CN115304372A - 氧化锆复合陶瓷及由其制备的骨植入假体 - Google Patents
氧化锆复合陶瓷及由其制备的骨植入假体 Download PDFInfo
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Abstract
本发明涉及氧化锆复合陶瓷,所述复合陶瓷由作为第一相的60~90vol%的Ce‑TZ、弥散分布在第一相中作为第二相的8~25vol%的Y‑TZ、和余量的第三相组成,其中所述第三相是板条状的铝酸锶晶体或铝酸镧晶体。本发明进一步涉及氧化锆复合陶瓷的制备方法,和由氧化锆复合陶瓷制备的骨植入假体。
Description
技术领域
本发明涉及氧化锆复合陶瓷,进一步涉及由该氧化锆复合陶瓷制备的骨植入假体。
背景技术
采用人工假体来替换受损的关节(包括髋关节、膝关节、肘关节、腕关节或踝关节)已经成为临床上治疗关节疾病的首要选择。目前,临床上用来替换受损髋关节或膝关节的人工假体有金属对聚乙烯型、金属对金属型、陶瓷对聚乙烯型和陶瓷对陶瓷型。其中,陶瓷对聚乙烯型和陶瓷对陶瓷型由于显著降低的磨损量而得到越来越普通的应用。采用的陶瓷材料主要是氧化铝陶瓷、氧化锆陶瓷、和氧化铝-氧化锆复合陶瓷。
氧化锆陶瓷有三种晶相:单斜相、四方相和立方相。当四方相转变为单斜相时,不仅伴随着能量的消耗,而且伴随着3-5%的体积膨胀。体积膨胀会导致压应力的产生。这种能量消耗和形成压应力的协同作用,有效地阻碍了裂纹的扩展,从而显著提高了氧化锆陶瓷的断裂韧性,使得四方相氧化锆陶瓷获得了“陶瓷钢”的美誉。
纯的氧化锆在1170℃以下时以单斜相存在,在1170~2370℃时以四方相形式存在,高于2370℃时以立方相形式存在。所以,人们为了在室温获得四方相氧化锆陶瓷,往往在氧化锆陶瓷中添加稳定剂,使得四方相能够保持到室温。常见的稳定剂有Y2O3、CeO2、MgO等。其中以Y2O3稳定的氧化锆由于能够在较低的温度烧结,得到晶粒细小、接近理论密度、具有最佳力学性能的氧化锆陶瓷,而得到了最广泛的应用。
但是,随着科技的发展,人们进一步发现,现有的Y2O3稳定的氧化锆陶瓷在100~400℃的水热环境下,会自发地转变成单斜相(称作“水热时效相变”)。这种自发相变不仅会导致氧化锆陶瓷中出现亚微米裂纹,而且由于相变伴随的3-5%的体积变化,会导致氧化锆陶瓷的表面粗糙度发生改变。这一现象限制了Y2O3稳定的四方相氧化锆陶瓷的进一步应用。
为了解决这一问题,人们采用了各种途径。以德国CeramTec公司开发的氧化铝/氧化锆/铝酸锶复合陶瓷为例,他们认为Y2O3稳定的氧化锆容易发生水热时效相变的主要原因,在于Y2O3的加入导致在氧化锆晶格中形成了氧空位,当和水接触时,水中的羟基离子会占据这些氧空位,从而导致氧化锆自发地相变。因此,他们提出采用力学方式,而非化学方式(化学方式,就是采用稳定剂比如Y2O3)来稳定氧化锆。也即,将氧化锆和氧化铝制成复合陶瓷,其中氧化锆弥散分布在连续的氧化铝基质中,依靠氧化铝基质的约束作用(因为氧化锆从四方相转变成单斜相伴随着3-5%的体积膨胀),来抑制四方相氧化锆在水热环境中发生自发相变。基于这种考虑,他们制备的复合陶瓷中,特别优选氧化锆不含任何化学稳定剂。具体请参见CN102869635B。
CeramTec的这种复合陶瓷的缺点在于主要成分——氧化铝陶瓷本身的力学性能偏低,四点抗弯强度仅仅为600MPa左右,断裂韧性仅仅为4MPa.m1/2左右,从而导致复合陶瓷的整体性能偏低。其次,主要成分氧化铝和次要成分氧化锆的热膨胀系数有明显差异,导致陶瓷烧结的冷却过程中由于收缩率不同,在复合陶瓷内残留着明显的烧结应力,容易导致在烧结体中形成裂纹。
