CN106390191B - 钬钨钴合金/聚硅氧烷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,涉及钬钨钴合金/聚硅氧烷支架材料的制备方法。该支架材料的制备方法的包括聚硅氧烷支架材料清洗、表面改性,催化活化及化学镀钬钨钴合金。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7.9,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。钬钨钴合金/聚硅氧烷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,涉及一种钬钨钴合金/聚硅氧烷支架材料的制备方法。
背景技术
随着全球老年人口数目的不断增加以及现代人工作压力大、生活不规律导致的慢性疾病患病率的逐年提高,人们对于生物医用材料的需求量持续攀升。近年来,生物医用材料的发展迅速,在全球市场中所占份额越来越大。目前,在临床应用中已经获得应用的典型生物医用金属材料包括不锈钢、钴铬合金和钛及钛合金。在这三种生物医用金属材料中,钴铬合金的刚度最大,钛合金的刚度最小。与钴铬合金和钛合金相比,不锈钢通常具有较高的韧性和循环扭转抗力。与钴铬合金和不锈钢相比,钛及钛合金具有最好的生物相容性、耐腐蚀性和比强度(抗拉强度与密度的比值)。与不锈钢和钛合金相比,钴铬合金具有最好的耐磨性和相对较高的强度。另外,其他生物医用金属材料如镁合金、铁、钽和铌虽然市场占有份额比较小,但在生物医用领域也占有着重要的地位。
医用聚硅氧烷包括:(1)硅橡胶,分热硫化型和室温硫化型两种,主要用于制造人工器官、整复材料、医用管腔制品、药物载体、手术防粘连膜等;(2)硅凝胶,为双组分室温硫化硅橡胶,可用作人工晶状体及整形材料;(3)硅油及乳液,具有很好的消泡功能,叮用于肺气肿和肠胃道及人工心肺机中的消泡剂、药物防结块剂、润滑剂等。
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。本发明是在聚硅氧烷表面被覆一层钬钨钴合金层,核心工艺是在铜铁复合催化活化下,在化学镀溶液中,稀土元素钬进入钨钴合金的晶格中,形成更加致密稳定的合金层,这样有效的将聚硅氧烷与人体隔离,使聚硅氧烷有机碳溢出率降低99%以上,不仅如此,钬钨钴合金/聚硅氧烷支架材料的莫氏硬度可达到7.9,是目前所有金属/聚硅氧烷复合支架材料中最好的;经180天模拟人体体液腐蚀测试,钬钨钴合金/聚硅氧烷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,本发明提出的钬钨钴合金/聚硅氧烷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,涉及一种钬钨钴合金/聚硅氧烷支架材料的制备方法。该制备方法的步骤如下:
1)将聚硅氧烷支架依次用重量百分比浓度为10%的氢氧化钾水溶液、5%的双氧水溶液、去离子水洗净、烘干;
2)将洗净的聚硅氧烷支架置于改性剂溶液中30分钟,取出,置于烘箱中于120℃干燥3小时,冷却至室温,得改性聚硅氧烷支架;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-脲丙基三甲氧基硅烷浓度3~6g/L,甲基丙烯酸羟乙酯浓度9~12g/L,过氧化苯甲酸浓度1~3g/L,丙酮浓度100~200g/L。
3)将改性聚硅氧烷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,得活化聚硅氧烷支架;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:氯化铜浓度20~30g/L,硫酸亚铁浓度20~30g/L,柠檬酸钠浓度20~30g/L。
4)将活化聚硅氧烷支架置于钬钨钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钬钨钴合金/聚硅氧烷支架材料。其中钬钨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:硝酸钬浓度20~30g/L;硝酸钴浓度20~30g/L;钨酸钠浓度40~60g/L;乙二胺四乙酸二钠浓度30~60g/L;柠檬酸钠浓度60~90g/L;二甲氨基硼烷浓度3~6g/L;碳酸氢钠浓度6~9g/L。
5)钬钨钴合金/聚硅氧烷支架材料测试表征。将钬钨钴合金/聚硅氧烷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,并与聚硅氧烷支架材料相比较,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,计算钬、钨、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,NaHCO3 0.35g/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钬钨钴合金/聚硅氧烷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
将聚硅氧烷支架依次用重量百分比浓度为10%的氢氧化钾水溶液、5%的双氧水溶液、去离子水洗净、烘干。
将4.8g 3-脲丙基三甲氧基硅烷,9.1g甲基丙烯酸羟乙酯,1.5g过氧化苯甲酸溶于160g丙酮中,添加去离子水,配成体积为1L的改性剂溶液。
将洗净的聚硅氧烷支架置于改性剂溶液中30分钟,取出,置于烘箱中于120℃干燥3小时,冷却至室温,得改性聚硅氧烷支架。
将24.1g氯化铜,22.6g硫酸亚铁,21.9g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。
将改性聚硅氧烷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,得活化聚硅氧烷支架。
将26.6g硝酸钬,25.3g硝酸钴,45.91g钨酸钠,56.3g乙二胺四乙酸二钠,80.8g柠檬酸钠,3.0g二甲氨基硼烷,6.1g碳酸氢钠溶于500mL去离子水中,再稀释成体积为1L的钬钨钴化学镀溶液。
