CN106086838B - 钕锌钴合金/聚丙烯支架材料的制备方法 - Google Patents
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Abstract
本发明属于生物医用材料技术领域,涉及一种钕锌钴合金/聚丙烯支架材料的制备方法。该支架材料的制备方法的包括聚丙烯支架材料清洗、表面改性,催化活化及化学镀钕锌钴合金。本发明制备方法的优点是:支架材料的有机碳溢出率降低99%以上,莫氏硬度可达到6.3,经180天模拟人体体液腐蚀测试,金属离子溢出率小于1ppm,即该材料具有极高的生物环境可靠性。钕锌钴合金/聚丙烯材料可用于组织工程支架材料,应用前景明朗,市场潜力巨大。
Description
技术领域
本发明属于生物医用材料技术领域,涉及一种钕锌钴合金/聚丙烯支架材料的制备方法。
背景技术
生物医用材料,是用于取代、修复活组织的天然或人造材料。生物医用材料与延长人类寿命和提高生活质量息息相关,因而生物材料领域越来越受到重视。近年来,材料学和生物学的研究进展为生物医用材料的发展奠定了基础。而随着全球人口老龄化进程的加速、人类对健康和长寿的追求、运动创伤的增多、疑难病患者的增加和需要替换组织的病人年龄降低等现象都对生物材料提出了非常大的需求。目前,不仅植入手术增加,植入后的修复手术也随之增加。修复手术给患者造成了疼痛,并且造价高成功率低,这就对生物材料提出了更高的要求。
医用聚丙烯是由丙烯聚合而得的一种塑料。可经受高压蒸汽灭菌、具有良好的力学性能和化学稳定性及生理·降性。主要用于制造医用导管、输液容器、平板式人工肾的夹板、包装材料、注射器等薄膜经表面活性剂处理,成为亲水性微孔膜,可制人工肺。纤维用作鼓泡式氧合器的血液消泡过滤网、腹壁修补片、手术缝线等。
医用支架材料中,金属支架密度大,在体内存留人体负担大;聚合物支架密度小,人体负担小,但聚合物易降解,产生“有机碳”溢出,对人体不利;金属/聚合物复合材料型支架能结合二者的优点,但金属的种类有限,多以贵金属金、银、铂等为主,价格昂贵。本发明是在聚丙烯表面被覆一层钕锌钴合金层,核心工艺是在铁锰复合催化活化下,在化学镀溶液中,稀土元素钕进入锌钴合金的晶格中,形成更加致密稳定的合金层,这样有效的将聚丙烯与人体隔离,使聚丙烯有机碳溢出率降低99%以上,不仅如此,钕锌钴合金/聚丙烯支架材料的莫氏硬度可达到6.3,是目前所有金属/聚丙烯复合支架材料中最好的;经180天模拟人体体液腐蚀测试,钕锌钴合金/聚丙烯支架材料的金属离子溢出率小于百万分之一(1ppm),说明该材料具有极高的生物环境可靠性。综上所述,本发明提出的钕锌钴合金/聚丙烯支架材料的制备方法具有突出的实质性特点和显著的进步,即具备创造性。
发明内容
本发明属于生物医用材料技术领域,涉及一种钕锌钴合金/聚丙烯支架材料的制备方法。该制备方法的步骤如下:
1)将聚丙烯支架依次用重量百分比浓度为10%的水合肼水溶液、5%的双氧水溶液、去离子水洗净、烘干;
2)将洗净的聚丙烯支架置于改性剂溶液中30分钟,取出,置于烘箱中于100℃干燥3小时,冷却至室温,得改性聚丙烯支架;其中改性剂溶液的配方是溶剂为去离子水,溶液中各种溶质浓度分别为:3-氨基丙基三乙氧基硅烷浓度3~6g/L,氰基丙烯酸乙酯浓度9~12g/L,过氧化环己酮浓度1~3g/L,丙酮浓度100~200g/L。
3)将改性聚丙烯支架置于活化剂溶液中30分钟,取出,用去离子水洗净,烘干,再置于重量百分比浓度为3%的硼氢化钠水溶液中10分钟,取出,洗净,得活化聚丙烯支架;其中活化剂溶液的配方是溶剂为去离子水,溶液中各种溶质浓度分别为:硝酸亚铁浓度20~30g/L,硝酸锰浓度20~30g/L,柠檬酸钠浓度20~30g/L。
4)将活化聚丙烯支架置于钕锌钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钕锌钴合金/聚丙烯支架材料。其中钕锌钴化学镀溶液的配方是溶剂为去离子水,溶液中各种溶质浓度分别为:硝酸钕浓度20~30g/L;硝酸钴浓度20~30g/L;硝酸锌浓度40~60g/L;磷酸二氢钠浓度30~60g/L;柠檬酸钠浓度60~90g/L;二甲氨基硼烷浓度3~6g/L;硫酸铵浓度6~9g/L。
