CN117653423A - 一种含仿生多孔薄层的钛合金股骨髁假体及其制备方法、人工膝关节 - Google Patents
一种含仿生多孔薄层的钛合金股骨髁假体及其制备方法、人工膝关节 Download PDFInfo
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- CN117653423A CN117653423A CN202311687425.XA CN202311687425A CN117653423A CN 117653423 A CN117653423 A CN 117653423A CN 202311687425 A CN202311687425 A CN 202311687425A CN 117653423 A CN117653423 A CN 117653423A
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- titanium alloy
- femoral condyle
- porous titanium
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- bionic porous
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Abstract
本发明提供了一种含仿生多孔薄层的钛合金股骨髁假体及其制备方法、人工膝关节,涉及医疗器械技术领域。本发明提供的钛合金股骨髁假体包括钛合金股骨髁基体和附着于所述钛合金骨髁基体内表面的仿生多孔钛合金层;所述仿生多孔钛合金层的孔隙率为55~80%,孔径为300~650μm;所述仿生多孔钛合金层的孔隙为三维贯通结构。本发明的仿生多孔钛合金层满足了诱导骨组织生长的要求,有利于骨细胞的粘附、生长和分化,同时多孔钛合金允许骨组织长入孔隙内,使植入体与骨组织之间形成生物固定,提高了界面结合强度,并且可以利用多孔结构实现载药功能,降低术后不良反应,提高治疗效果,加快骨组织的生长过程。
Description
技术领域
本发明涉及医疗器械技术领域,尤其涉及一种含仿生多孔薄层的钛合金股骨髁假体及其制备方法、人工膝关节。
背景技术
人工膝关节置换术能有效根除晚期膝关节病痛,恢复膝关节功能,以及提高患者生存质量,已经成为治疗各种原因导致的膝关节终末期疾病的最有效的方法。
在膝关节置换手术中,人工膝关节的固定方式主要分骨水泥固定型和非骨水泥固定型两类。目前应用最广泛的是骨水泥固定型假体,通过在安装假体与骨床之间充填骨水泥,使得假体固定在骨水泥中。然而骨水泥固定存在骨水泥疲劳,使得骨水泥在维持人工关节的长期稳定性方面并不理想。非骨水泥固定假体,如各种微孔型或羟基磷灰石(HA)涂层假体,是通过人工关节的多孔表面与骨紧密接触,实现骨长入达到生物闭锁的一种固定方式。有研究表明,适宜于骨长入孔径应为150~700μm,当孔径小于100μm时,骨组织无法长入孔内。现有的与非骨水泥固定假体关联的产品难以实现有效的骨组织长入并形成稳定的三维骨组织/假体网络连接,因而中、远期固定效果并未改观。
发明内容
本发明的目的在于提供一种含仿生多孔薄层的钛合金股骨髁假体及其制备方法、人工膝关节,本发明能够实现股骨髁假体与骨床之间骨组织长入,实现良好的生物学固定效果。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种钛合金股骨髁假体,包括钛合金股骨髁基体和附着于所述钛合金股骨髁基体内表面的仿生多孔钛合金层;所述仿生多孔钛合金层的孔隙率为55~80%,孔径为300~650μm;所述仿生多孔钛合金层的孔隙为三维贯通结构。
优选的,还包括附着于所述钛合金股骨髁基体外表面的硬质碳基薄膜。
优选的,所述硬质碳基薄膜的厚度为0.8~2.0μm;硬度为15~22GPa。
优选的,所述仿生多孔钛合金层的厚度为1~4mm。
优选的,所述钛合金股骨髁基体与所述仿生多孔钛合金层通过烧结以冶金方式连接。
本发明提供了上述方案所述钛合金股骨髁假体的制备方法,包括以下步骤:
