CN113385677B - 真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法 - Google Patents
真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法 Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 84
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- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 66
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- 238000000034 method Methods 0.000 claims abstract description 25
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
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Abstract
本发明真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法涉及的是一种提高真空烧结钛颗粒涂层与基体结合强度的粉末颗粒搅拌球磨预处理方法,是一种开放式多孔钛涂层的制备方法,适用于提高骨科、牙科等植入物性能。真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法,采用多孔钛真空烧结涂层的粉末颗粒搅拌球磨预处理方法,通过首先选择不锈钢球,球料比1:2,同时加入搅拌球磨罐,预抽真空至10Pa以下,然后通入4N高纯氩气至0.08MPa,再通入4N高纯氢气至0.09‑0.11MPa,以搅拌棒最大运动速度为2米/秒‑15米/秒搅拌球磨1‑10小时,球磨结束后筛选合适粒度的钛粉末颗粒作为涂层用粉末颗粒备用;再采用真空烧结工艺在骨科、牙科植入物表面获得了开放式多孔钛涂层。
Description
技术领域
本发明真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法涉及的是一种提高真空烧结钛颗粒涂层与基体结合强度的粉末颗粒搅拌球磨预处理方法,是一种开放式多孔钛涂层的制备方法,属于粉末冶金材料、生物材料领域。适用于提高骨科、牙科等植入物性能,尤其是提高植入物表面多孔钛涂层与钛合金基体的结合强度。
背景技术
植入物涂层技术经过多年的发展,逐步成熟。以人工关节为例,当今成熟的工艺主要有空气等离子喷涂工艺、真空等离子喷涂工艺、真空烧结工艺和电化学工艺,涂层材料主要有钛、羟基磷灰石(以下简称HA)和两者复合。当前主要的生物型人工关节的生物涂层技术采用真空烧结钛涂层以及在钛涂层上再采用等离子喷涂HA的技术,由于其良好的骨长入临床效果和低成本,在生物型人工关节上得到了大量的应用,例如,美国DEPUY公司的SUMMIT全髋关节假体和PFC全膝关节假体中的生物型假体,美国ZIMMER公司的NEXGEN全膝关节假体,SMITH-NEPHEW公司的PROFIX全膝关节假体以及BIOMET公司的MAXIN全膝关节假体。
上述产品均需要首先在钛合金基体表面通过真空烧结形成钛涂层,钛涂层与钛合金基体的结合强度决定了该工件是否能够进入后续工艺,在保证钛涂层具有适宜孔隙度的前提下,需要钛涂层与钛合金基体间具有足够的连接强度,这是保障植入物安全、骨结合强度和骨长入效果的前提。但采用常规烧结工艺制备的钛涂层与钛合金基体间在保证孔隙度的情况下连接强度往往偏低,导致涂层可靠性下降。真空烧结钛涂层所采用的粉末主要有球形钛粉末和不规则钛粉末两类,涂层与基体连接强度偏低问题在采用不规则钛粉末时尤其突出。因此,后续分析与实验主要围绕涂层选用不规则钛粉末时的情况,而解决问题的发明显然同样适用于球形钛粉末。
发明内容
