CN110304917B - 用于骨组织工程的钛酸钡压电陶瓷支架及其制备方法 - Google Patents

用于骨组织工程的钛酸钡压电陶瓷支架及其制备方法 Download PDF

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CN110304917B
CN110304917B CN201910670959.9A CN201910670959A CN110304917B CN 110304917 B CN110304917 B CN 110304917B CN 201910670959 A CN201910670959 A CN 201910670959A CN 110304917 B CN110304917 B CN 110304917B
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barium titanate
tissue engineering
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bioactive glass
piezoelectric ceramic
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朱敏
何鑫
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University of Shanghai for Science and Technology
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Abstract

本发明提供了一种用于骨组织工程的钛酸钡压电陶瓷支架，其特征在于，包括：将60‑80wt％的包覆生物活性玻璃的钛酸钡粉末、10‑20wt％乙醇、5‑15wt％的粘结剂聚乙烯吡咯烷酮混合，搅拌，得到打印墨水；使用三维建模软件设计50％‑90％孔隙率的多孔模型，进行三维打印，得到多孔支架素坯；将多孔支架素坯置于管式炉中烧结，得到用于骨组织工程的钛酸钡压电陶瓷支架。本发明以包覆生物活性玻璃的钛酸钡为原料，采用三维打印技术制备出多孔复合陶瓷支架，具有很好的生物活性和压电性，能够精确控制支架的内部结构，成型过程简单。