将仿生多孔钛合金层的制备原料混合,得到钛合金浆料;以质量百分比计,所述仿生多孔钛合金层的制备原料包括:羟丙基甲基纤维素0.5~1%、琼脂1~2%、聚乙二醇三甲基壬基醚1~3%、第一钛合金粉末45~65%和水余量;
将所述钛合金浆料注入到模具中,进行凝胶固化,干燥,得到凝胶状多孔钛合金坯体;
将所述凝胶状多孔钛合金坯体进行预烧结脱脂,得到预烧结仿生多孔钛合金;
将所述预烧结仿生多孔钛合金加工成目标尺寸,得到仿生多孔钛合金层;
向所述仿生多孔钛合金层与股骨髁基体接触的外表面层涂覆聚甲醛进行表面孔隙填充,得到外表面孔填充的仿生多孔钛合金层;
将钛合金股骨髁基体的制备原料混合,进行造粒,得到喂料;所述钛合金股骨髁基体的制备原料包括第二钛合金粉末和粘结剂;
将所述外表面孔填充的仿生多孔钛合金层预先置于股骨髁模具中,然后将所述喂料注入到所述股骨髁模具中,进行注射成型,得到股骨髁假体胚胎;
将所述股骨髁假体胚胎进行排胶,除去股骨髁基体中的粘结剂和仿生多孔钛合金层表面填充的聚甲醛,得到钛合金股骨髁假体前驱体;
将所述钛合金股骨髁假体前驱体进行真空烧结,得到钛合金股骨髁假体。
优选的,所述真空烧结后,还包括:采用磁控溅射在所述钛合金股骨髁基体外表面沉积硬质碳基薄膜。
优选的,以质量百分含量计,所述粘结剂包括:聚甲醛55~65%、聚乙二醇10~12%、低密度聚乙烯20~25%、聚丙烯1~3%、石蜡2~4%和硬脂酸1~3%;所述粘结剂的质量为第二钛合金粉末质量的10~15%。
优选的,所述真空烧结的温度为1200~1300℃,保温时间为2.5~3.5h。
本发明提供了一种人工膝关节,包括上述方案所述的钛合金股骨髁假体或上述方案所述制备方法制备得到的钛合金股骨髁假体。
本发明提供了一种钛合金股骨髁假体,包括钛合金股骨髁基体和附着于所述钛合金股骨髁基体内表面的仿生多孔钛合金层;所述仿生多孔钛合金层的孔隙率为55~80%,孔径为300~650μm;所述仿生多孔钛合金层的孔隙为三维贯通结构。股骨髁内侧多孔钛合金的孔隙为三维贯通孔结构,开孔率>99%,孔隙率范围为55~80%,孔径分布在300~650μm,满足了诱导骨组织生长的要求,有利于骨细胞的粘附、生长和分化,同时多孔钛合金允许骨组织长入孔隙内,使植入体与骨组织之间形成生物固定,提高了界面结合强度,并且可以利用多孔结构实现载药功能,降低术后不良反应,提高治疗效果,加快骨组织的生长过程。
此外,金属钛合金具有良好的生物兼容性,减少了股骨髁假体在人体内的不良反应。
进一步的,股骨髁假体内侧多孔钛合金与钛合金股骨髁基体通过冶金结合,结合强度高。
进一步的,本发明在股骨髁基体外层还附着有硬质碳基薄膜,具有良好的耐磨性能,且碳材料本身结构稳定,具有良好的生物兼容性。股骨髁外侧碳基硬质薄膜与聚乙烯材料的摩擦系数可以低至0.03~0.04,极大地降低了高分子聚乙烯垫片的磨损。
本发明还提供了上述方案所述钛合金股骨髁假体的制备方法,可以通过控制第一钛合金粉末的含量,制备凝胶、浆料时搅拌的速度和时间等参数,进而控制仿生多孔钛合金层的孔隙率,平均孔径大小,孔径分布,最终得到与人骨弹性模量、力学性能具有良好匹配度的仿生多孔结构。
附图说明
图1为本发明人工膝关节的结构示意图,其中,1-钛合金股骨髁基底、2-仿生多孔钛合金层、3-硬质碳基薄膜、4-垫片、5-钛合金胫骨托;
图2为实施例1制备的仿生多孔钛合金层的SEM图;
图3为多孔钛合金圆柱形植入物骨组织生长情况图。
具体实施方式
本发明提供了一种钛合金股骨髁假体,包括钛合金股骨髁基体和附着于所述钛合金骨髁基体内表面的仿生多孔钛合金层;所述仿生多孔钛合金层的孔隙率为55~80%,孔径为300~650μm;所述仿生多孔钛合金层的孔隙为三维贯通结构。
在本发明中,所述钛合金股骨髁基体与仿生多孔钛合金层中的钛合金优选为Ti6Al4V、Ti6Al7Nb、Ti5Al3Mo4Zr、Ti5Al2.5Fe、Ti40Ta、Ti15Mo3Nb、Ti12Mo6Zr2Fe、Ti35Nb7Zr5Ta、Ti15Mo、Ti12Mo5Zr3Al、Ti8Fe8Ta或Ti8Fe8Ta4Zr。金属钛合金具有良好的生物兼容性,能够减少股骨髁假体在人体内的不良反应。
