聚醚醚酮/羟基磷灰石复合植入物的制备及性能研究
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摘要
为了解决聚醚醚酮(PEEK)无法满足植入物材料的生物学性能要求的难题,提出采用熔融沉积成形(FDM)和溶液共混的方法,在聚醚醚酮基体表面涂覆聚醚醚酮/羟基磷灰石(HA)复合涂层,增强涂层与基体之间的结合,制备出高强度高生物活性的复合植入物,并研究了HA含量、烧结温度和烧结时间对复合植入物力学性能的影响。根据缺损模型制备出了具有复杂结构的个性化狗下颌髁状突PEEK/HA复合假体,对假体形状精度进行了评价,完成了假体置换实验,结合细胞毒性实验对复合植入物的生物相容性进行了评价。研究结果表明:HA的质量分数为40%时,涂层与基体结合强度较好。当烧结温度为240℃、烧结时间为20 min时,涂覆效果和样件的力学性能最好。细胞毒性实验和假体置换实验结果表明,采用该工艺制造的复合假体具有优良的生物相容性,且形状精度满足使用要求。
A method for fabricating high-strength and high-biological composite implants is proposed to solve the problem that the polyetheretherketone(PEEK) cannot meet the implant materials requirements for biological properties. The method combines FDM and solution blending, and applies PEEK/HA on the surface of PEEK to enhance the bonding strength between the coating and substrate. The mechanical properties of the composite implants are studied and their biological properties are evaluated by cytotoxicity experiments and implant replacement experiments. A personalized mandibular condylar PEEK/HA composite implant with complex structure is fabricated based on a defect model, and its accuracy is evaluated. Results show that when the mass fraction of HA is 40%, the bonding strength between the coating and the substrate is higher. When the sintering temperature is 240 ℃ and the sintering time is 20 minutes, both the coating effect and the mechanical properties are the best. Results of cytotoxicity experiments and implant replacement experiments show that the composite implant has excellent biocompatibility, and the shape accuracy of the implant meets operating requirements.
A method for fabricating high-strength and high-biological composite implants is proposed to solve the problem that the polyetheretherketone(PEEK) cannot meet the implant materials requirements for biological properties. The method combines FDM and solution blending, and applies PEEK/HA on the surface of PEEK to enhance the bonding strength between the coating and substrate. The mechanical properties of the composite implants are studied and their biological properties are evaluated by cytotoxicity experiments and implant replacement experiments. A personalized mandibular condylar PEEK/HA composite implant with complex structure is fabricated based on a defect model, and its accuracy is evaluated. Results show that when the mass fraction of HA is 40%, the bonding strength between the coating and the substrate is higher. When the sintering temperature is 240 ℃ and the sintering time is 20 minutes, both the coating effect and the mechanical properties are the best. Results of cytotoxicity experiments and implant replacement experiments show that the composite implant has excellent biocompatibility, and the shape accuracy of the implant meets operating requirements.
引文
[1]BLUMER M J F,LONGATOS F.Structure,formation and role of cartilage canals in the developing bone[J].Annals of Anatomy-Anatomischer Anzeiger,2008,190(4):305-315.
[2]BARLOW J W,LEE G,GRAWFORDR H,et al.Artificial bone implants:U.S.Patent 6,183,515[P].2001-02-06.
[3]MEURSINGE REYNDERS R,RONCHI L,LADUL,et al.Insertion torque and orthodontic mini implants:a systematic review of the artificial bone literature[J].Proceedings of the Institution of Mechanical Engineers:Part H Journal of Engineering in Medicine,2013,227(11):1181-1202.
[4]DU Dajiang,USHIDA T,FURUKAWA K S.Influence of cassette design on three-dimensional perfusion culture of artificial bone[J].Journal of Biomedical Materials Research:Part B Applied Biomaterials,2015,103(1):84-91.
[5]PANAYOTOV L V,ORTI V,CUISINIER F,et al.Polyetheretherketone(PEEK)for medical applications[J].Journal of Materials Science:Materials in Medicine,2016,27(7):118.
[6]PATRICIA R M,BRUNO H,ANTONIO P N,et al.Mechanical and biological behavior of biomedical PEEKmatrix composites:a focused review[J].Materials Letters,2016,185:593-597.
