CN106365628A - 一种碳纳米管复合生物陶瓷 - Google Patents

一种碳纳米管复合生物陶瓷 Download PDF

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CN106365628A
CN106365628A CN201610822314.9A CN201610822314A CN106365628A CN 106365628 A CN106365628 A CN 106365628A CN 201610822314 A CN201610822314 A CN 201610822314A CN 106365628 A CN106365628 A CN 106365628A
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Abstract

一种碳纳米管复合生物陶瓷，涉及生物医用材料领域，复合生物陶瓷由包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管构成，两者的质量之比10‑20:1；羟基磷灰石粉体的平均粒径为5‑20μm，表面包覆的二氧化硅粒子层的厚度为50‑200nm；一种羟基磷灰石/碳纳米管复合生物陶瓷的制备方法，制备步骤包括：水热法制备羟基磷灰石粉体；化学气相沉积反应；干燥冷压成型；高温煅烧和冷却。本发明提供的羟基磷灰石/碳纳米管复合生物陶瓷，是以羟基磷灰石为基础，在此基础之上利用碳纳米管优良的机械性能和其对于骨骼细胞的增殖作用来使得复合生物陶瓷具有较高的骨损伤修复性能。

Description

一种碳纳米管复合生物陶瓷
技术领域
本发明属于生物医用材料领域，特别涉及一种羟基磷灰石/碳纳米管复合生物陶瓷及该生物陶瓷的制备方法。
背景技术
生物陶瓷是与生物体有关的新型陶瓷，生物陶瓷不仅具有不锈钢塑料所具有的特性，而且具有亲水性、能与细胞等生物组织表现出良好的亲和性。
生物陶瓷材料分为生物惰性陶瓷材料和生物活性陶瓷材料，羟基磷灰石生物陶瓷属于生物活性陶瓷，羟基磷灰石的结构与生物骨相似，因此，合成的羟基磷灰石生物陶瓷常用作骨骼的替代或修复材料。
碳纳米管，又名巴基管，是一种具有特殊结构的一维量子材料，具有径向尺寸为纳米量级，轴向尺寸为微米量级，管子两端基本上都封口的结构特点。
碳纳米管作为一维纳米材料，重量轻，六边形结构连接完美，具有许多异常的力学、电学和化学性能。近些年随着碳纳米管及纳米材料研究的深入其广阔的应用前景也不断地展现出来。生物医学材料是对于碳纳米管研究利用的新的领域。
关于碳纳米管的生物利用的研究中，有科学家将成骨细胞接种到碳纳米管上，考察其增殖和功能，发现碳纳米管促进细胞增殖，增加了碱性磷酸酶活性、细胞内蛋白合成和细胞外钙沉积。虽然，碳纳米管有一定的细胞毒性，但是其优良的性能，还是带动了其在生物材料的应用。
申请号为201210555876.3的专利文献“碳纳米管增强羟基磷灰石复合材料的制备方法”公开了一种羟基磷灰石/碳纳米管复合材料的制备方法，是在羟基磷灰石粉体中合成碳纳米管，并利用羟基磷灰石进行碳纳米管表面修饰，进而制备碳纳米管增强羟基磷灰石复合材料的方法，先用碳酸镍与羟基磷灰石粉末制备碳纳米管-羟基磷灰石粉末，再制备羟基磷灰石修饰的碳纳米管-羟基磷灰石粉末，最终制得碳纳米管增强羟基磷灰石复合材料。
由此可知，该技术方案提供的复合材料，是利用羟基磷灰石进行碳纳米管表面修饰，以提高碳纳米管与羟基磷灰石基体之间浸润性，并有助于材料的成型，是一种行之有效的复合材料制备方法。
发明内容
本发明解决的技术问题：针对上述不足，克服现有技术的缺陷，本发明的目的是提供一种羟基磷灰石/碳纳米管复合生物陶瓷及其制备方法。
本发明的技术方案：一种羟基磷灰石/碳纳米管复合生物陶瓷，复合生物陶瓷由包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管构成，其中，羟基磷灰石粉体的平均粒径为5-20μm，表面包覆的二氧化硅粒子层的厚度为50-200nm；
其中，包覆有二氧化硅纳米粒子层的羟基磷灰石粉体与碳纳米管的质量之比例为10-20:1。
作为优选，所述羟基磷灰石根据水热法制备而成。