鉴于此,本发明创造性地提出采用两种不同化学稳定剂稳定的氧化锆——氧化钇稳定的四方相氧化锆(以下简称为“Y-TZ”)和氧化铈稳定的四方相氧化锆(以下简称为“Ce-TZ”),制备成复合陶瓷。一方面,由于Ce-TZ和Y-TZ的热膨胀系数几乎相同,所以不会产生残余热应力;另一方面,Ce-TZ中氧空位少,具有优异的抗水热时效相变能力,作为主要成分,形成连续的Ce-TZ基质,依靠力学方式来抑制Y-TZ的水热时效相变。从而获得具有优异的抗水热时效相变能力和极佳力学性能的氧化锆复合陶瓷。
发明内容
本发明涉及氧化锆复合陶瓷,所述复合陶瓷由作为第一相的60~90vol%的Ce-TZ、弥散分布在第一相中作为第二相的8~25vol%的Y-TZ、和余量的第三相组成,其中所述第三相是板条状的铝酸锶晶体或铝酸镧晶体。
根据本发明的实施方案,所述Ce-TZ是含有10~12mol%,优选11~12mol%氧化铈(CeO2)的四方相氧化锆;所述Y-TZ是含有2.0~4.0mol%,优选3.0mol%氧化钇(Y2O3)的四方相氧化锆。
根据本发明的实施方案,所述Y-TZ的晶粒度≤0.4微米,优选≤0.3微米;所述Ce-TZ的晶粒度≤3微米,优选≤1.5微米;所述第三相晶粒的平均长宽比为6∶1~3∶1,优选5∶1~4∶1,并且晶粒长度为4~10微米,优选5~7微米。
本发明进一步涉及氧化锆复合陶瓷的制备方法,包括:1)采用共沉淀法制备Ce-TZ粉体,粉体粒度小于200纳米,优选小于100纳米;2)采用共沉淀法制备Y-TZ粉体,粉体粒度小于100纳米,优选小于60纳米;3)将得到的Ce-TZ粉体、Y-TZ粉体和第三相粉体按照一定的比例混合;4)将3)中得到的混合粉体压制成型,得到坯体;5)将4)中的坯体放入烧结炉中,在1350-1500℃烧结1-5小时。
本发明还涉及由氧化锆复合陶瓷制备的骨植入假体,包括髋关节假体、膝关节假体、肘关节假体、腕关节假体和踝关节假体等等。
本发明的氧化锆复合陶瓷也可以用于其它工业用途。
在自然界中,铪(Hf)和锆元素是以固溶体的形式存在,难以分离,所以在本申请中,“氧化锆(ZrO2)”中含有≤5wt%氧化铪。
在本申请中,“水热处理”是指在高压釜中在134±2℃的温度、0.2MPa的压力下暴露于水蒸气中,具体可以参见ISO 13356的第4.8小节。
在本申请中,“vol%”是指体积百分比,“wt%”是指质量百分比,“mol%”是指摩尔百分比。
在本申请中,采用X射线衍射分析(简称为“XRD”,Cukα,30KV,15mA)来确定晶相含量。所以,得到的晶相含量是指XRD分析中X射线所穿透的表层中的晶相含量。
在本申请中,室温是指-20℃~40℃。
具体实施方式
通过以下实施例进一步具体地阐述本发明,但本发明不限于这些实施例。
实施例1a 制备Y-TZ粉体
采用共沉淀法制备。具体而言,将浓度15wt%的ZrOCl2.8H2O水溶液和浓度为20wt%的YCl3溶液,按照ZrO2∶Y2O3的摩尔比为97.0∶3.0的比例混合。加热至75℃,在不断搅拌下逐滴加入氨水至pH为8.5,生成白色胶体沉淀。过滤出白色胶体沉淀物,用去离子水洗涤至滤液中检测不出氯离子。于50℃真空干燥后,以100℃/小时的速率升温至800℃煅烧2小时。即得到平均粒度为25纳米的Y-TZ粉体。
实施例1b 制备Y-TZ粉体
采用共沉淀法制备。具体而言,将浓度15wt%的ZrOCl2.8H2O水溶液、浓度为20wt%的YCl3溶液、和浓度为25wt%的AlCl3溶液,按照ZrO2∶Y2O3∶Al2O3的摩尔比为96.8∶3.0∶0.2的比例混合。加热至75℃,在不断搅拌下逐滴加入氨水至pH为8.5,生成白色胶体沉淀。过滤出白色胶体沉淀物,用去离子水洗涤至滤液中检测不出氯离子。于50℃真空干燥后,以100℃/小时的速率升温至850℃煅烧2小时。即得到平均粒度为40纳米的Y-TZ粉体。