5)钕锌钴合金/聚丙烯支架材料测试表征。将钕锌钴合金/聚丙烯支架材料置于模拟人体体液中,于37℃放置180天,取出,测试溶液中有机碳溢出量,并与聚丙烯支架材料相比较,计算有机碳溢出降低率;以能量弥散X射线探测器(EDX)测试支架材料的元素含量,计算钕、锌、钴离子的溢出率;以万能材料试验机测试支架材料的弯曲模量,以莫氏硬度计测试支架材料的表面硬度。其中模拟人体体液各成分含量:NaCl 8g/L,KCl 0.4g/L,NaHCO30.35g/L,CaCl2 0.14g/L,Na2HPO4 0.06g/L,KH2PO4 0.06g/L,MgSO4.7H2O 0.2g/L,葡萄糖1g/L。
以本发明的制备方法制备的钕锌钴合金/聚丙烯支架材料可用于组织工程支架材料包括:骨、软骨、血管、神经、皮肤和人工器官,如肝、脾、肾、膀胱等的组织支架材料。
具体实施方式
下面通过实施例进一步描述本发明
实施例1
将聚丙烯支架依次用重量百分比浓度为10%的水合肼水溶液、5%的双氧水溶液、去离子水洗净、烘干。
将3.6g 3-氨基丙基三乙氧基硅烷,9g氰基丙烯酸乙酯,2.7g过氧化环己酮溶于168g丙酮中,添加去离子水,配成体积为1L的改性剂溶液。
将洗净的聚丙烯支架置于改性剂溶液中30分钟,取出,置于烘箱中于100℃干燥3小时,冷却至室温,得改性聚丙烯支架。
将29g硝酸亚铁,21g硝酸锰,25g柠檬酸钠溶于500mL去离子水中,再稀释成体积为1L的活化剂溶液。
将改性聚丙烯支架置于活化剂溶液中30分钟,取出,用去离子水洗净,烘干,再置于重量百分比浓度为3%的硼氢化钠水溶液中10分钟,取出,洗净,得活化聚丙烯支架。
将24g硝酸钕,23g硝酸钴,49g硝酸锌,57g磷酸二氢钠,75g柠檬酸钠,4g二甲氨基硼烷,9g硫酸铵溶于500mL去离子水中,再稀释成体积为1L的钕锌钴化学镀溶液。
将活化聚丙烯支架置于钕锌钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钕锌钴合金/聚丙烯支架材料。
将8g NaCl,0.4g KCl,0.35g NaHCO3,0.14g CaCl2,0.06g Na2HPO4,0.06g KH2PO4,0.2g MgSO4.7H2O,1g葡萄糖溶于500mL去离子水中,再稀释成体积为1L的模拟人体体液。
将钕锌钴合金/聚丙烯支架材料置于模拟人体体液中,于37℃放置180天,取出,测试溶液中有机碳溢出量,并与聚丙烯支架材料相比较,计算有机碳溢出降低率为99.4%;以能量弥散X射线探测器(EDX)测试支架材料的元素含量,计算钕、锌、钴离子的溢出率分别为0.7ppm、0.6ppm、0.8ppm;以万能材料试验机测试支架材料的弯曲模量为1.09GPa,以莫氏硬度计测试支架材料的表面硬度为7.9。
实施例2
将聚丙烯支架依次用重量百分比浓度为10%的水合肼水溶液、5%的双氧水溶液、去离子水洗净、烘干。
将6g 3-氨基丙基三乙氧基硅烷,12g氰基丙烯酸乙酯,3g过氧化环己酮溶于200g丙酮中,添加去离子水,配成体积为1L的改性剂溶液。
将洗净的聚丙烯支架置于改性剂溶液中30分钟,取出,置于烘箱中于100℃干燥3小时,冷却至室温,得改性聚丙烯支架。
将30g硝酸亚铁,30g硝酸锰,30g柠檬酸钠溶于500mL去离子水中,再稀释成体积为1L的活化剂溶液。
将改性聚丙烯支架置于活化剂溶液中30分钟,取出,用去离子水洗净,烘干,再置于重量百分比浓度为3%的硼氢化钠水溶液中10分钟,取出,洗净,得活化聚丙烯支架。
将30g硝酸钕,30g硝酸钴,60g硝酸锌,60g磷酸二氢钠,90g柠檬酸钠,6g二甲氨基硼烷,9g硫酸铵溶于500mL去离子水中,再稀释成体积为1L的钕锌钴化学镀溶液。
将活化聚丙烯支架置于钕锌钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钕锌钴合金/聚丙烯支架材料。
