CN105837197A - 作为人工骨核治疗骨结核的复合生物陶瓷 - Google Patents

作为人工骨核治疗骨结核的复合生物陶瓷 Download PDF

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CN105837197A
CN105837197A CN201610401413.XA CN201610401413A CN105837197A CN 105837197 A CN105837197 A CN 105837197A CN 201610401413 A CN201610401413 A CN 201610401413A CN 105837197 A CN105837197 A CN 105837197A
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Qinhuangdao Stone Technology Co ltd
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Abstract

本发明公开了一种作为人工骨核治疗骨结核的复合生物陶瓷，包括：制备羟基磷灰石粉体：通过水热法制备羟基磷灰石，然后干燥粉碎过筛，羟基磷灰石粉体的平均粒径为10‑50μm，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：以四氯化锆为原料，控制原料温度为350‑370℃，通入氢气和氩气，反应室旋转速率30‑60r/min，时间20‑40min，待反应结束，冷却至室温取出；将包覆有纳米氧化锆的羟基磷灰石粉体进行冷压成型；所述纳米氧化锆包覆层的厚度为100‑300nm；将成型后的材料进行高温煅烧，温度为1000‑1400℃，压力1.5‑2.5GPa，时间0.5‑1h；煅烧之后，待冷却取出。

Description

作为人工骨核治疗骨结核的复合生物陶瓷
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/氧化锆复合生物陶瓷及该生物陶瓷的制备方法。
背景技术
生物材料是对机体组织进行修复、替代与再生等性能的材料。由于不锈钢存在溶析、腐蚀和疲劳问题，塑料存在稳定性差和强度低的问题。生物陶瓷材料得到广泛发展，具有较为广阔的使用前景。
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，氧化锆生物陶瓷属于生物惰性陶瓷材料，具有优良的耐磨性能和机械强度，一般用作牙齿修复或替代材料；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。
氧化锆生物陶瓷的机械强度好，硬度高，在重负荷下，容易对机体造成伤害；羟基磷灰石生物陶瓷具有较好的生物相容性，且具有诱发刺激生长性能，缺点是机械强度较差，不耐磨，因此，如果将两种材料结合在一起，做到优势互补，得到的复合生物陶瓷将具备较好的使用前景。
申请号为200510027284.4的专利文献“羟基磷灰石-二氧化锆复合生物陶瓷材料及其制备方法”公开了一种羟基磷灰石/氧化锆复合生物陶瓷及其制备方法，该技术方案以二氧化锆为基体中心层，并在其上下面分别铺上按不同比例混合的二氧化锆和羟基磷灰石的混合中间层，最外面铺上一层纯羟基磷灰石的表面层，形成一种梯度叠层复合结构；在钢模中，在压力为10～30MPa下干压成形，再在1500～1600℃高温下无压烧结，就可得到羟基磷灰石-二氧化锆复合生物陶瓷材料。
由此可知，该技术方案提供羟基磷灰石/氧化锆复合生物陶瓷材料是将羟基磷灰石和二氧化锆制作成层状结构，通过冷压成型之后，高温烧结制备。制备得到的复合生物材料，其机械性能较之羟基磷灰石生物材料有所提高，但是仍不理想，材料的密度较小，高温固相之后，形成的层状结构中二氧化锆和羟基磷灰石的联系并不紧密，影响了材料的韧性，因此，材料的性能介入两者之间，并没有达到更好的提升。
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/氧化锆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/氧化锆复合生物陶瓷，以羟基磷灰石粉体为基体材料，以纳米氧化锆为包覆材料，在羟基磷灰石粉体表面包覆纳米氧化锆；
其中，羟基磷灰石粉体的平均粒径为10-50μm，纳米氧化锆包覆层的厚度为100-300nm；
其中，羟基磷灰石粉体通过沉淀反应法或水热法制备。
作为优选，所述羟基磷灰石中Ga和P之比为1:1.67。
一种羟基磷灰石/氧化锆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：通过水热法或沉淀反应法制备羟基磷灰石，然后干燥粉碎过筛；
（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：以四氯化锆为原料，控制原料温度为350-370℃，通入氢气和氩气，氢气的气体流量为400-600ml/min，氩气的气体流量为100-300ml/min，调整反应室温度至820-1300℃，反应室旋转速率30-60r/min，时间20-40min，待反应结束，冷却至室温取出；