本发明目的是针对上述不足之处,提供一种真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法,具体方法是首先对搅拌球磨罐先预抽真空至10Pa以下,然后通入4N高纯氩气至0.08MPa,再通入4N高纯氢气至0.09~0.11MPa,以搅拌棒最大运动速度为2米/秒~15米/秒搅拌球磨1~10小时,球磨结束后筛选合适粒度的钛粉末颗粒作为涂层用粉末颗粒备用。再采用真空烧结工艺在骨科、牙科等植入物表面获得了开放式多孔钛涂层。该涂层一方面保持了高真空烧结钛涂层良好的空间结构,另一方面通过粉末颗粒的搅拌球磨预处理使植入物表面钛涂层与钛合金基体的结合强度获得了大幅度提高,提升了植入物的可靠性与安全性。且该工艺成本较低。
真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法是采取以下技术方案实现:
真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法,采用多孔钛真空烧结涂层的粉末颗粒搅拌球磨预处理方法,通过首先选择不锈钢球,球料比1: 2,同时加入搅拌球磨罐,预抽真空至10Pa以下,然后通入4N高纯氩气至0.08MPa,再通入4N高纯氢气至0.09-0.11MPa,以搅拌棒最大运动速度为2米/秒-15米/秒搅拌球磨1-10小时,球磨结束后筛选合适粒度的钛粉末颗粒作为涂层用粉末颗粒备用。再采用真空烧结工艺在骨科、牙科等植入物表面获得了开放式多孔钛涂层。
所述的不锈钢球选择直径为6-10毫米的不锈钢球。
所述的预处理后钛粉末颗粒粒度为50~250微米(μm)。
真空烧结多孔钛涂层的真空烧结工艺为在清洗洁净后的植入物表面采用上述预处理后符合植入物技术要求的钛粉末颗粒放置于植入物表面,在钛合金植入物表面放置平均厚度为600~1000μm的钛颗粒,将处理好的植入物移入真空炉中,抽真空至10-2帕以上,升温烧结,烧结制度为:以1-30℃/min的速度从室温升温至烧结温度1000-1400℃,在烧结温度保温0.5-10小时,再以1-10℃/min的速度从烧结温度降温至室温,取出已烧结钛珠涂层的植入物,采用蒸馏水、医用酒精清洗,包装即可。采用搅拌球磨预处理后,真空烧结钛合金颗粒涂层与基体结合强度得到有效提高,从不进行球磨预处理的40-55MPa提高到62-85MPa。
本发明的有益效果与优点:
在植入体表面制作多孔钛涂层的目的是让新生骨组织长入多孔钛珠涂层孔隙内,使植入体与骨组织固定在一起。这种利用骨长入多孔表面而实现植入体固定的方式称为生物固定。由于骨组织长入孔隙内,使骨和植入体的界面面积大大增加,加之骨和多孔表面之间的机械嵌合作用,植入体和骨界面的剪切强度也大大增加。但在真空烧结多孔钛涂层的过程中发现,采用常规烧结工艺制备的钛涂层与钛合金基体间在保证孔隙度的情况下连接强度往往偏低,导致涂层可靠性不足。真空烧结钛涂层所采用的粉末主要有雾化球形钛粉末和不规则钛粉末两类,涂层与基体连接强度偏低问题在采用不规则钛粉末时尤其突出。
本发明针对上述问题,采用多孔钛真空烧结涂层的粉末颗粒搅拌球磨预处理方法,通过首先选择直径6-10毫米的不锈钢球,球料比1: 2,同时加入搅拌球磨罐,预抽真空至10Pa以下,然后通入4N高纯氩气至0.08MPa,再通入4N高纯氢气至0.09~0.11MPa,以搅拌棒最大运动速度为2米/秒~15米/秒搅拌球磨1~10小时,球磨结束后筛选合适粒度的钛粉末颗粒作为涂层用粉末颗粒备用。再采用真空烧结工艺在骨科、牙科等植入物表面获得了开放式多孔钛涂层。该涂层一方面保持了高真空烧结钛涂层良好的空间结构,另一方面通过添加氢气的搅拌球磨预处理使植入物表面钛涂层与钛合金基体的结合强度获得了大幅度提高,且最终成品中已无氢化物存在,产品符合“细胞毒性试验、致敏试验、皮内反应试验、急性全身毒性(静脉途径)、遗传毒性试验(Ames)”等生物学性能检测的全部要求。
本发明真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法是一种提高真空烧结钛合金颗粒涂层与基体结合强度的粉末颗粒搅拌球磨预处理方法,有效提升了钛合金涂层与基体的结合性能,提高了植入物的可靠性与安全性,且该工艺成本较低。
具体实施方式
