CN110002894A - 一种生物压电多孔陶瓷支架的制备方法 - Google Patents

一种生物压电多孔陶瓷支架的制备方法 Download PDF

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CN110002894A
CN110002894A CN201910232687.4A CN201910232687A CN110002894A CN 110002894 A CN110002894 A CN 110002894A CN 201910232687 A CN201910232687 A CN 201910232687A CN 110002894 A CN110002894 A CN 110002894A
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porous ceramics
piezoelectricity
piezoelectric ceramic
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汤玉斐
焦梦珍
赵康
吴聪
张琦
任盈颖
段灯
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Xian University of Technology
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Abstract

本发明公开了一种一种生物压电多孔陶瓷支架的制备方法，首先将压电相和生物相混合均匀，得到生物压电陶瓷前驱体固相粉；其次将生物压电陶瓷前驱体固相粉、冷冻介质溶和分散剂制备生物压电陶瓷前驱体悬浊液；接着将所得生物压电陶瓷前驱体悬浊液注入冻干模具中定向冷冻干燥得到复合多孔支架之后经过养护反应成型得到多孔陶瓷支架；最后将得到的多孔陶瓷支架进行极化，得到生物压电多孔陶瓷支架。本发明一种生物压电多孔陶瓷支架的制备方法，所得生物压电多孔陶瓷支架不需高温烧结且具有定向直通孔结构，有利于骨细胞长入，同时还具有压电骨诱导性能，在促进骨细胞生长、缩短骨修复周期方面具有广阔的应用前景。

Description

一种生物压电多孔陶瓷支架的制备方法
技术领域
本发明属于医用材料制备技术领域，涉及一种生物压电多孔陶瓷支架的制备方法。
背景技术
近年来，生物学和生命科学飞速发展，每年因各种疾病及交通事故造成的骨组织创伤和缺损患者日益增多，同时,我国人口老龄化日趋严重，骨质疏松人数有加无减，这一现状促进了人工骨替代材料领域的研究和发展。
人体骨骼具有再生能力，对较小尺寸的缺损具有自我修复能力，但当骨缺损超过临界尺寸时则不能自行修复。人工合成的骨修复材料克服了自体骨移植和异体骨移植的缺陷，受到了材料学家和医学工作者的广泛关注。目前，人工骨材料主要有钛及钛合金、生物陶瓷、高分子材料及其复合材料。压电材料是一种可将能量进行转换的功能材料，将其植入骨缺损处后，随着机体的运动能将机械应力产生的形变转化为电效应，产生微电流。压电材料促进成骨的机制确切地说是电刺激成骨的机制，电刺激可改善局部血液供应，增加局部组织营养，加速骨形成。
传统的压电陶瓷/骨水泥复合材料大多通过物理共混制得，压电相含量很高时才能达到较高的压电系数，但骨水泥含量很少，导致骨传导性丧失很多，若减少压电相含量，则会让压电颗粒相互孤立，导致压电系数很低，达不到刺激细胞增殖分化的目的。如目前研究较多的BT/HA复合材料，由于钛酸钡和羟基磷灰石通过共混后烧结制得，而钛酸钡的最佳烧结温度为1300℃，羟基磷灰石烧结温度在1200℃左右，在同一温度共烧后会让材料无法达到性能最佳。