（3）将包覆有纳米氧化锆的羟基磷灰石粉体进行冷压成型；
（4）将成型后的材料进行高温煅烧，温度为1000-1400℃，压力1.5 -2.5GPa，时间0.5-1h；
（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/氧化锆复合生物陶瓷。
作为优选，步骤（2）化学气相沉积反应中，反应室的温度为918℃。
作为优选，步骤（2）化学气相沉积反应中，氢气的气体流量为450-550ml/min。
作为优选，步骤（4）中高温煅烧的温度为1100-1250℃，压力1.8-2.2GPa。
有益效果：本发明提供的羟基磷灰石/氧化锆复合生物陶瓷，是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的柱状晶型纳米氧化锆，再通过高温固相的方法，形成复合生物陶瓷材料。
在制备过程中，首先利用水热法或沉淀反应法制备羟基磷灰石，得到的羟基磷灰石纯度较高，细度更为理想，然后理想化学气相沉积，在反应中，通过控制氢气的流量和反应室温度，使得形成的纳米氧化锆呈现均匀一致的柱状晶型，然后高温高压快速烧结，得到复合生物陶瓷材料。
由此羟基磷灰石/氧化锆复合生物陶瓷，结合了羟基磷灰石生物陶瓷和氧化锆生物陶瓷的优势，使得复合陶瓷具有较高的机械强度和具有较好的生物相容性，可作为牙齿或者牙槽的修补和填充、骨缺损的修复，以及可作为人工骨核治疗骨结核。
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/氧化锆复合生物陶瓷，以羟基磷灰石粉体为基体材料，以纳米氧化锆为包覆材料，在羟基磷灰石粉体表面包覆纳米氧化锆。
根据本发明提供的制备方法制备上述羟基磷灰石/氧化锆复合生物陶瓷，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95℃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，然后干燥过200目筛；
（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：以四氯化锆为原料，控制原料温度为355℃，通入氢气和氩气，氢气的气体流量为450ml/min，氩气的气体流量为200ml/min，调整反应室温度至836℃，反应室旋转速率30r/min，时间30min，待反应结束，冷却至室温取出；其中，纳米氧化锆包覆层的厚度为110nm；
（3）将包覆有纳米氧化锆的羟基磷灰石粉体进行冷压成型；
（4）将成型后的材料进行高温煅烧，温度为1200℃，压力2GPa，时间1h；
（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/氧化锆复合生物陶瓷。
对得到的块状羟基磷灰石/氧化锆复合生物陶瓷进行性能检测：密度3.84kg/m3；抗压强度620MPa；抗弯强度440MPa；韧性11MPa·m1/2；弹性模量72GPa。
实施例 2：
一种羟基磷灰石/氧化锆复合生物陶瓷，以羟基磷灰石粉体为基体材料，以纳米氧化锆为包覆材料，在羟基磷灰石粉体表面包覆纳米氧化锆。
根据本发明提供的制备方法制备上述羟基磷灰石/氧化锆复合生物陶瓷，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95℃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，然后干燥过200目筛；
（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：以四氯化锆为原料，控制原料温度为355℃，通入氢气和氩气，氢气的气体流量为600ml/min，氩气的气体流量为300ml/min，调整反应室温度至1276℃，反应室旋转速率60r/min，时间30min，待反应结束，冷却至室温取出；其中，纳米氧化锆包覆层的厚度为280nm；
（3）将包覆有纳米氧化锆的羟基磷灰石粉体进行冷压成型；
（4）将成型后的材料进行高温煅烧，温度为1250℃，压力2GPa，时间1h；
（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/氧化锆复合生物陶瓷。
对得到的块状羟基磷灰石/氧化锆复合生物陶瓷进行性能检测：密度4.16kg/m3；抗压强度660MPa；抗弯强度470MPa；韧性12.5MPa·m1/2；弹性模量77GPa。
实施例 3：
一种羟基磷灰石/氧化锆复合生物陶瓷，以羟基磷灰石粉体为基体材料，以纳米氧化锆为包覆材料，在羟基磷灰石粉体表面包覆纳米氧化锆。
根据本发明提供的制备方法制备上述羟基磷灰石/氧化锆复合生物陶瓷，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95℃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，然后干燥过200目筛；
（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：以四氯化锆为原料，控制原料温度为355℃，通入氢气和氩气，氢气的气体流量为500ml/min，氩气的气体流量为200ml/min，调整反应室温度至918℃，反应室旋转速率45r/min，时间35min，待反应结束，冷却至室温取出；其中，纳米氧化锆包覆层的厚度为210nm；
