CN108478859B - 一种3d冷打印制备羟基磷灰石-生物医用合金植入体的方法 - Google Patents
一种3d冷打印制备羟基磷灰石-生物医用合金植入体的方法 Download PDFInfo
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Abstract
一种3D冷打印制备羟基磷灰石‑生物医用合金植入体的方法,属于近净成形3D打印制备生物材料的领域。本发明将使用甲基纤维素打印体系,通过多入料口3D冷打印设备,一次性打印出具有羟基磷灰石和过渡层的生物医用合金植入体。该方法采用无毒打印体系,成形性好,结合强度高,制备的生物医用合金植入体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。可根据不同需求自主设计调整形状大小以及涂层厚度,适用性高,具有无模制造且近净成形的优点,可一次加工制备出复杂形状的制品,并且精度高,提高了材料利用率,降低了加工成本。
Description
技术领域
本发明属于近净成形3D打印制备生物材料的领域,提供了一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法。
背景技术
3D冷打印技术是一种在室温或低温(<100℃)条件下打印金属零件的新型3D打印技术。其将发展得较为成熟的低粘度、高固相含量浆料制备和原位成型技术和逐层增加的3D打印成型原理相结合,形成新型的3D冷打印成型设备并对相关技术进行研发。首先将原材料粉末调制成低粘度、高固相含量的浆料,用这种浆料当做打印机的“墨水”,在打印过程中,通过热引发、化学引发实现浆料的原位固化成型,实现金属坯体的逐层打印。具有不受原料限制、成形复杂构件、产品精度高、设备造价低等优点。
羟基磷灰石(HA)现在被广泛研究证明是一种优良的具有骨诱导性是一种新型的人工骨置换材料,具有吸附蛋白质、氨基酸、脂质和葡聚糖的作用,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。但由于羟基磷灰石(HA)该类材料有自身强度低、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,做成生物医药的植入体,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。使用具有羟基磷灰石涂层的金属复合材料作为植入体,使植入体兼具两者特点,既能具有一定强度韧性,可作为称重部位的骨植入体材料;还能提供良好的生物相容性和兼容的弹性模量,使植入体与人体自身组织结合良好。
使用3D冷打印的方法制备制备羟基磷灰石-生物医用合金植入体的,不仅可以得到涂层复合材料,还能净尽成形等材制造,根据需要直接制备出符合尺寸要求具有复杂形状的植入体,同时解决材料制备和成形的问题。
本发明是一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,使用该方法可近净成形,一次制备出复杂形状具有羟基磷灰石涂层的生物医用植入体,既有良好的生物相容性又能具备金属的高强度和良好的支撑性,净尽成形大大降低了成本,并能自主设计调整形状适用性高。
发明内容
本发明的目的提供了一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,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3D冷打印制备的羟基磷灰石-生物医用合金植入体,本发明采用了以下技术方案,具体步骤如下:
(1)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1-10%、造孔剂0.03-5%、余量是溶剂,搅拌至溶解完全;
(2)制备浆料:按照体积分数百分比量取粉末和预混液进行配制,分别称量体积分数30-85vol.%的羟基磷灰石粉a、过渡层粉末b、金属合金粉末c,在a、b、c三种粉体中分别加入步骤(1)中的预混液,再加入抗氧化剂0.01-0.5%、分散剂0.01-1.5%和消泡剂0.01-0.8%搅拌均匀,得到浆料A、B、C,然后分别将浆料A、B、C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A、B、C三种浆料取出备用;
(3)建模:利用三维画图软件进行画图建模,并在3D冷打印机专门的切片软件中进行转换,将程序输入3D冷打印机中;
(4)打印成型:在步骤(2)中球磨后的A、B、C三种浆料中分别滴入不同比例的引发剂,然后分别依次装入1、2、3号入料口中,使用多入料口3D冷打印设备根据已建好模的模型按顺序逐层打印出所需形状制品;
(5)脱脂烧结:将步骤(4)中打印好的坯体放入在脱脂炉中加热至450-900℃,保温30-200min,冷却至室温;再放入真空炉中烧结,烧结温度550-1350℃,保温60-240min,真空度为10-1-10-3Pa。