在本发明中,所述仿生多孔钛合金层的孔隙率优选为60~75%,更优选为65~70%;所述仿生多孔钛合金层的孔径优选为350~600μm,更优选为400~550μm。在本发明中,所述仿生多孔钛合金层的厚度优选为1.5~3.5mm,更优选为2~3mm。在本发明中,所述仿生多孔钛合金层的孔隙为三维贯通结构。本发明所述仿生多孔钛合金层的孔结构三维贯通,配合其孔隙率和孔径,满足了诱导骨组织生长的要求,有利于骨细胞的粘附、生长和分化,同时多孔钛合金允许骨组织长入孔隙内,使植入体与骨组织之间形成生物固定,提高了界面结合强度,并且可以利用多孔结构实现载药功能,降低术后不良反应,提高治疗效果,加快骨组织的生长过程。
在本发明中,所述钛合金股骨髁基体与所述仿生多孔钛合金层优选通过烧结以冶金方式连接。本发明采用冶金方式连接,能够提高股骨髁基体与仿生多孔钛合金层的结合强度。
在本发明中,所述钛合金股骨髁假体优选还包括附着于所述钛合金股骨髁基体外表面的硬质碳基薄膜。在本发明中,所述硬质碳基薄膜的厚度优选为0.8~2.0μm,更优选为1.0~1.8μm;硬度优选为15~22GPa,更优选为17~20GPa。本发明在股骨髁基体外层附着硬质碳基薄膜,能够提高股骨髁假体的耐磨性能,且碳材料本身结构稳定,具有良好的生物兼容性。本发明通过设置硬质碳基薄膜,股骨髁外侧硬质碳基薄膜与聚乙烯材料的摩擦系数可以低至0.03~0.04,极大地降低了高分子聚乙烯垫片的磨损。
本发明对所述硬质碳基薄膜的具体组成和结构不做特殊要求,本领域熟知的满足上述硬度要求的碳基薄膜均可。在本发明的实施例中,所述硬质碳基薄膜具体为申请号为2023114350300公开的硬质碳基薄膜;所述硬质碳基薄膜包括依次层叠的碳化钛底层、碳化钛-碳过渡层、碳-碳化钛多层和非晶碳顶层;所述碳化钛底层与钛合金股骨髁基体接触;所述碳化钛-碳过渡层由碳与碳化钛组成;所述碳-碳化钛多层由交替层叠的碳层和碳化钛层组成。所述碳化钛底层的厚度优选为100~200nm,所述碳化钛-碳过渡层的厚度优选为100~200nm,所述非晶碳顶层的厚度优选为50~100nm。以相邻碳层和碳化钛层的总厚度作为一个调制周期,所述碳-碳化钛多层的调制周期优选为5~10nm;所述碳-碳化钛多层的总厚度优选为550~1500nm。以上结构设计,使得整体的硬质碳基薄膜既具有高的强度(耐磨)又具有小的摩擦系数(减摩),而且与钛合金股骨髁基体结合力好。
本发明采用上述结构的硬质碳基薄膜,根据ASTM F1160-14标准,试棒静态弯曲失效时,对应弯曲应力582MPa下,经1000万次循环,镀膜钛合金试棒薄膜未见开裂、剥落。
本发明提供了上述方案所述钛合金股骨髁假体的制备方法,包括以下步骤:
将仿生多孔钛合金层的制备原料混合,得到钛合金浆料;以质量百分比计,所述仿生多孔钛合金层的制备原料包括:羟丙基甲基纤维素0.5~1%、琼脂1~2%、聚乙二醇三甲基壬基醚1~3%、第一钛合金粉末45~65%和水余量;
将所述钛合金浆料注入到模具中,进行凝胶固化,干燥,得到凝胶状多孔钛合金坯体;
将所述凝胶状多孔钛合金坯体进行预烧结脱脂,得到预烧结仿生多孔钛合金;
将所述预烧结仿生多孔钛合金加工成目标尺寸,得到仿生多孔钛合金层;
向所述仿生多孔钛合金层与股骨髁基体接触的外表面层涂覆聚甲醛进行表面孔隙填充,得到外表面孔填充的仿生多孔钛合金层;
将钛合金股骨髁基体的制备原料混合,进行造粒,得到喂料;所述钛合金股骨髁基体的制备原料包括第二钛合金粉末和粘结剂;
将所述外表面孔填充的仿生多孔钛合金层预先置于股骨髁模具中,然后将所述喂料注入到所述股骨髁模具中,进行注射成型,得到股骨髁假体胚胎;
将所述股骨髁假体胚胎进行排胶,除去股骨髁基体中的粘结剂和仿生多孔钛合金层表面填充的聚甲醛,得到钛合金股骨髁假体前驱体;
将所述钛合金股骨髁假体前驱体进行真空烧结,得到钛合金股骨髁假体。
在本发明中,未经特殊说明,所用原料均为本领域熟知的市售商品。
本发明将仿生多孔钛合金层的制备原料混合,得到钛合金浆料。