生物陶瓷材料由于其化学稳定性好、化学亲和性好、无毒性、无致癌作用，受到了广泛关注。但当前的常用生物陶瓷材料普遍为烧结致密的产品，比表面积小，开口气孔极少，与生物体内组织接触面积小，内部环境相对封闭，细胞增殖和生长的空间受到限制，从而抑制了生物材料修复的效率。相比而言，多孔的骨支架材料则具有较大的比表面积，孔隙结构有利于人体内营养物质和细胞的进入，可呈现出更加优异的修复效果。
目前，采用磷酸钙骨水泥粉末和纳米压电粉末混合，加入液相固化的方法，该方法中压电颗粒加入量较小，随机分散在骨水泥基体中，无法实现压电颗粒的相互连通，因此压电系数不高，达不到刺激细胞增殖分化的目的，同时，没有孔道供细胞长入。采用发泡法制备多孔铌酸锂钠钾/羟基磷灰石(LNK-HA)生物压电复合材料，当LNK与HA粉体质量比为9:1时，压电常数值为16.3pC/N，该方法用蛋清进行发泡，所得多孔结构气孔率高，但以闭合孔为主，不利于骨细胞长入。通过冰模板法制备了孔隙率为40％，50％和60％的多孔羟基磷灰石(HA)/钛酸钡(BaTiO3)压电复合材料，但是该材料中压电相BaTiO3含量高达90％才能获得适合的压电系数，另外HA和BaTiO3的最佳烧结温度相差100℃左右，共烧所得材料的力学性能、压电性能和生物性能无法统一达到最佳。
发明内容
本发明的目的是提供一种生物压电多孔陶瓷支架的制备方法，解决了现有技术中存在的骨水泥难以形成连通孔的问题。
本发明所采用的技术方案是，一种生物压电多孔陶瓷支架的制备方法，具体按照下述步骤进行：
步骤1，将压电相和生物相混合均匀，得到生物压电陶瓷前驱体固相粉；
步骤2，将所述生物压电陶瓷前驱体固相粉和分散剂加入冷冻介质溶液中混合均匀，得到生物压电陶瓷前驱体悬浊液；
步骤3，将所述生物压电陶瓷前驱体悬浊液注入冻干模具中，定向冷冻，真空干燥，得到复合多孔支架；
步骤4，将所述复合多孔支架进行养护后，得到多孔陶瓷支架；
步骤5，将所述多孔陶瓷支架进行极化，到生物压电多孔陶瓷支架。
本发明的特点还在于：
生物压电陶瓷前驱体固相粉中，压电相的体积百分比为30％～70％，生物相的体积百分比为30％～70％，以上各组份的体积百分比总和为100％。
压电相为钛酸钡、钛酸钙、铌酸锂钠钾、铌酸钾钠、钛酸铋钠和锆钛酸钡钙中的任意一种或混合物；按照质量百分比，生物相由30％～50％磷酸四钙和50％～70％磷酸氢钙组成，以上各组份的质量百分比总和为100％。
生物压电陶瓷前驱体固相粉和冷冻介质溶液体积比为6～11：9～14，分散剂为生物压电陶瓷前驱体固相粉质量的0.2％-1％。
冷冻介质为叔丁醇、崁烯或乙醇。
分散剂为柠檬酸、聚乙烯吡咯烷酮、聚丙烯酸钠或羧甲基纤维素钠。
定向冷冻时间为2h-4h，真空干燥时间为12h-36h。
养护温度为35℃-45℃、养护湿度为90％-100％、养护水汽流速为100mm/s～200mm/s、养护时间为12h-36h。
极化温度100℃-180℃，极化电压10KV～15KV，极化时间10min-30min。
本发明的有益效果是：一种生物压电多孔陶瓷支架的制备方法，解决了目前骨水泥固化过程中难以形成连通孔，传统物理共混生物/压电陶瓷烧结温度高且共同烧结综合性能不高的问题；所得生物压电多孔陶瓷支架不需高温烧结且具有定向直通孔结构，有利于骨细胞长入，同时还具有压电骨诱导性能，在促进骨细胞生长、缩短骨修复周期方面具有广阔的应用前景。
具体实施方式
下面结合具体实施方式对本发明进行详细说明。
本发明一种生物压电多孔陶瓷支架的制备方法，具体按照下述步骤进行：