将8g NaCl,0.4g KCl,0.35g NaHCO3,0.14g CaCl2,0.06g Na2HPO4,0.06g KH2PO4,0.2g MgSO4.7H2O,1g葡萄糖溶于500mL去离子水中,再稀释成体积为1L的模拟人体体液。
将钕锌钴合金/聚丙烯支架材料置于模拟人体体液中,于37℃放置180天,取出,测试溶液中有机碳溢出量,并与聚丙烯支架材料相比较,计算有机碳溢出降低率为99.7%;以能量弥散X射线探测器(EDX)测试支架材料的元素含量,计算钕、锌、钴离子的溢出率分别为0.27ppm、0.46ppm、0.61ppm;以万能材料试验机测试支架材料的弯曲模量为1.33GPa,以莫氏硬度计测试支架材料的表面硬度为6.8。
实施例3
将聚丙烯支架依次用重量百分比浓度为10%的水合肼水溶液、5%的双氧水溶液、去离子水洗净、烘干。
将4.4g 3-氨基丙基三乙氧基硅烷,11.2g氰基丙烯酸乙酯,2.1g过氧化环己酮溶于155g丙酮中,添加去离子水,配成体积为1L的改性剂溶液。
将洗净的聚丙烯支架置于改性剂溶液中30分钟,取出,置于烘箱中于100℃干燥3小时,冷却至室温,得改性聚丙烯支架。
将22.6g硝酸亚铁,27.3g硝酸锰,26.7g柠檬酸钠溶于500mL去离子水中,再稀释成体积为1L的活化剂溶液。
将改性聚丙烯支架置于活化剂溶液中30分钟,取出,用去离子水洗净,烘干,再置于重量百分比浓度为3%的硼氢化钠水溶液中10分钟,取出,洗净,得活化聚丙烯支架。
将21.8g硝酸钕,22.9g硝酸钴,53.4g硝酸锌,51.2g磷酸二氢钠,88.6g柠檬酸钠,4.4g二甲氨基硼烷,6.8g硫酸铵溶于500mL去离子水中,再稀释成体积为1L的钕锌钴化学镀溶液。
将活化聚丙烯支架置于钕锌钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钕锌钴合金/聚丙烯支架材料。
将8g NaCl,0.4g KCl,0.35g NaHCO3,0.14g CaCl2,0.06g Na2HPO4,0.06g KH2PO4,0.2g MgSO4.7H2O,1g葡萄糖溶于500mL去离子水中,再稀释成体积为1L的模拟人体体液。
将钕锌钴合金/聚丙烯支架材料置于模拟人体体液中,于37℃放置180天,取出,测试溶液中有机碳溢出量,并与聚丙烯支架材料相比较,计算有机碳溢出降低率为99.7%;以能量弥散X射线探测器(EDX)测试支架材料的元素含量,计算钕、锌、钴离子的溢出率分别为0.33ppm、0.36ppm、0.38ppm;以万能材料试验机测试支架材料的弯曲模量为1.11GPa,以莫氏硬度计测试支架材料的表面硬度为6.6。
实施例4
将聚丙烯支架依次用重量百分比浓度为10%的水合肼水溶液、5%的双氧水溶液、去离子水洗净、烘干。
将3.2g 3-氨基丙基三乙氧基硅烷,11.5g氰基丙烯酸乙酯,2.6g过氧化环己酮溶于163g丙酮中,添加去离子水,配成体积为1L的改性剂溶液。
将洗净的聚丙烯支架置于改性剂溶液中30分钟,取出,置于烘箱中于100℃干燥3小时,冷却至室温,得改性聚丙烯支架。
将28.1g硝酸亚铁,23.4g硝酸锰,26.1g柠檬酸钠溶于500mL去离子水中,再稀释成体积为1L的活化剂溶液。
将改性聚丙烯支架置于活化剂溶液中30分钟,取出,用去离子水洗净,烘干,再置于重量百分比浓度为3%的硼氢化钠水溶液中10分钟,取出,洗净,得活化聚丙烯支架。
将23.8g硝酸钕,26.9g硝酸钴,42.1g硝酸锌,56.7g磷酸二氢钠,77.6g柠檬酸钠,5.1g二甲氨基硼烷,7.8g硫酸铵溶于500mL去离子水中,再稀释成体积为1L的钕锌钴化学镀溶液。
将活化聚丙烯支架置于钕锌钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钕锌钴合金/聚丙烯支架材料。
将8g NaCl,0.4g KCl,0.35g NaHCO3,0.14g CaCl2,0.06g Na2HPO4,0.06g KH2PO4,0.2g MgSO4.7H2O,1g葡萄糖溶于500mL去离子水中,再稀释成体积为1L的模拟人体体液。