在本发明中,以质量百分比计,所述仿生多孔钛合金层的制备原料包括:羟丙基甲基纤维素0.5~1%、琼脂1~2%、聚乙二醇三甲基壬基醚1~3%、第一钛合金粉末45~65%和水余量;作为优选的方案,所述羟丙基甲基纤维素优选为0.6~1.0%,所述琼脂优选为1.2~1.8%,所述聚乙二醇三甲基壬基醚优选为1.5~2.5%,所述第一钛合金粉末优选为50~60%。
在本发明中,所述羟丙基甲基纤维素(HPMC)的作用是作为增稠剂,提高凝胶状多孔钛合金坯体的力学强度,并改善气泡的稳定性。琼脂是凝胶体系的核心,对浆料的性能起决定性作用,具体的,琼脂的含量对浆料粘度影响巨大,当琼脂的浓度过高时,既会增大浆料粘度,影响注模,也会使坯体中的有机物含量增多,在脱脂过程中会增大Ti的碳化物或者氧化物等杂质出现的可能性;当琼脂含量过低时,会导致坯体的强度变低,从而影响加工和烧结。琼脂在较高温度下溶于水(约80℃),当冷却时,琼脂糖链重组成螺旋结构,由于与水分子的结合而稳定,这种效应会导致悬浮液粘度的增加。进一步冷却后,会得到最终的凝胶结构,形成一个多层螺旋结构组成的复合结构,在这个阶段,大量的水被结合,形成凝胶状的结构。由于琼脂凝胶体系形成的坯体强度不够高,容易在脱模、脱脂等过程中发生损坏,因此要引入HPMC作为增稠剂来提高坯体的力学强度。聚乙二醇三甲基壬基醚(Tergitol)作为发泡剂。在本发明中,所述第一钛合金粉末的粒径优选为30~60μm。
在本发明中,所述混合优选包括:将水、琼脂和羟丙基甲基纤维素进行第一混合,得到预混液;将钛合金粉和聚乙二醇三甲基壬基醚加入至所述预混液进行第二混合,得到钛合金浆料。在本发明中,所述第一混合的温度优选为60~90℃,所述第一混合优选在搅拌条件下进行,本发明对所述第一混合的时间没有特殊要求,能够保证形成淡黄色、澄清透明的预混液即可。在本发明中,所述第二混合优选在60~90℃和搅拌条件下进行,所述搅拌的速度优选为300~400r/min,更优选为320~380r/min;搅拌时间优选为20~30min,更优选为22~28min。
得到钛合金浆料后,本发明将所述钛合金浆料注入到模具中,进行凝胶固化,干燥,得到凝胶状多孔钛合金坯体。
在本发明中,所述模具的材质优选为聚甲基丙烯酸甲酯(PMMA),在本发明中,所述凝胶固化和干燥的温度独立地优选为0~10℃,更优选为2~8℃,进一步优选为4~6℃。
得到凝胶状多孔钛合金坯体后,本发明将所述凝胶状多孔钛合金坯体进行预烧结脱脂,得到预烧结仿生多孔钛合金。
在本发明中,所述预烧结脱脂的温度优选为600~800℃,更优选为650~750℃;保温时间优选为2~4h,更优选为2.5~3.5h;升温至所述预烧结脱脂的温度的速率优选为150℃/h。在本发明中,所述预烧结脱脂优选在氩气保护下进行,所述氩气优选为高纯氩气,所述氩气的流速优选为400~600sccm。本发明在所述预烧结脱脂中,去除除钛合金外的所有其他成分,形成多孔结构。
得到预烧结仿生多孔钛合金后,本发明将所述预烧结仿生多孔钛合金加工成目标尺寸,得到仿生多孔钛合金层。本发明优选为机械加工;本发明对所述加工的过程不做特殊要求。
得到仿生多孔钛合金层后,本发明向所述仿生多孔钛合金层与股骨髁基体接触的外表面层涂覆聚甲醛进行表面孔隙填充,得到外表面孔填充的仿生多孔钛合金层;
本发明对所述聚甲醛的注射条件没有特殊要求,能够将仿生多孔钛合金层中的孔隙充分填充即可。本发明通过填充聚甲醛,能够防止随后注射成型时钛合金粉末进入仿生多孔钛合金层的空隙中。
本发明将钛合金股骨髁基体的制备原料混合,进行造粒,得到喂料。
在本发明中,所述钛合金股骨髁基体的制备原料包括第二钛合金粉末和粘结剂;以质量百分含量计,所述粘结剂优选包括:聚甲醛(POM)55~65%、聚乙二醇(PEG)10~12%、低密度聚乙烯(LDPE)20~25%、聚丙烯(PP)1~3%、石蜡(PW)2~4%和硬脂酸(SA)1~3%;作为更优选的方案,所述聚甲醛优选为57~62%;所述聚乙二醇更优选为10.5~11.5%;所述低密度聚乙烯更优选为22~24%;所述聚丙烯更优选为1.5~2.5%;所述石蜡更优选为2.5~3.5%;所述硬脂酸更优选为1.5~2.5%。在本发明中,所述粘结剂的质量优选为第二钛合金粉末质量的10~15%,更优选为11~14%,进一步优选为12~13%。在本发明中,所述第二钛合金粉末的粒径优选为30~60μm。
