CN115400264B - 一种陶瓷人工关节对磨副制备方法 - Google Patents

一种陶瓷人工关节对磨副制备方法 Download PDF

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CN115400264B
CN115400264B CN202210974055.7A CN202210974055A CN115400264B CN 115400264 B CN115400264 B CN 115400264B CN 202210974055 A CN202210974055 A CN 202210974055A CN 115400264 B CN115400264 B CN 115400264B
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冷永祥
郭静
经佩佩
李颖欣
向颖
苏奕衡
龚艳丽
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Abstract

本发明公开了一种陶瓷人工关节对磨副制备方法，具体为：首先采用快速热压烧结方法制备金属掺杂的多孔氧化锆增韧氧化铝(Me‑ZTA)陶瓷，然后以盐酸多巴胺(DA)改性表面得到PDA‑Me‑ZTA人工关节对磨副，再以聚乙烯醇(PVA)、聚多巴胺(PDA)为原料，在PDA‑Me‑ZTA人工关节对磨副陶瓷表面制备聚多巴胺(PDA)‑聚乙烯醇(PVA)复合水凝胶涂层，构建仿生关节软骨材料。本发明提高了陶瓷关节的润滑与耐磨性能，大幅度降低陶瓷人工关节接触应力、磨损及摩擦噪声，降低陶瓷关节临床应用存在的磨损、破裂、异响等并发症的发生率，提高陶瓷关节的质量及患者舒适度。

Description

一种陶瓷人工关节对磨副制备方法
技术领域
本发明属于生物材料及材料表面改性技术领域，尤其涉及一种陶瓷人工关节对磨副制备方法。
背景技术
对于晚期关节炎及关节功能丧失的患者而言，关节置换已经成为了最有效也是最终的治疗方案[裴福兴,中国髋、膝关节置换的现状及展望,中国骨与关节杂志01(1)(2012)4-8.]。临床应用的人工关节按照关节头—关节臼配副材料的种类主要分为金属(或陶瓷)—高分子关节(MoP或CoP)、金属—金属(MoM)关节及陶瓷—陶瓷(CoC)关节三种。目前临床上使用性能最优的关节配副为陶瓷—陶瓷(CoC)关节，其磨损率低[T.M.Grupp,M.Holderied,M.A.Mulliez,R.Streller,M.JaGer,W.BloMer,S.Utzschneider,Biotribology of a vitamin E-stabilized polyethylene for hip arthroplasty–Influence of artificial ageing and third-body particles on wear,ActaBiomaterialia 10(7)(2014)3068-3078.]，抗刮擦与耐腐蚀性能好[Kocagoz,S.,B.,Underwood,R.,J.,MacDonald,D.,W.,Gilbert,Ceramic Heads Decrease Metal ReleaseCaused by Head-taper Fretting and Corrosion,Clinical Orthopaedics&RelatedResearch 474(4)(2016)985-994.][C.Piconi,A.A.Porporati,R.M.Streicher,Ceramicsin THR Bearings:Behavior under Off-Normal Conditions,Key EngineeringMaterials 631(2014)3-7.]