将钕锌钴合金/聚丙烯支架材料置于模拟人体体液中,于37℃放置180天,取出,测试溶液中有机碳溢出量,并与聚丙烯支架材料相比较,计算有机碳溢出降低率为99.0%;以能量弥散X射线探测器(EDX)测试支架材料的元素含量,计算钕、锌、钴离子的溢出率分别为0.22ppm、0.34ppm、0.54ppm;以万能材料试验机测试支架材料的弯曲模量为1.01GPa,以莫氏硬度计测试支架材料的表面硬度为6.8。
实施例5
将聚丙烯支架依次用重量百分比浓度为10%的水合肼水溶液、5%的双氧水溶液、去离子水洗净、烘干。
将3g 3-氨基丙基三乙氧基硅烷,9g氰基丙烯酸乙酯,1g过氧化环己酮溶于100g丙酮中,添加去离子水,配成体积为1L的改性剂溶液。
将洗净的聚丙烯支架置于改性剂溶液中30分钟,取出,置于烘箱中于100℃干燥3小时,冷却至室温,得改性聚丙烯支架。
将20g硝酸亚铁,20g硝酸锰,20g柠檬酸钠溶于500mL去离子水中,再稀释成体积为1L的活化剂溶液。
将改性聚丙烯支架置于活化剂溶液中30分钟,取出,用去离子水洗净,烘干,再置于重量百分比浓度为3%的硼氢化钠水溶液中10分钟,取出,洗净,得活化聚丙烯支架。
将20g硝酸钕,20g硝酸钴,40g硝酸锌,30g磷酸二氢钠,60g柠檬酸钠,3g二甲氨基硼烷,6g硫酸铵溶于500mL去离子水中,再稀释成体积为1L的钕锌钴化学镀溶液。
将活化聚丙烯支架置于钕锌钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钕锌钴合金/聚丙烯支架材料。
将8g NaCl,0.4g KCl,0.35g NaHCO3,0.14g CaCl2,0.06g Na2HPO4,0.06g KH2PO4,0.2g MgSO4.7H2O,1g葡萄糖溶于500mL去离子水中,再稀释成体积为1L的模拟人体体液。
将钕锌钴合金/聚丙烯支架材料置于模拟人体体液中,于37℃放置180天,取出,测试溶液中有机碳溢出量,并与聚丙烯支架材料相比较,计算有机碳溢出降低率为99.6%;以能量弥散X射线探测器(EDX)测试支架材料的元素含量,计算钕、锌、钴离子的溢出率分别为0.32ppm、0.61ppm、0.77ppm;以万能材料试验机测试支架材料的弯曲模量为1.41GPa,以莫氏硬度计测试支架材料的表面硬度为6.3。
Claims (1)
1.一种钕锌钴合金/聚丙烯支架材料的制备方法,其特征在于:
1)将聚丙烯支架依次用重量百分比浓度为10%的水合肼水溶液、5%的双氧水溶液、去离子水洗净、烘干;
2)将洗净的聚丙烯支架置于改性剂溶液中30分钟,取出,置于烘箱中于100℃干燥3小时,冷却至室温,得改性聚丙烯支架;
3)将改性聚丙烯支架置于活化剂溶液中30分钟,取出,用去离子水洗净,烘干,再置于重量百分比浓度为3%的硼氢化钠水溶液中10分钟,取出,用去离子水洗净,得活化聚丙烯支架;
4)将活化聚丙烯支架置于钕锌钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钕锌钴合金/聚丙烯支架材料;
其中改性剂溶液的配方是溶剂为去离子水,溶液中各种溶质浓度分别为:
3-氨基丙基三乙氧基硅烷浓度3~6g/L;
氰基丙烯酸乙酯浓度9~12g/L;
过氧化环己酮浓度1~3g/L;
丙酮浓度100~200g/L;
其中活化剂溶液的配方是溶剂为去离子水,溶液中各种溶质浓度分别为:
硝酸亚铁浓度20~30g/L;
硝酸锰浓度20~30g/L;
柠檬酸钠浓度20~30g/L;
其中钕锌钴化学镀溶液的配方是溶剂为去离子水,溶液中各种溶质浓度分别为:
硝酸钕浓度20~30g/L;
硝酸钴浓度20~30g/L;
硝酸锌浓度40~60g/L;
磷酸二氢钠浓度30~60g/L;
柠檬酸钠浓度60~90g/L;
二甲氨基硼烷浓度3~6g/L;
硫酸铵浓度6~9g/L;
其中钕锌钴合金/聚丙烯支架材料的性能为:莫氏硬度可达到6.3;经180天模拟人体体液腐蚀测试,金属离子溢出率小于1ppm。
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