本发明对所述混合和造粒的过程没有特殊要求,采用本领域熟知的混合和造粒方式即可。在本发明的实施例中,具体是将第二钛合金粉末与粘结剂放入混炼造粒机中,进行加热、混炼、造粒,制备喂料;所述密炼机的搅拌速率优选为800~1200r/min,加热温度优选为100~200℃,混炼时间优选为0.5~2h。
得到喂料后,本发明将所述外表面孔填充的仿生多孔钛合金层预先置于股骨髁模具中,然后将所述喂料注入到所述股骨髁模具中,进行注射成型,得到股骨髁假体胚胎。
本发明优选根据钛合金股骨髁假体产品结构特点及材料的收缩率设计注射成型所用股骨髁模具及浇注系统;结构设计时同时需考虑安放仿生多孔钛合金层的位置。
在本发明中,所述注射成型的注射温度优选为140~180℃,更优选为150~170℃;所述注射成型的压力优选为80~120MPa,更优选为90~100MPa;保压时间优选为30~45秒,更优选为35~40秒。
得到股骨髁假体胚胎后,本发明将所述股骨髁假体胚胎进行排胶,除去股骨髁基体中的粘结剂和仿生多孔钛合金层表面填充的聚甲醛,得到钛合金股骨髁假体前驱体。
在本发明中,所述排胶优选在含草酸介质的排胶炉中进行;本发明利用草酸去除聚甲醛。本发明对所述草酸的具体用量没有特殊要求,能够将聚甲醛去除即可。在本发明的实施例中,所述草酸的用量具体为8.0g/min。所述排胶的温度优选为250~500℃,更优选为300~450℃,进一步优选为350~400℃;所述排胶的时间优选为5~10h,更优选为6~8h。
本发明在所述排胶过程中除去股骨髁基体中的粘结剂和仿生多孔钛合金层表面填充的聚甲醛,从而得到目标结构的钛合金股骨髁基体和仿生多孔钛合金层。
得到钛合金股骨髁假体前驱体后,本发明将所述钛合金股骨髁假体前驱体进行真空烧结,得到钛合金股骨髁假体。
在本发明中,所述真空烧结的真空度优选为3×10-3Pa;所述真空烧结的温度优选为1200~1300℃,更优选为1220~1280℃,进一步优选为1240~1260℃;所述真空烧结的保温时间优选为2.5~3.5h,更优选为3h。本发明通过真空烧结实现
本发明对所述钛合金股骨髁基体与其内表面仿生多孔钛合金层的冶金结合,结合强度高。
在本发明中,完成真空烧结后,本发明优选还包括采用磁控溅射在所述钛合金股骨髁基体外表面沉积硬质碳基薄膜。本发明对所述磁控溅射的条件不做特殊要求,不同组成的硬质碳基薄膜适合不同的磁控溅射条件,本发明根据硬质碳基薄膜的组成选择合适的磁控溅射条件即可。
在本发明中,当硬质碳基薄膜为申请号为2023114350300公开的硬质碳基薄膜时,所述磁控溅射为:利用磁控溅射在所述钛合金股骨髁基体表面依次沉积碳化钛底层、碳化钛-碳过渡层、碳-碳化钛多层和非晶碳顶层。
在本发明中,所述磁控溅射优选为闭合场非平衡磁控溅射。
本发明优选将附着有仿生多孔钛合金层的钛合金股骨髁基体置放于旋转工作台上,在旋转工作台的外围呈90°分别放置石墨靶、碳化钛靶、石墨靶和碳化钛靶(也即4个靶材之间任意相邻靶材之间的夹角呈90°),将腔体预抽真空,通入氩气,进行预溅射,然后再开始沉积碳化钛底层。
在本发明中,所述预溅射的时间优选为30min,偏压优选为-500V。本发明通过预溅射去除钛合金股骨髁基体表面的氧化物杂质。
在本发明中,所述碳化钛底层的沉积条件优选包括:碳化钛靶电流为2.5~4A,更优选为2.5~3.5A;氩气流量为40~45sccm,更优选为42~44sccm;偏压优选为-100~-150V,更优选为-110~-140V,进一步优选为-120~-130V;沉积时间为10~15min。在本发明中,沉积碳化钛底层时,所述工作台不旋转,2个碳化钛靶同时工作。
形成碳化钛底层后,本发明在所述碳化钛底层表面沉积碳化钛-碳过渡层。在本发明中,所述碳化钛-碳过渡层的沉积条件优选包括:碳化钛靶电流为2~3A,更优选为2.2~2.8A,进一步优选为2.4~2.6A;石墨靶电流从0.5A逐渐增加到2.5A;偏压为-100~-200V,更优选为-120~-180V,进一步优选为-140~-160V;氩气流量优选为20~30sccm,更优选为22~28sccm,进一步优选为24~26sccm;沉积时间优选为10~15min,更优选为12~13min。在本发明中,沉积碳化钛-碳过渡层时,所述工作台不旋转,4个靶材同时工作。
