CN107374784B - 一种基于高分子聚合物增材制造的多孔植入物的制备方法 - Google Patents
一种基于高分子聚合物增材制造的多孔植入物的制备方法 Download PDFInfo
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Abstract
本发明提供一种基于高分子聚合物增材制造的多孔植入物的制备方法，包括如下步骤：使用增材制造方法制备具有梯度微观结构的多孔植入物模型的高分子聚合物负型模具；将金属粉与粘结剂混合均匀后压制高分子聚合物负型模具中，然后置入有机溶剂中去除高分子聚合物负型模具，得到初步的金属多孔植入物；将其置入真空高温炉中并利用化学气相沉积法在植入物表面沉积金属涂层进一步增强植入物的强度；最后将金属多孔植入物置入电解液中进行阳极氧化处理，得到具有表面纳米结构的定制化金属多孔植入物。该方法将增材制造与粉末冶金技术相结合，解决了孔隙尺寸及分布不可控的问题，且实现了表面结构的纳米化开辟具有宏微纳结构的多孔植入物制备的新途径。
Description
技术领域
本发明涉及一种基于增材制造的多孔植入物的制备方法，改方法属于生物增材制造(3D打印)领域，可应用于生物医疗领域。
背景技术
传统的粉末冶金-造孔剂法是制备金属生物医用支架最有效的方法，可以制备不同孔隙水平，支架的多孔结构是由造孔剂的种类、尺寸和形态来决定，内部的微观孔隙结构分布不均匀且不易控制和定制化制备。增材制造技术对于制造个性化植入物具有无可比拟的优势，能对定制化的微观结构进行制备。
目前的多孔植入物不具有可控宏微观一体化结构和纳米化结构：合理的设计宏观和微观的一体化结构能够减少多孔植入物的应力问题，增强其力学性能；纳米结构不仅有利于体内骨细胞的粘附、还能促进骨细胞的再生和分化，提高植入物的生物相容性。增材制造技术能够实现多孔植入物的微观梯度结构的控制制造，阳极氧化技术能够形成纳米结构。因此，如何解决多孔植入物微观仿生梯度结构不可控及无纳米结构的问题，制备出生物相容性和力学性能俱佳的多孔植入物是其应用于临床的关键问题之一。
传统的多孔金属植入物的制造方法主要包括：有机泡沫浸渍法、造孔剂-粉末烧结法、气相沉积法。但这些工艺可控性差，难以实现对植入物宏观结构的个性化和微观仿生梯度孔隙结构的主动控制，而且无法成形纳米结构，此外工艺制备流程复杂、投资大、生产成本高。
发明内容
为了克服多孔植入物支架微观梯度结构不可控及不能形成纳米结构等不足，本发明的目的在于提供一种基于增材制造的多孔植入物的制备方法，该方法将增材制造技术、粉末冶金技术、化学气相技术和阳极氧化技术相结合，可实现微观梯度结构可控成形，并形成纳米结构利于细胞活动，提高多孔植入物的生物相容性，有望开辟多孔支架制备的新途径，对于促进多孔植入物的临床应用具有重要意义。
为达到上述目的，本发明采用了以下技术方案：
一种基于高分子聚合物增材制造的多孔植入物的制备方法，包括如下的步骤：
1)使用增材制造方法制备具有梯度微观结构的多孔植入物模型的高分子聚合物负型模具；
2)将金属粉与粘结剂混合均匀后压制到步骤1)中制得的高分子聚合物负型模具中；
3)将步骤2)中金属粉与高分子聚合物负型模具一同置入有机溶剂中去除高分子聚合物负型模具，得到初步的金属多孔植入物；
4)将步骤3)制得的初步的金属多孔植入物置入真空高温炉中增强金属多孔植入物的强度；
5)将步骤4)中制得的金属多孔植入物利用化学气相沉积法在植入物表面沉积金属涂层进一步增强强度；
6)将步骤5)中制得的金属多孔植入物置入电解液中进行阳极氧化处理，得到表面具有金属氧化物纳米管的定制化金属多孔植入物。
本发明的进一步的改进在于，步骤1)中，高分子聚合物负型模具的材料为聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚丙烯晴(AS\ABS)、尼龙(PA)、有机玻璃亚克力(PMMA)、聚碳酸酯(PC)、聚氨酯(PU)、硅橡胶、聚己内酯(PCL)、聚乳酸(PLA)、聚醚醚酮(PEEK)、环氧树脂、聚乙烯醇(PVA)中的至少一种以及碳纤维、石墨烯、单壁及多壁碳纳米管与以上材料的复合材料。
本发明的进一步的改进在于，步骤1)中，所用的增材制造方法为光固化成形(SLA)、熔融沉积成形(FDM)、激光选区烧结(SLS)、3DP中的至少一种。
本发明的进一步的改进在于，步骤2)中，金属粉为钽、钛铌或铍等高熔点金属，金属粉的粒径范围0.1-200μm。
本发明的进一步的改进在于，步骤2)中，粘结剂为乙醇、甘油、聚乙烯醇(PVA)中的至少一种。
