡,毛大立等.等离子喷涂羟基磷灰石涂层的材料学特征无机材料学报,2000,15(5)：952-956
32. Tong Weidong, Chen Jiyong, Zhang Xingdong. Amorphorization and recry-stallization during plasma spraying of hydroxyapatite.Biomaterials, 1995,16:829-832
33. J.Weng,X.G.Liu,X.D Zhang and X.Y.Ji. Thermal Decomposition of Hydroxyapatite Structure Induced by Titanium and Its Dioxide.J.of Materials Science Letters. 1994,13:159-161
34.常程康,石建民,胡仲寅等.喷涂功率对真空等离子喷涂羟基磷灰石涂层的影响.无机材料学报,1998,13(2)：219-224
35.郑学斌,黄民辉,黄静琪等喷涂距离和喷涂功率对羟基磷灰石涂层的影响.无机材料学报,1999,14(5)：783-788
36. Quek C H, Khor K A, Cheang P. Influence of processing parameters in the plasma spraying of hydroxyapatite/Ti-6Al-4V composite coatings. Journal of Materials Processing Technology,1999,89-90:550-555
37. Lu Y P, Li S T, Zhu R F, etal. Further studies on the effect of stand-off distance on characteristics of plasma sprayed hydroxyl-apatite coating. Surface and Coatings Technology,2002,157:221-225
38. Weng. Jie, Liu Xiaoguang, Li Xudong, etal. Intrinsic factors of apatite influencing its amorphization during plasma-spray coating.Biomaterials,1995,16:39-44
39. K.A.Gross and C.C.Berndt. Thermal Spraying of Hydroxyapatite for bioceramic applications. Key Engineering Materials.1991,53-55:124-129
1 Kim YH,Kim JS,Oh SH,etal. Comparison of porous-coated titanium femoral stems with and without hydroxyapatite coating.J Bone Joint Surg(Am),2003,85:1682-1688.
2 Bierbaum BE,Zeegen EN, Dayton MR. Hydroxyapatite coatingon the femoral stem in primary total hip arthroplastv. Orthonedics.2003.26:913-914
3 Kokubo T, Kim H M, Kawashita M. Novel bioactive materials with different mechanical properties. Biomaterials,2003,24 (13) 2161-2175
4 Cook SD, Barrack RL, Thomas KA, etal. Quantitative analysis of tissue growth into human porous total hip components J Arthroplasty.1988,3:249-262.
5 Engh CA, Hooten JP Jr, Zettl-Schaffer KF, etal. Porous-coated total hip replacement Clin Orthop,1994. (298):89-96.
6 Geesink RG, de GrootK Klein CP. Chemical implant fixation using hydroxyl-apatite coatings the development of a human total hip pro-sthesis for chemical fixation to bone using hydroxyl-apatite coatings on titanium substrates. Clin Orthop,1988. (225):147-170.
7 Bloebaum RD, Beeks D, Dorr LD, etal Complications with hydroxyapatite particulate separation in total hip arthroplasty. Clin Orthop,1994;298; 19-26
8 Morscher EW, Hefti A, Aebi U. Severe osteolysis after third-body wear due to hydroxyapatite particles from ace-tabular cup coating.Joint Surg Br,1998;80 (2); 267-272
9 Galante J, RostokerW, LueckR, etal Sintered fibermetal composites as a basis for attachment of implants to bone. J Bone Joint Surg(Am),1971,53(1):101-114.
10 SpectorM. Historical review of porous-coated implants. J Arthroplasty,1987,2(2): 163-177.
11 Frenkel SR, Jaffe WL, Dimaano F, etal Bone response to a novel highly porous surface in a canine implantable chamber. JBiomedMater ResB ApplBiomater,2004, 71(2):387-391.
12 LopesMA, Knowles JC, Kuru L, etal Flow cytometry for assessin biocompatibility. J Biomed Mater Res,1998,41(4):649-656.
13 Chou BY, ChangE. Plasma-sprayed zirconia bond coatas an intermediate layer forhydroxyapatite coating on titanium alloy substrate. J Mater Sci Mater Med,2002, 13(6):589-595.
14 Kim HW, KimHE, SalihV, etal Hydroxyapatite and titania solgel composite coatings on titanium for hard tissue implants; mechanical and in vitro biological performance. J Biomed MaterResB ApplBiomater,2005,72(1):1-8.
