CN108273133B - 一种凝胶注模制备生物医用合金ha涂层的方法 - Google Patents
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Abstract
一种凝胶注模制备生物医用合金HA涂层的方法,属于凝胶注模制备生物材料的领域。本发明将使用甲基纤维素凝胶体系,离心浇注制备羟基磷灰石、过渡层及生物医学合金复合涂层材料,使生物医学金属材料外高强度结合一层羟基磷灰石涂层。该方法制备的HA涂层生物医用合金表现出良好生物相容性和优良机械性性能,耐蚀性好、比强度高。采用无毒凝胶体系,成形性好,结合强度高。工艺简单,能近净成形,可一次加工制备出复杂形状的制品,提高了材料利用率,降低了加工成本。
Description
技术领域
本发明属于凝胶注模制备生物材料的领域,提供了一种凝胶注模制备生物医用合金HA涂层的方法。
背景技术
羟基磷灰石(HA)具有吸附蛋白质、氨基酸、脂质和葡聚糖的作用。体内埋植实验表明,羟基磷灰石涂层可以强有力地与骨形成化学结合,具有相当高的生物相容性,植入人体后在体液的作用下,钙和磷会游离出材料的表面被机体吸收与原骨结合成一体,形成牢固的骨性结合,即使偶然破裂,也能在体内愈合。羟基磷灰石不但具有骨传导性,而且还具有骨诱导性是一种新型的人工骨置换材料。
但由于羟基磷灰石(HA)该类材料克服不了自身强度低、脆性大的弱点,大大限制了其在临床医学中的应用,仅能应用于非承载的小型种植体,如人工齿骨、耳骨、充填骨缺损等。为了解决上述问题,人们将它涂敷于钛合金等金属表面,对生物金属材料进行表面改性,做成人工器件,具有高强度、韧性好等特点,取代受损组织以补偿或恢复其原来的功能,取得了很大成效。
但是此类涂层制备方法仍然存在一些问题,例如无法一次制备出具有涂层和金属基体的材料,工艺复杂时间耗费长,对于一些复杂形状的构件存在加工成形困难的特点。因此使用一种新的凝胶注模制备生物医用合金HA涂层的方法,不仅可以制备出既有良好生物相容性又有优良机械性的羟基磷灰石金属材料,净尽成型,根据不同的需求量身打造等材制备出所需制品,提高了材料利用率降低了加工成本。
发明内容
本发明的目的提供了一种凝胶注模制备生物医用合金HA涂层的方法,该方法在制备出既有良好生物相容性又有优良机械性的羟基磷灰石金属材料上取得了令人满意的成果,并能近净成形,根据不同的需求量身打造出所需制品,提高了材料利用率,降低了加工成本。
为了获得上述的凝胶注模制备的生物医用合金HA涂层,本发明采用了以下技术方案,具体步骤如下:
(1)模具制备:根据使用需求制备出符合形状要求的空腔凝胶注模模具;
(2)配制预混液:按照体积分数百分比配制预混液,在溶剂中加入有机体和造孔剂,其中有机体0.8-8%、造孔剂0.03-5%、余量是溶剂,搅拌至溶解完全;
(3)制备浆料:分别称量35-80vol.%的羟基磷灰石粉、过渡层粉末和金属合金粉末,在三种粉体中分别加入步骤(2)中的预混液,再分别加入抗氧化剂0.01-0.5%、分散剂0.01-1.5%和消泡剂0.01-0.8%,搅拌均匀,然后分别将三种浆料放入行星球磨机中,进行混料,其中球料比为3:1-7:1,刚玉球的直径为1-5mm,球磨速度为100r/min-250r/min,球磨时间5-20min,将球磨后的羟基磷灰石浆料、过渡层浆料、金属合金粉浆料取出备用;
(4)模具预处理:将步骤(1)中制备好的凝胶注模模具内层均匀喷洒一层脱模剂,然后将空腔模具固定安置在离心机的旋转转台上;
