CN108611611A - 一种钛镍钴记忆合金膜的制备方法 - Google Patents
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Abstract
本发明公开了一种钛镍钴记忆合金膜的制备方法,该方法克服了现有的多孔TiNiCo形状记忆合金制备方法中孔隙率和孔径及孔型均难以控制以及合金产品的阻尼性能及其他力学性能尚需提高的缺陷,本发明采用磁控溅射的方法,并采用低温轧制的手段,形成的稀土记忆合膜具有较高的屈服强度,使得膜表面均匀致密、膜基结合强度高、力学性能优良。
Description
技术领域
本发明涉及合金材料制造领域,具体涉及一种钛镍钴记忆合金膜的制备方法。
背景技术
形状记忆合金(Shape Memory Alloy,SMA)是指经过适当变形后,在一定物理条件变化下能自动做功而恢复变形前形状的合金。形状记忆合金因其具有较高的可恢复性形变,已成为一种重要的功能材料,获得了广泛应用。镍钛系形状记忆具有记忆恢复原形、无磁性、耐磨耐蚀、耐高温、无毒性的特点。不过,当前的形状记忆合金的屈服强度一般在700MPa以下。
记忆合金常用于人体关节等外科植入物,它相比不锈钢和钛合金而言,其机械性能更接近骨皮质的机械性能,拥有较高的耐磨性。但这种材料的低腐蚀性却带来了一些负面影响,合金表面产生的腐蚀性产物导致细胞毒性增加,使细胞非正常死亡。然而这些材料的微结构和表面形态学的均一性可改变记忆合金的抗腐蚀性和耐磨损性。
TiNi基形状记忆合金具有丰富的马氏体相变现象、优异的形状恢复特性以及生物相容性、阻尼特性等,因此在航空航天、机械电子、生物医疗等领域获得广泛应用。TiNi基合金的优良特性多来自于其母相与马氏体相之间的相变行为。TiNi基合金的马氏体相变产物较多,包括单斜结构的B19′马氏体相、正交结构的B19马氏体相与菱方结构的R相。与其他两种马氏体相变比较,B2母相与R相之间的转变具有很多优点,如热滞后小(不超过5℃)、循环稳定性好、阻尼损耗因子高、响应频率高等。
发明内容
本发明提供一种钛镍钴记忆合金膜的制备方法,该方法克服了现有的多孔TiNiCo形状记忆合金制备方法中孔隙率和孔径及孔型均难以控制以及合金产品的阻尼性能及其他力学性能尚需提高的缺陷,本发明采用磁控溅射的方法,并采用低温轧制的手段,形成的稀土记忆合膜具有较高的屈服强度,使得膜表面均匀致密、膜基结合强度高、力学性能优良。
为了实现上述目的,本发明提供了一种钛镍钴记忆合金膜的制备方法,该方法包括如下步骤:
(1)配料
按以下重量份配制混合粉
钛粉 25-28份;
镍粉 42-45份;
钴粉 12-16份
钇粉 0.5-1.5份
将混合粉置于不锈钢球磨罐中,注满无水乙醇后密封,在行星式球磨机上球磨3-4h,球磨中采用的球料比为10∶1,球磨机的转速为400-500r/min,之后,将球磨好的混合粉取出并置于滤纸上静置6-8分钟,得到原料粉;
(2)制备记忆合金靶材
上述原料粉与去结晶水KCl颗粒均匀混合,去结晶水KCl颗粒的用量为其占混合粉与去结晶水KCl颗粒混合物的体积百分比的65-75%,将该混合物在混料机中混合45-50min后装入内壁涂覆硬脂酸锌的不锈钢模具中,单向加压380-400MPa制得生坯,之后将该生坯装入氧化铝坩埚,并置于管式真空烧结炉中,待炉内真空抽至1-5Pa后,以5-10℃/min的速率加热至800-810℃,保温3-4h后,再以10-15℃/分钟的速率加热至960-980℃,保温3-4h后随炉冷却至室温,将烧结体从炉内取出,置于超声波水浴中清洗15-20min后烘干,制得多孔合金靶材;
(3)采用上述合金靶材,使用磁控溅射方法,在基体上形成薄膜状的钛镍钴记忆合金膜:
抽真空至10-4Pa以上,充入氮气,然后再抽真空至10-4Pa,调整工作电压为500V,溅射占空比65-68%,开始进行溅射沉积,控制厚度为150-250μm得到薄膜状的钛镍钴记忆合金膜;
启动轧机系统,设定上下轧辊的速比为1.2-1.5 ,设定每次轧制形变量为2-3%;设定低速辊的速度为0.05-0.1m/s,开始钛镍钴记忆合金膜的轧制过程;一次轧制过后,重复进行轧制3-5次,轧制过程中,保持环境温度为-30至-20摄氏度;在150-200摄氏度进行低温热处理1-2h,得到产品。
本发明具备以下优点:
(1)克服了现有的多孔TiNiCo形状记忆合金制备方法中孔隙率和孔径及孔型均难以控制以及合金产品的阻尼性能及其他力学性能尚需提高的缺陷;