15 TakemotoM, Fujibayashi S, NeoM, etal Bone-bonding ability of a hydroxyapatite coated zirconia-alumina nanocomposite with a microporous surface. J BiomedMaterResA,2006,78(4):693-701.
16 Onsten I, NordqvistA, CarlssonAS, etal Hydroxyapatite augmentation of the porous coating improves fixation of tibial components randomised RSA study in 116 patients. JBone JointSurg(Br),1998,80(3):417-425.
17 Lugscheider E,Weber T,Knepper M,etal. Production of biocompatible coatings by atmospheric plasma spraying. Mater Sci E,1991, A139:45-48
18郑学斌,丁传贤等离子喷涂HA/Ti复合涂层研究.无机材料学报,2000,15(5)：899-902
19 Lee T M, yang C, Y, Chang E, etal Comparison of plasma sprayed hydroxyapatitc coatings and zirconia-reinforced hydroxyapatite composite coatings:in vivo study. Journal of Biomedical Materials Research Part A,2004,71A (4):652-660
20 Ding S J, Ju C P, Chern L J H. Morphology and immersionbehavior of plasma-prayed hydroxyapatite/bioactive glass coatings. J Mater Sri:Matar Med.2000.11 (4):183-190
21 Hassan TU Rego C A,.Ali N, etal. An investigation of the structural properties of diamond films deposited by pulsed bias enhanced hot filament CVD. Thin Solid Films, 1999,355:134-138
22 Cui F Z, Luo Z S, Feng Q L, etal. Highly adhesive hydrocyapatite coatings on titanium alloy formed by ion beam assisted deposition. Journal of Materials Science: Materials in Medicine.1997.8(7):403-405
23 Antonov E N, Bagratashvili V N, Ball M, etal. Influence of target density on properties of laser deposited calcium phosphate coatings. Key Engineering Materials, 2001,192-195(22-26):107-110
24张国珍,张光磊,张久兴,等放电等离子烧结技术制备HA/'Ti生物活性复合材料的研究.粉末冶金技术,2004,22(1)：16-18
25 Ziya Engin Erkmen The effect of heat treatment on the morphology of D-Gun sprayed hydroxyapatite coatings.Journal of Biomedical Materials Research 1999,48(6): 861-868
26 Wu H H, Lu X Y, Long B H etal. The effects of cathodic and anodic voltages on the characteristics of porous nanocrystalline titania coatings fabricated by microarc oxidation. Mater Lett,2005,59:370-375
27 Long H L, Kim H W, Lee S H, etal. Biocompatibility of titanium implants modified by microarc oxidation and hydraxyapatite coating. Journal of Biomedical Materials Research Part A,2005,73A(1):48-54
28 Zhang H Q, Yan Y H, Li S P. Structural Characteristics of Porous Hydroxyapatite Coating on CaO-SiO2 System Class. Key Engineerine Materials.2001,192-195(22-26): 311-314
29陈晓明,李志刚,闰玉华等.钛合金人工关节柄烧结复合生物活性玻璃陶瓷涂层的研究.中国生物医学工程学报,2001,20(1)：25-32.