真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法,采用多孔钛真空烧结涂层的粉末颗粒搅拌球磨预处理方法,通过首先选择不锈钢球,球料比1: 2,同时加入搅拌球磨罐,预抽真空至10Pa以下,然后通入4N高纯氩气至0.08MPa,再通入4N高纯氢气至0.09~0.11MPa,以搅拌棒最大运动速度为2米/秒~15米/秒搅拌球磨1-10小时,球磨结束后筛选合适粒度的钛粉末颗粒作为涂层用粉末颗粒备用。再采用真空烧结工艺在骨科、牙科等植入物表面获得了开放式多孔钛涂层。
所述的不锈钢球选择直径为6-10毫米的不锈钢球。
所述的预处理后钛粉末颗粒粒度为50-250微米(μm)。
真空烧结多孔钛涂层的真空烧结工艺为在清洗洁净后的植入物表面采用上述预处理后符合植入物技术要求的钛粉末颗粒放置于植入物表面,在钛合金植入物表面放置平均厚度为600~1000μm的钛颗粒,将处理好的植入物移入真空炉中,抽真空至10-2帕以上,升温烧结,烧结制度为:以1-30℃/min的速度从室温升温至烧结温度1000-1400℃,在烧结温度保温0.5-10小时,再以1-10℃/min的速度从烧结温度降温至室温,取出已烧结钛珠涂层的植入物,采用蒸馏水、医用酒精清洗,包装即可。采用搅拌球磨预处理后,真空烧结钛合金颗粒涂层与基体结合强度得到有效提高,从不进行球磨预处理的40~55MPa提高到62~85MPa。
以下将结合实施例对本发明作进一步说明:
对比例:
用标准筛筛选合适粒度的钛粉末颗粒作为涂层用粉末,在钛合金植入物表面放置平均厚度为~800μm的钛颗粒,将处理好的植入物移入真空炉中,抽真空至10-2帕以上,升温烧结。烧结制度为:以5℃/min的速度从室温升温至1400℃,在烧结温度保温0.5小时,再以1℃/min的速度从烧结温度降温至室温,取出已烧结钛珠涂层的植入物和随炉强度测试试样。采用蒸馏水、医用酒精等清洗,包装即可。按照ASTM F1147 或EN 582标准,测试强度测试试样的钛颗粒涂层抗拉强度,抗拉强度为48 MPa。
实施例1:
称量1公斤钛粉末颗粒,选择直径6毫米的不锈钢球,按照球料比1: 2,共同加入搅拌球磨罐,预抽真空至10Pa以下,然后通入4N高纯氩气至0.08MPa,再通入4N高纯氢气至0.10MPa,以搅拌棒最大运动速度为8.5米/秒搅拌球磨5小时,球磨结束后筛选合适粒度的钛粉末颗粒作为涂层用粉末颗粒备用。在钛合金植入物表面放置平均厚度为800μm的钛颗粒,将处理好的植入物移入真空炉中,抽真空至10-2帕以上,升温烧结。烧结制度为:以5℃/min的速度从室温升温至1400℃,在烧结温度保温0.5小时,再以1℃/min的速度从烧结温度降温至室温,取出已烧结钛珠涂层的植入物和随炉强度测试试样。采用蒸馏水、医用酒精等清洗,包装即可。按照ASTM F1147 或EN 582标准,测试强度测试试样的钛颗粒涂层抗拉强度,抗拉强度为85 MPa。
实施例2:
称量1公斤钛粉末颗粒,选择直径10毫米的不锈钢球,按照球料比1: 2,共同加入搅拌球磨罐,预抽真空至10Pa以下,然后通入4N高纯氩气至0.08MPa,再通入4N高纯氢气至0.11MPa,以搅拌棒最大运动速度为2米/秒搅拌球磨1小时,球磨结束后筛选合适粒度的钛粉末颗粒作为涂层用粉末颗粒备用。在钛合金植入物表面放置平均厚度为600μm的钛颗粒,将处理好的植入物移入真空炉中,抽真空至10-2帕以上,升温烧结。烧结制度为:以1℃/min的速度从室温升温至1000℃,在烧结温度保温5小时,再以10℃/min的速度从烧结温度降温至室温,取出已烧结钛珠涂层的植入物和随炉强度测试试样。采用蒸馏水、医用酒精等清洗,包装即可。按照ASTM F1147 或EN 582标准,测试强度测试试样的钛颗粒涂层抗拉强度,抗拉强度为62 MPa。
实施例3:
称量1公斤钛粉末颗粒,选择直径8毫米的不锈钢球,按照球料比1: 2,共同加入搅拌球磨罐,预抽真空至10Pa以下,然后通入4N高纯氩气至0.08MPa,再通入4N高纯氢气至0.09MPa,以搅拌棒最大运动速度为15米/秒搅拌球磨10小时,球磨结束后筛选合适粒度的钛粉末颗粒作为涂层用粉末颗粒备用。在钛合金植入物表面放置平均厚度为1000μm的钛颗粒,将处理好的植入物移入真空炉中,抽真空至10-2帕以上,升温烧结。烧结制度为:以30℃/min的速度从室温升温至1300℃,在烧结温度保温10小时,再以5℃/min的速度从烧结温度降温至室温,取出已烧结钛珠涂层的植入物和随炉强度测试试样。采用蒸馏水、医用酒精等清洗,包装即可。按照ASTM F1147 或EN 582标准,测试强度测试试样的钛颗粒涂层抗拉强度,抗拉强度为70 MPa。