本发明的进一步的改进在于，步骤2)中，压制金属粉的压力为1MPa-1000Mpa。
本发明的进一步的改进在于，步骤3)中，溶剂为水、三氯甲烷、甲醇、丙酮、环己酮、苯酚、甲酸、二甲基甲酰胺、苯、乙醚、乙醇、乙二醇中的至少一种。
本发明的进一步的改进在于，步骤4)中，真空烧结的真空度需≥5×10-2Pa。
本发明的进一步的改进在于，步骤4)中，烧结工艺参数为：先使升温2℃～30℃/h，从室温升至150℃～600℃，然后保温0.5～5小时；再以2℃～30℃/h升至300℃～800℃，保温0.5～5小时；最后以40℃～200℃/h升至1100℃～1600℃，保温2～5小时；保温后关闭电炉电源，自然降至室温取出。
本发明的进一步的改进在于，步骤5)中，利用气相沉积的方法在多孔植入物支架表面沉积金属涂层，反应温度为500-2000℃，涂层厚度为10-500μm，反应气氛为氢气。
本发明的进一步的改进在于，步骤6)中，阳极为金属植入物，阴极为石墨棒、铂片，两电极间距为0.5-15cm，电解液为氢氟酸(0.05mol/L-5mol/L)和硫酸(2mol/L-18.4mol/L)的乙二醇溶液、水溶液、无水甘油溶液，，电压0.1-300V，阳极氧化时间10s-4h，反应温度为10-300℃。
本发明技术与现有技术相比具有如下优点：
1.本发明将增材制造技术与粉末冶金-造孔剂法以及阳极氧化技术相结合，能够实现对多孔植入物微观梯度结构的成形控制以及表面纳米结构的制备。
2.制备的多孔植入物具有纳米结构，利于细胞活动，提高植入物的生物相容性。
具体实施方式
本发明所述一种基于高分子聚合物增材制造的多孔植入物的制备方法，包括增材制造技术、粉末冶金技术、化学气相技术和阳极氧化技术四个环节：
所述制备方法使用增材制造方法制备具有梯度微观结构的多孔植入物模型的高分子聚合物负型模具。
所述制备方法制备的高分子聚合物负型模具的材料为聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚丙烯晴(AS\ABS)、尼龙(PA)、有机玻璃亚克力(PMMA)、聚碳酸酯(PC)、聚氨酯(PU)、硅橡胶、聚己内酯(PCL)、聚乳酸(PLA)、聚醚醚酮(PEEK)、环氧树脂、聚乙烯醇(PVA)中的至少一种以及碳纤维、石墨烯、单壁及多壁碳纳米管与以上材料的复合材料。
所述制备方法制备高分子聚合物负型模具的增材制造方法为光固化成形(SLA)、熔融沉积成形(FDM)、激光选区烧结(SLS)、3DP中的至少一种。
所述制备方法将金属粉与粘结剂混合均匀后压制到高分子聚合物负型模具中。
所述制备方法使用金属粉为钽、钛铌或铍等高熔点金属，金属粉的粒径范围0.1-200μm。
所述混合金属粉使用的粘结剂为乙醇、甘油、聚乙烯醇(PVA)中的至少一种。
所述压制金属粉的压力为1MPa-1000MPa。
所述制备方法将金属粉与高分子聚合物负型模具一同置入有机溶剂中去除高分子聚合物负型模具，得到初步的金属多孔植入物。
所述溶解高分子聚合物负型磨具的溶剂为水、三氯甲烷、甲醇、丙酮、环己酮、苯酚、甲酸、二甲基甲酰胺、苯、乙醚、乙醇、乙二醇中的至少一种。
所述制备方法将制得的初步的金属多孔植入物置入真空高温炉中增强金属多孔植入物的强度；
所述真空烧结的真空度需≥5×10-2Pa。
所述烧结工艺参数为：先使升温2℃～30℃/h，从室温升至150℃～600℃，然后保温0.5～5小时；再以2℃～30℃/h升至300℃～800℃，保温0.5～5小时；最后以40℃～200℃/h升至1100℃～1600℃，保温2～5小时；保温后关闭电炉电源，自然降至室温取出。
所述制备方法将制得的金属多孔植入物利用化学气相沉积法在植入物表面沉积金属涂层进一步增强强度。
所述利用化学气相沉积方法孔植入物支架表面沉积金属涂层，反应温度为500-2000℃，涂层厚度为10-500μm，反应气氛为氢气。
所述制备方法将制得的金属多孔植入物置入电解液中进行阳极氧化处理，得到表面具有金属氧化物纳米管的定制化金属多孔植入物。
所述阳极氧化处理的阳极为金属植入物，阴极为石墨棒、铂片，两电极间距为0.5-15cm，电解液为氢氟酸(0.05mol/L-5mol/L)和硫酸(2mol/L-18.4mol/L)的乙二醇溶液、水溶液、无水甘油溶液，，电压0.1-300V，阳极氧化时间10s-4h，反应温度为10-300℃。
实施例
一种基于高分子聚合物增材制造的多孔植入物的制备方法，包括增材制造技术、粉末冶金技术、化学气相技术和阳极氧化技术四个环节：