，显著降低了骨溶解、假体松动及感染等并发症的发生率[J.P.Kretzer,U.Mueller,M.R.Streit,H.Kiefer,J.Reinders,Ion release in ceramicbearings for total hip replacement:Results from an in vitro and an in vivostudy,International Orthopaedics 42(1)(2017)1-6.][A.Beraudi,S.Stea,D.DePasquale,B.Bordini,S.Catalani,P.Apostoli,A.Toni,Metal ion release:also aconcern for ceramic-on-ceramic couplings,Hip International the Journal ofClinical&Experimental Research on Hip Pathology&Therapy 24(4)(2014)321-326.][R.Sorrentino,A.Cochis,B.Azzimonti,C.Caravaca,J.Chevalier,M.Kuntz,A.A.Porporati,R.M.Streicher,L.Rimondini,Reduced bacterial adhesion onceramics used for arthroplasty applications,Journal of the European CeramicSociety(2017)S0955221917306763.]，具有良好的市场前景，市场占有率逐年上升。由德国赛琅泰克公司推出的第4代
Figure GDA0003892577100000011
系列是目前最先进、使用效果最好、临床应用最广的一类陶瓷关节，拥有15年的成功临床经验，已在全球范围内售出超过800万个陶瓷植入组[https://www.ceramtec-medical.com/en/biolox/implant-material[2022.02.23]][https://www.ceramtec.com.br/materiais-de-ceramica/biolox/delta/[2022.02.23]。
虽然陶瓷关节极大降低了骨溶解、假体松动及感染等并发症的发生率，但由于陶瓷材料本身韧性不足，并且关节软骨的切除使得陶瓷关节摩擦界面润滑状态变差，关节的缓冲能力大为下降，接触应力变大，实际应用中陶瓷人工关节仍然存在磨损[Walter,W.L.,Insley,G.M.,Walter,W.K.and Tuke,M.A.,2004.Edge loading in third generationalumina ceramic-on-ceramic bearings:Stripe wear.Journal of Arthroplasty,19(4),pp.402–413.]、破裂[Winter,M.,Griss,P.,Scheller,G.and Moser,T.,1992.Ten-to14-year results of a ceramic hip prosthesis.Clinical Orthopaedics and RelatedResearch,282(9),pp.73–80.]、异响[Walter,W.L.,O’Toole,G.C.,Walter,W.K.,Ellis,A.and Zicat,B.A.,2007.Squeaking in ceramic-on-ceramic hips.Journal ofArthroplasty,22(4),pp.496–503.]等并发症，陶瓷关节的功能同健康人体的关节仍存在较大差距。
如何使陶瓷人工关节达到天然关节的润滑及耐磨水平，提高陶瓷关节的缓冲能力，减轻摩擦界面的接触应力，降低现有临床应用陶瓷人工关节存在的磨损、破裂、异响等并发症的发生率，是提高陶瓷人工关节产品质量，进一步促进陶瓷关节临床应用的关键。
天然关节拥有优异的润滑和耐磨性能，包覆在骨关节表面的重要软组织——关节软骨在减小骨与骨之间的摩擦以及缓冲运动时产生的震动等方面起着至关重要的作用，能够在较高的赫兹接触压力下呈现出极低的摩擦系数(0.0005-0.04)[Forster,Fisher,Theinfluence of loading time and lubricant on the friction of articularcartilage,Proceedings of the Institution of Mechanical Engineers.Part H,Journal of engineering in medicine 210(1996)109-119.]。关节软骨自上而下可分为3层：透明软骨层、钙化软骨层和软骨下骨层。