CN112522674B - 一种钛合金表面复合涂层及其制备方法 - Google Patents
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Abstract
本发明涉及一种钛合金表面复合涂层及其制备方法,其中,复合涂层为Ta2O5‑TiO2‑稀土氧化物,通过设置Ti+TiO2过渡层提高了钛合金基体与Ta2O5‑TiO2‑稀土氧化物复合涂层的结合强度,并且,通过向现有的Ta2O5‑TiO2涂层中掺入特定的稀土氧化物,使得Ta2O5‑TiO2涂层的耐腐蚀性能进一步提高,将其应用于人工关节领域可以满足更多、更严苛的使用需求。
Description
技术领域
本发明涉及一种医用钛合金表面涂层领域,具体涉及一种钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层及其制备方法。
背景技术
因生物相容性好,耐腐蚀性能优异,可加工性强,Ti6Al4V合金已成为当今医用植入体的首选材料。然而,随着服役时间的增加,人体液体的腐蚀作用会使Ti6Al4V合金释放对人体细胞有毒的金属离子,使得宿主组织出现中度,过敏,致癌等不良反应,并最终导致植入体失效。因此,提高Ti6Al4V合金的耐腐蚀性能是一项长期的研究课题。针对此课题,众多科研人员付出了大量的劳动,其中最为有效的是在Ti6Al4V合金表面制备耐腐蚀涂层。然而,现有的涂层在耐腐蚀场景要求极为严苛的情况下的临床表现并不理想。
发明内容
针对现有技术存在的问题,本发明的目的在于提供一种钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层及其制备方法,上述涂层具有优异的耐腐蚀性能,对扩展钛合金表面涂层的医用应用领域有着重大意义。
一种钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层,所述钛合金为Ti6Al4V合金,所述稀土氧化物为CeO2和Y2O3中的一种或两种,所述复合涂层采用Ta2O5-TiO2-稀土氧化物复合靶材通过磁控溅射法制备而得,所述Ta2O5-TiO2-稀土氧化物复合靶材中稀土氧化物的摩尔含量为4%-12%,TiO2的摩尔含量为20-30%。
优选地,所述钛合金的尺寸为50×50×3mm。
进一步地,所述稀土氧化物为CeO2和Y2O3。
本发明还提供了一种钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层的制备方法,包括以下步骤:
A.基体选择:选用Ti6Al4V合金作为基体材料,所述基体材料的尺寸为50×50×3mm;
B.预处理:分别用丙酮、无水乙醇和去离子水对钛合金进行超声清洗,清洗温度为25℃,清洗时间为10min,然后真空烘干待用;
C.制备Ti过渡层:将清洗后的钛合金基体放入磁控溅射镀膜机中,对镀膜机抽真空并通入氩气为工作气体,选用纯度超过99.9%的Ti靶为溅射源,在钛合金基体表面制备Ti过渡层,溅射过程中溅射功率220V,溅射时间18min,氩气流量20sccm;
D.制备TiO2过渡层:选用纯度超过99.9%的TiO2靶为溅射源,在氩气气氛下,在Ti过渡层表面继续溅射TiO2过渡层,溅射过程中溅射功率250V,溅射时间20min,氩气流量20sccm;
E.制备Ta2O5-TiO2-稀土氧化物复合涂层:选用Ta2O5-TiO2-稀土氧化物复合靶材为溅射源,在氩气气氛下,在TiO2过渡层表面制备Ta2O5-TiO2-稀土氧化物复合涂层,其中溅射功率300V,溅射时间25min,氩气流量30sccm。
进一步地,所述稀土氧化物为CeO2和Y2O3中的一种或两种。
进一步地,所述稀土氧化物为CeO2和Y2O3。
本发明还提供了一种钛合金表面复合涂层在人工关节领域的应用,所述复合涂层为上述钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层或采用上述方法制备而得。
Ta2O5-TiO2-稀土氧化物复合涂层中Ta2O5、TiO2和稀土氧化物三者缺一不可,缺少任何一种都无法达到与本发明相同的耐腐蚀性能,并且,当稀土氧化物为CeO2和Y2O3时,耐腐蚀性能的提升效果最为优异。