形成碳化钛-碳过渡层后,本发明在所述碳化钛-碳过渡层表面沉积碳-碳化钛多层。
在本发明中,所述碳-碳化钛多层的沉积条件优选包括:碳化钛靶电流为2~3A,更优选为2.2~2.8A,进一步优选为2.4~2.6A;石墨靶电流为1.5~2.5A,更优选为1.8~2.3A,进一步优选为2~2.1A;偏压为-100~-200V,优选为-120~-180V,更优选为-140~-160V;氩气流量为20~30sccm,更优选为22~28sccm,进一步优选为24~26sccm;沉积时间为1.5~4.5h,更优选为2~4h,进一步优选为2.5~3.5h。在本发明中,所述沉积碳-碳化钛多层过程中,旋转工作台的转速优选为3~5rpm,4个靶材同时工作。
形成碳-碳化钛多层后,本发明在所述碳-碳化钛多层表面沉积非晶碳顶层。在本发明中,所述非晶碳顶层的沉积条件优选包括:石墨靶电流为2.5~3.5A,更优选为2.7~3.3A,进一步优选为2.9~3.1A;氩气流量为40~45sccm,更优选为42~43sccm;偏压为-100~-150V,更优选为-110~-140V,进一步优选为-120~-130V;偏压调节频率为0.5~1V/min,更优选为0.6~0.9V/min,进一步优选为0.7~0.8V/min;沉积时间优选为10~15min,更优选为11~14min,进一步优选为12~13min。在本发明中,沉积非晶碳顶层时,所述工作台不旋转,2个石墨靶同时工作。
本发明提供了一种人工膝关节,包括上述方案所述的钛合金股骨髁假体或上述方案所述制备方法制备得到的钛合金股骨髁假体;优选还包括钛合金胫骨托和垫片;所述垫片优选为高交联聚乙烯垫片。
图1为本发明人工膝关节的结构示意图,如图1所示,1为钛合金股骨髁基底;2为仿生多孔钛合金层;3为硬质碳基薄膜;4为垫片;5为钛合金胫骨托。
下面结合实施例对本发明提供的含仿生多孔薄层的钛合金股骨髁假体及其制备方法、人工膝关节进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1
(1)取12g琼脂和7g羟丙基甲基纤维素溶于300g去离子水中,在80℃下搅拌0.5h,形成预混液;
(2)取500g粒径为30~60μm的Ti6Al4V粉末,20g聚乙二醇三甲基壬基醚Tergitol,加入到步骤(1)预混液中,以350r/min的速度搅拌25min。
(3)将步骤(2)得到的钛合金浆料注入至PMMA模具中,0℃凝胶固化后干燥,得到凝胶状多孔钛合金坯体。
(4)将所述凝胶状多孔钛合金坯体进行预烧结脱脂,钛预烧结脱脂过程在通入高纯氩流速为500sccm下进行,预烧结脱脂温度为750℃,保温3h。得到预烧结仿生多孔钛合金。
(5)将步骤(4)所述预烧结仿生多孔钛合金按照设计要求加工成3mm厚度形状;
(6)将步骤(5)加工好的3mm厚多孔钛合金部件的冶金结合面上涂覆一层聚甲醛,然后装入股骨髁烧结模具。然后按照以下步骤制备注射成型钛合金喂料以及股骨髁注射成型:将粒径为30~60μm的Ti6Al4V粉末与聚甲醛、聚乙二醇、低密度聚乙烯、聚丙烯、石蜡及硬脂酸放入混炼造粒机中,进行加热、混炼、造粒,制备喂料。其制备工艺:搅拌速率为1000r/min,温度150℃,混炼时间1h。粘结剂配方:聚甲醛(POM)60%、聚乙二醇(PEG)12%、低密度聚乙烯(LDPE)22%、聚丙烯(PP)1%、石蜡(PW)3%、硬脂酸(SA)2%。所述粘结剂质量为钛合金粉末质量的12%。将制备的喂料放入注射机料槽中,然后加热、注射。注射工艺:注射温度为160℃,注射压力为90MPa,保压时间为30秒。
(7)将步骤(6)注射成型的钛合金胚胎放入含草酸介质排胶炉中进行排胶,排胶温度为400℃,时间为6h。