其中，透明软骨层厚度在2～6mm之间，主要由水(70％)、胶原纤维(20％)和蛋白聚糖(5-10％)组成的细胞外基质组成[A.Komarraju,S.Goldberg-Stein,R.Pederson,C.Mccrum,A.Chhabra,Spectrum of Common anduncommon causes of Knee Joint Hyaline Cartilage Degeneration and their KeyImaging Features,European Journal of Radiology 129(January-February(1)(2020)109097.]，软骨细胞分布其中，弹性模量约为1.9～15MPa[Z.Ying,W.Fuyou,T.Hongbo,C.Guangxing,G.Lin,Y.Liu,Analysis of the Mineral Composition of the HumanCalcified Cartilage Zone,International Journal of Medical Sciences 9(5)(2012)353-360.][D.L.Bader,G.E.Kempson,The short-term compressive properties ofadult human articular cartilage,Bio-medical materials and engineering 4(3)(1994)245.]，在关节运动期间，透明软骨吸收并释放滑液，从而提供有效的润滑[G.Li,E.P.Sang,L.E.Defrate,M.E.Schutzer,L.Ji,T.J.Gill,H.E.Rubash,The cartilagethickness distribution in the tibiofemoral joint and its correlation withcartilage-to-cartilage contact,Clinical Biomechanics 20(7)(2005)736-744.]；软骨下骨具有良好的力学性能，弹性模量高达4GPa[Z.Ying,W.Fuyou,T.Hongbo,C.Guangxing,G.Lin,Y.Liu,Analysis of the Mineral Composition of the HumanCalcified Cartilage Zone,International Journal of Medical Sciences 9(5)(2012)353-360.][P.L.Mente,J.L.Lewis,Elastic modulus of calcified cartilage is anorder of magnitude less than that of subchondral bone,Journal of OrthopaedicResearch 12(5)(1994)637-647.]，在关节运动期间起支撑作用；中间的钙化软骨层作为连接层，弹性模量约为0.32GPa[Z.Ying,W.Fuyou,T.Hongbo,C.Guangxing,G.Lin,Y.Liu,Analysis of the Mineral Composition of the Human Calcified Cartilage Zone,International Journal of Medical Sciences 9(5)(2012)353-360.][敖彧农,李忠,张成昌,段小军,关节软骨钙化层相关研究进展,中国矫形外科杂志27(8)(2019)722-725.]，向上与透明软骨通过波浪状的潮线结构相连，向下与软骨下骨通过紧密的梳齿状黏合线结构相连，这种紧密的交互锚合方式，增加了组织界面之间的接触面积，强化了界面之间的连接强度，使得透明软骨层得以强有力地固定于软骨下骨之上，同时有利于向软骨下骨传导分散关节软骨承受的瞬时应力[敖彧农,李忠,张成昌,段小军,关节软骨钙化层相关研究进展,中国矫形外科杂志27(8)(2019)722-725.][段小军,王富友,杨柳,骨软骨组织界面结构及骨软骨复合组织构建研究,中国矫形外科杂志21(17)(2013)1729-1733.]。