本发明通过设置Ti+TiO2过渡层提高了钛合金基体与Ta2O5-TiO2-稀土氧化物复合涂层的结合强度,并且,通过向现有的Ta2O5-TiO2涂层中掺入特定的稀土氧化物,使得Ta2O5-TiO2涂层的耐腐蚀性能进一步提高,将其应用于人工关节领域可以满足更多、更严苛的使用需求,为拓展钛合金涂层的应用领域做出了巨大的贡献。
具体实施方式
以下通过具体实施例进一步验证本发明的技术效果,但是本发明的实施方式不局限于此。
实施例1
一种钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层的制备方法,包括以下步骤:
A.基体选择:选用Ti6Al4V合金作为基体材料,所述基体材料的尺寸为50×50×3mm;
B.预处理:分别用丙酮、无水乙醇和去离子水对钛合金进行超声清洗,清洗温度为25℃,清洗时间为10min,然后真空烘干待用;
C.制备Ti过渡层:将清洗后的钛合金基体放入磁控溅射镀膜机中,对镀膜机抽真空并通入氩气为工作气体,选用纯度超过99.9%的Ti靶为溅射源,在钛合金基体表面制备Ti过渡层,溅射过程中溅射功率220W,溅射时间18min,氩气流量20sccm;
D.制备TiO2过渡层:选用纯度超过99.9%的TiO2靶为溅射源,在氩气气氛下,在Ti过渡层表面继续溅射TiO2过渡层,溅射过程中溅射功率250W,溅射时间20min,氩气流量20sccm;
E.制备Ta2O5-TiO2-CeO2复合涂层:选用Ta2O5-TiO2-CeO2复合靶材(其中TiO2的摩尔比为30%,CeO2的摩尔比为8%)为溅射源,在氩气气氛下,在TiO2过渡层表面制备Ta2O5-TiO2-CeO2复合涂层,其中溅射功率300W,溅射时间25min,氩气流量30sccm。
实施例2
一种钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层的制备方法,包括以下步骤:
A.基体选择:选用Ti6Al4V合金作为基体材料,所述基体材料的尺寸为50×50×3mm;
B.预处理:分别用丙酮、无水乙醇和去离子水对钛合金进行超声清洗,清洗温度为25℃,清洗时间为10min,然后真空烘干待用;
C.制备Ti过渡层:将清洗后的钛合金基体放入磁控溅射镀膜机中,对镀膜机抽真空并通入氩气为工作气体,选用纯度超过99.9%的Ti靶为溅射源,在钛合金基体表面制备Ti过渡层,溅射过程中溅射功率220W,溅射时间18min,氩气流量20sccm;
D.制备TiO2过渡层:选用纯度超过99.9%的TiO2靶为溅射源,在氩气气氛下,在Ti过渡层表面继续溅射TiO2过渡层,溅射过程中溅射功率250W,溅射时间20min,氩气流量20sccm;
E.制备Ta2O5-TiO2-Y2O3复合涂层:选用Ta2O5-TiO2-Y2O3复合靶材(其中TiO2的摩尔比为30%,Y2O3的摩尔比为8%)为溅射源,在氩气气氛下,在TiO2过渡层表面制备Ta2O5-TiO2-Y2O3复合涂层,其中溅射功率300W,溅射时间25min,氩气流量30sccm。
实施例3
一种钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层的制备方法,包括以下步骤:
A.基体选择:选用Ti6Al4V合金作为基体材料,所述基体材料的尺寸为50×50×3mm;
B.预处理:分别用丙酮、无水乙醇和去离子水对钛合金进行超声清洗,清洗温度为25℃,清洗时间为10min,然后真空烘干待用;
C.制备Ti过渡层:将清洗后的钛合金基体放入磁控溅射镀膜机中,对镀膜机抽真空并通入氩气为工作气体,选用纯度超过99.9%的Ti靶为溅射源,在钛合金基体表面制备Ti过渡层,溅射过程中溅射功率220W,溅射时间18min,氩气流量20sccm;
D.制备TiO2过渡层:选用纯度超过99.9%的TiO2靶为溅射源,在氩气气氛下,在Ti过渡层表面继续溅射TiO2过渡层,溅射过程中溅射功率250W,溅射时间20min,氩气流量20sccm;
E.制备Ta2O5-TiO2-Y2O3复合涂层:选用Ta2O5-TiO2-Y2O3复合靶材(其中TiO2的摩尔比为25%,Y2O3的摩尔比为12%)为溅射源,在氩气气氛下,在TiO2过渡层表面制备Ta2O5-TiO2-Y2O3复合涂层,其中溅射功率300W,溅射时间25min,氩气流量30sccm。