(2)本发明采用磁控溅射的方法,并采用低温轧制的手段,形成的稀土记忆合膜具有较高的屈服强度,使得膜表面均匀致密、膜基结合强度高、力学性能优良。
具体实施方式
实施例一
按以下重量份配制混合粉
钛粉 25份;
镍粉 42份;
钴粉 12份
钇粉 0.5份
将混合粉置于不锈钢球磨罐中,注满无水乙醇后密封,在行星式球磨机上球磨3h,球磨中采用的球料比为10∶1,球磨机的转速为400r/min,之后,将球磨好的混合粉取出并置于滤纸上静置6分钟,得到原料粉。
上述原料粉与去结晶水KCl颗粒均匀混合,去结晶水KCl颗粒的用量为其占混合粉与去结晶水KCl颗粒混合物的体积百分比的65%,将该混合物在混料机中混合45min后装入内壁涂覆硬脂酸锌的不锈钢模具中,单向加压380MPa制得生坯,之后将该生坯装入氧化铝坩埚,并置于管式真空烧结炉中,待炉内真空抽至1Pa后,以5℃/min的速率加热至800℃,保温3h后,再以10℃/分钟的速率加热至960℃,保温3h后随炉冷却至室温,将烧结体从炉内取出,置于超声波水浴中清洗15min后烘干,制得多孔合金靶材。
采用上述合金靶材,使用磁控溅射方法,在基体上形成薄膜状的钛镍钴记忆合金膜:抽真空至10-4Pa以上,充入氮气,然后再抽真空至10-4Pa,调整工作电压为500V,溅射占空比65%,开始进行溅射沉积,控制厚度为150μm得到薄膜状的钛镍钴记忆合金膜。
启动轧机系统,设定上下轧辊的速比为1.2 ,设定每次轧制形变量为2%;设定低速辊的速度为0.05m/s,开始钛镍钴记忆合金膜的轧制过程;一次轧制过后,重复进行轧制3次,轧制过程中,保持环境温度为-30至-20摄氏度;在150摄氏度进行低温热处理1h,得到产品。
实施例二
按以下重量份配制混合粉
钛粉 28份;
镍粉 45份;
钴粉 16份
钇粉 1.5份
将混合粉置于不锈钢球磨罐中,注满无水乙醇后密封,在行星式球磨机上球磨3-4h,球磨中采用的球料比为10∶1,球磨机的转速为400-500r/min,之后,将球磨好的混合粉取出并置于滤纸上静置6-8分钟,得到原料粉。
上述原料粉与去结晶水KCl颗粒均匀混合,去结晶水KCl颗粒的用量为其占混合粉与去结晶水KCl颗粒混合物的体积百分比的75%,将该混合物在混料机中混合50min后装入内壁涂覆硬脂酸锌的不锈钢模具中,单向加压400MPa制得生坯,之后将该生坯装入氧化铝坩埚,并置于管式真空烧结炉中,待炉内真空抽至5Pa后,以10℃/min的速率加热至810℃,保温4h后,再以15℃/分钟的速率加热至980℃,保温4h后随炉冷却至室温,将烧结体从炉内取出,置于超声波水浴中清洗20min后烘干,制得多孔合金靶材。
采用上述合金靶材,使用磁控溅射方法,在基体上形成薄膜状的钛镍钴记忆合金膜:抽真空至10-4Pa以上,充入氮气,然后再抽真空至10-4Pa,调整工作电压为500V,溅射占空比68%,开始进行溅射沉积,控制厚度为250μm得到薄膜状的钛镍钴记忆合金膜。
启动轧机系统,设定上下轧辊的速比为1.5 ,设定每次轧制形变量为3%;设定低速辊的速度为0.1m/s,开始钛镍钴记忆合金膜的轧制过程;一次轧制过后,重复进行轧制5次,轧制过程中,保持环境温度为-20摄氏度;在200摄氏度进行低温热处理2h,得到产品。
Claims (1)
1.一种钛镍钴记忆合金膜的制备方法,该方法包括如下步骤:
(1)配料
按以下重量份配制混合粉
钛粉 25-28份;
镍粉 42-45份;
钴粉 12-16份
钇粉 0.5-1.5份
将混合粉置于不锈钢球磨罐中,注满无水乙醇后密封,在行星式球磨机上球磨3-4h,球磨中采用的球料比为10∶1,球磨机的转速为400-500r/min,之后,将球磨好的混合粉取出并置于滤纸上静置6-8分钟,得到原料粉;
(2)制备记忆合金靶材
上述原料粉与去结晶水KCl颗粒均匀混合,去结晶水KCl颗粒的用量为其占混合粉与去结晶水KCl颗粒混合物的体积百分比的65-75%,将该混合物在混料机中混合45-50min后装入内壁涂覆硬脂酸锌的不锈钢模具中,单向加压380-400MPa制得生坯,之后将该生坯装入氧化铝坩埚,并置于管式真空烧结炉中,待炉内真空抽至1-5Pa后,以5-10℃/min的速率加热至800-810℃,保温3-4h后,再以10-15℃/分钟的速率加热至960-980℃,保温3-4h后随炉冷却至室温,将烧结体从炉内取出,置于超声波水浴中清洗15-20min后烘干,制得多孔合金靶材;