对上述处理后的植入物进行了生物学性能检测,检测项目包括“细胞毒性试验、致敏试验、皮内反应试验、急性全身毒性(静脉途径)、遗传毒性试验(Ames)”。依据的检测标准是:
1)GB/T16886.5-2003医疗器械生物学评价第五部分:体外细胞毒性试验;
2)GB/T16886.10-2005医疗器械生物学评价第十部分:刺激与迟发型超敏反应试验;
3)GB/T16886.11-1997医疗器械生物学评价第十一部分:全身毒性试验;
4)GB/T16886.3-1997医疗器械生物学评价第三部分:遗传毒性、致癌性和生殖毒性试验;
5)中华人民共和国药典2005版附录XID热原试验。
检测结果表明上述经处理后的植入物均符合上述五标准要求。
本发明涉及一种在植入物表面获得高结合强度、生物活性、开放式多孔非球形钛粉末颗粒涂层的制备方法。适用于生物固定型骨科、牙科等植入物,可以改善植入物的骨长入效果和提高骨结合强度,提高植入物的可靠性。其方法为对预烧结的钛粉末颗粒进行搅拌球磨预处理。具体方法是首先对搅拌球磨罐先预抽真空至10Pa以下,然后通入4N高纯氩气至0.08MPa,再通入4N高纯氢气至0.09~0.11MPa,以搅拌棒最大运动速度为2米/秒~15米/秒搅拌球磨1~10小时,球磨结束后筛选合适粒度的钛粉末颗粒作为涂层用粉末颗粒备用。在清洗洁净后的植入物表面采用符合植入物技术要求的钛粉末颗粒放置于植入物表面,将处理好的植入物移入真空炉中,抽真空至10-2帕以上,升温烧结,烧结制度为:以1~30℃/min的速度从室温升温至烧结温度1000~1400℃,在烧结温度保温0.5~10小时,再以1~10℃/min的速度从烧结温度降温至室温,取出已烧结钛珠涂层的植入物,采用蒸馏水、医用酒精清洗,包装即可。采用搅拌球磨预处理后,真空烧结钛合金颗粒涂层与基体结合强度得到有效提高,从不进行球磨预处理的40~55MPa提高到62~85MPa。
Claims (4)
1.真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法,其特征在于,采用多孔钛真空烧结涂层的粉末颗粒搅拌球磨预处理方法,通过首先选择不锈钢球,球料比1: 2,同时加入搅拌球磨罐,预抽真空至10Pa以下,然后通入4N高纯氩气至0.08MPa,再通入4N高纯氢气至0 .09-0.11MPa,以搅拌棒最大运动速度为2米/秒-15米/秒搅拌球磨1-10小时,球磨结束后筛选合适粒度的钛粉末颗粒作为涂层用粉末颗粒备用;再采用真空烧结工艺在骨科、牙科钛合金植入物表面获得了开放式多孔钛涂层;
真空烧结多孔钛涂层的真空烧结工艺为在清洗洁净后的钛合金植入物表面采用预处理后符合钛合金植入物技术要求的钛粉末颗粒放置于钛合金植入物表面,在钛合金植入物表面放置平均厚度为600 ~1000μm的钛颗粒,将处理好的钛合金植入物移入真空炉中,抽真空至10-2帕以上,升温烧结,烧结制度为:以1-30℃/min的速度从室温升温至烧结温度1000-1400℃,在烧结温度保温0 .5-10小时,再以1-10℃/min的速度从烧结温度降温至室温,取出已烧结钛珠涂层的钛合金植入物,采用蒸馏水、医用酒精清洗,包装即可。
2.根据权利要求1所述的真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法,其特征在于,采用搅拌球磨预处理后,真空烧结钛合金颗粒涂层与基体结合强度提高到62~85MPa。
3.根据权利要求1所述的真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法,其特征在于,所述的不锈钢球选择直径为6-10毫米的不锈钢球。
4.根据权利要求1所述的真空烧结多孔钛涂层的钛粉末颗粒搅拌球磨预处理方法,其特征在于,所述的预处理后钛粉末颗粒粒度为50 ~250微米。
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