步骤1，配置生物压电陶瓷前驱体固相粉，按体积百分比，采用阿基米德排水法量取体积，分别量取压电相30％～70％，生物相30％～70％混合均匀，以上各组份的体积百分比总和为100％，得到生物压电陶瓷前驱体固相粉。
按照质量百分比，生物相由30％～50％磷酸四钙和50％～70％磷酸氢钙组成，以上各组份的质量百分比总和为100％。
压电相为钛酸钡、钛酸钙、铌酸锂钠钾、铌酸钾钠、钛酸铋钠和锆钛酸钡钙中的任意一种或混合物。
步骤2，制备生物压电陶瓷前驱体悬浊液，采用阿基米德排水法量取体积，将步骤1得到的生物压电陶瓷前驱体固相粉和冷冻介质溶液按体积比为6～11：9～14量取，分散剂为生物压电陶瓷前驱体固相粉质量的0.2％-1％，混合均匀后经真空除气后得到生物压电陶瓷前驱体悬浊液。
冷冻介质为叔丁醇、崁烯或乙醇。
分散剂为柠檬酸、聚乙烯吡咯烷酮、聚丙烯酸钠或羧甲基纤维素钠。
步骤3，定向冷冻干燥，将步骤2所得生物压电陶瓷前驱体悬浊液注入冻干模具中，定向冷冻时间为2h-4h，真空干燥时间为12h-36h，得到复合多孔支架。
步骤4，高湿度下养护反应成型，将步骤3所得复合多孔支架在温度为35℃-45℃、湿度为90％-100％、水汽流速为100mm/s～200mm/s的环境中养护12h-36h，得到多孔陶瓷支架。
步骤5，极化处理，将步骤4得到的多孔陶瓷支架在温度为100℃～180℃、电压为10KV～15KV条件下进行极化10min～30min，得到生物压电多孔陶瓷支架。
本发明一种生物压电多孔陶瓷支架的制备方法，其优点在于，将生物相和压电相混合成生物压电陶瓷前驱体固相粉，并配制成稳定的悬浊液，采用定向冷冻干燥技术，将悬浊液中固相颗粒不断被排挤到定向生长的冷冻介质结晶体间，再经真空干燥，得到定向排列的直通孔。此外，将冷冻干燥得到的多孔陶瓷支架在高湿度下养护，孔壁中磷酸四钙和磷酸氢钙在水汽作用下直接发生反应生成羟基磷灰石并自固化，最终在室温即可得到一种生物压电多孔陶瓷支架，既为骨细胞长入提供了合适的孔道，又解决了骨水泥无法造孔以及生物/压电陶瓷共烧综合性能不佳的问题，在促进骨细胞生长、缩短骨修复周期方面具有广阔的应用前景。
实施例1
步骤1，配置生物压电陶瓷前驱体固相粉，按体积百分比，采用阿基米德排水法量取体积，分别量取压电相钛酸钡粉末70％，生物相30％，以上各组份的体积百分比总和为100％；按照质量百分比，生物相由30％磷酸四钙和70％磷酸氢钙组成，以上各组份的质量百分比总和为100％，混合均匀后得到生物压电陶瓷前驱体固相粉。
步骤2，制备生物压电陶瓷前驱体悬浊液，采用阿基米德排水法量取体积，将步骤1得到的生物压电陶瓷前驱体固相粉和叔丁醇按体积比为3：7量取，柠檬酸为生物压电陶瓷前驱体固相粉质量的0.2％，混合均匀后经真空除气后得到生物压电陶瓷前驱体悬浊液。
步骤3，定向冷冻干燥，将步骤2所得生物压电陶瓷前驱体悬浊液注入冻干模具中，定向冷冻时间为4h，真空干燥时间为12h，得到复合多孔支架。
步骤4，高湿度下养护反应成型，将步骤3所得复合多孔支架在温度为35℃、湿度为90％、水汽流速为100mm/s的环境中养护12h，得到多孔陶瓷支架。
步骤5，极化处理，将步骤4得到的多孔陶瓷支架在温度为100℃、电压为10KV条件下进行极化10min，得到生物压电多孔陶瓷支架。
实施例2
步骤1，配置生物压电陶瓷前驱体固相粉，按体积百分比，采用阿基米德排水法量取体积，分别量取压电相钛酸钙粉末60％，生物相40％，以上各组份的体积百分比总和为100％；按照质量百分比，生物相由40％磷酸四钙和60％磷酸氢钙组成，以上各组份的质量百分比总和为100％，混合均匀后得到生物压电陶瓷前驱体固相粉。