[7]FANJ P,TSUIC P,TANGC Y.Modeling of the mechanical behavior of HA/PEEK biocomposite under quasistatic tensile load[J].Materials Science and Engineering:A,2004,382(1):341-350.
[8]PACE N,MARINELLI M,SPURIO S.Technical and histologic analysis of a retrieved carbon fiber-reinforced poly-ether-ether-ketone composite alumina-bearing liner 28months after implantation[J].The Journal of Arthroplasty,2008,23(1):151-155.
[9]赵峰,李涤尘,靳忠民,等.PEEK熔融沉积成形温度对零件拉伸性能的影响[J].电加工与模具,2015(5):43-47.ZHAO Feng,LI Dichen,JIN Zhongmin,et al.Effect of PEEK fused deposition modeling temperature on tensile properties of parts[J].Electrical Machining and Mould,2015(5):43-47.
[10]ZHANG J,KIRKHAM J,WALKWORK M L,et al.Use of self-assembled monolayer as substrates for atomic force imaging of hydroxyapatite crystals from mammalian skeletal tissues[J].Langmuir,1999,15(23):8178-8183.
[11]徐淑华,罗承萍,王迎军.羟基磷灰石生物活性梯度涂层材料的界面特点[J].中国有色金属报,2002,12(2):163-167.XU Shuhua,LUO Chengping,WANG Yingjun.Interfacial characterization of hydroxyapatite bioactive gradient coating[J].The Chinese Journal of Nonferrous Metals,2002,12(2):163-167.
[12]BAKER M S A,CHEONG P,KHOR K A.Mechanical properties of injection molded hudroxyapatite-polyetheretherketone biocomposites[J].Composites Science&Technology,2003,63(3):421-425.
[13]KUO M C,YEN S K.The process of electrochemical deposited hydroxyapatite coatings on biomedical titanium at room temperature[J].Materials Science and Engineering:C,2002,20(1/2):153-160.
[14]黄紫洋,刘榕芳,肖秀峰.电泳沉积羟基磷灰石生物陶瓷涂层的研究进展[J].硅酸盐学报,2003,31(6):591-596.HUANG Ziyang,LIU Rongfang,XIAO Xiufeng.Advancement in electrophoretic deposition hydroxyapatite bioceramic coating[J].Journal of the Chinese Ceramic Society,2003,31(6):591-596.
[15]韩建业,于振涛,周廉.溶胶凝胶法制备羟基磷灰石/TiO2复合生物活性涂层的研究[J].硅酸盐通报,2008,27(2):334-339.HAN Jianye,YU Zhentao,ZHOU Lian.Hydrosyapatite/titania composite bioactive coating on titanium metal substrate processed by sol-gel method[J].Bulletin of the Chinese Ceramic Society,2008,27(2):334-339.
[16]雷金平.聚醚醚酮/羟基磷灰石复合涂层的制备及性能研究[D].哈尔滨:哈尔滨工业大学,2011:5-7.
[17]宋禹奠.溶液共混法制备聚醚醚酮/羟基磷灰石复合材料[D].哈尔滨:哈尔滨工业大学,2010:5-6.
[18]REGOB T,NETO W A R,DE PAULA A C C,et al.Mechanical properties and stem cell adhesion of injection-molded poly(ether ether ketone)and hydroxyapatite nanocomposites[J].Journal of Applied Polymer Science,2015,132(14):1-13.
[19]王和照,张建军.金刚石薄膜的人工合成及其结合力的评估[J].微细加工技术,1994(2):58-62.WANG Hezhao,ZHANG Jianjun.Synthesis of diamond films and assessment of adhesion[J].Microfabrication Technology,1994(2):58-62.
[2]BARLOW J W,LEE G,GRAWFORDR H,et al.Artificial bone implants:U.S.Patent 6,183,515[P].2001-02-06.
[3]MEURSINGE REYNDERS R,RONCHI L,LADUL,et al.Insertion torque and orthodontic mini implants:a systematic review of the artificial bone literature[J].Proceedings of the Institution of Mechanical Engineers:Part H Journal of Engineering in Medicine,2013,227(11):1181-1202.