天然关节软骨具有的这种多层梯度结构使其拥有极其优异的润滑与耐磨性能，可支撑人体长达几十年的正常运动过程而不显示出磨损迹象。若能在陶瓷人工关节摩擦副上构建出类天然软骨的多层梯度结构，就能极大改善陶瓷关节存在的界面润滑不足、接触应力大等问题，从而降低陶瓷人工关节现存的磨损、破裂、异响等并发症的发生率，提高陶瓷关节服役质量及患者舒适度，延长陶瓷关节的服役寿命。
发明内容
为制备一种摩擦系数低、摩擦噪声小的陶瓷人工关节对磨副(关节头、关节臼)，本发明提供一种陶瓷人工关节对磨副制备方法。
本发明的一种陶瓷人工关节对磨副制备方法，包括以下步骤：
步骤1：金属掺杂的多孔氧化锆增韧氧化铝Me-ZTA陶瓷的制备。
将含金属元素的化合物粉体溶入无水乙醇中，然后加入氧化铝粉体、氧化锆粉体和氧化钇粉体，用行星球磨机混合12～48h，得到均一的陶瓷浆料，将陶瓷浆料在烘箱中以60℃烘干，然后进行332℃的热处理，将热处理完的粉体再次球磨、干燥，得到金属掺杂的氧化锆—氧化铝复相陶瓷粉体；将混合均匀的陶瓷粉体，装入石墨模具中，然后在快速热压烧结炉中烧结，得到金属掺杂的多孔氧化锆增韧氧化铝Me-ZTA，然后机械加工制备陶瓷人工关节对磨副。
步骤2：Me-ZTA陶瓷人工关节对磨副表面多巴胺DA改性。
将Me-ZTA陶瓷浸入2～10mg/mL多巴胺的Tris-HCl溶液中10～48h，然后用去离子水将多余的多巴胺溶液冲掉，得到多巴胺表面改性的Me-ZTA陶瓷，即PDA-Me-ZTA人工关节对磨副。
步骤3：水凝胶的制备。
将1.0～5.0wt.％PDA粉末、11.0～15.0wt.％PVA粉末及～84wt.％去离子水在90℃水浴搅拌3h，得到PDA-PVA水凝胶前驱液；随后将PDA-PVA前驱液以6500pm离心5min以去除气泡，再将PDA-PVA前驱液涂覆在PDA-Me-ZTA上，在-15～-60℃冷冻10～48h，室温下解冻8～25h，循环冻融3～6次使水凝胶成胶；最后将陶瓷/水凝胶样品在45～90℃退火6～24h，再在磷酸盐缓冲液PBS中浸泡12～72h。
进一步的，步骤1中多孔氧化锆增韧氧化铝Me-ZTA掺杂的金属元素为Cu、Ag、Fe、Mn中的一种，掺杂金属元素的含量为1.5～10.0wt.％。
优选的，步骤2中将Me-ZTA陶瓷浸入含有多巴胺的Tris-HCl溶液中，多巴胺浓度为2mg/mL，浸泡时间为12h。
优选的，步骤3中PDA的质量分数是1.0wt.％，PVA是5.0wt.％，冷冻温度为-20℃，冷冻时间是16h，室温下解冻时间8h，循环冻融次数为4次，陶瓷/水凝胶样品在60℃退火12h，在磷酸盐缓冲液PBS中再水化24h。
进一步的，步骤3中所述的PVA的醇解度为98.0～99.0％(mol/mol)，粘度为54.0～66.0mPa·s。
本发明的有益技术效果为：
一、金属掺杂多孔氧化锆增韧氧化铝陶瓷材料可以满足人骨的力学性能需求，在摩擦过程中起到支撑作用。
二、在金属掺杂多孔氧化锆增韧氧化铝陶瓷材料表面构建聚水凝胶软骨层，陶瓷的多孔表面与水凝胶之间形成的复合结构在连接拓扑、化学键和耗散机制的协同作用下，实现多孔陶瓷基底与水凝胶之间的强稳结合。
三、水凝胶涂层拥有和关节软骨相似的物理化学性质，对施加载荷的动态响应可以改善陶瓷关节材料摩擦界面润滑状态，降低界面摩擦系数及界面接触应力，降低陶瓷关节在临床应用上存在的破裂、磨损及异响等并发症的发生率，提高陶瓷关节的服役质量及患者舒适度。
附图说明
图1为本发明的研究思路。
图2为实施例1制备的水凝胶与陶瓷的结合性能测试结果。
图3为实施例1制备的水凝胶/陶瓷复合结构的陶瓷材料在PBS溶液中测得的摩擦系数。
具体实施方式
下面结合附图和具体实施例对本发明做进一步详细说明。
本发明的研究思路如图1所示，本发明仿生天然软骨的多层梯度结构(透明软骨层、钙化软骨层、软骨下骨层)，设计制备水凝胶修饰的金属掺杂多孔氧化锆增韧氧化铝(ZTA)陶瓷人工关节。具体利用表面改性技术和仿生学材料设计理念，在制备金属掺杂氧化锆增韧氧化铝陶瓷的基础上，构建多孔金属掺杂氧化锆增韧氧化铝陶瓷/水凝胶复合结构，应用于陶瓷人工关节，大幅度降低陶瓷人工关节接触应力、磨损及摩擦噪声，降低陶瓷关节临床应用存在的磨损、破裂、异响等并发症的发生率，提高陶瓷关节的质量。本发明首先采用快速热压烧结方法制备金属掺杂的多孔氧化锆增韧氧化铝(ZTA)陶瓷，然后以聚乙烯醇(PVA)、盐酸多巴胺(DA)、聚多巴胺(PDA)为原料，在多巴胺改性的金属掺杂多孔氧化锆增韧氧化铝(ZTA)陶瓷表面制备聚多巴胺(PDA)-聚乙烯醇(PVA)复合水凝胶涂层，构建仿生关节软骨材料。