将活化聚硅氧烷支架置于钬钨钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钬钨钴合金/聚硅氧烷支架材料。
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。
将钬钨钴合金/聚硅氧烷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,并与聚硅氧烷支架材料相比较,计算有机碳溢出降低率为99.3%;以能量弥散X射线探测器(EDX)测试支架材料的元素含量,计算钬、钨、钴离子的溢出率分别为0.45ppm、0.06ppm、0.52ppm;以万能材料试验机测试支架材料的弯曲模量为1.31GPa,以莫氏硬度计测试支架材料的表面硬度为8.1。
实施例2
将聚硅氧烷支架依次用重量百分比浓度为10%的氢氧化钾水溶液、5%的双氧水溶液、去离子水洗净、烘干。
将4.3g 3-脲丙基三甲氧基硅烷,9.9g甲基丙烯酸羟乙酯,1.6g过氧化苯甲酸溶于145g丙酮中,添加去离子水,配成体积为1L的改性剂溶液。
将洗净的聚硅氧烷支架置于改性剂溶液中30分钟,取出,置于烘箱中于120℃干燥3小时,冷却至室温,得改性聚硅氧烷支架。
将23.6g氯化铜,25.9g硫酸亚铁,25.1g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。
将改性聚硅氧烷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,得活化聚硅氧烷支架。
将28.3g硝酸钬,20.6g硝酸钴,51.9g钨酸钠,52.9g乙二胺四乙酸二钠,71.8g柠檬酸钠,3.9g二甲氨基硼烷,6.5g碳酸氢钠溶于500mL去离子水中,再稀释成体积为1L的钬钨钴化学镀溶液。
将活化聚硅氧烷支架置于钬钨钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钬钨钴合金/聚硅氧烷支架材料。
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。
将钬钨钴合金/聚硅氧烷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,并与聚硅氧烷支架材料相比较,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,计算钬、钨、钴离子的溢出率分别为0.21ppm、0.11ppm、0.18ppm;以万能材料试验机测试支架材料的弯曲模量为1.21GPa,以莫氏硬度计测试支架材料的表面硬度为8.0。
实施例3
将聚硅氧烷支架依次用重量百分比浓度为10%的氢氧化钾水溶液、5%的双氧水溶液、去离子水洗净、烘干。
将6g 3-脲丙基三甲氧基硅烷,12g甲基丙烯酸羟乙酯,3g过氧化苯甲酸溶于200g丙酮中,添加去离子水,配成体积为1L的改性剂溶液。
将洗净的聚硅氧烷支架置于改性剂溶液中30分钟,取出,置于烘箱中于120℃干燥3小时,冷却至室温,得改性聚硅氧烷支架。
将30g氯化铜,30g硫酸亚铁,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。
将改性聚硅氧烷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,得活化聚硅氧烷支架。
将30g硝酸钬,30g硝酸钴,60g钨酸钠,60g乙二胺四乙酸二钠,90g柠檬酸钠,6g二甲氨基硼烷,9g碳酸氢钠溶于500mL去离子水中,再稀释成体积为1L的钬钨钴化学镀溶液。
将活化聚硅氧烷支架置于钬钨钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钬钨钴合金/聚硅氧烷支架材料。
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。
将钬钨钴合金/聚硅氧烷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,并与聚硅氧烷支架材料相比较,计算有机碳溢出降低率为99.1%;以能量弥散X射线探测器(EDX)测试支架材料的元素含量,计算钬、钨、钴离子的溢出率分别为0.03ppm、0.49ppm、0.37ppm;以万能材料试验机测试支架材料的弯曲模量为1.53GPa,以莫氏硬度计测试支架材料的表面硬度为7.9。
实施例4
将聚硅氧烷支架依次用重量百分比浓度为10%的氢氧化钾水溶液、5%的双氧水溶液、去离子水洗净、烘干。
将3.1g 3-脲丙基三甲氧基硅烷,11.1g甲基丙烯酸羟乙酯,2.1g过氧化苯甲酸溶于113g丙酮中,添加去离子水,配成体积为1L的改性剂溶液。
将洗净的聚硅氧烷支架置于改性剂溶液中30分钟,取出,置于烘箱中于120℃干燥3小时,冷却至室温,得改性聚硅氧烷支架。
将26.3g氯化铜,21.2g硫酸亚铁,25.8g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。
将改性聚硅氧烷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,得活化聚硅氧烷支架。
将23.1g硝酸钬,25.2g硝酸钴,48.6g钨酸钠,51.8g乙二胺四乙酸二钠,71.2g柠檬酸钠,4.1g二甲氨基硼烷,7.5g碳酸氢钠溶于500mL去离子水中,再稀释成体积为1L的钬钨钴化学镀溶液。
将活化聚硅氧烷支架置于钬钨钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钬钨钴合金/聚硅氧烷支架材料。
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。