进一步地,步骤(1)中所述的有机体主要由甲基纤维素(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(1)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(1)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(2)中所述的羟基磷灰石的粒度为10-100nm。
进一步地,步骤(2)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(2)中所述的金属合金粉末是不锈钢、钴铬钼合金、钛及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)中所述的不同比例的引发剂按照体积分数比,分别为浆料A的0.05-0.1%,浆料B的0.03-0.7%,浆料A的0.01-0.8%
进一步地,步骤(4)中所述的喷头打印A、B、C号料浆的打印速度为8-15mm/s,打印压力为0.15-0.35MPa,喷头直径为0.2-0.5mm,打印层高为0.25-0.45mm。
进一步地,步骤(4)中所述的A、B、C三种料浆的打印顺序依次为A浆料,然后为B浆料,最后为C浆料。
本发明的优点:
1、无模制造且近净成形,可一次加工制备出复杂形状的制品,并且精度高,提高了材料利用率,降低了加工成本。
2、制得的材料表现出良好生物相容性和优良机械性性能,具有良好的支撑性,可作为承重部位的植入体。
3、打印出的坯体成形性好,各层之间结合强度高。
4、可根据不同需求自主设计调整形状大小以及涂层厚度,适用性高。
5、采用多入料口的3D打印系统进行打印,可打印出不同成分梯度、不同含量梯度的制品。
附图说明
图1是本发明实施案例中采用的打印喷头的结构示意图。
具体实施方式
实施案例1:
一种3D冷打印制备羟基磷灰石-TC4钛合金颅面植入体的方法。按如下步骤制备:
(1)配制预混液:在溶剂中加入有机体和造孔剂,按体积百分数,其中溶剂为二甲苯93.96%,有机体为甲基纤维素(MC)3.5%、羟丙基甲基纤维素(HPMC)2.5%,造孔剂卵清蛋白为0.04%,搅拌至溶解完全;
(2)制备浆料:称量20nm的羟基磷灰石粉,标记为a;称量15nm的过渡层粉末,标记为b,其中过渡层粉末中含二氧化钛56%、二氧化锆44%;称量45μm的球形TC4粉,标记为c;在a、b、c三种粉体中分别加入59vol.%的预混液,再加入抗氧化剂0.05%、分散剂0.9%和消泡剂0.15%,搅拌均匀,得到浆料A、B、C,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4:1,球磨速度为200r/min,球磨5min,将球磨后的A、B、C三种浆料分别取出备用;
(3)建模:利用三维画图软件进行画图建模,绘制所打印的颅面模型,并在3D冷打印机专门的切片软件中进行转换,将程序输入3D冷打印机中;
(4)打印成型:在步骤(2)中配制好的A、B、C三种浆料按质量分数称取,配比为15:5:80;然后分别滴入0.07%、0.03%、0.02%的引发剂,然后分别依次对应装入1、2、3号入料口中,使用多入料口3D冷打印设备根据已建好模的模型按顺序逐层打印出颅面形状的植入体;
(5)脱脂烧结:将步骤(4)中打印好的颅面坯体放入在脱脂炉中加热至600℃,保温90min,冷却至室温;再放入真空炉中烧结,烧结温度1320℃,保温120min,真空度为10-2Pa。
实施案例2:
一种3D冷打印制备羟基磷灰石-不锈钢胫骨植入体的方法。按如下步骤制备:
(1)配制预混液:在溶剂中加入有机体和造孔剂,按体积百分数,其中溶剂为无水乙醇92.37%,有机体为甲基纤维素(MC)4.1%、羟丙基甲基纤维素(HPMC)3.5%,造孔剂聚乙二醇为0.03%,搅拌至溶解完全;
(2)制备浆料:称量20nm的羟基磷灰石粉,标记为a;称量15nm的过渡层粉末,标记为b,其中过渡层粉末中含二氧化钛26%、二氧化锆44%、硅酸镁30%;称量30μm的水雾化不锈钢粉,标记为c;按体积分数比称取粉末,在a、b、c三种粉体中分别加入61vol.%的预混液,再加入抗氧化剂0.02%、分散剂0.7%和消泡剂0.15%,搅拌均匀,得到浆料A、B、C,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2-6mm,球料比为5:1,球磨速度为150r/min,球磨0min,将球磨后的A、B、C三种浆料分别取出备用;
(3)建模:利用三维画图软件进行画图建模,绘制所打印的胫骨模型,并在3D冷打印机专门的切片软件中进行转换,将程序输入3D冷打印机中;