(3)采用上述合金靶材,使用磁控溅射方法,在基体上形成薄膜状的钛镍钴记忆合金膜:
抽真空至10-4Pa以上,充入氮气,然后再抽真空至10-4Pa,调整工作电压为500V,溅射占空比65-68%,开始进行溅射沉积,控制厚度为150-250μm得到薄膜状的钛镍钴记忆合金膜;
启动轧机系统,设定上下轧辊的速比为1.2-1.5 ,设定每次轧制形变量为2-3%;设定低速辊的速度为0.05-0.1m/s,开始钛镍钴记忆合金膜的轧制过程;一次轧制过后,重复进行轧制3-5次,轧制过程中,保持环境温度为-30至-20摄氏度;在150-200摄氏度进行低温热处理1-2h,得到产品。
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Cited By (2)
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---|---|---|---|---|
CN114850219A (zh) * | 2022-04-11 | 2022-08-05 | 西安诺博尔稀贵金属材料股份有限公司 | 一种高精度细径薄壁镍钛合金管材的制备方法 |
US20220372611A1 (en) * | 2021-05-24 | 2022-11-24 | Vactronix Scientific, Llc | Pvd deposited ternary and quaternary niti alloys and methods of making same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102341527A (zh) * | 2009-02-02 | 2012-02-01 | 梯尔镀层有限公司 | 多层涂层 |
CN106591627A (zh) * | 2016-12-31 | 2017-04-26 | 镇江市丹徒区硕源材料科技有限公司 | 一种高强度的形状记忆合金及其制备方法和应用 |
CN107008905A (zh) * | 2017-02-25 | 2017-08-04 | 河北工业大学 | TiNiCu形状记忆合金基阻尼复合材料的制备方法 |
-
2018
- 2018-04-02 CN CN201810285188.7A patent/CN108611611A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102341527A (zh) * | 2009-02-02 | 2012-02-01 | 梯尔镀层有限公司 | 多层涂层 |
CN106591627A (zh) * | 2016-12-31 | 2017-04-26 | 镇江市丹徒区硕源材料科技有限公司 | 一种高强度的形状记忆合金及其制备方法和应用 |
CN107008905A (zh) * | 2017-02-25 | 2017-08-04 | 河北工业大学 | TiNiCu形状记忆合金基阻尼复合材料的制备方法 |
Non-Patent Citations (1)
Title |
---|
M.A. ARRANZ ET AL.: "Shape memory effect in sputtered Ti–Ni thin films", 《JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20220372611A1 (en) * | 2021-05-24 | 2022-11-24 | Vactronix Scientific, Llc | Pvd deposited ternary and quaternary niti alloys and methods of making same |
CN114850219A (zh) * | 2022-04-11 | 2022-08-05 | 西安诺博尔稀贵金属材料股份有限公司 | 一种高精度细径薄壁镍钛合金管材的制备方法 |
CN114850219B (zh) * | 2022-04-11 | 2023-10-27 | 西安诺博尔稀贵金属材料股份有限公司 | 一种高精度细径薄壁镍钛合金管材的制备方法 |
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