Description

用于骨组织工程的钛酸钡压电陶瓷支架及其制备方法
技术领域
本发明属于材料学领域，具体来说是一种用于骨组织工程的钛酸钡压电陶瓷支架及其制备方法。
背景技术
骨组织工程作为骨缺损修复领域最具有前景的方法得到了广泛的认可，它的提出和发展改变了传统的骨缺损修复治疗模式。骨组织工程包括三个基本要素—细胞、支架材料和信号分子，其中支架材料作为构建骨组织工程最基本的载体材料，在骨组织工程中扮演着非常重要的角色。除此以外，研究表明物理刺激如超声刺激、脉冲电刺激、直流电刺激等也具有促进骨缺损的修复，它们的作用机理是促进了与成骨相关基因的表达，增加了局部血流量、营养物质、生长因子的运输以及代谢废物的转移等。钛酸钡压电陶瓷作为支架材料已经证明具有很好的促成骨作用，而生物玻璃具有极佳的生物活性，并且其降解产物也是骨修复过程中所必须的。因此钛酸钡压电陶瓷支架因人体机械运动产生的压电效应协同生物玻璃优秀的生物活性具有很好的促成骨作用，加速骨缺损的修复。
传统制备陶瓷支架的方法主要为造孔剂法，冷冻干燥法和有机泡沫浸渍法。但是这些方法都不能精确调控支架的内部结构和孔的连通性。研究发现，支架的内部结构包括孔的大小、形状和连通性等都会影响支架的降解、离子释放、营养物质输送、细胞粘附及生长等情况，对细胞行为产生重要影响。
三维打印技术作为一种新型快速成型技术能够精确控制支架的外观以及内部孔的形状、大小和连通性，制备出有利于细胞生长和成骨的骨组织工程支架。此外，三维打印技术操作便捷、重复性强，对材料本身性质影响较小。
发明内容
本发明的目的是提供一种基于3D打印的骨组织工程的钛酸钡压电陶瓷支架的制备方法。
为了达到上述目的，本发明提供了一种用于骨组织工程的钛酸钡压电陶瓷支架，其特征在于，包括：
步骤1：将钛酸钡纳米颗粒分散在乙醇中，加入乙酸活化，搅拌，超声处理后，边搅拌边加入正硅酸四乙酯，加入氨水调节pH值为8-9.5，搅拌，再加入四水硝酸钙，35-45℃搅拌，离心收集所得固体并洗涤至中性，烘干，得到包覆生物活性玻璃的钛酸钡粉末(BTO@BG)；
步骤2：将60-80wt％的包覆生物活性玻璃的钛酸钡粉末、10-20wt％乙醇、5-15wt％的粘结剂聚乙烯吡咯烷酮混合，搅拌，得到打印墨水；
步骤3：使用三维建模软件设计50％-90％孔隙率的多孔模型，并将所述的多孔模型数据导入到3D打印机配套软件中，对所述的多孔模型进行切片、调平，将步骤2得到的打印墨水装进三维打印机的料筒中；启动三维打印程序，将打印墨水以层层堆积的方式沉积在载物平台的玻璃培养皿中，打印完成后将所得的支架干燥，得到多孔支架素坯；
步骤4：将步骤3得到的多孔支架素坯置于管式炉中烧结，所述的烧结包括：先从室温以0.8-1.2℃/min的速度加热到300-500℃，保温1-2小时，然后以2.5-3.5℃/min的速度加热到1150-1250℃，保温1-3小时，最后自然冷却至室温，得到用于骨组织工程的钛酸钡压电陶瓷支架。
优选地，所述的3D打印机的针头直径为400-1000μm，三维打印的条件包括：气压为1-5bar，打印速度为1.0-12.0mm/s，墨水相邻两层走向夹角为45-90°。
优选地，所述的步骤1中的包覆生物活性玻璃的钛酸钡粉末用溶胶凝胶法制得。
优选地，所述的步骤1中的包覆生物活性玻璃的钛酸钡粉末中生物活性玻璃均匀地包覆在钛酸钡表面，钛酸钡和生物活性玻璃的质量比为100：5-20。
优选地，所述的钛酸钡纳米颗粒的粒径尺寸≤1微米。
优选地，所述的三维建模软件是Soild edge、SolidWorks、C4D或AUTOCAD。
优选地，所述的3D打印机是***3-D BioplotterTM(EnvisionTEC GmbH，Germany)打印机。
优选地，所述的钛酸钡纳米颗粒、正硅酸四乙酯以及四水硝酸钙的质量比为1：2.4-8：8.7-25。
与现有技术相比，本发明的有益效果是：
1、本发明以包覆生物活性玻璃的钛酸钡为原料，采用三维打印技术制备出多孔复合陶瓷支架，具有很好的生物活性和压电性，能够精确控制支架的内部结构，成型过程简单。
2、本发明的方法提高了支架的生物学性能并且实现电刺激促进成骨作用。
3、对所述多孔支架的理化性能和生物学性能检测得知，支架具有三维连通的大孔结构，孔径为50-1000微米，孔隙率在50-90％可调，力学性能良好(2-10MPa)，并且对人体骨髓间质干细胞的增殖、分化和成骨起促进作用。本发明的多孔支架制备方法为骨组织工程陶瓷支架的制备提供了新的技术，有望为骨组织工程支架制备及骨缺损修复治疗带来新的策略。
4、本发明解决了目前3D打印钛酸钡过程中，打印过程复杂，不能精确调控支架的内部结构和孔的连通性的技术问题。
附图说明
图1是本发明实施例1所制备的多孔BTO@BG陶瓷支架的光学照片。
图2是本发明实施例1所制备的多孔BTO@BG陶瓷支架的SEM图。
图3是本发明实施例1所制备的多孔BTO@BG粉体的TEM图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
以下实施例中所用的3D打印机是***3-D BioplotterTM(EnvisionTEC GmbH，Germany)打印机。
以下实施例中所用到的各原料均为市售产品。
实施例1
一种用于骨组织工程的钛酸钡压电陶瓷支架，具体步骤为：
步骤1：将20g粒径尺寸≤1微米的钛酸钡纳米颗粒分散在100mL乙醇中，加入5mL摩尔浓度为17.5mol/L的乙酸活化，搅拌30min，超声处理30min后，边搅拌边加入8g正硅酸四乙酯，加入摩尔浓度为14.8mol/L的氨水调节pH值为9，搅拌，再加入2g四水硝酸钙，40℃搅拌4h，离心收集所得固体并洗涤至中性，60℃烘干，得到包覆生物活性玻璃的钛酸钡粉末(BTO@BG)，生物活性玻璃均匀地包覆在钛酸钡表面，钛酸钡和生物活性玻璃质量比为100：15。
