CN105177523B - 一种医用多孔钽金属材料 - Google Patents

一种医用多孔钽金属材料 Download PDF

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CN105177523B
CN105177523B CN201510712170.7A CN201510712170A CN105177523B CN 105177523 B CN105177523 B CN 105177523B CN 201510712170 A CN201510712170 A CN 201510712170A CN 105177523 B CN105177523 B CN 105177523B
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tantalum metal
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CN105177523A (zh
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赵德伟
王本杰
谢辉
黄诗博
尉晓蔚
王威
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Weitan Dalian Biomaterials Co ltd
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Abstract

本发明公开了一种医用多孔钽金属材料及其制备方法。所述医用多孔钽金属材料是利用化学气相沉积方法，将钽金属化合物还原为钽金属粉，均匀沉积于多孔硅支架表面形成钽涂层制备得到；其中所述钽金属化合物为五氯化钽、氟化钽中的一种；所述多孔硅支架的孔隙率>70％，孔径为100～600μm；所述钽涂层的厚度为10～50μm。本发明的多孔钽金属材料孔隙率高，且孔隙均一，为互相连通的多孔结构，孔隙死腔少，与人体松质骨相似，可促进骨长入，可应用于体内多部位的骨创伤及骨坏死后骨缺损的修复。

Description

一种医用多孔钽金属材料
技术领域
本发明涉及一种医用多孔金属材料及其制备方法，具体涉及可应用于骨科承力部位的医用多孔钽金属材料及其制备方法。
背景技术
骨创伤及坏死后形成的骨缺损修复存在力学及骨诱导性能不佳的问题。多孔材料在体内的重要性被揭示后，这一问题有望得到较好的解决。研究发现多孔材料的孔隙率和孔的大小是决定植入物成功与否的重要因素，增加孔隙率或减少“死腔”将有利于骨长入。一般认为空隙率大于60％，空隙直径大于150μm，将有利于骨的长入，当孔隙大小为200μm-400μm的最有利于新骨生长。同时，较大的空隙率可以减少植入材料的重量，并可使其在生物力学指标上与人体骨骼接近。但对材料的加工提出较高的要求。制备孔隙率大，孔隙形状规则均匀，孔隙联通率高的医用植入材料是研发的目标。
钽是高熔点(2996℃)，耐腐蚀的金属，已被广泛用于化工、冶金、宇航等领域。此外，钽与体液无反应、对机体组织无刺激,也成为制作外科植入物的理想材料。这方面的应用历史己超过半个世纪，包括心脏起博器、颅骨缺损修补、血管夹、股骨柄假体、用于神经修复的金属丝、片或网等等。自1907年用氢气还原钽的氯化物得到金属钽以来，化学气相沉积(CVD)钽受到重视。CVD法可以在金属或非金属材料的零部件上沉积金属钽。多孔钽金属因其良好的生物相容性及稳定性，有望在体内负重区骨骼的重建中起到重要作用。
但由于钽的高熔点，传统的粉末松装烧结法等加工较困难，制备的材料孔隙率较低，孔隙大小不均匀且闭孔率高。采用化学气相沉积的方法是制备多孔钽金属的可行方法，但镀钽涂层通常厚度有限，降低了产品的力学性能；而且该方法对骨架材料的物理及生物性能提出了较高的要求，即要求骨架材料本身有耐高温、与植入环境相适应的力学性能及无细胞毒性。
本发明所采用的多孔碳化硅支架材料，具备了应用化学气相沉积的方法制备多孔钽金属材料的支架条件；在镀钽前，可加工成适用于体内应用的不规则形态，减少了因后期加工而对孔隙产生破坏的可能。同时通过控制化学气相沉 积过程中反应气体浓度、沉积温度及反应时间等参数，使钽金属涂层致密、颗粒大小仅1～5μm、纯度则超过99.5％，并有足够厚度，从而使材料获得足够的机械强度。
发明内容
本发明的目的在于提供一种与人体骨骼的力学性能相近，并可作为永久植入材料应用于人体负重骨或非负重部位的医用多孔钽金属材料及其制备方法。本发明的医用多孔钽金属材料是利用化学气相沉积的方法，在多孔碳化硅或多孔硅材料表面均匀沉积钽金属涂层制备得到，具有高孔隙率>70％，弹性模量<30Gpa。
本发明的技术方案为如下：
一种医用多孔钽金属材料，所述医用多孔钽金属材料是利用化学气相沉积方法，将钽金属化合物还原为钽金属粉，均匀沉积于多孔硅材料支架表面形成钽涂层制备得到；
其中所述钽金属化合物为五氯化钽、氟化钽；所述多孔硅材料的孔隙率>70％，孔径为100～600μm；所述钽涂层的厚度为10～50μm。
进一步地，所述的多孔硅材料为多孔碳化硅。
进一步地，所述的钽金属化合物为粒径400目的粉末。
进一步地，所述的本发明所述的医用多孔钽金属材料的孔隙率>70％，弹性模量<30Gpa。
本发明还提供上述医用多孔钽金属材料的制备方法，该制备方法包括如下步骤：
(1)将权利要求1所述多孔硅材料支架用按质量比40％氟氢酸：68％硝酸：水＝1：5：6的混合溶液超声震荡后，用干燥氮气吹干，置入气相沉积反应室内；
(2)气相沉积反应室抽真空、在惰性气体保护下加热至900～1500℃；