以尼龙作为高分子聚合物模具通过增材制造、粉末冶金及阳极氧化制备具有微纳结构的多孔钽植入物为例。首先使用选区激光烧结(SLS)制备已设计好的具有微观梯度结构的多孔钽植入物模型的负型尼龙模具。然后将钽粉与粘结剂混合压制入尼龙模具中，置于三氯甲烷溶液中溶解尼龙，得到初步多孔钽植入物，真空烧结去除粘结剂、增强多孔钽植入物的强度，再利用气相沉积的方法在多孔钽表面沉积钽涂层，最后置入电解液中进行阳极氧化处理，得到表面具有氧化钽纳米管的定制化多孔钽植入物。
使用选区激光烧结法制备负型尼龙模具，将钽粉与粘结剂混合均匀，控制压力降钽粉压制入尼龙模具中，置入三氯甲烷绕那个月中溶解尼龙，获得初步的多孔钽支架，置入真空高温炉中，按照烧结工艺进行升温、保温和降温进行烧结增强强度，利用气相沉积的方法在多孔钽植入物表面沉积钽涂层，及控制反应温度、钽涂层厚度和反应气氛。最后置入电解液中进行阳极氧化处理，阳极为多孔钽支架，阴极为石墨棒电解液为氢氟酸和硫酸的混合溶液，控制电极间距反应电压、阳极氧化时间、反应温度。
Claims (8)
1.一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于，包括如下的步骤：
1)使用增材制造方法制备具有梯度微观结构的多孔植入物模型的高分子聚合物负型模具；高分子聚合物负型模具的材料为聚乙烯PE、聚丙烯PP、聚苯乙烯PS、聚丙烯晴AS\ABS、尼龙PA、有机玻璃亚克力PMMA、聚碳酸酯PC、聚氨酯PU、硅橡胶、聚己内酯PCL、聚乳酸PLA、聚醚醚酮PEEK、环氧树脂、聚乙烯醇PVA中的至少一种以及碳纤维、石墨烯、单壁及多壁碳纳米管与以上材料的复合材料；所用的增材制造方法为光固化成形SLA、熔融沉积成形FDM、激光选区烧结SLS、3DP中的至少一种；
2)将金属粉与粘结剂混合均匀后压制到步骤1)中制得的高分子聚合物负型模具中；
3)将步骤2)中金属粉与高分子聚合物负型模具一同置入有机溶剂中去除高分子聚合物负型模具，得到初步的金属多孔植入物；
4)利用粉末冶金-造孔剂法，将步骤3)制得的初步的金属多孔植入物置入真空高温炉中增强金属多孔植入物的强度；
5)将步骤4)中制得的金属多孔植入物利用化学气相沉积法在植入物表面沉积金属涂层进一步增强强度；
6)将步骤5)中制得的金属多孔植入物置入电解液中进行阳极氧化处理，得到表面具有金属氧化物纳米管的定制化金属多孔植入物。
2.根据权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤2)中，金属粉为钽、钛铌或铍高熔点金属，金属粉的粒径范围0.1-200μm，粘结剂为乙醇、甘油、聚乙烯醇PVA中的至少一种。
3.权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤2)中，压制金属粉的压力为1MPa-1000Mpa。
4.权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤3)中，溶剂为水、三氯甲烷、甲醇、丙酮、环己酮、苯酚、甲酸、二甲基甲酰胺、苯、乙醚、乙醇、乙二醇中的至少一种。
5.根据权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤4)中，真空烧结的真空度需≥5×10-2Pa。
6.根据权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤4)中，烧结工艺参数为：先使升温2℃-30℃/h，从室温升至150℃-600℃，然后保温0.5-5小时；再以2℃-30℃/h升至300℃-800℃，保温0.5-5小时；最后以40℃-200℃/h升至1100℃-1600℃，保温2-5小时；保温后关闭电炉电源，自然降至室温取出。
7.根据权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤5)中，利用气相沉积的方法在多孔植入物支架表面沉积金属涂层，反应温度为500-2000℃，涂层厚度为10-500μm，反应气氛为氢气。
8.根据权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤6)中，阳极为金属植入物，阴极为石墨棒、铂片，两电极间距为0.5-15cm，电解液为0.05mol/L-5mol/L氢氟酸和2mol/L-18.4mol/L硫酸的乙二醇溶液、水溶液、无水甘油溶液，电压0.1-300V，阳极氧化时间10s-4h，反应温度为10-300℃。
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