实施例2 制备Ce-TZ粉体
采用共沉淀法制备。具体而言,将浓度15wt%的ZrOCl2.8H2O水溶液、和浓度为12wt%的Ce(NO3)3.6H2O溶液,按照ZrO2∶CeO2的摩尔比为88.0∶12.0的比例混合。加热至82℃,在不断搅拌下逐滴加入氨水至pH为8.5,生成白色胶体沉淀。过滤出白色胶体沉淀物,用去离子水洗涤至滤液中检测不出氯离子和硝酸根离子。于55℃真空干燥后,以100℃/小时的速率升温至1000℃煅烧2小时。即得到平均粒度为120纳米的Ce-TZ粉体。
实施例3a 制备氧化锆复合陶瓷
将实施例1a制备的Y-TZ粉体、实施例2制备的Ce-TZ粉体和晶粒平均长宽比为4∶1、晶粒平均长度为5微米的铝酸锶粉体,按照体积比15∶80∶5的比例,加入无水乙醇,在球磨机中球磨24小时。然后倒在瓷盘中,置于烘箱中于100℃烘干。然后,经50MPa压力下干压成型,接着经150MPa压力冷等静成型后,在空气气氛的高温炉中以3℃/分的速率升温至1450℃并保温2小时。以1℃/分的速率冷却到300℃并炉冷到室温后,得到氧化锆复合陶瓷。
X射线衍射分析该复合陶瓷的氧化锆晶体中,含有95.1vol%的四方相氧化锆和4.9vol%的单斜相氧化锆,在SEM(扫描电子显微镜)下采用背散射电子可以发现,该复合陶瓷中,第一相Ce-TZ晶粒度为2.0μm,第二相Y-TZ晶粒度为0.35μm,均匀分散在第一相中,第三相为板条状铝酸锶晶体,晶粒度为6.0微米。在力学试验机进行四点抗弯强度和断裂韧性测试,抗弯强度为1250MPa,断裂韧性为13.8MPa.m1/2。
该复合陶瓷经0.2MPa的压力于水蒸气134℃水热处理5小时后,其抗弯强度为1245MPa,断裂韧性为14.0MPa.m1/2,单斜相氧化锆含量为4.9vol%,四方相氧化锆含量为95.1vol%。表明没有发生水热时效相变。
该复合陶瓷经0.2MPa的压力于水蒸气134℃水热处理10小时后,其抗弯强度为1250MPa,断裂韧性为13.2MPa.m1/2,单斜相氧化锆含量为5.1vol%,四方相氧化锆含量为94.9vol%。表明有极少的水热时效相变。
该复合陶瓷经0.2MPa的压力于水蒸气134℃水热处理20小时后,其抗弯强度为1256MPa,断裂韧性为13.9MPa.m1/2,单斜相氧化锆含量为6.9vol%,四方相氧化锆含量为83.1vol%。表明略微有水热时效相变发生。
实施例3b 制备氧化锆复合陶瓷
将实施例1b制备的Y-TZ粉体、实施例2制备的Ce-TZ粉体和晶粒的平均长宽比为4∶1、平均长度为5微米的铝酸锶粉体,按照体积比20∶72∶8的比例,加入无水乙醇,在球磨机中球磨24小时。然后倒在瓷盘中,置于烘箱中于100℃烘干。然后,经50MPa压力下干压成型,接着经190MPa压力冷等静成型后,在空气气氛的高温炉中以3℃/分的速率升温至1400℃并保温2小时。以1℃/分的速率冷却到300℃并炉冷到室温后,得到氧化锆复合陶瓷。
X射线衍射分析该复合陶瓷的氧化锆晶体中,含有100vol%的四方相氧化锆,在SEM(扫描电子显微镜)下采用背散射电子可以发现,该复合陶瓷中,第一相Ce-TZ晶粒度为1.5μm,第二相Y-TZ晶粒度为0.25μm,均匀分散在第一相中,第三相为板条状铝酸锶晶体,晶粒度为6.0微米。在力学试验机进行四点抗弯强度和断裂韧性测试,抗弯强度为1300MPa,断裂韧性为14.2MPa.m1/2。