(3)气相沉积反应室内同时通入处理气体和氢气，在900～1500℃，真空度10～15Pa条件下，反应2～3小时；其中所述处理气体包含钽金属化合物和载气，将钽金属化合物放入源罐中，加热至200～300℃，300℃惰性气体为载气通入至反应室。
上述制备方法还包括，在步骤(3)中反应结束后，在惰性气体保护下将气相沉积反应室内的温度降温至200℃的步骤。
上述制备方法中，所述惰性气体优选氩气、氦气中的一种或两种的混合，最优选氩气。
上述制备方法中，所述处理气体的流量优选为80～100ml/min。
上述制备方法中，所述氢气的流量优选为100～150ml/min。
本发明的方法制备的多孔钽金属材料具有高孔隙率>85％，弹性模量<30Gpa，与人体骨骼的力学性能相近，并可作为永久植入材料应用于人体负重骨或非负重部位，如髋膝关节，颅骨，椎间融合器等。另外，本发明的方法制备的多孔钽金属材料的钽金属涂层致密，钽涂层厚度10～50μm，也可以满足作为医用植入物的硬度以及生物相容性条件。钽涂层厚度可以为10～15μm，有利于降低成本。
本发明的医用多孔钽金属材料，采用以耐高温的多孔硅材料作为基底材料，构建与骨骼微结构相似的三维多孔支架，该骨架为三维网状结构，具有开孔率及连通孔隙度高，重量轻，强度适中，无细胞毒性，生物相容性好等优点。
本发明的有益效果：
①本发明的医用多孔钽金属材料孔隙率高，且孔隙均一，为互相连通的多孔结构，孔隙死腔少，与人体松质骨相似，可促进骨长入。
②钽金属涂层的支架材料生物相容性好，并根据涂层及支架孔隙直径获得最佳的生物力学性能。减少其植入体内后的相邻骨质发生应力遮挡等不良效应。
③本发明的制备方法相对简单，多孔硅材料多孔碳化硅，其生物学强度较高，具有密度小、强度高、耐腐蚀等独特性能，在镀钽前易于加工成与植入部位相适应的不规则形状，避免了多孔钽材料本身难以加工，加工过程中对材料破坏大，破坏空隙等问题。同时通过控制化学气相沉积过程中反应气体浓度、沉积温度及反应时间等参数，使钽金属涂层致密、颗粒大小仅1～5μm、纯度则超过99.5％，并有足够厚度，从而使材料获得足够的机械强度。
④本发明的多孔钽金属材料，可应用于体内多部位的骨创伤及骨坏死后骨缺损的修复。
附图说明
图1为多孔碳化硅支架钽金属涂层前和涂层后的SEM图，其中图1A为多孔碳化硅支架钽涂层前的SEM图，图1B为多孔碳化硅支架钽涂层后的SEM图；
图2为钽金属涂层前后多孔碳化硅支架的表面形貌的SEM图，其中图2A为钽金属涂层前多孔碳化硅支架的表面形貌的SEM图，图2B为钽金属涂层后多孔碳化硅支架的表面形貌的SEM图。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。下述实施例中，如无特殊说明，所使用的实验方法均为常规方法，所用试剂等均可从化学试剂公司购买。所述多孔碳化硅及其他多孔硅材料为商品化的产品，在市面上可以购得。
实施例1
一种医用多孔钽金属材料的制备，包括如下步骤：
(1)将孔隙率为85％，孔径为500μm的多孔碳化硅支架用40％HF：68％HNO3：H2O＝1：5：6混合溶液超声震荡清洗后，用干燥氮气吹干，置入气相沉积反应室内；
(2)连接好进/排气管道装置，检查反应室密封情况，抽真空，然后在氩气保护下进行加热至950℃；
(3)将粒径为400目的五氯化碳粉末放入源罐中，加热至200℃，以高温氩气(300℃)为载气通入至反应室，载气流量为120ml/min，反应室温度为950℃,反应室真空度为10Pa；反应室中以氩气为载气通入五氯化钽粉末的同时，以120ml/min流量通入氢气，还原反应2小时，使还原成金属粉末的钽金属均匀沉积于多孔碳化硅支架表面以及其空隙表面，得本发明的医用多孔钽金属材料成品。
实施例1制备的医用多孔钽金属材料成品的孔隙率为85％，弹性模量为10GPa，最大抗压强度为35MPa.，其中孔隙率为根据国家标准GB/T 21650.1-2008，弹性模量为根据国家标准GB/T 22315-2008中所述的方法检测。
图1和图2为上述医用多孔钽植入材料成品的SEM(扫描电子显微镜)图，其中图1A为多孔碳化硅支架钽涂层前的SEM图，图1B为多孔碳化硅支架钽涂层后的SEM图，可见多孔碳化硅表面有深黑色钽金属附着，反光性明显减弱； 图2A和2B分别表示高倍率下的钽金属涂层前后多孔碳化硅支架的表面形貌，可见钽涂层前(图2A)多孔碳化硅支架的表面色泽明亮，在数字显微图像中显示较强的反光性，不利于细微结构清晰显示；而涂层后(图2B)多孔碳化硅支架的表面反光性明显减弱，可以清晰的观察到多孔支架的细微结构和孔的形态特征，展现了良好的三维联通性，同时钽涂层呈现凹凸不平粗糙表面不仅有利于细胞的粘附和组织的嵌入，而且还有增强支架与骨组织的链接强度。
实施例2
一种医用多孔钽金属材料的制备，包括如下步骤：
(1)将孔隙率为85％，孔径为400μm的多孔碳化硅支架用40％HF：68％HNO3：H2O＝1：5：6混合溶液超声震荡清洗后，用干燥氮气吹干，置入气相沉积反应室内；
(2)连接好进/排气管道装置，检查反应室密封情况，抽真空，然后在氩气保护下进行加热至1050℃；
(3)将粒径为400目的五氯化碳粉末放入源罐中，加热至250℃，以高温氩气(300℃)为载气通入至反应室，载气流量为120ml/min，反应室温度为1050℃，反应室真空度为15Pa；反应室中以氩气为载气通入五氯化钽粉末的同时，以120ml/min流量通入氢气，还原反应2.5小时，使还原成金属粉末的钽金属均匀沉积于多孔碳化硅支架表面以及其空隙表面，得本发明的医用多孔钽金属材料成品。
实施例2制备的医用多孔钽金属材料成品的孔隙率为85％，弹性模量为12GPa，最大抗压强度为50MPa，其中孔隙率为根据国家标准GB/T21650.1-2008，弹性模量为根据国家标准GB/T 22315-2008中所述的方法检测。