步骤2：将70wt％的包覆生物活性玻璃的钛酸钡粉末、20wt％乙醇、10wt％的粘结剂聚乙烯吡咯烷酮(K60)混合，迅速搅拌均匀，得到打印墨水；
步骤3：使用CAD三维建模软件设计多孔结构，得到50％孔隙率的多孔模型，并将所述的多孔模型数据导入到3D打印机配套软件中，调整参数对所述的多孔模型进行切片、调平，将步骤2得到的打印墨水装进三维打印机的料筒中，针头直径为400μm；启动三维打印程序，调节气压为2bar，打印速度为6.0mm/s，墨水相邻两层走向夹角为90°，将打印墨水以层层堆积的方式沉积在载物平台的玻璃培养皿中，打印完成后将所得的支架在37℃烘箱中干燥24小时，得到多孔支架素坯；
步骤4：将步骤3得到的多孔支架素坯置于管式炉中烧结，所述的烧结包括：先从室温以1℃/min的速度加热到300℃，保温2小时，然后以3℃/min的速度加热到1150℃，保温3小时，最后自然冷却至室温，得到用于骨组织工程的钛酸钡压电陶瓷支架，如图1-3所示。
将得到的钛酸钡支架进行极化，将支架放在极化装置中，温度设定为100℃，计划电压为3kV，极化时间为10min，极化后将支架清洗干净，烘干消毒后，分别进行CCK-8和碱性磷酸酶(ALP)检测，以此来判断支架的生物相容性和成骨分化情况，结果显示支架材料都具有很好的细胞相容性，并且具有生物玻璃包覆的支架比纯钛酸钡支架具有更好地促进干细胞成骨分化的作用。
实施例2
一种用于骨组织工程的钛酸钡压电陶瓷支架，具体步骤为：
步骤1：将20g粒径尺寸≤1微米的钛酸钡纳米颗粒分散在100mL乙醇中，加入5mL摩尔浓度为17.5mol/L的乙酸活化，搅拌30min，超声处理30min后，边搅拌边加入5g正硅酸四乙酯，加入摩尔浓度为14.8mol/L氨水调节pH值为9.5，搅拌，再加入1.5g四水硝酸钙，40℃搅拌4h，离心收集所得固体并洗涤至中性，60℃烘干，得到包覆生物活性玻璃的钛酸钡粉末(BTO@BG)，生物活性玻璃均匀地包覆在钛酸钡表面，钛酸钡和生物活性玻璃质量比为100：10。
步骤2：将75wt％的包覆生物活性玻璃的钛酸钡粉末、10wt％乙醇、15wt％的粘结剂聚乙烯吡咯烷酮(K60)混合，迅速搅拌均匀，得到打印墨水；
步骤3：使用CAD三维建模软件设计多孔结构，得到60％孔隙率的多孔模型，并将所述的多孔模型数据导入到3D打印机配套软件中，调整参数对所述的多孔模型进行切片、调平，将步骤2得到的打印墨水装进三维打印机的料筒中，针头直径为600μm；启动三维打印程序，调节气压为2bar，打印速度为10mm/s，墨水相邻两层走向夹角为90°，将打印墨水以层层堆积的方式沉积在载物平台的玻璃培养皿中，打印完成后将所得的支架在37℃烘箱中干燥12小时，得到多孔支架素坯；
步骤4：将步骤3得到的多孔支架素坯置于管式炉中烧结，所述的烧结包括：先从室温以1℃/min的速度加热到300℃，保温2小时，然后以3℃/min的速度加热到1200℃，保温3小时，最后自然冷却至室温，得到用于骨组织工程的钛酸钡压电陶瓷支架。
将得到的钛酸钡支架进行极化，将支架放在极化装置中，温度设定为100℃，计划电压为3kV，极化时间为10min，极化后将支架清洗干净，烘干消毒后，分别进行CCK-8和碱性磷酸酶(ALP)检测，以此来判断支架的生物相容性和成骨分化情况，结果显示支架材料都具有很好的细胞相容性，并且具有生物玻璃包覆的支架比纯钛酸钡支架具有更好地促进干细胞成骨分化的作用。
实施例3
一种用于骨组织工程的钛酸钡压电陶瓷支架，具体步骤为：
步骤1：将20g粒径尺寸≤1微米的钛酸钡纳米颗粒分散在100mL乙醇中，加入5mL摩尔浓度为17.5mol/L的乙酸活化，搅拌30min，超声处理30min后，边搅拌边加入3g正硅酸四乙酯，加入摩尔浓度为14.8mol/L氨水调节pH值为8.5，搅拌，再加入0.8g四水硝酸钙，40℃搅拌4h，离心收集所得固体并洗涤至中性，60℃烘干，得到包覆生物活性玻璃的钛酸钡粉末(BTO@BG)，生物活性玻璃均匀地包覆在钛酸钡表面，钛酸钡和生物活性玻璃质量比为100：20。
步骤2：将60wt％的包覆生物活性玻璃的钛酸钡粉末、15wt％乙醇、25wt％的粘结剂聚乙烯吡咯烷酮(K30)混合，迅速搅拌均匀，得到打印墨水；
步骤3：使用CAD三维建模软件设计多孔结构，得到70％孔隙率的多孔模型，并将所述的多孔模型数据导入到3D打印机配套软件中，调整参数对所述的多孔模型进行切片、调平，将步骤2得到的打印墨水装进三维打印机的料筒中，针头直径为400μm；启动三维打印程序，调节气压为1.5bar，打印速度为12.0mm/s，墨水相邻两层走向夹角为90°，将打印墨水以层层堆积的方式沉积在载物平台的玻璃培养皿中，打印完成后将所得的支架在37℃烘箱中干燥12小时，得到多孔支架素坯；
步骤4：将步骤3得到的多孔支架素坯置于管式炉中烧结，所述的烧结包括：先从室温以1℃/min的速度加热到300℃，保温2小时，然后以3℃/min的速度加热到1250℃，保温3小时，最后自然冷却至室温，得到用于骨组织工程的钛酸钡压电陶瓷支架。
将得到的钛酸钡支架进行极化，将支架放在极化装置中，温度设定为100℃，计划电压为3kV，极化时间为10min，极化后将支架清洗干净，烘干消毒后，分别进行CCK-8和碱性磷酸酶(ALP)检测，以此来判断支架的生物相容性和成骨分化情况，结果显示支架材料都具有很好的细胞相容性，并且具有生物玻璃包覆的支架比纯钛酸钡支架具有更好地促进干细胞成骨分化的作用。
上述内容详细描述了本发明较佳具体实例。应当理解，对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本发明的保护范围。