(8)将步骤(7)所述排胶烧结后的股骨髁样件放入真空炉进行烧结。烧结工艺:真空度3×10-3Pa,烧结温度为1250℃;保温时间3h,随炉冷却至室温。同时将步骤(4)所述预烧结多孔钛合金加工成的多孔钛合金圆柱形植入物,在同样条件下按照步骤(7)(8)进行烧结,作为样件进行骨长入验证。
(9)将步骤(8)所制备内含多孔钛合金股骨髁进行股骨髁外面抛光后,采用磁控溅射技术表面镀覆1.2μm厚硬质碳膜,获得钛合金股骨髁假体。
本实施例所制备的仿生多孔钛合金层孔隙率为71%,孔径300~500μm(如图2所示),弹性模量为2.7GPa,抗压强度为68MPa,均接近人骨的力学性能。将步骤(8)所述制备的的多孔钛合金圆柱形植入物,植入比格犬腿骨内。术后12周,新骨成功桥接骨缺损,多孔钛合金充满骨组织(如图3所示)。
实施例2
(1)取10g琼脂和5g羟丙基甲基纤维素溶于300g去离子水中,在80℃下搅拌0.5h,形成预混液;
(2)取500g粒径为30~60μm的Ti6Al4V粉末,15g聚乙二醇三甲基壬基醚Tergitol,加入到步骤(1)预混液中,以320r/min的速度搅拌25min。
(3)将步骤(2)得到的钛合金浆料注入至PMMA模具中,4℃凝胶固化后干燥,得到凝胶状多孔钛合金坯体。
(4)将所述凝胶状多孔钛合金坯体进行预烧结脱脂,钛预烧结脱脂过程在通入高纯氩流速为500sccm下进行,预烧结脱脂温度为750℃,保温3h。得到预烧结仿生多孔钛合金。
(5)将步骤(4)所述预烧结仿生多孔钛合金按照设计要求加工成3mm厚度形状;
(6)将步骤(5)加工好的3mm厚多孔钛合金部件的冶金结合面上涂覆一层聚甲醛,然后装入股骨髁烧结模具。然后按照以下步骤制备注射成型钛合金喂料以及股骨髁注射成型:将30~60μm的Ti6Al4V粉末与聚甲醛、聚乙二醇、低密度聚乙烯、聚丙烯、石蜡及硬脂酸放入混炼造粒机中,进行加热、混炼、造粒,制备喂料。其制备工艺:搅拌速率为1000r/min,温度150℃,混炼时间1h。粘结剂配方:聚甲醛(POM)60%、聚乙二醇(PEG)12%、低密度聚乙烯(LDPE)22%、聚丙烯(PP)1%、石蜡(PW)3%、硬脂酸(SA)2%。所述粘结剂质量为钛合金粉末质量的12%。将制备的喂料放入注射机料槽中,然后加热、注射。注射工艺:注射温度为160℃,注射压力为100MPa,保压时间为30秒。
(7)将步骤6)注射成型的钛合金胚胎放入含草酸介质排胶炉中进行排胶,排胶温度为400℃,时间为6h。
(8)将步骤(7)所述排胶烧结后的股骨髁样件放入真空炉进行烧结。烧结工艺:真空度3×10-3Pa,烧结温度为1250℃;保温时间3h,随炉冷却至室温。
(9)将步骤(8)所制备内含多孔钛合金股骨髁进行股骨髁外面抛光后,采用磁控溅射技术表面镀覆1.5μm厚硬质碳膜,获得钛合金股骨髁假体。
本实施例所制备的仿生多孔钛合金层孔隙率为58%,孔径300~450μm,弹性模量为16GPa,抗压强度为198MPa,均接近人骨的力学性能。
实施例3
(1)取15g琼脂和8g羟丙基甲基纤维素溶于300g去离子水中,在80℃下搅拌0.5h,形成预混液;
(2)取500g粒径为30~60μm的Ti6Al4V粉末,21g聚乙二醇三甲基壬基醚Tergitol,加入到步骤(1)预混液中,以380r/min的速度搅拌25min。
(3)将步骤(2)得到的钛合金浆料注入至PMMA模具中,0℃凝胶固化后干燥,得到凝胶状多孔钛合金坯体。
(4)将所述凝胶状多孔钛合金坯体进行预烧结脱脂,钛预烧结脱脂过程在通入高纯氩流速为500sccm下进行,预烧结脱脂温度为700℃,保温4h。得到预烧结仿生多孔钛合金。
(5)将步骤(4)所述预烧结仿生多孔钛合金按照设计要求加工成2mm厚度形状;
(6)将步骤(5)加工好的2mm厚多孔钛合金部件的冶金结合面上涂覆一层聚甲醛,然后装入股骨髁烧结模具。然后按照以下步骤制备注射成型钛合金喂料以及股骨髁注射成型:将粒径为30~60μm的Ti6Al4V粉末与聚甲醛、聚乙二醇、低密度聚乙烯、聚丙烯、石蜡及硬脂酸放入混炼造粒机中,进行加热、混炼、造粒,制备喂料。其制备工艺:搅拌速率为1000r/min,温度150℃,混炼时间1h。粘结剂配方:聚甲醛(POM)55%、聚乙二醇(PEG)11%、低密度聚乙烯(LDPE)21%、聚丙烯(PP)1%、石蜡(PW)2.6%、硬脂酸(SA)1.8%。所述粘结剂质量为钛合金粉末质量的13%。将制备的喂料放入注射机料槽中,然后加热、注射。注射工艺:注射温度为160℃,注射压力为80MPa,保压时间为30秒。