步骤2，制备生物压电陶瓷前驱体悬浊液，采用阿基米德排水法量取体积，将步骤1得到的生物压电陶瓷前驱体固相粉和崁烯按体积比为11：9量取，聚乙烯吡咯烷酮为生物压电陶瓷前驱体固相粉质量的1.0％，混合均匀后经真空除气后得到生物压电陶瓷前驱体悬浊液。
步骤3，定向冷冻干燥，将步骤2所得生物压电陶瓷前驱体悬浊液注入冻干模具中，定向冷冻时间为3.5h，真空干燥时间为18h，得到复合多孔支架。
步骤4，高湿度下养护反应成型，将步骤3所得复合多孔支架在温度为40℃、湿度为95％、水汽流速为125mm/s的环境中养护18h，得到多孔陶瓷支架。
步骤5，极化处理，将步骤4得到的多孔陶瓷支架在温度为120℃、电压为11KV条件下进行极化15min，得到生物压电多孔陶瓷支架。
实施例3
步骤1，配置生物压电陶瓷前驱体固相粉，按体积百分比，采用阿基米德排水法量取体积，分别量取压电相铌酸锂钠钾粉末50％，生物相50％，以上各组份的体积百分比总和为100％；按照质量百分比，生物相由50％磷酸四钙和50％磷酸氢钙组成，以上各组份的质量百分比总和为100％，混合均匀后得到生物压电陶瓷前驱体固相粉。
步骤2，制备生物压电陶瓷前驱体悬浊液，采用阿基米德排水法量取体积，将步骤1得到的生物压电陶瓷前驱体固相粉和乙醇按体积比为2：3量取，聚丙烯酸钠为生物压电陶瓷前驱体固相粉质量的1.0％，混合均匀后经真空除气后得到生物压电陶瓷前驱体悬浊液。
步骤3，定向冷冻干燥，将步骤2所得生物压电陶瓷前驱体悬浊液注入冻干模具中，定向冷冻时间为3h，真空干燥时间为24h，得到复合多孔支架。
步骤4，高湿度下养护反应成型，将步骤3所得复合多孔支架在温度为40℃、湿度为100％、水汽流速为150mm/s的环境中养护24h，得到多孔陶瓷支架。
步骤5，极化处理，将步骤4得到的多孔陶瓷支架在温度为140℃、电压为12KV条件下进行极化20min，得到生物压电多孔陶瓷支架。
实施例4
步骤1，配置生物压电陶瓷前驱体固相粉，按体积百分比，采用阿基米德排水法量取体积，分别量取压电相铌酸钾钠粉末40％，生物相60％，以上各组份的体积百分比总和为100％；按照质量百分比，生物相由60％磷酸四钙和40％磷酸氢钙组成，以上各组份的质量百分比总和为100％，混合均匀后得到生物压电陶瓷前驱体固相粉。
步骤2，制备生物压电陶瓷前驱体悬浊液，采用阿基米德排水法量取体积，将步骤1得到的生物压电陶瓷前驱体固相粉和叔丁醇按体积比为1：1量取，羧甲基纤维素钠为生物压电陶瓷前驱体固相粉质量的0.5％，混合均匀后经真空除气后得到生物压电陶瓷前驱体悬浊液。
步骤3，定向冷冻干燥，将步骤2所得生物压电陶瓷前驱体悬浊液注入冻干模具中，定向冷冻时间为2.5h，真空干燥时间为30h，得到复合多孔支架。
步骤4，高湿度下养护反应成型，将步骤3所得复合多孔支架在温度为43℃、湿度为98％、水汽流速为175mm/s的环境中养护30h，得到多孔陶瓷支架。
步骤5，极化处理，将步骤4得到的多孔陶瓷支架在温度为160℃、电压为13KV条件下进行极化25min，得到生物压电多孔陶瓷支架。
实施例5
步骤1，配置生物压电陶瓷前驱体固相粉，按体积百分比，采用阿基米德排水法量取体积，分别量取压电相钛酸铋钠粉末30％，生物相70％，以上各组份的体积百分比总和为100％；按照质量百分比，生物相由70％磷酸四钙和30％磷酸氢钙组成，以上各组份的质量百分比总和为100％，混合均匀后得到生物压电陶瓷前驱体固相粉。
步骤2，制备生物压电陶瓷前驱体悬浊液，采用阿基米德排水法量取体积，将步骤1得到的生物压电陶瓷前驱体固相粉和乙醇按体积比为11：9量取，柠檬酸为生物压电陶瓷前驱体固相粉质量的0.8％，混合均匀后经真空除气后得到生物压电陶瓷前驱体悬浊液。
步骤3，定向冷冻干燥，将步骤2所得生物压电陶瓷前驱体悬浊液注入冻干模具中，定向冷冻时间为2h，真空干燥时间为26h，得到复合多孔支架。