一种羟基磷灰石/碳纳米管复合生物陶瓷的制备方法，制备步骤如下：
（1）制备羟基磷灰石粉体：通过水热法制备羟基磷灰石，然后干燥研磨过筛；
（2）将羟基磷灰石粉体放入化学气相沉积反应室中，进行化学气相沉积反应：预热至600-800℃，以正硅酸乙酯为原料，控制原料的蒸发温度为85-110℃，通入氩气保护气体，反应室旋转速率为30-60r/min，反应时间20-60min，反应结束后，待冷却至室温，取出；
（3）将包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管放入球磨机进行研磨分散，混合均匀之后，真空干燥；
（4）将干燥后的混合粉体进行在1.2-2GPa压力下冷压成型；
（5）将成型后的材料进行高温煅烧，温度为1100-1500℃，压力2-5GPa，时间1-3h；
（6）煅烧之后，待冷却取出，即得到块状羟基磷灰石/碳纳米管复合生物陶瓷。
作为优选，步骤（2）进行化学气相沉积反应中氩气的气体流量为100-400ml/min。
作为优选，步骤（5）高温煅烧的温度为1250-1400℃。
作为优选，步骤（4）中高温煅烧的压力2.5-4GPa。
有益效果：本发明提供的羟基磷灰石/碳纳米管复合生物陶瓷，是以羟基磷灰石为基础，在此基础之上利用碳纳米管优良的机械性能和其对于骨骼细胞的增殖作用来使得复合生物陶瓷具有较高的骨损伤修复性能。
碳纳米管是一种优良的材料，但是其在固体中的分散性能较差，会因聚集而导致性能下降。简单将碳纳米管和羟基磷灰石粉体混合后高温煅烧，会因为碳纳米管与羟基磷灰石基体之间浸润性差与界面结合强度低的特点，导致相互之间的作用较小，而只能以单独的形态存在，从而不利于性能上的加强，且表面负载碳纳米管的羟基磷灰石粉体难以成型的特点，也导致复合陶瓷材料的机械性能不佳。
因此，本发明利用化学气相沉积法，在羟基磷灰石粉体表面包覆一层紧密二氧化硅纳米粒子层，通过二氧化硅和碳纳米管在高温固相中的作用，而将碳纳米管与羟基磷灰石粉体相结合，达到性能上的增强，得到的复合陶瓷材料不仅具有较好的机械性能，其生物功能性也较佳，且克服了生物相容性不足的缺陷。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解， 这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
实施例1：
一种羟基磷灰石/碳纳米管复合生物陶瓷，复合生物陶瓷由包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管构成，包覆有二氧化硅纳米粒子层的羟基磷灰石粉体与碳纳米管的质量之比例为20:1。
根据本发明提供的制备方法制备羟基磷灰石/碳纳米管复合生物陶瓷，步骤如下：
（1）制备羟基磷灰石粉体：将CaHPO4与CaCO3按物质的量之比6：4进行配料；然后进行湿法球磨，时间24h；将球磨好的浆料倒入容器中，加入蒸馏水，在90℃恒温情况下进行搅拌，反应完毕后，放置沉淀得到白色的羟基磷灰石沉淀物，然后干燥研磨过筛；
（2）将羟基磷灰石粉体放入化学气相沉积反应室中，进行化学气相沉积反应：预热至735℃，以正硅酸乙酯为原料，控制原料的蒸发温度为90℃，通入氩气保护气体，200ml/min，反应室旋转速率为60r/min，反应时间30min，反应结束后，待冷却至室温，取出；
经检测，羟基磷灰石粉体的平均粒径为10μm，表面包覆的二氧化硅粒子层的厚度为70nm；
（3）将包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管放入球磨机进行研磨分散，混合均匀之后，真空干燥；
（4）将干燥后的混合粉体进行在1.5GPa压力下冷压成型；
（5）将成型后的材料进行高温煅烧，温度为1300℃，压力3GPa，时间2h；
（6）煅烧之后，待冷却取出，即得到块状羟基磷灰石/碳纳米管复合生物陶瓷。
对得到的块状羟基磷灰石/碳纳米管复合生物陶瓷进行性能检测：密度3.12kg/m3；抗压强度450MPa；抗弯强度470MPa；韧性10MPa·m1/2；弹性模量28GPa。
实施例2：