30 Yamada K,Imamura K,Itoh H,etal. Bone bonding behavior of the hydroxyapatite containing glass-titanium composite prepared by the Cullet method. Biomaterials,2001, 22:2207-2214
31朱明刚,李卫.钛基底HA涂层生体活性的改性研究金属功能材料,2000,7(5)：32-35
32 Milella E,Coseniino F,Licciulli A, etal. Preparation and characterization of titania/hydroxyapatite composite coatings obtained by sol-gel process. Biomaterials, 2001,22:1425-1431
33 Ramires Y A, Romito A, Cosentino F, etal. The influence of titania/hydroxyapatite composite coatings on in vitro osteoblasts behaviour. Riomaterials.2001,22:1467-474
34 Haddow D B, Thompson M S, Beny S R,etal. Compositional and structural control in bone regenerative coatings. Journal of Materials Science:Materials in Medicine,1999, 10(4):219-22
35沈王争,王银萍,黄庆安. 医用生物材料的研制与电沉积技术.电镀与精饰,2001,23(2)：20-2
36刘榕芳,肖秀峰,林岚云等.电沉积HA/TiO:复合涂层的结合强度和热稳定性研究.无机材料化学,2004,20(2)：226-30
37 Dasarathy H, Riley C, Coble H D, etal. Hydroxyapatite/metal composite coatings formed by electrodeposition. J Biomed:Mater Res,1996,31:81-9
38林昌健,胡皓冰,胡仁等.钛基表面钙磷陶瓷／高聚物膜层的电化学共沉积.2000年中国材料研讨会论文摘要集(上).北京：中国建筑材料出版社,2000.303页
39 Ma J,Wang C, Peng K M. Electrophoretic deposition of porous hydroxyapatite scaffold. Biomaterials; 2003,24:3505-510
40 Layrolle P, van der Valk, Dalmeijer R, etal. Biomimetic calcium phosphate coatings and their biological performances. Key Engineering Material,2001,192-95(22-6): 391-94
41 Pham M T, Matz W, Reuther H, etal. Hydroxyapatite nucle-anon on Na ion implanted Ti. Journal of Materials Science Letters,2000,1912:1029-031
42 Gao Y F,Kunihito K Bio-inspired ceramic processing:an example of SrTi03 deposition. Journal of Shanxi University of Science and Technology.2004,12(5):48-9
43 Lee TM, Yang CY, Chan E, etal Comparison of plasma-sprayed hydroxyapatite coatings and zirconia-reinforced hydroxyapatite composite coatings:in vivo study. JBiomedMaterResA,2004,71(4):652-60
44 Sun L,Berndt CC,Khor KA,etal. Surface characteristics and dissolution behavior of plasma-sprayed hydroxyapatite coating.J Biomed Mater Res 2002;62:228-236.
45 Michele Rocca, etal. Osteointegration hydroxyapatite-coated and uncoated titanium screws in long-term ovatiectomized sheep. Biomaterials,2002;23:1017-1023.
46 P.G.Laing,A B.Jr Fergosun and E.S.Hodge, Tissue Reaction in Rabbit Muscle Exposed to Metallic Implants.J.of Biomedical Materials Research.1967,1:135-149
47 D.P.Perl and A.R.Brody. Alzeimer's Disease.Ⅹ-ray Spectrometric Evidence of Aluminum Accumulation in Neurofibrillary Tangle-bearing Neurons. Science.1980, 208:297-299
48 Jinno T,Goldberg VM,Davy D,etal. Osseointegration of surface-blasted implants made of titanium alloy and cobalt-chromium alloy in a rabbit intramedullary model.J Biomed Mater Res,1998,42:20-29.
49 de Groot K,etal. Plasma sprayed coating of hydroxyapatite J. Biomed. Mater. Res.,1987;21:1375-1381.
50孙常太,黄公怡.羟基磷灰石涂层假体植入的实验研究及应用现状.中华骨科杂志,1998,18：561-564.
51 Kokubo T, Kim HM, Kawashita M. Novel bioactive materials with different mechanical properties.Biomaterials,2003,24:2161-2175.
52 Chang BS,Lee CK,Hong KS,etal. Osteoconduction at porous hydroxyapatite with various pore configurations.Biomaterials,2000,21:1291-1298.
53毛大立,曹海萍,常程康等. 羟基磷灰石涂层的骨结合行为.上海交通大学学报,2003,37：264-268.
1. Hench L L. Bioceramics from concept to clinic[J].Am ceram Soc,1991,74:1487-1 510.
2. Velich N, Neneth Z, Hrabak K. Repair of bony defect with combination bio-materials[J]. J Craniofac Surg,2004,15(1):11-15.
3. Geesink RG, de GrootK, Klein CP. Chemical implant fixation using hydroxyl-apatite coatings.The developmentofa human totalhip prosthesis for chemical fixation to bone using hydroxyl-apatite coatings on titanium substrates. Clin Orthop RelatRes,1987, 225:147-170.
4. Caja VL,Piza G. Hydroxyapatite coating of external fixation pins to decrease axialdeformity during tibial lengthening for short stature.J Bone Joint Surg(Am),2003,85(8):1527-1531.
5. Lopes MA, Knowles JC, Kuru L, etal Flow cytometry for assessing biocompatibility. J BiomedMaterRes,1998,41(4):649-656.
6. Heimann RB, Schurmann N, MullerRT. In vitro and in vivo performance ofTi6Al4V implantswith plasma-sprayed osteoconductive hydroxyapatite-bioinert titania bond coat"duplex"systems:an experimental study in sheep. JMaterSciMaterMed,2004, 15(9):1045-1052.