实施例4
一种钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层的制备方法,包括以下步骤:
A.基体选择:选用Ti6Al4V合金作为基体材料,所述基体材料的尺寸为50×50×3mm;
B.预处理:分别用丙酮、无水乙醇和去离子水对钛合金进行超声清洗,清洗温度为25℃,清洗时间为10min,然后真空烘干待用;
C.制备Ti过渡层:将清洗后的钛合金基体放入磁控溅射镀膜机中,对镀膜机抽真空并通入氩气为工作气体,选用纯度超过99.9%的Ti靶为溅射源,在钛合金基体表面制备Ti过渡层,溅射过程中溅射功率220W,溅射时间18min,氩气流量20sccm;
D.制备TiO2过渡层:选用纯度超过99.9%的TiO2靶为溅射源,在氩气气氛下,在Ti过渡层表面继续溅射TiO2过渡层,溅射过程中溅射功率250W,溅射时间20min,氩气流量20sccm;
E.制备Ta2O5-TiO2-CeO2复合涂层:选用Ta2O5-TiO2-CeO2复合靶材(其中TiO2的摩尔比为25%,CeO2的摩尔比为12%)为溅射源,在氩气气氛下,在TiO2过渡层表面制备Ta2O5-TiO2-CeO2复合涂层,其中溅射功率300W,溅射时间25min,氩气流量30sccm。
实施例5
一种钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层的制备方法,包括以下步骤:
A.基体选择:选用Ti6Al4V合金作为基体材料,所述基体材料的尺寸为50×50×3mm;
B.预处理:分别用丙酮、无水乙醇和去离子水对钛合金进行超声清洗,清洗温度为25℃,清洗时间为10min,然后真空烘干待用;
C.制备Ti过渡层:将清洗后的钛合金基体放入磁控溅射镀膜机中,对镀膜机抽真空并通入氩气为工作气体,选用纯度超过99.9%的Ti靶为溅射源,在钛合金基体表面制备Ti过渡层,溅射过程中溅射功率220W,溅射时间18min,氩气流量20sccm;
D.制备TiO2过渡层:选用纯度超过99.9%的TiO2靶为溅射源,在氩气气氛下,在Ti过渡层表面继续溅射TiO2过渡层,溅射过程中溅射功率250W,溅射时间20min,氩气流量20sccm;
E.制备Ta2O5-TiO2-CeO2-Y2O3复合涂层:选用Ta2O5-TiO2-CeO2-Y2O3复合靶材(其中TiO2的摩尔比为25%,CeO2的摩尔比为8%,Y2O3的摩尔比为4%)为溅射源,在氩气气氛下,在TiO2过渡层表面制备Ta2O5-TiO2-CeO2-Y2O3复合涂层,其中溅射功率300W,溅射时间25min,氩气流量30sccm。
实施例6
一种钛合金表面Ta2O5-TiO2-稀土氧化物复合涂层的制备方法,包括以下步骤:
A.基体选择:选用Ti6Al4V合金作为基体材料,所述基体材料的尺寸为50×50×3mm;
B.预处理:分别用丙酮、无水乙醇和去离子水对钛合金进行超声清洗,清洗温度为25℃,清洗时间为10min,然后真空烘干待用;
C.制备Ti过渡层:将清洗后的钛合金基体放入磁控溅射镀膜机中,对镀膜机抽真空并通入氩气为工作气体,选用纯度超过99.9%的Ti靶为溅射源,在钛合金基体表面制备Ti过渡层,溅射过程中溅射功率220W,溅射时间18min,氩气流量20sccm;
D.制备TiO2过渡层:选用纯度超过99.9%的TiO2靶为溅射源,在氩气气氛下,在Ti过渡层表面继续溅射TiO2过渡层,溅射过程中溅射功率250W,溅射时间20min,氩气流量20sccm;
E.制备Ta2O5-TiO2-CeO2-Y2O3复合涂层:选用Ta2O5-TiO2-CeO2-Y2O3复合靶材(其中TiO2的摩尔比为25%,CeO2的摩尔比为4%,Y2O3的摩尔比为8%)为溅射源,在氩气气氛下,在TiO2过渡层表面制备Ta2O5-TiO2-CeO2-Y2O3复合涂层,其中溅射功率300W,溅射时间25min,氩气流量30sccm。
对比例1
表面没有涂层的Ti6Al4V合金基体。
对比例2
表面仅包含Ti过渡层和TiO2过渡层的Ti6Al4V合金基体。
对比例3