Claims (4)

1.一种用于骨组织工程的钛酸钡压电陶瓷支架，其特征在于，包括：
步骤1：将钛酸钡纳米颗粒分散在乙醇中，加入乙酸活化，搅拌，超声处理后，边搅拌边加入正硅酸四乙酯，加入氨水调节pH值为8-9.5，搅拌，再加入四水硝酸钙，35-45℃搅拌，离心收集所得固体并洗涤至中性，烘干，得到包覆生物活性玻璃的钛酸钡粉末；所述包覆生物活性玻璃的钛酸钡粉末中生物活性玻璃均匀地包覆在钛酸钡表面，钛酸钡和生物活性玻璃的质量比为100：5-20；
步骤2：将60-80wt%的包覆生物活性玻璃的钛酸钡粉末、10-20wt%乙醇、5-15wt%的粘结剂聚乙烯吡咯烷酮混合，搅拌，得到打印墨水；所述包覆生物活性玻璃的钛酸钡粉末、乙醇和粘结剂聚乙烯吡咯烷酮的质量百分数之和为100%；
步骤3：使用三维建模软件设计50%-90%孔隙率的多孔模型，并将所述的多孔模型数据导入到3D打印机配套软件中，对所述的多孔模型进行切片、调平，将步骤2得到的打印墨水装进三维打印机的料筒中；启动三维打印程序，将打印墨水以层层堆积的方式沉积在载物平台的玻璃培养皿中，打印完成后将所得的支架干燥，得到多孔支架素坯；
步骤4：将步骤3得到的多孔支架素坯置于管式炉中烧结，所述的烧结包括：先从室温以0.8-1.2℃/min的速度加热到300-500℃，保温1-2小时，然后以2.5-3.5℃/min的速度加热到1150-1250℃，保温1-3小时，最后自然冷却至室温，得到用于骨组织工程的钛酸钡压电陶瓷支架。
2.如权利要求1所述的用于骨组织工程的钛酸钡压电陶瓷支架，其特征在于，所述的3D打印机的针头直径为400-1000μm，三维打印的条件包括：气压为1-5bar，打印速度为1.0-12.0mm/s，墨水相邻两层走向夹角为45-90°。
3.如权利要求1所述的用于骨组织工程的钛酸钡压电陶瓷支架，其特征在于，所述的三维建模软件是Soild edge、SolidWorks、C4D或AUTOCAD。
4.如权利要求1所述的用于骨组织工程的钛酸钡压电陶瓷支架，其特征在于，所述的3D打印机是*** 3-D Bioplotter™打印机。
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