7. Lu YP, LiMS, Li ST, etal Plasma-sprayed hydroxyapatite+titania composite bond coat for hydroxyapatite coating on titanium substrate. Biomaterials,2004,25(18): 4393-4403.
8. Chou BY, ChangE. Plasma-sprayed zirconia bond coatas an intermediate layer forhydroxyapatite coating on titanium alloy substrate. J MaterSciMaterMed,2002, 13(6):589-595.
9. Kim HW, KimHE, SalihV, etal Hydroxyapatite and titania sol-gel composite coatings on titanium for hard tissue implants; mechanical and in vitro biological performance. J BiomedMaterResB ApplBiomater,2005,72(1):1-8.
10. Toni A, Lewis CG, Sudanese A, etal Bone demineralization induced by cementless alumina-coated femoral stems. J Arthroplasty,1994,9(4):435-444.
11. Inadome T, HayashiK, NakashimaY, etal Comparison ofbone-implant interface shear strength ofhydroxylapatite-coated and alumina coated metal implants. J Biomed Mater Res,1995,29(1):19-24.
12. Ning CY, WangYJ, LuWW, etal Nano-structuralbioactive gradient coating fabricated by computer controlled plasma-spraying technology. J MaterSciMaterMed,2006, 17(10):875-884.
13. van Noort, R., Titanium:the implant material of today, J. Mater. Sei. 1987,22,3801-3811
14. Galante J, RostokerW, LueckR, etal Sintered fibermetal composites as a basis for attachment of implants to bone. J Bone Joint Surg(Am),1971,53(1):101-114.
15. SpectorM. Historical review of porous-coated implants. JArthroplasty,1987,2(2): 163-177.
16. Heimann RB, Schurmann N, MullerRT. In vitro and in vivo performance of Ti6A14V implantswith plasma-sprayed osteoconductive hydroxyapatite-bioinert titania bond coat"duplex"systems:an experiment a study in sheep. JMaterSciMaterMed,2004, 15(9):1045-1052.
17. FrenkelSR, JaffeWL, Dimaano F, etal Bone response to a novel highly porous surface in a canine implantable chamber. J Biomed Mater ResB Appl Biomater,2004, 71(2):387-391.
18. Bobyn JD, Poggie RE, Krygier JJ, etal Clinical validation of a structural porous tantalum biomaterial for adult reconstruction. J Bone JointSurg(Am),2004,86(Suppl2): 123-129.
19. Bobyn JD, StackpoolGJ, Hacking SA, etal Characteristics of bone ingrowth and interfacemechanics of a new porous tantalum biomaterial J Bone JointSurg (Br),1999, 81(5):907-914.
20. Gruen TA, Poggie RA, Lewallen DG, etal Radiographic evaluation of amonoblock acetabular component:amulticenter studywith 2to 5year results. J Arthroplasty,2005, 20(3):369-378.
21. Stuberg SD. Five-year follow-up of a tantalum, monoblock acetabular component (Abstract). J Arthroplasty,2004,19(2):257.
22. MittelmeierH. Totalhip replacementwith the autopher cementfree ceramic prostheses. In:MorscherE, ed.Cementless fixation ofhip endo-prostheses. Heidelberg, New York: Springer.1983.33.
23. Lord G, BancelP. Themadreporic cementless total hip arthroplasty.New experimental data and a seven-year clinical follow-up study. Clin Orthop RelatRes,1983,176: 67-76.
24. Bobyn JD, PilliarRM, CameronHU, etal The effectofporous surface configuration on the tensile strength of fixation of implantsby bone ingrowth. Clin Orthop RelatRes, 1980,149:291-298.
25. Won YY, Dorr LD, Wan Z. Comparison of proximal porous-coated and grit-blasted surfaces of hydroxyapatite-coated stems. J Bone Joint Surg (Am),2004,86(1): 124-128.
26. Overgaard S, Lind M, Glerup H, etal Porous-coated versus grit blasted surface texture of hydroxyapatite-coated implants during controlled micromotion:mechanical and histomorphometric results. J Arthroplasty,1998,13(4):449-458.
27. Chou BY, ChangE. Plasma-sprayed zirconia bond coatas an intermediate layer forhydroxyapatite coating on titanium alloy substrate. J Mater Sci Mater Med,2002, 13(6):589-595.