(5)挂浆:分别称取步骤(3)中配制好的羟基磷灰石浆料5-25wt.%,过渡层浆料3-16wt.%,余量是金属合金粉浆料。首先将称量好的羟基磷灰石浆料倒入固定在旋转台上的空腔模具内,在50-200r/min的转速下旋转5-15min,使羟基磷灰石浆料均匀浇覆在模具内层,然后将称量好的过渡层浆料倒入旋转台上的模具内,在50-200r/min的转速下旋转10-20min,使过渡层浆料均匀浇覆在羟基磷灰石外侧;
(6)注模:将步骤(5)中内侧依次浇覆有羟基磷灰石和过渡层浆料的模具从旋转台上取下,将称量好的金属合金粉浆料浇注于模具内,并进行真空消泡处理,在烘箱40-70℃中保温5-12h。
(7)脱胶烧结:将步骤(6)中浇注好的模具取出脱模,在脱脂炉中加热至400-900℃,保温30-150min,冷却至室温;再放入真空炉中烧结,烧结温度500-1350℃,保温60-150min,真空度为10-1-10-3Pa。
进一步地,步骤(1)中所述的凝胶注模空腔模具是利用3D打印机打印出的空腔模具,或打印出任意材料、低填充量的实体模具再制成硅胶、玻璃或塑料的空腔模具。
进一步地,步骤(2)中所述的有机体为甲基纤维素凝胶注模体系,主要由甲基纤维素(MC)和羟丙基甲基纤维素(HPMC)组成,其中甲基纤维素30-70vol.%,余量是羟丙基甲基纤维素。
进一步地,步骤(2)中所述的溶剂为水、甲苯、二甲苯、酒精、丙酮或二氯甲烷中的一种或几种。
进一步地,步骤(2)中所述的造孔剂为卵清蛋白、聚乙二醇或碳酸氢铵中的一种或几种。
进一步地,步骤(3)中所述的羟基磷灰石的粒度为10-100nm。
进一步地,步骤(3)中所述的过渡层粉末是二氧化钛、二氧化锆、硅酸镁或生物玻璃中的一种或几种,粉末粒径为10-150nm。
进一步地,步骤(3)中所述的金属合金粉末是不锈钢、钴铬钼合金、钛合金或镁合金粉末中的一种或几种,粉末粒径为5-50μm。
进一步地,步骤(4)中所述的脱模剂是硅烷基或聚醚基脱模剂。
本发明的优点:
1、制得的材料表现出良好生物相容性和优良机械性性能,耐蚀性好、比强度高。
2、采用无毒凝胶体系,离心浇注制备羟基磷灰石、过渡层及生物医学合金复合涂层材料,成形性好,结合强度高。
3、工艺简单,能近净成形,可一次加工制备出复杂形状的制品,提高了材料利用率,降低了加工成本。
具体实施方式
实施案例1:
一种凝胶注模制备钛合金HA涂层的方法,具体步骤如下:
步骤(1):使用3D打印机打印出骨关节的模具,然后用硅胶分模浇注骨关节,制得凝胶注模模具;
步骤(2):按照体积分数百分比配制预混液,在溶剂中加入有机体和造孔剂,其中溶剂为无水乙醇95%,有机体为甲基纤维素(MC)1.2%、羟丙基甲基纤维素(HPMC)3.75%,造孔剂聚乙二醇为0.05%,搅拌至溶解完全;
步骤(3):称量35nm的羟基磷灰石粉42vol.%,标记为A;称量20nm的过渡层粉末42vol.%,标记为B,其中过渡层粉末中含二氧化钛50%、二氧化锆30%、硅酸镁20%;称量40μm的球形TC4粉,标记为C;
步骤(4):在A、B、C三种粉体中分别加入57vol.%的预混液,再加入抗氧化剂0.08%、分散剂0.8%和消泡剂0.12%,搅拌均匀,然后分别将浆料放入行星球磨机中进行混料,其中刚玉球的直径为1-5mm,球料比为5:1,球磨速度为200r/min,球磨10min,将球磨后的A、B、C三种浆料分别取出备用;