底部的金属掺杂的多孔氧化锆增韧氧化铝陶瓷基体可以满足人骨的力学性能要求，在摩擦过程中起到和软骨下骨层一样的支撑作用；顶部的水凝胶涂层拥有和透明软骨层相似的物理化学性质，水凝胶双相结构可以实现对施加载荷的动态响应，提高陶瓷关节的润滑性能，降低陶瓷关节接触应力；陶瓷的多孔结构可以与水凝胶表面形成连接拓扑，金属掺杂多孔陶瓷材料释放出的金属离子可以与水凝胶中的羟基配位形成化学键，摩擦过程中水凝胶对应力的响应机制可以实现能量耗散。因此，金属掺杂多孔氧化锆增韧氧化铝通过连接拓扑、化学键和耗散机制的协同作用，同天然软骨中的钙化软骨层一样，与搭载的水凝胶紧密锚合，如图2所示，增加了组织界面之间的接触面积，强化了界面之间的连接强度，同时多孔表面也有利于分散水凝胶承受的瞬时应力，使得水凝胶得以强有力地固定于陶瓷基底之上。这种仿生天然软骨梯度结构设计制备的水凝胶/多孔陶瓷复合材料，可以极大地降低陶瓷关节摩擦界面的接触应力，降低关节磨损，增强界面润滑，如图3所示，有效降低陶瓷关节在临床应用上存在的破裂、磨损及异响等并发症的发生率，提高陶瓷关节的服役质量及患者舒适度。
实施例1
A、原料准备：聚乙烯醇(PVA)粉末、盐酸多巴胺(DA)粉末、聚多巴胺(PDA)粉末、Tris-HCl缓冲液、磷酸盐缓冲液(PBS)、三水硝酸铜粉体、氧化铝粉体、氧化锆粉体、氧化钇粉体作为原料，Cu的质量百分比为1.5wt.％。
B、制备步骤
a)铜掺杂多孔氧化锆增韧氧化铝(Cu-ZTA)陶瓷的制备；
将三水硝酸铜粉体、氧化铝粉体、氧化锆粉体和氧化钇粉体，用行星球磨机混合12h，此时Cu的质量百分比为1.5wt.％。然后60℃烘干，在332℃下进行热处理，随后再次球磨、干燥。混合均匀的陶瓷粉体，装入石墨模具中，通过快速热压烧结炉中烧结，得到铜掺杂的氧化锆增韧氧化铝(Cu-ZTA)。
b)Cu-ZTA表面多巴胺(DA)改性；
将Cu-ZTA陶瓷浸入2mg/mL多巴胺的Tris-HCl溶液中24h，得到多巴胺表面改性的Cu-ZTA陶瓷(PDA-Cu-ZTA)。
c)水凝胶的制备；
①将1wt.％PDA、15wt.％PVA及84wt.％去离子水在90℃水浴搅拌3h，得到PDA-PVA水凝胶前驱液；②再将PDA-PVA前驱液涂覆在PDA-Cu-ZTA上，在-20℃冷冻16h，室温下解冻8h，重复四次使水凝胶成胶；③最后在60℃退火12h，磷酸盐缓冲液(PBS)中浸泡24h。
实施2～12中各工艺参数具体数值如表1所示。
表1实施2～12工艺参数
Figure GDA0003892577100000061
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实施例13
A、原料准备：聚乙烯醇(PVA)粉末、盐酸多巴胺(DA)粉末、聚多巴胺(PDA)粉末、Tris-HCl缓冲液、磷酸盐缓冲液(PBS)、九水硝酸铁粉体、氧化铝粉体、氧化锆粉体、氧化钇粉体作为原料，Fe的质量百分比为1.5wt.％。
B、制备步骤
a)铁掺杂多孔氧化锆增韧氧化铝(Fe-ZTA)陶瓷的制备
将九水硝酸铁粉体、氧化铝粉体、氧化锆粉体和氧化钇粉体，用行星球磨机混合12h，此时Fe的质量百分比为1.5wt.％。然后60℃烘干，在332℃下进行热处理，随后再次球磨、干燥。混合均匀的陶瓷粉体，装入石墨模具中，通过快速热压烧结炉中烧结，得到铁掺杂的氧化锆增韧氧化铝(Fe-ZTA)。
b)Fe-ZTA表面多巴胺(DA)改性
将Fe-ZTA陶瓷浸入2mg/mL多巴胺的Tris-HCl溶液中24h，得到多巴胺表面改性的Fe-ZTA陶瓷(PDA-Fe-ZTA)。
c)水凝胶的制备
①将1wt.％PDA、15wt.％PVA及84wt.％去离子水在90℃水浴搅拌3h，得到PDA-PVA水凝胶前驱液；②再将PDA-PVA前驱液涂覆在PDA-Fe-ZTA上，在-20℃冷冻16h，室温下解冻8h，重复四次使水凝胶成胶；③最后在60℃退火12h，磷酸盐缓冲液(PBS)中浸泡24h。
实施14～24中各工艺参数具体数值如表2所示。
表2实施14～24工艺参数
Figure GDA0003892577100000071
实施例25