该复合陶瓷经0.2MPa的压力于水蒸气134℃水热处理5小时后,其抗弯强度为1310MPa,断裂韧性为14.0MPa.m1/2,含有100vol%的四方相氧化锆。表明没有发生水热时效相变。
该复合陶瓷经0.2MPa的压力于水蒸气134℃水热处理10小时后,其抗弯强度为1290MPa,断裂韧性为13.9MPa.m1/2,含有100vol%的四方相氧化锆。表明没有发生水热时效相变。
该复合陶瓷经0.2MPa的压力于水蒸气134℃水热处理20小时后,其抗弯强度为1285MPa,断裂韧性为13.9MPa.m1/2,单斜相氧化锆含量为0.9vol%,四方相氧化锆含量为99.1vol%。表明有极少的水热时效相变发生。
实施例4 髋关节置换用氧化锆基陶瓷股骨头的制备
在上述实施例3a-3b中,在干压成型时采用髋关节置换用股骨头形状的橡胶模具。从而在烧结后得到球形的氧化锆复合陶瓷烧结体。将该球形的烧结体经研磨加工制备成髋关节复合陶瓷股骨头假体。
实施例5 膝关节置换用氧化锆基陶瓷假体的制备
在上述实例3a-3b中,在干压成型时采用膝关节假体胫骨平台托形状的橡胶模具。从而在烧结后得到胫骨平台托形状的氧化锆复合陶瓷烧结体。经研磨加工制备成膝关节置换用氧化锆复合陶瓷假体。
Claims (10)
1.氧化锆复合陶瓷,所述复合陶瓷由作为第一相的60~90vol%的Ce-TZ、弥散分布在第一相中作为第二相的8~25vol%的Y-TZ、和余量的第三相组成,其中所述第三相是板条状的铝酸锶晶体或铝酸镧晶体。
2.根据权利要求1所述的氧化锆复合陶瓷,所述复合陶瓷由作为第一相的70~90vol%的Ce-TZ、弥散分布在第一相中作为第二相的15~20vol%的Y-TZ、和余量的第三相组成,其中所述第三相是板条状的铝酸锶晶体或铝酸镧晶体。
3.根据权利要求1或2所述的氧化锆复合陶瓷,其中所述Ce-TZ是含有10.0~12.0mol%氧化铈的四方相氧化锆,所述Y-TZ是含有2.0~4.0mol%氧化钇的四方相氧化锆。
4.根据权利要求1或2所述的氧化锆复合陶瓷,其中所述Ce-TZ是含有10.0~12.0mol%氧化铈的四方相氧化锆,所述Y-TZ是含有2.0~4.0mol%氧化钇和0.10~0.25mol%氧化铝的四方相氧化锆。
5.根据权利要求4所述的氧化锆复合陶瓷,其中所述Ce-TZ是含有11.0~12.0mol%氧化铈的四方相氧化锆,所述Y-TZ是含有3.0mol%氧化钇和0.20mol%氧化铝的四方相氧化锆。
6.根据权利要求3所述的氧化锆复合陶瓷,其中所述Y-TZ的晶粒度≤0.4微米;所述Ce-TZ的晶粒度≤3微米;所述第三相晶粒的平均长宽比为6∶1~3∶1,并且晶粒平均长度为4~10微米。
7.根据权利要求6所述的氧化锆复合陶瓷,其中所述Y-TZ的晶粒度≤0.3微米;所述Ce-TZ的晶粒度≤1.5微米;所述第三相晶粒的平均长宽比为5∶1~4∶1,并且晶粒平均长度为5~7微米。
8.根据权利要求1-7任一的氧化锆复合陶瓷的制备方法,包括:1)采用共沉淀法制备Ce-TZ粉体,粉体粒度小于200纳米;2)采用共沉淀法制备Y-TZ粉体,粉体粒度小于100纳米;3)将得到的Ce-TZ粉体、Y-TZ粉体和第三相粉体按照一定的比例混合,得到混合粉体;4)将3)中得到的混合粉体压制成型,得到坯体;5)将4)中的坯体放入烧结炉中,在1350-1500℃烧结1-5小时。
9.制备根据权利要求8所述的制备方法,其中所述Ce-TZ粉体的粉体粒度小于100纳米;所述Y-TZ粉体的粉体粒度小于60纳米。
10.利用根据权利要求1-7任一的氧化锆复合陶瓷制备的骨植入假体,包括髋关节置换用人工股骨头和内衬以及膝关节置换用膝关节假体。
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