步骤(5):将步骤(1)中制备好的凝胶注模模具内层均匀喷洒一层硅烷基脱模剂,然后将空腔模具固定安置在离心机的旋转转台上;
步骤(6):分别称取配制好的羟基磷灰石浆料20wt.%,过渡层浆料9wt.%,余量是TC4浆料。首先将称量好的羟基磷灰石浆料倒入固定在旋转台上的空腔模具内,在80r/min的转速下旋转8min,使羟基磷灰石浆料均匀浇覆在模具内层;然后将称量好的过渡层浆料倒入旋转台上的模具内,在100r/min的转速下旋转10min,使过渡层浆料均匀浇覆在羟基磷灰石外侧;
步骤(7):将步骤(6)中内侧依次浇覆有羟基磷灰石和过渡层浆料的模具从转台上取下,将称量好的TC4浆料浇注于模具内,并进行真空消泡处理,在烘箱中45℃保温5h。
步骤(8):将步骤(7)中浇注好的模具取出脱模,在脱脂炉中加热至900℃,保温30min,然后放入真空炉中烧结,烧结温度1330℃,烧结90min,真空度为10-2Pa,制得具有HA涂层的TC4合金骨关节材料。
实施案例2:
一种凝胶注模制备镁合金HA涂层的方法,具体步骤如下:
步骤(1):使用3D打印机打印出尺骨的模具,然后用聚氨酯分模浇注尺骨制得凝胶注模模具;
步骤(2):按照体积分数百分比配制预混液,在溶剂中加入有机体和造孔剂,其中溶剂为二氯甲烷94%,有机体为甲基纤维素(MC)2.34%、羟丙基甲基纤维素(HPMC)3.6%,造孔剂聚乙二醇为0.06,搅拌至溶解完全;
步骤(3):称量25nm的羟基磷灰石粉50vol.%,标记为A;称量15nm的过渡层粉末50vol.%,标记为B,其中过渡层粉末中含二氧化钛20%、二氧化锆20%、硅酸镁60%;称量40μm的球形AZ91E镁合金粉,标记为C;
步骤(4):在A、B、C三种粉体中分别加入49.18vol.%的预混液,再加入抗氧化剂0.07%、分散剂0.60%和消泡剂0.15%,搅拌均匀,然后将浆料放入行星球磨机中,其中刚玉球的直径为1-5mm,球料比为6:1,球磨速度为150r/min,球磨5min,将球磨后的A、B、C三种浆料分别取出备用;
步骤(5):将步骤(1)中制备好的凝胶注模模具内层均匀喷洒一层硅烷基脱模剂,然后将空腔模具固定安置在离心机的旋转转台上;
步骤(6):分别称取配制好的羟基磷灰石浆料30wt.%,过渡层浆料10wt.%,余量是AZ91E镁合金粉浆料。首先将称量好的羟基磷灰石浆料倒入固定在旋转台上的空腔模具内,在80r/min的转速下旋转5min,使羟基磷灰石浆料均匀浇覆在模具内层;然后将称量好的过渡层浆料倒入旋转台上的模具内,在100r/min的转速下旋转8min,使过渡层浆料均匀浇覆在羟基磷灰石外侧;
步骤(7):将步骤(6)中内侧依次浇覆有羟基磷灰石和过渡层浆料的模具从转台上取下,将称量好的AZ91E镁合金粉浆料浇注于模具内,并进行真空消泡处理,在烘箱中60℃保温6h。
步骤(8):将步骤(7)中浇注好的模具取出脱模,在脱脂炉中加热至410℃保温60min,然后放入真空炉中烧结,烧结温度600℃,保温60min,真空度为10-1Pa,制得具有HA涂层的AZ91E镁合金尺骨材料。
Claims (9)
1.一种凝胶注模制备生物医用合金HA涂层的方法,其特征在于,按如下步骤制备:
(1)模具制备:根据使用需求制备出符合形状要求的空腔凝胶注模模具;
(2)配制预混液:按照体积分数百分比配制预混液,在溶剂中加入有机体和造孔剂,其中有机体0.8-8%、造孔剂0.03-5%、余量是溶剂,搅拌至溶解完全;