A、原料准备：聚乙烯醇(PVA)粉末、盐酸多巴胺(DA)粉末、聚多巴胺(PDA)粉末、Tris-HCl缓冲液、磷酸盐缓冲液(PBS)、四水硝酸锰粉体、氧化铝粉体、氧化锆粉体、氧化钇粉体作为原料，Mn的质量百分比为1.5wt.％。
B、制备步骤
a)锰掺杂多孔氧化锆增韧氧化铝(Mn-ZTA)陶瓷的制备
将四水硝酸锰粉体、氧化铝粉体、氧化锆粉体和氧化钇粉体，用行星球磨机混合12h，此时Mn的质量百分比为1.5wt.％。然后60℃烘干，在332℃下进行热处理，随后再次球磨、干燥。混合均匀的陶瓷粉体，装入石墨模具中，通过快速热压烧结炉中烧结，得到锰掺杂的氧化锆增韧氧化铝(Mn-ZTA)。
b)Mn-ZTA表面多巴胺(DA)改性
将Mn-ZTA陶瓷浸入2mg/mL多巴胺的Tris-HCl溶液中24h，得到多巴胺表面改性的Mn-ZTA陶瓷(PDA-Mn-ZTA)。
c)水凝胶的制备
①将1wt.％PDA、15wt.％PVA及84wt.％去离子水在90℃水浴搅拌3h，得到PDA-PVA水凝胶前驱液；②再将PDA-PVA前驱液涂覆在PDA-Mn-ZTA上，在-20℃冷冻16h，室温下解冻8h，重复四次使水凝胶成胶；③最后在60℃退火12h，磷酸盐缓冲液(PBS)中浸泡24h。
实施26～37中各工艺参数具体数值如表3所示。
表3实施26～36工艺参数
Figure GDA0003892577100000081
对本发明实施例进行水凝胶与陶瓷的结合性能测试，结果如图2所示，结果显示，金属掺杂多孔氧化锆增韧氧化铝陶瓷表面修饰水凝胶的界面结合力优于传统氧化锆增韧氧化铝陶瓷表面修饰水凝胶的界面结合力。
对本发明实施例水凝胶/陶瓷复合结构的陶瓷材料在PBS溶液中摩擦测试结果如图3所示，结果表明，和氧化锆增韧氧化铝陶瓷材料相比，水凝胶/陶瓷复合结构的陶瓷材料摩擦系数低。

Claims (5)

1.一种陶瓷人工关节对磨副制备方法，其特征在于，包括以下步骤：
步骤1：金属掺杂的多孔氧化锆增韧氧化铝Me-ZTA陶瓷的制备；
将含金属元素的化合物粉体溶入无水乙醇中，然后加入氧化铝粉体、氧化锆粉体和氧化钇粉体，用行星球磨机混合12～48h，得到均一的陶瓷浆料，将陶瓷浆料在烘箱中以60℃烘干，然后进行332℃的热处理，将热处理完的粉体再次球磨、干燥，得到金属掺杂的氧化锆—氧化铝复相陶瓷粉体；将混合均匀的陶瓷粉体，装入石墨模具中，然后在快速热压烧结炉中烧结，得到金属掺杂的多孔氧化锆增韧氧化铝Me-ZTA，然后机械加工制备陶瓷人工关节对磨副；
步骤2：Me-ZTA陶瓷人工关节对磨副表面多巴胺DA改性；
将Me-ZTA陶瓷浸入2～10mg/mL多巴胺的Tris-HCl溶液中10～48h，然后用去离子水将多余的多巴胺溶液冲掉，得到多巴胺表面改性的Me-ZTA陶瓷，即PDA-Me-ZTA人工关节对磨副；
步骤3：水凝胶的制备；
将1.0～5.0wt.％PDA粉末、11.0～15.0wt.％PVA粉末及84wt.％去离子水在90℃水浴搅拌3h，得到PDA-PVA水凝胶前驱液；随后将PDA-PVA前驱液以6500pm离心5min以去除气泡，再将PDA-PVA前驱液涂覆在PDA-Me-ZTA上，在-15～-60℃冷冻10～48h，室温下解冻8～25h，循环冻融3～6次使水凝胶成胶；最后将陶瓷/水凝胶样品在45～90℃退火6～24h，再在磷酸盐缓冲液PBS中浸泡12～72h。
2.根据权利要求1所述的一种陶瓷人工关节对磨副制备方法，其特征在于，所述步骤1中多孔氧化锆增韧氧化铝Me-ZTA掺杂的金属元素为Cu、Ag、Fe、Mn中的一种，掺杂金属元素的含量为1.5～10.0wt.％。
3.根据权利要求1所述的一种陶瓷人工关节对磨副制备方法，其特征在于，所述步骤2中将Me-ZTA陶瓷浸入含有多巴胺的Tris-HCl溶液中，多巴胺浓度为2mg/mL，浸泡时间为12h。
4.根据权利要求1所述的一种陶瓷人工关节对磨副制备方法，其特征在于，所述步骤3中PDA的质量分数是1.0wt.％，PVA是15.0wt.％，冷冻温度为-20℃，冷冻时间是16h，室温下解冻时间8h，循环冻融次数为4次，陶瓷/水凝胶样品在60℃退火12h，在磷酸盐缓冲液PBS中再浸泡24h。
5.根据权利要求1所述的一种陶瓷人工关节对磨副制备方法，其特征在于，所述步骤3中所述的PVA的醇解度为98.0～99.0％(mol/mol)，粘度为54.0～66.0mPa·s。
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