表面包含Ti过渡层、TiO2过渡层和Ta2O5涂层的Ti6Al4V合金基体。
对比例4
表面包含Ti过渡层、TiO2过渡层和Ta2O5-TiO2涂层(其中TiO2的摩尔比为38%)的Ti6Al4V合金基体。
对比例5
表面包含Ti过渡层、TiO2过渡层和Ta2O5-Y2O3涂层(其中Y2O3的摩尔比为8%)的Ti6Al4V合金基体。
为了避免工艺参数的差异带来的不良影响,对比例1-5中制备同种涂层时采用与实施例相同的工艺参数并保证基体材料的预处理工艺完全相同。
对实施例1-6和对比例1-5做浸泡实验,即在模拟体液(SBF)中,37℃下对钛合金长期保护能力测试以衡量其耐腐蚀性能。本发明将裸露的钛合金片和包含涂层的钛合金片进行封装,防止边缘效应,而后将其各自置于盛有模拟液的容器中,用保鲜膜封住容器口,放入37℃的恒温水浴锅中,每两天更新一次模拟体液,并记录样品开始发生腐蚀的情况,具体情况如表1所示,其中“例1-6”和“比1-5”分别对应实施例1-6和对比例1-5的样品,“时间”表示样品开始发生腐蚀的时间。
表1 耐腐蚀性能测试数据
样品 | 例1 | 例2 | 例3 | 例4 | 例5 | 例6 | 比1 | 比2 | 比3 | 比4 | 比5 |
时间/h | 632 | 671 | 692 | 651 | 753 | 728 | 59 | 253 | 418 | 505 | 472 |
通过表1的实验数据可以看出:
稀土氧化物的掺入有利于提高钛合金表面Ta2O5-TiO2涂层的耐腐蚀性能,并且,一定范围内,稀土氧化物的掺入量越多,则耐腐性性能的提高越明显;
当只掺入单种稀土氧化物时,相同掺入量的Y2O3和CeO2相比,Y2O3对耐腐蚀性能的影响比CeO2更为显著;
钛合金表面复合涂层的耐腐蚀性能是Ta2O5、TiO2和Y2O3综合表现的结果,三者缺一不可;
同时掺入Y2O3和CeO2时,耐腐蚀性能的提升效果最佳,有趣的是,当两者同时掺入时,耐腐蚀性能的提高并非同等含量的Y2O3优于CeO2,这可能是两种稀土氧化物或者稀土氧化物在整个涂层体系下发生了某种未知的作用关系,局限于时间成本和人力成本,本发明不对此现象深入探究。
Claims (4)
1.一种钛合金表面复合涂层,其特征在于:所述复合涂层为Ta2O5-TiO2-稀土氧化物,所述钛合金为Ti6Al4V合金,所述稀土氧化物为CeO2和Y2O3,所述复合涂层采用Ta2O5-TiO2-稀土氧化物复合靶材通过磁控溅射法制备而得,所述Ta2O5-TiO2-稀土氧化物复合靶材中稀土氧化物的摩尔含量为4%-12%,TiO2的摩尔含量为20-30%。
2.一种如权利要求1所述的钛合金表面复合涂层,其特征在于:所述钛合金的尺寸为50×50×3mm。
3.一种权利要求1所述的钛合金表面复合涂层的制备方法,其特征在于:所述复合涂层为Ta2O5-TiO2-稀土氧化物,所述制备方法包括以下步骤:
A.基体选择:选用Ti6Al4V合金作为基体材料,所述基体材料的尺寸为50×50×3mm;
B.预处理:分别用丙酮、无水乙醇和去离子水对钛合金进行超声清洗,清洗温度为25℃,清洗时间为10min,然后真空烘干待用;
C.制备Ti过渡层:将清洗后的钛合金基体放入磁控溅射镀膜机中,对镀膜机抽真空并通入氩气为工作气体,选用纯度超过99.9%的Ti靶为溅射源,在钛合金基体表面制备Ti过渡层,溅射过程中溅射功率220W,溅射时间18min,氩气流量20sccm;
D.制备TiO2过渡层:选用纯度超过99.9%的TiO2靶为溅射源,在氩气气氛下,在Ti过渡层表面继续溅射TiO2过渡层,溅射过程中溅射功率250W,溅射时间20min,氩气流量20sccm;
E.制备Ta2O5-TiO2-稀土氧化物复合涂层:选用Ta2O5-TiO2-稀土氧化物复合靶材为溅射源,在氩气气氛下,在TiO2过渡层表面制备Ta2O5-TiO2-稀土氧化物复合涂层,其中溅射功率300W,溅射时间25min,氩气流量30sccm;所述稀土氧化物为CeO2和Y2O3。
4.一种钛合金表面复合涂层在人工关节领域的应用,其特征在于:所述复合涂层为权利要求1-2中任一项所述的钛合金表面复合涂层或采用权利要求3所述方法制备而得。
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