(7)将步骤6)注射成型的钛合金胚胎放入含草酸介质排胶炉中进行排胶,排胶温度为400℃,时间为6h。
(8)将步骤(7)所述排胶烧结后的股骨髁样件放入真空炉进行烧结。烧结工艺:真空度3×10-3Pa,烧结温度为1300℃;保温时间3h,随炉冷却至室温。
(9)将步骤(8)所制备内含多孔钛合金股骨髁进行股骨髁外面抛光后,采用磁控溅射技术表面镀覆1.2μm厚硬质碳膜,获得钛合金股骨髁假体。
本实施例所制备的仿生多孔钛合金层孔隙率为78%,孔径350~650μm,弹性模量为1.1GPa,抗压强度为38MPa,均接近人骨的力学性能。
由以上实施例可知,本发明提供了一种钛合金股骨髁假体及其制备方法、人工膝关节,本发明能够实现股骨髁假体与骨床之间骨组织长入,实现良好的生物学固定效果。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种钛合金股骨髁假体,其特征在于,包括钛合金股骨髁基体和附着于所述钛合金股骨髁基体内表面的仿生多孔钛合金层;所述仿生多孔钛合金层的孔隙率为55~80%,孔径为300~650μm;所述仿生多孔钛合金层的孔隙为三维贯通结构。
2.根据权利要求1所述的钛合金股骨髁假体,其特征在于,还包括附着于所述钛合金股骨髁基体外表面的硬质碳基薄膜。
3.根据权利要求2所述的钛合金股骨髁假体,其特征在于,所述硬质碳基薄膜的厚度为0.8~2.0μm;硬度为15~22GPa。
4.根据权利要求1所述的钛合金股骨髁假体,其特征在于,所述仿生多孔钛合金层的厚度为1~4mm。
5.根据权利要求1或4所述的钛合金股骨髁假体,其特征在于,所述钛合金股骨髁基体与所述仿生多孔钛合金层通过烧结以冶金方式连接。
6.权利要求1~5任一项所述钛合金股骨髁假体的制备方法,包括以下步骤:
将仿生多孔钛合金层的制备原料混合,得到钛合金浆料;以质量百分比计,所述仿生多孔钛合金层的制备原料包括:羟丙基甲基纤维素0.5~1%、琼脂1~2%、聚乙二醇三甲基壬基醚1~3%、第一钛合金粉末45~65%和水余量;
将所述钛合金浆料注入到模具中,进行凝胶固化,干燥,得到凝胶状多孔钛合金坯体;
将所述凝胶状多孔钛合金坯体进行预烧结脱脂,得到预烧结仿生多孔钛合金;
将所述预烧结仿生多孔钛合金加工成目标尺寸,得到仿生多孔钛合金层;
向所述仿生多孔钛合金层与股骨髁基体接触的外表面层涂覆聚甲醛进行表面孔隙填充,得到外表面孔填充的仿生多孔钛合金层;
将钛合金股骨髁基体的制备原料混合,进行造粒,得到喂料;所述钛合金股骨髁基体的制备原料包括第二钛合金粉末和粘结剂;
将所述外表面孔填充的仿生多孔钛合金层预先置于股骨髁模具中,然后将所述喂料注入到所述股骨髁模具中,进行注射成型,得到股骨髁假体胚胎;
将所述股骨髁假体胚胎进行排胶,除去股骨髁基体中的粘结剂和仿生多孔钛合金层表面填充的聚甲醛,得到钛合金股骨髁假体前驱体;
将所述钛合金股骨髁假体前驱体进行真空烧结,得到钛合金股骨髁假体。
7.根据权利要求6所述的制备方法,其特征在于,所述真空烧结后,还包括:采用磁控溅射在所述钛合金股骨髁基体外表面沉积硬质碳基薄膜。
8.根据权利要求6所述的制备方法,其特征在于,以质量百分含量计,所述粘结剂包括:聚甲醛55~65%、聚乙二醇10~12%、低密度聚乙烯20~25%、聚丙烯1~3%、石蜡2~4%和硬脂酸1~3%;所述粘结剂的质量为第二钛合金粉末质量的10~15%。
9.根据权利要求6或7所述的制备方法,其特征在于,所述真空烧结的温度为1200~1300℃,保温时间为2.5~3.5h。
10.一种人工膝关节,其特征在于,包括权利要求1~5任一项所述的钛合金股骨髁假体或权利要求6~9任一项所述制备方法制备得到的钛合金股骨髁假体。
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