[4]DU Dajiang,USHIDA T,FURUKAWA K S.Influence of cassette design on three-dimensional perfusion culture of artificial bone[J].Journal of Biomedical Materials Research:Part B Applied Biomaterials,2015,103(1):84-91.
[5]PANAYOTOV L V,ORTI V,CUISINIER F,et al.Polyetheretherketone(PEEK)for medical applications[J].Journal of Materials Science:Materials in Medicine,2016,27(7):118.
[6]PATRICIA R M,BRUNO H,ANTONIO P N,et al.Mechanical and biological behavior of biomedical PEEKmatrix composites:a focused review[J].Materials Letters,2016,185:593-597.
[7]FANJ P,TSUIC P,TANGC Y.Modeling of the mechanical behavior of HA/PEEK biocomposite under quasistatic tensile load[J].Materials Science and Engineering:A,2004,382(1):341-350.
[8]PACE N,MARINELLI M,SPURIO S.Technical and histologic analysis of a retrieved carbon fiber-reinforced poly-ether-ether-ketone composite alumina-bearing liner 28months after implantation[J].The Journal of Arthroplasty,2008,23(1):151-155.
[9]赵峰,李涤尘,靳忠民,等.PEEK熔融沉积成形温度对零件拉伸性能的影响[J].电加工与模具,2015(5):43-47.ZHAO Feng,LI Dichen,JIN Zhongmin,et al.Effect of PEEK fused deposition modeling temperature on tensile properties of parts[J].Electrical Machining and Mould,2015(5):43-47.
[10]ZHANG J,KIRKHAM J,WALKWORK M L,et al.Use of self-assembled monolayer as substrates for atomic force imaging of hydroxyapatite crystals from mammalian skeletal tissues[J].Langmuir,1999,15(23):8178-8183.
[11]徐淑华,罗承萍,王迎军.羟基磷灰石生物活性梯度涂层材料的界面特点[J].中国有色金属报,2002,12(2):163-167.XU Shuhua,LUO Chengping,WANG Yingjun.Interfacial characterization of hydroxyapatite bioactive gradient coating[J].The Chinese Journal of Nonferrous Metals,2002,12(2):163-167.
[12]BAKER M S A,CHEONG P,KHOR K A.Mechanical properties of injection molded hudroxyapatite-polyetheretherketone biocomposites[J].Composites Science&Technology,2003,63(3):421-425.
[13]KUO M C,YEN S K.The process of electrochemical deposited hydroxyapatite coatings on biomedical titanium at room temperature[J].Materials Science and Engineering:C,2002,20(1/2):153-160.
[14]黄紫洋,刘榕芳,肖秀峰.电泳沉积羟基磷灰石生物陶瓷涂层的研究进展[J].硅酸盐学报,2003,31(6):591-596.HUANG Ziyang,LIU Rongfang,XIAO Xiufeng.Advancement in electrophoretic deposition hydroxyapatite bioceramic coating[J].Journal of the Chinese Ceramic Society,2003,31(6):591-596.
[15]韩建业,于振涛,周廉.溶胶凝胶法制备羟基磷灰石/TiO2复合生物活性涂层的研究[J].硅酸盐通报,2008,27(2):334-339.HAN Jianye,YU Zhentao,ZHOU Lian.Hydrosyapatite/titania composite bioactive coating on titanium metal substrate processed by sol-gel method[J].Bulletin of the Chinese Ceramic Society,2008,27(2):334-339.
[16]雷金平.聚醚醚酮/羟基磷灰石复合涂层的制备及性能研究[D].哈尔滨:哈尔滨工业大学,2011:5-7.
[17]宋禹奠.溶液共混法制备聚醚醚酮/羟基磷灰石复合材料[D].哈尔滨:哈尔滨工业大学,2010:5-6.
[18]REGOB T,NETO W A R,DE PAULA A C C,et al.Mechanical properties and stem cell adhesion of injection-molded poly(ether ether ketone)and hydroxyapatite nanocomposites[J].Journal of Applied Polymer Science,2015,132(14):1-13.
[19]王和照,张建军.金刚石薄膜的人工合成及其结合力的评估[J].微细加工技术,1994(2):58-62.WANG Hezhao,ZHANG Jianjun.Synthesis of diamond films and assessment of adhesion[J].Microfabrication Technology,1994(2):58-62.