CN107119304B - 一种磁性TiO2生物活性涂层的微弧氧化制备方法 - Google Patents
一种磁性TiO2生物活性涂层的微弧氧化制备方法 Download PDFInfo
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Abstract
本发明公开了一种磁性TiO2生物活性涂层的微弧氧化制备方法,在空气环境下,取含钙盐、磷盐以及铁盐的电解液,调节电解液的pH值为5.0‑5.3,以钛或钛合金为阳极,不锈钢为阴极,采用脉冲电源对钛或钛合金进行微弧氧化处理,同时维持电解液温度在5‑25℃,处理时间1‑8min,即在钛或钛合金表层生成磁性TiO2生物活性涂层。采用本发明工艺能制备出具有磁性的(Ms为0.2696‑1.101emu/g)生物活性良好的TiO2磁性涂层。
Description
技术领域
本发明涉及钛和钛合金构件的表面改性领域,具体涉及一种磁性TiO2生物活性涂层的微弧氧化制备方法。
背景技术
钛及钛合金因其优异的力学性能、耐腐蚀性以及生物相容性,目前在硬组织植入材料中应用较为广泛。但它同时也具有生物惰性,在植入后,无法与植入体组织进行化学与生物学上的骨性结合限制了其在生物体植入方面更为广泛的的应用。而含钙、磷元素的生物陶瓷因其骨相容性成为骨组织再生的一种潜在的生物活性材料,因此在钛及其合金表面沉积一层含钙、磷的生物陶瓷涂层是一种有效提高钛及其合金生物活性的方法。磁场对生物系统的影响已经成为近几年的热门话题。磁场能够影响骨修复的过程,能够阻止骨的矿物质损失,促进治疗骨愈合。研究发现中等强度的磁场能够促进成骨细胞的生物矿化过程,中等强度的磁场能够促进细胞的贴附增殖分化,同时影响细胞在材料表面的迁移和取向,以及改变细胞膜上面离子的运输通道。磁场不仅影响前期的生物矿化行为,对后期的成骨基因和蛋白的表达也会产生影响。因为后期蛋白的生成与前期生物的矿化成正比。目前磁性硬组织植入材料的常见制备方法分为两种:其一,将已经制备好的支架材料浸泡在含有磁性粒子的溶液里面,使磁性粒吸附在材料表面;其二,将磁性粒子与其它物质复合在一起,通过共混或者静电纺丝来直接制备含有磁性粒子的支架。这些依靠物理吸附制备的硬组织工程支架,粒子与基材的结合力弱,在植入后会引发颗粒在体内释放造成细胞的免疫排斥等问题,限制了磁性硬组织材料的实际的临床应用。
发明内容
本发明的目的在于提供一种磁性TiO2生物活性涂层的微弧氧化制备方法,以克服上述现有技术存在的缺陷,本发明采用微弧氧化技术,制备了磁性TiO2生物活性涂层,解决目前制备方法制备的磁性硬组织植入材料植入后的细胞毒性以及后期粒子释放等的问题,在保证涂层结合力和强度的同时,使得涂层具有一定的顺磁性。
为达到上述目的,本发明采用如下技术方案:
一种磁性TiO2生物活性涂层的微弧氧化制备方法,在空气环境下,取含钙盐、磷盐以及铁盐的电解液,调节电解液的pH值为5.0-5.3,其中钙盐、磷盐以及铁盐的摩尔比为10:1:(0.125-0.625),然后以钛或钛合金为阳极,不锈钢为阴极,采用脉冲电源对钛或钛合金进行微弧氧化处理,同时维持电解液温度在5-25℃,处理时间1-8min,即在钛或钛合金表层生成磁性TiO2生物活性涂层。
进一步地,电解液中钙盐的浓度为0.2mol/L。
进一步地,所述的钙盐为乙酸钙、氯化钙、硝酸钙中的任一种。
进一步地,所述的磷盐为β-甘油磷酸钠、磷酸钠、磷酸氢钠中的任一种。
进一步地,所述的铁盐是EDTA铁钠、FeCl3、FeCl2中的任一种。
进一步地,采用弱酸溶液调节电解液的pH值。
进一步地,所述的弱酸是乙酸、碳酸、磷酸中的任一种。
进一步地,所述的脉冲电源的电压为400V–550V、频率为100-500Hz、占空比为7.5-60%。
进一步地,阴极和阳极之间的间距为3-8cm。
与现有技术相比,本发明具有以下有益的技术效果:
本发明采用微弧氧化技术,制备了磁性TiO2生物活性涂层,解决目前制备方法制备的磁性硬组织植入材料植入后的细胞毒性以及后期粒子释放等的问题,在保证涂层结合力和强度的同时,使得涂层具有一定的顺磁性(Ms 为0.2696-1.101emu/g)。在生物性能上,一方面保留了传统微弧氧化涂层的良好生物相容性;另一方面,通过在钛的微弧氧化陶瓷层中掺入Fe离子,使得涂层在具有良好的生物活性的同时具有一定的磁性,进一步提高了材料的骨诱导、骨再生能力,加快了骨组织的修复、愈合。对于改善钛及其合金的生物活性具有重要的理论和实际意义。
附图说明
图1为本发明实施例1得到的微弧氧化涂层的SEM照片;
图2为本发明实施例1得到的微弧氧化涂层的能谱图;
图3为本发明实施例1得到的微弧氧化涂层的VSM曲线。
具体实施方式
下面对本发明的实施方式做进一步详细描述:
一种磁性TiO2生物活性涂层的微弧氧化制备方法:在空气环境下,以去离子水为溶剂,将钙、磷盐溶解在去离子水中得到含钙磷的电解液后,在电解液中加入铁盐,使钙盐、磷盐以及铁盐的摩尔比例为10:1:(0.125-0.625),并用弱酸溶液调节电解液的PH值为5.0-5.3,得到稳定的含Fe3+的电解液,电解液中钙盐的浓度为0.2mol/L。微弧氧化以纯钛或钛合金为阳极、不锈钢为阴极,脉冲电源电压为400-550V、频率为100-500Hz、占空比为7.5-60%以及阴阳极板间距为3-8cm的条件下对钛或钛合金进行微弧氧化处理,处理时间1-8min,维持电解液温度在5-25℃,待反应结束后,即在钛或钛合金的表层生成多孔含Ca、P及Fe的磁性TiO2生物活性涂层。
其中,钙盐为乙酸钙、氯化钙、硝酸钙中的任一种;磷盐为β-甘油磷酸钠、磷酸钠、磷酸氢钠中的任一种;铁盐是EDTA铁钠、FeCl3、FeCl2中的任一种;弱酸是乙酸、碳酸、磷酸中的任一种。
本发明采用的微弧氧化技术利用基体金属与氧离子、电解质离子在热化学、电化学、等离子体化学的共同作用下发生强烈反应,经历熔融、喷发、结晶、高温相变,最终在基体表面熔覆,烧结形成陶瓷层。利用微弧氧化技术在金属表面原位生成的磁性陶瓷膜层在具有顺磁性的同时,基体结合力强、耐磨和耐蚀性好、综合性能优良,是一种应用前景广阔的磁性硬组织植入材料。
下面结合实施例对本发明做进一步详细描述:
实施例1
以去离子水为溶剂,以醋酸钙、β-甘油磷酸二钠盐和EDTA铁钠盐为溶质的电解液中,通过乙酸溶液调节电解液的PH为5.3,且醋酸钙、β-甘油磷酸二钠盐和EDTA铁钠盐的摩尔比为10:1:0.625,电解液中醋酸钙的浓度为0.2mol/L,然后以纯钛为阳极、不锈钢为阴极,采用脉冲电源在电压为550V、频率为500Hz、占空比为7.5%、阴阳极板间距为8cm的条件下对钛进行微弧氧化处理,处理时间8分钟,保持电解液的温度在5-25℃,可在钛表面形成多孔含Ca、P的磁性TiO2生物活性涂层,其饱和磁化强度可达1.101emu/g。
实施例2
以去离子水为溶剂,以氯化钙、磷酸钠和氯化铁为溶质的电解液中,通过碳酸溶液调节电解液的PH为5,且氯化钙、磷酸钠和二氯化铁的摩尔比为10:1:0.125,电解液中氯化钙的浓度为0.2mol/L,然后以钛合金为阳极、不锈钢为阴极,采用脉冲电源在电压为500V、频率为200Hz、占空比为25%、阴阳极板间距为6cm的条件下对钛进行微弧氧化处理,处理时间3分钟,保持电解液的温度在5-25℃,可在钛表面形成多孔含Ca、P的磁性TiO2生物活性涂层,其饱和磁化强度可达0.2696emu/g。
实施例3
以去离子水为溶剂,以硝酸钙、磷酸氢钠和三氯化铁为溶质的电解液中,通过乙酸溶液调节PH为5.2,硝酸钙、磷酸氢钠和氯化铁的摩尔比为10:1: 0.375,电解液中硝酸钙的浓度为0.2mol/L,然后以纯钛为阳极、不锈钢为阴极,采用脉冲电源在电压为400V、频率为100Hz、占空比为60%、阴阳极板间距为3cm的条件下对钛进行微弧氧化处理,处理时间1分钟,保持电解液的温度在5-25℃,可在钛表面形成多孔含Ca、P的磁性TiO2生物活性涂层,其饱和磁化强度可达0.689emu/g。
Claims (7)
1.一种磁性TiO2生物活性涂层的微弧氧化制备方法,其特征在于,在空气环境下,取含钙盐、磷盐以及铁盐的电解液,调节电解液的pH值为5.0-5.3,其中钙盐、磷盐以及铁盐的摩尔比为10:1:(0.125-0.625),然后以钛或钛合金为阳极,不锈钢为阴极,采用脉冲电源对钛或钛合金进行微弧氧化处理,同时维持电解液温度在5-25℃,处理时间1-8min,即在钛或钛合金表层生成磁性TiO2生物活性涂层,所述的钙盐为乙酸钙、氯化钙、硝酸钙中的任一种,所述的磷盐为β-甘油磷酸钠、磷酸钠、磷酸氢钠中的任一种。
2.根据权利要求1所述的一种磁性TiO2生物活性涂层的微弧氧化制备方法,其特征在于,电解液中钙盐的浓度为0.2mol/L。
3.根据权利要求1所述的一种磁性TiO2生物活性涂层的微弧氧化制备方法,其特征在于,所述的铁盐是EDTA铁钠、FeCl3、FeCl2中的任一种。
4.根据权利要求1所述的一种磁性TiO2生物活性涂层的微弧氧化制备方法,其特征在于,采用弱酸溶液调节电解液的pH值。
5.根据权利要求4所述的一种磁性TiO2生物活性涂层的微弧氧化制备方法,其特征在于,所述的弱酸是乙酸、碳酸、磷酸中的任一种。
6.根据权利要求1所述的一种磁性TiO2生物活性涂层的微弧氧化制备方法,其特征在于,所述的脉冲电源的电压为400V–550V、频率为100-500Hz、占空比为7.5-60%。
7.根据权利要求1所述的一种磁性TiO2生物活性涂层的微弧氧化制备方法,其特征在于,阴极和阳极之间的间距为3-8cm。
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