(4)打印成型:在步骤(2)中配制好的A、B、C三种浆料按质量分数称取,配比为7:5:88;然后分别滴入0.05%、0.03%、0.15%的引发剂,然后分别依次对应装入1、2、3号入料口中,使用多入料口3D冷打印设备根据已建好模的模型按顺序逐层打印出胫骨形状的植入体;
(5)脱脂烧结:将步骤(4)中打印好的胫骨坯体放入在脱脂炉中加热至600℃,保温110min,冷却至室温;再放入真空炉中烧结,烧结温度1260℃,保温120min,真空度为10-2Pa。
Claims (9)
1.一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,其特征在于,按如下步骤制备:
(1)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1-10%、造孔剂0.03-5%、余量是溶剂,搅拌至溶解完全;
(2)制备浆料:按照体积分数百分比量取粉末和预混液进行配制,分别称量体积分数30-85vol.%的羟基磷灰石粉、过渡层粉末、金属合金粉末,在a、b、c三种粉体中分别加入步骤(1)中的预混液,再加入抗氧化剂0.01-0.5%、分散剂0.01-1.5%和消泡剂0.01-0.8%搅拌均匀,得到浆料A、B、C,然后分别将浆料A、B、C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A、B、C三种浆料取出备用;
(3)建模:利用三维画图软件进行画图建模,并在3D冷打印机专门的切片软件中进行转换,将程序输入3D冷打印机中;
(4)打印成型:在步骤(2)中球磨后的A、B、C三种浆料中分别滴入不同比例的引发剂,然后分别依次对应装入1、2、3号入料口中,使用多入料口3D冷打印设备根据已建好模的模型按顺序逐层打印出所需形状制品;
(5)脱脂烧结:将步骤(4)中打印好的坯体放入在脱脂炉中加热至450-900℃,保温30-200min,冷却至室温;再放入真空炉中烧结,烧结温度550-1350℃,保温60-240min,真空度为10-1-10-3Pa;
步骤(1)中所述的有机体主要由甲基纤维素(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;
步骤(2)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;
步骤(2)中所述的金属合金粉末是不锈钢、钴铬钼合金、钛及钛合金或镁合金粉末中的一种或几种。
2.根据权利要求1所述的一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,其特征在于:步骤(1)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。
3.根据权利要求1所述的一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,其特征在于:步骤(1)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。
4.根据权利要求1所述的一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,其特征在于:步骤(2)中所述的羟基磷灰石的粒度为10-100nm。
5.根据权利要求1所述的一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,其特征在于:步骤(2)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。
6.根据权利要求1所述的一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,其特征在于:步骤(2)中所述的金属合金粉末是不锈钢、钴铬钼合金、钛及钛合金或镁合金粉末中的一种或几种,粉末粒径为5-50μm。
7.根据权利要求1所述的一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,其特征在于:步骤(4)中所述的不同比例的引发剂按照体积分数比,分别为浆料A的0.05-0.1%,浆料B的0.03-0.7%,浆料C的0.01-0.8%。
8.根据权利要求1所述的一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,其特征在于:步骤(4)中所述的打印A、B、C三种料浆的打印速度为8-15mm/s,打印压力为0.15-0.35MPa,喷头直径为0.2-0.5mm,打印层高为0.25-0.45mm。
9.根据权利要求1所述的一种3D冷打印制备羟基磷灰石-生物医用合金植入体的方法,其特征在于:步骤(4)中所述的A、B、C三种料浆的打印顺序依次为A浆料,然后为B浆料,最后为C浆料。
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