（3）将包覆有纳米氧化锆的羟基磷灰石粉体进行冷压成型；
（4）将成型后的材料进行高温煅烧，温度为1200℃，压力2GPa，时间h；
（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/氧化锆复合生物陶瓷。
对得到的块状羟基磷灰石/氧化锆复合生物陶瓷进行性能检测：密度4.05kg/m3；抗压强度650MPa；抗弯强度450MPa；韧性11.5MPa·m1/2；弹性模量72GPa。
实施例4：
一种羟基磷灰石/氧化锆复合生物陶瓷，以羟基磷灰石粉体为基体材料，以纳米氧化锆为包覆材料，在羟基磷灰石粉体表面包覆纳米氧化锆。
根据本发明提供的制备方法制备上述羟基磷灰石/氧化锆复合生物陶瓷，步骤如下：
（1）制备羟基磷灰石粉体：将此法用Ca(NO3)2与(NH4)2HPO4进行反应，得到白色的羟基磷灰石沉淀，然后干燥过200目筛；
（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：以四氯化锆为原料，控制原料温度为360℃，通入氢气和氩气，氢气的气体流量为500ml/min，氩气的气体流量为250ml/min，调整反应室温度至918℃，反应室旋转速率60r/min，时间40min，待反应结束，冷却至室温取出；其中，纳米氧化锆包覆层的厚度为230nm；
（3）将包覆有纳米氧化锆的羟基磷灰石粉体进行冷压成型；
（4）将成型后的材料进行高温煅烧，温度为1250℃，压力2.5GPa，时间0.5h；
（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/氧化锆复合生物陶瓷。
对得到的块状羟基磷灰石/氧化锆复合生物陶瓷进行性能检测：密度4.12kg/m3；抗压强度660MPa；抗弯强度460MPa；韧性12MPa·m1/2；弹性模量74GPa。
实施例5：
一种羟基磷灰石/氧化锆复合生物陶瓷，以羟基磷灰石粉体为基体材料，以纳米氧化锆为包覆材料，在羟基磷灰石粉体表面包覆纳米氧化锆。
根据本发明提供的制备方法制备上述羟基磷灰石/氧化锆复合生物陶瓷，步骤如下：
（1）制备羟基磷灰石粉体：将此法用Ca(NO3)2与(NH4)2HPO4进行反应，得到白色的羟基磷灰石沉淀，然后干燥过200目筛；
（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：以四氯化锆为原料，控制原料温度为365℃，通入氢气和氩气，氢气的气体流量为550ml/min，氩气的气体流量为300ml/min，调整反应室温度至918℃，反应室旋转速率60r/min，时间30min，待反应结束，冷却至室温取出；
其中，纳米氧化锆包覆层的厚度为200nm；
（3）将包覆有纳米氧化锆的羟基磷灰石粉体进行冷压成型；
（4）将成型后的材料进行高温煅烧，温度为1200℃，压力2GPa，时间1h；
（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/氧化锆复合生物陶瓷。
对得到的块状羟基磷灰石/氧化锆复合生物陶瓷进行性能检测：密度3.96kg/m3；抗压强度630MPa；抗弯强度470MPa；韧性12MPa·m1/2；弹性模量75GPa。
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/氧化锆复合生物陶瓷的制备方法，其特征在于，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，然后干燥粉碎过筛，羟基磷灰石粉体的平均粒径为10-50μm，羟基磷灰石中Ga和P之比为1:1.67；
（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：以四氯化锆为原料，控制原料温度为350-370℃，通入氢气和氩气，氢气的气体流量为450-550ml/min，氩气的气体流量为100-300ml/min，调整反应室温度至820-1300℃，反应室旋转速率30-60r/min，时间20-40min，待反应结束，冷却至室温取出；
（3）将包覆有纳米氧化锆的羟基磷灰石粉体进行冷压成型；所述纳米氧化锆包覆层的厚度为100-300nm；
（4）将成型后的材料进行高温煅烧，温度为1000-1400℃，压力1.5 -2.5GPa，时间0.5-1h；
（5）煅烧之后，待冷却取出，即得到块状羟基磷灰石/氧化锆复合生物陶瓷。
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CN104399116A (zh) 2015-03-11
CN105837198A (zh) 2016-08-10
CN105859275A (zh) 2016-08-17
CN105859276A (zh) 2016-08-17
CN105837198B (zh) 2018-08-21
CN105837197B (zh) 2018-06-26
CN105859275B (zh) 2018-07-20

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