一种羟基磷灰石/碳纳米管复合生物陶瓷，复合生物陶瓷由包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管构成，包覆有二氧化硅纳米粒子层的羟基磷灰石粉体与碳纳米管的质量之比例为10:1。
根据本发明提供的制备方法制备羟基磷灰石/碳纳米管复合生物陶瓷，步骤如下：
（1）制备羟基磷灰石粉体：将CaHPO4与CaCO3按物质的量之比6：4进行配料；然后进行湿法球磨，时间24h；将球磨好的浆料倒入容器中，加入蒸馏水，在90℃恒温情况下进行搅拌，反应完毕后，放置沉淀得到白色的羟基磷灰石沉淀物，然后干燥研磨过筛；
（2）将羟基磷灰石粉体放入化学气相沉积反应室中，进行化学气相沉积反应：预热至750℃，以正硅酸乙酯为原料，控制原料的蒸发温度为95℃，通入氩气保护气体，200ml/min，反应室旋转速率为30r/min，反应时间45min，反应结束后，待冷却至室温，取出；
经检测，羟基磷灰石粉体的平均粒径为10μm，表面包覆的二氧化硅粒子层的厚度为60nm；
（3）将包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管放入球磨机进行研磨分散，混合均匀之后，真空干燥；
（4）将干燥后的混合粉体进行在1.5GPa压力下冷压成型；
（5）将成型后的材料进行高温煅烧，温度为1300℃，压力3GPa，时间2h；
（6）煅烧之后，待冷却取出，即得到块状羟基磷灰石/碳纳米管复合生物陶瓷。
对得到的块状羟基磷灰石/碳纳米管复合生物陶瓷进行性能检测：密度3.07kg/m3；抗压强度410MPa；抗弯强度420MPa；韧性11MPa·m1/2；弹性模量23GPa。
实施例3：
一种羟基磷灰石/碳纳米管复合生物陶瓷，复合生物陶瓷由包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管构成，包覆有二氧化硅纳米粒子层的羟基磷灰石粉体与碳纳米管的质量之比例为15:1。
根据本发明提供的制备方法制备羟基磷灰石/碳纳米管复合生物陶瓷，步骤如下：
（1）制备羟基磷灰石粉体：将CaHPO4与CaCO3按物质的量之比6：4进行配料；然后进行湿法球磨，时间24h；将球磨好的浆料倒入容器中，加入蒸馏水，在90℃恒温情况下进行搅拌，反应完毕后，放置沉淀得到白色的羟基磷灰石沉淀物，然后干燥研磨过筛；
（2）将羟基磷灰石粉体放入化学气相沉积反应室中，进行化学气相沉积反应：预热至800℃，以正硅酸乙酯为原料，控制原料的蒸发温度为100℃，通入氩气保护气体，300ml/min，反应室旋转速率为60r/min，反应时间40min，反应结束后，待冷却至室温，取出；
经检测，羟基磷灰石粉体的平均粒径为10μm，表面包覆的二氧化硅粒子层的厚度为150nm；
（3）将包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管放入球磨机进行研磨分散，混合均匀之后，真空干燥；
（4）将干燥后的混合粉体进行在1.5GPa压力下冷压成型；
（5）将成型后的材料进行高温煅烧，温度为1350℃，压力3GPa，时间2h；
（6）煅烧之后，待冷却取出，即得到块状羟基磷灰石/碳纳米管复合生物陶瓷。
对得到的块状羟基磷灰石/碳纳米管复合生物陶瓷进行性能检测：密度3.13kg/m3；抗压强度450MPa；抗弯强度460MPa；韧性12MPa·m1/2；弹性模量25GPa。
实施例4：
一种羟基磷灰石/碳纳米管复合生物陶瓷，复合生物陶瓷由包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管构成，包覆有二氧化硅纳米粒子层的羟基磷灰石粉体与碳纳米管的质量之比例为12:1。
根据本发明提供的制备方法制备羟基磷灰石/碳纳米管复合生物陶瓷，步骤如下：
（1）制备羟基磷灰石粉体：将CaHPO4与CaCO3按物质的量之比6：4进行配料；然后进行湿法球磨，时间24h；将球磨好的浆料倒入容器中，加入蒸馏水，在90℃恒温情况下进行搅拌，反应完毕后，放置沉淀得到白色的羟基磷灰石沉淀物，然后干燥研磨过筛；