28. Kim HW, KimHE, SalihV, etal Hydroxyapatite and titania sol-ge composite coatings on titanium for hard tissue implants; mechanica and in vitro biological performance. J Biomed Mater Res B ApplBio-mater,2005,72(1):1-8.
29. TakemotoM, Fujibayashi S, NeoM, etal Bone-bonding ability of a hydroxyapatite coated zirconia-alumina nanocomposite with a microporous surface. J Biomed Mater ResA,2006,78(4):693-701.
30. Onsten I, NordqvistA, CarlssonAS, etal Hydroxyapatite augmentation of the porous coating improves fixation of tibial components. A randomised RSA study in 116 patients. JBone JointSurg(Br),1998,80(3):417-425.
31. Tateyama S, Uchida K, Hidaka T, Hirao M,Yamaguchi R. Expression of Bone Morphogenetic Protein-6 (BMP-6) in myoepithelial cells in canine mammary gland tumors. Vet Pathol 2001; 38:703-709.
32. Braddock M, Parul H, Callum C, Ashcroft P. Born again bone:Tissue engineering for bone repair. News Physiol Sci 2001;16:208-213
33.邓世钧.高性能陶瓷涂层[M].北京：化学工业出版社,2005.289
34. Millet P, Girardin E Braham C, etal. Stress Influences on Interface in. Plasma-sprayed Hydroxyapatite Coatings on Titanium Alloy J Biomed Mater Res,2002,60(4):679-684
35. WEN Jian-weng, J.L. Baptista*. Alkoxide route for preparing hydroxyapatite and its coatings[J].Biomaterials,1998,19:125.
36. DING S J, SU Y M, JU C P, et al. Structure and Immersion Behavior of Plasma-sprayed Apatite-matrix Coatings [J]. Biomaterials,2001,22:833-845.
37. J.M. Zhang, C.J. Lin*,Z.D. Feng, Z.W. Tian. Mechanistic studies of electrodeposition for bioceramic coatings of calcium phosphates by an insitu pH microsensor technique[J].Journal of Electro analytical Chemistry,1998(452):235.
38.陈晓明,李志刚.钛合金人工关节柄烧结复合生物活性玻璃陶瓷涂层的研究[J].中国生物医学上程学报.2000,1：28-32(47)
39. WeiM, Ruys AJ, Swain MV, etal Hydroxyapatite-coated metals:interfacial reactions during sintering. JMaterSciMaterMed,2005,16(2):101-106.
40.付涛,李浩,徐可为. 羟基磷灰石梯度涂层的制备及其结构特征[J].硅酸盐学报.1999,27(5)：622-625.
41. Lee SH, KimHW, LeeEJ, etal Hydroxyapatite-TiO2hybrid coating on Ti implants. J Biomater App,l 2006,20(3):195-208.
42. BigiA, Boanini E, Bracci B, etal Nanocrystalline hydroxyapatite coatings on titanium: a new fast biomimetic method. Biomaterials,2005,26(19):4085-4089.
43.宁成云. 纳米结构特征的生物活性梯度涂层材料研究[D].广州：华南理工大学,2003.
44.郑岳华,侯小妹,杨兆雄.多孔羟基磷灰石生物陶瓷的进展[J].硅酸盐通报.1995,3：20-24.
45. Fujishiro Y. Coating of hydroxyapatite on metal plates using thermal dissociation of calcium-EDTA chelate in phosphate solutions under hydrothermal conditions[J].J Mater Sci:Mater Med.1995,6:172-176.
46.憨勇,徐可为. 羟基磷灰石生物陶瓷涂层制备方法综述[J].硅酸盐通报.1997,5：47-50.
47. Weng W, Baptista J L. Alkoxide route for preparing hydroxyapatite and its coatings[J].Biomaterials.1998,19:125-131.
48. Cavalli M, Gnappi G, Montenero A. Hydroxy and Fluorapatite Films onTiAlloy Substrates:Sol-gel Preparation and Characterization[J].Journal of Materials Science. 2001,36(13):3253-3260.
49.程速等.生物陶瓷涂层J7.材料科学与上程,1998,16(3)8-12
50.陈彩风. 金属基纳米羚基磷灰石涂层材料研究进展[J].陶瓷学报.2002,23(4)：241-245.
51. Jasim R, Rawlings R, West D. Metal-ceramic functionally gradient material produced by laser processing[J].J.Mater. Sci.1993,128 (10):2820-2826.