步骤4，高湿度下养护反应成型，将步骤3所得复合多孔支架在温度为37℃、湿度为93％、水汽流速为200mm/s的环境中养护36h，得到多孔陶瓷支架。
步骤5，极化处理，将步骤4得到的多孔陶瓷支架在温度为180℃、电压为15KV条件下进行极化30min，得到生物压电多孔陶瓷支架。
本发明实施例1、2、3、4、5制备的一种生物压电多孔陶瓷支架和通过物理共混共烧、发泡法制得的压电复合多孔支架的抗压强度、压电相含量、压电系数、孔隙率的比较如下表所示：
表1本发明生物压电多孔陶瓷支架和通过物理共混共烧、发泡法制得的压电复合多孔支架的各参数比较
由表1可以看出，与传统的物理共混共烧法相比，本方法制备的生物压电多孔陶瓷支架具有更高的压电系数和强度，与发泡法制备的多孔压电复合材料相比，本方法制备的多孔陶瓷支架孔径大小、孔径分布更加可控，同时通过冷冻干燥法制备保证了压电相颗粒的相互连接，压电系数更高。

Claims (9)

1.一种生物压电多孔陶瓷支架的制备方法，其特征在于，具体按照下述步骤进行：
步骤1，将压电相和生物相混合均匀，得到生物压电陶瓷前驱体固相粉；
步骤2，将所述生物压电陶瓷前驱体固相粉和分散剂加入冷冻介质溶液中混合均匀，得到生物压电陶瓷前驱体悬浊液；
步骤3，将所述生物压电陶瓷前驱体悬浊液注入冻干模具中，定向冷冻，真空干燥，得到复合多孔支架；
步骤4，将所述复合多孔支架进行养护后，得到多孔陶瓷支架；
步骤5，将所述多孔陶瓷支架进行极化，到生物压电多孔陶瓷支架。
2.根据权利要求1所述的一种生物压电多孔陶瓷支架的制备方法，其特征在于，所述生物压电陶瓷前驱体固相粉中，压电相的体积百分比为30％～70％，所述生物相的体积百分比为30％～70％，以上各组份的体积百分比总和为100％。
3.根据权利要求1所述的一种生物压电多孔陶瓷支架的制备方法，其特征在于，所述压电相为钛酸钡、钛酸钙、铌酸锂钠钾、铌酸钾钠、钛酸铋钠和锆钛酸钡钙中的任意一种或混合物；按照质量百分比，所述生物相由30％～50％磷酸四钙和50％～70％磷酸氢钙组成，以上各组份的质量百分比总和为100％。
4.根据权利要求1所述的一种生物压电多孔陶瓷支架的制备方法，其特征在于，所述生物压电陶瓷前驱体固相粉和冷冻介质溶液体积比为6～11：9～14，分散剂为生物压电陶瓷前驱体固相粉质量的0.2％-1％。
5.根据权利要求1所述的一种生物压电多孔陶瓷支架的制备方法，其特征在于，所述冷冻介质为叔丁醇、崁烯或乙醇。
6.根据权利要求1所述的一种生物压电多孔陶瓷支架的制备方法，其特征在于，所述分散剂为柠檬酸、聚乙烯吡咯烷酮、聚丙烯酸钠或羧甲基纤维素钠。
7.根据权利要求1所述的一种生物压电多孔陶瓷支架的制备方法，其特征在于，所述定向冷冻时间为2h-4h，真空干燥时间为12h-36h。
8.根据权利要求1所述的一种生物压电多孔陶瓷支架的制备方法，其特征在于，所述养护温度为35℃-45℃、养护湿度为90％-100％、养护水汽流速为100mm/s～200mm/s、养护时间为12h-36h。
9.根据权利要求1所述的一种生物压电多孔陶瓷支架的制备方法，其特征在于，所述极化温度100℃-180℃，极化电压10KV～15KV，极化时间10min-30min。
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CN114751742A (zh) * 2022-04-18 2022-07-15 陕西工业职业技术学院 一种多孔生物压电陶瓷浆料及其支架的制备方法
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