（2）将羟基磷灰石粉体放入化学气相沉积反应室中，进行化学气相沉积反应：预热至650℃，以正硅酸乙酯为原料，控制原料的蒸发温度为90℃，通入氩气保护气体，200ml/min，反应室旋转速率为30r/min，反应时间60min，反应结束后，待冷却至室温，取出；
经检测，羟基磷灰石粉体的平均粒径为10μm，表面包覆的二氧化硅粒子层的厚度为110nm；
（3）将包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管放入球磨机进行研磨分散，混合均匀之后，真空干燥；
（4）将干燥后的混合粉体进行在1.5GPa压力下冷压成型；
（5）将成型后的材料进行高温煅烧，温度为1350℃，压力3.5GPa，时间2h；
（6）煅烧之后，待冷却取出，即得到块状羟基磷灰石/碳纳米管复合生物陶瓷。
对得到的块状羟基磷灰石/碳纳米管复合生物陶瓷进行性能检测：密度3.11kg/m3；抗压强度460MPa；抗弯强度480MPa；韧性11MPa·m1/2；弹性模量24GPa。
实施例5：
一种羟基磷灰石/碳纳米管复合生物陶瓷，复合生物陶瓷由包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管构成，包覆有二氧化硅纳米粒子层的羟基磷灰石粉体与碳纳米管的质量之比例为16:1。
根据本发明提供的制备方法制备羟基磷灰石/碳纳米管复合生物陶瓷，步骤如下：
（1）制备羟基磷灰石粉体：将CaHPO4与CaCO3按物质的量之比6：4进行配料；然后进行湿法球磨，时间24h；将球磨好的浆料倒入容器中，加入蒸馏水，在90℃恒温情况下进行搅拌，反应完毕后，放置沉淀得到白色的羟基磷灰石沉淀物，然后干燥研磨过筛；
（2）将羟基磷灰石粉体放入化学气相沉积反应室中，进行化学气相沉积反应：预热至728℃，以正硅酸乙酯为原料，控制原料的蒸发温度为92℃，通入氩气保护气体，300ml/min，反应室旋转速率为45r/min，反应时间40min，反应结束后，待冷却至室温，取出；
经检测，羟基磷灰石粉体的平均粒径为10μm，表面包覆的二氧化硅粒子层的厚度为120nm；
（3）将包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管放入球磨机进行研磨分散，混合均匀之后，真空干燥；
（4）将干燥后的混合粉体进行在1.5GPa压力下冷压成型；
（5）将成型后的材料进行高温煅烧，温度为1400℃，压力4GPa，时间1.5h；
（6）煅烧之后，待冷却取出，即得到块状羟基磷灰石/碳纳米管复合生物陶瓷。
对得到的块状羟基磷灰石/碳纳米管复合生物陶瓷进行性能检测：密度3.10kg/m3；抗压强度420MPa；抗弯强度430MPa；韧性10MPa·m1/2；弹性模量26GPa。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (1)

1.一种羟基磷灰石/碳纳米管复合生物陶瓷，其特征在于：复合生物陶瓷由包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管，其中，羟基磷灰石粉体的平均粒径为5-20μm，表面包覆的二氧化硅粒子层的厚度为50-200nm；
其中，包覆有二氧化硅纳米粒子层的羟基磷灰石粉体与碳纳米管的质量比例为15:1；所述羟基磷灰石根据水热法制备而成；
所述的羟基磷灰石/碳纳米管复合生物陶瓷的制备方法，如下：
（1）制备羟基磷灰石粉体：通过水热法制备羟基磷灰石，然后干燥研磨过筛；
（2）将羟基磷灰石粉体放入化学气相沉积反应室中，进行化学气相沉积反应：预热至800℃，以正硅酸乙酯为原料，控制原料的蒸发温度为100℃，通入氩气保护气体，300ml/min，反应室旋转速率为60r/min，反应时间40min，反应结束后，待冷却至室温，取出；
（3）将包覆有二氧化硅纳米粒子层的羟基磷灰石粉体和碳纳米管放入球磨机进行研磨分散，混合均匀之后，真空干燥；
（4）将干燥后的混合粉体进行在1.5GPa压力下冷压成型；
（5）将成型后的材料进行高温煅烧，温度为1350℃，压力3GPa，时间2h；
（6）煅烧之后，待冷却取出，即得到块状羟基磷灰石/碳纳米管复合生物陶瓷。
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