Claims (3)

1.一种医用多孔钽金属材料，其特征在于，所述医用多孔钽金属材料是利用化学气相沉积方法，将钽金属化合物还原为钽金属粉，均匀沉积于多孔硅材料支架表面形成钽涂层制备得到；
其中所述钽金属化合物为五氯化钽、氟化钽中的一种；所述多孔硅材料的孔隙率>70％，孔径为100～600μm；所述钽涂层的厚度为10～50μm；
所述的多孔硅为多孔碳化硅；所述医用多孔钽金属材料的孔隙率>70％，弹性模量<30Gpa；
制备所述医用多孔钽金属材料的方法，包括如下步骤：
(1)将所述多孔硅材料支架用按质量比40％氟氢酸：68％硝酸：水＝1：5：6的混合溶液超声震荡后，用干燥氮气吹干，置入气相沉积反应室内；
(2)气相沉积反应室抽真空、在惰性气体保护下加热至900～1500℃；
(3)气相沉积反应室内同时通入处理气体和氢气，在900～1500℃，真空度10～15Pa条件下，反应2～3小时；其中所述处理气体包含钽金属化合物和载气，将钽金属化合物放入源罐中，加热至200～300℃，将源罐中的钽金属化合物以300℃惰性气体为载气通入至反应室；
所述处理气体的流量为80～100ml/min；
所述氢气的流量为100～150ml/min。
2.根据权利要求1所述的医用多孔钽金属材料，其特征在于，所述钽金属化合物为粒径400目的粉末。
3.根据权利要求1所述的医用多孔钽金属材料，其特征在于，所述惰性气体为氩气、氦气中的一种或两种的混合。
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