将钬钨钴合金/聚硅氧烷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,并与聚硅氧烷支架材料相比较,计算有机碳溢出降低率为99.1%;以能量弥散X射线探测器(EDX)测试支架材料的元素含量,计算钬、钨、钴离子的溢出率分别为0.36ppm、0.04ppm、0.44ppm;以万能材料试验机测试支架材料的弯曲模量为1.51GPa,以莫氏硬度计测试支架材料的表面硬度为7.9。
实施例5
将聚硅氧烷支架依次用重量百分比浓度为10%的氢氧化钾水溶液、5%的双氧水溶液、去离子水洗净、烘干。
将3g 3-脲丙基三甲氧基硅烷,9g甲基丙烯酸羟乙酯,1g过氧化苯甲酸溶于100g丙酮中,添加去离子水,配成体积为1L的改性剂溶液。
将洗净的聚硅氧烷支架置于改性剂溶液中30分钟,取出,置于烘箱中于120℃干燥3小时,冷却至室温,得改性聚硅氧烷支架。
将20g氯化铜,20g硫酸亚铁,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。
将改性聚硅氧烷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,得活化聚硅氧烷支架。
将20g硝酸钬,20g硝酸钴,40g钨酸钠,30g乙二胺四乙酸二钠,60g柠檬酸钠,3g二甲氨基硼烷,6g碳酸氢钠溶于500mL去离子水中,再稀释成体积为1L的钬钨钴化学镀溶液。
将活化聚硅氧烷支架置于钬钨钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钬钨钴合金/聚硅氧烷支架材料。
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。
将钬钨钴合金/聚硅氧烷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,并与聚硅氧烷支架材料相比较,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,计算钬、钨、钴离子的溢出率分别为0.35ppm、0.36ppm、0.31ppm;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7.9。
Claims (1)
1.一种钬钨钴合金/聚硅氧烷支架材料的制备方法,其特征在于:
1)将聚硅氧烷支架依次用重量百分比浓度为10%的氢氧化钾水溶液、5% 的双氧水溶液、去离子水洗净、烘干;
2)将洗净的聚硅氧烷支架置于改性剂溶液中30分钟,取出,置于烘箱中于120℃干燥3小时,冷却至室温,得改性聚硅氧烷支架;
3)将改性聚硅氧烷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,得活化聚硅氧烷支架;
4)将活化聚硅氧烷支架置于钬钨钴化学镀溶液中,于75℃化学镀3小时,取出洗净,烘干,得钬钨钴合金/聚硅氧烷支架材料;
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-脲丙基三甲氧基硅烷浓度 3~6 g/L;
甲基丙烯酸羟乙酯浓度9~12 g/L;
过氧化苯甲酸浓度1~3 g/L;
丙酮浓度100~200 g/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:
氯化铜浓度 20~30g/L;
硫酸亚铁浓度 20~30g/L;
柠檬酸钠浓度20~30g/L;
其中钬钨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:
硝酸钬浓度 20~30g/L;
硝酸钴浓度 20~30g/L;
钨酸钠浓度 40~60g/L;
乙二胺四乙酸二钠浓度 30~60g/L;
柠檬酸钠浓度60~90g/L;
二甲氨基硼烷浓度 3~6g/L;
碳酸氢钠浓度6~9g/L;
其中钬钨钴合金/聚硅氧烷支架材料的性能是,莫氏硬度为7.9;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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Citations (4)
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CN100360191C (zh) * | 2005-05-13 | 2008-01-09 | 中国科学院上海硅酸盐研究所 | 一种镁黄长石多孔骨组织工程支架材料及其制备方法 |
CN102400115A (zh) * | 2011-10-20 | 2012-04-04 | 复旦大学 | 一种微米级线宽的柔性铜电极图形的制备方法 |
CN103418028A (zh) * | 2013-07-31 | 2013-12-04 | 苏州纳埃净化科技有限公司 | 一种多孔支架材料的制备方法 |
CN103561787A (zh) * | 2011-06-03 | 2014-02-05 | 新特斯有限责任公司 | 外科植入物 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100360191C (zh) * | 2005-05-13 | 2008-01-09 | 中国科学院上海硅酸盐研究所 | 一种镁黄长石多孔骨组织工程支架材料及其制备方法 |
CN103561787A (zh) * | 2011-06-03 | 2014-02-05 | 新特斯有限责任公司 | 外科植入物 |
CN102400115A (zh) * | 2011-10-20 | 2012-04-04 | 复旦大学 | 一种微米级线宽的柔性铜电极图形的制备方法 |
CN103418028A (zh) * | 2013-07-31 | 2013-12-04 | 苏州纳埃净化科技有限公司 | 一种多孔支架材料的制备方法 |
Non-Patent Citations (1)
Title |
---|
稀土在化学镀中应用研究现状;黄庆荣等;《稀土》;20070228;第102-106页 |
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