(3)制备浆料:分别称量35-80vol.%的羟基磷灰石粉、过渡层粉末和金属合金粉末,在三种粉体中分别加入步骤(2)中的预混液,再分别加入抗氧化剂0.01-0.5%、分散剂0.01-1.5%和消泡剂0.01-0.8%,搅拌均匀,然后分别将三种浆料放入行星球磨机中,进行混料,其中球料比为3:1-7:1,刚玉球的直径为1-5mm,球磨速度为100r/min-250r/min,球磨时间5-20min,将球磨后的羟基磷灰石浆料、过渡层浆料、金属合金粉浆料取出备用;
(4)模具预处理:将步骤(1)中制备好的凝胶注模模具内层均匀喷洒一层脱模剂,然后将空腔模具固定安置在离心机的旋转转台上;
(5)挂浆:分别称取步骤(3)中配制好的羟基磷灰石浆料5-25wt.%,过渡层浆料3-16wt.%,余量是金属合金粉浆料;首先将称量好的羟基磷灰石浆料倒入固定在旋转台上的空腔模具内,在50-200r/min的转速下旋转5-15min,使羟基磷灰石浆料均匀浇覆在模具内层,然后将称量好的过渡层浆料倒入旋转台上的模具内,在50-200r/min的转速下旋转10-20min,使过渡层浆料均匀浇覆在羟基磷灰石外侧;
(6)注模:将步骤(5)中内侧依次浇覆有羟基磷灰石和过渡层浆料的模具从旋转台上取下,将称量好的金属合金粉浆料浇注于模具内,并进行真空消泡处理,在烘箱40-70℃中保温5-12h;
(7)脱胶烧结:将步骤(6)中浇注好的模具取出脱模,在脱脂炉中加热至400-900℃,保温30-150min,冷却至室温;再放入真空炉中烧结,烧结温度500-1350℃,保温60-150min,真空度为10-1-10-3Pa。
2.根据权利要求1所述的一种凝胶注模制备生物医用合金HA涂层的方法,其特征在于:步骤(1)中所述的凝胶注模空腔模具是利用3D打印机打印出的空腔模具,或打印出任意材料、低填充量的实体模具再制成硅胶、玻璃或塑料的空腔模具。
3.根据权利要求1所述的一种凝胶注模制备生物医用合金HA涂层的方法,其特征在于:步骤(2)中所述的有机体为甲基纤维素凝胶注模体系,主要由甲基纤维素(MC)和羟丙基甲基纤维素(HPMC)组成,其中甲基纤维素30-70vol.%,余量是羟丙基甲基纤维素。
4.根据权利要求1所述的一种凝胶注模制备生物医用合金HA涂层的方法,其特征在于:步骤(2)中所述的溶剂为水、甲苯、二甲苯、酒精、丙酮或二氯甲烷中的一种或几种。
5.根据权利要求1所述的一种凝胶注模制备生物医用合金HA涂层的方法,其特征在于:步骤(2)中所述的造孔剂为卵清蛋白、聚乙二醇或碳酸氢铵中的一种或几种。
6.根据权利要求1所述的一种凝胶注模制备生物医用合金HA涂层的方法,其特征在于:步骤(3)中所述的羟基磷灰石的粒度为10-100nm。
7.根据权利要求1所述的一种凝胶注模制备生物医用合金HA涂层的方法,其特征在于:步骤(3)中所述的过渡层粉末是二氧化钛、二氧化锆、硅酸镁或生物玻璃中的一种或几种,粉末粒径为10-150nm。
8.根据权利要求1所述的一种凝胶注模制备生物医用合金HA涂层的方法,其特征在于:步骤(3)中所述的金属合金粉末是不锈钢、钴铬钼合金、钛合金或镁合金粉末中的一种或几种,粉末粒径为5-50μm。
9.根据权利要求1所述的一种凝胶注模制备生物医用合金HA涂层的方法,其特征在于:步骤(4)中所述的脱模剂是硅烷基或聚醚基脱模剂。
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