CN115305384A - 一种具有形状记忆功能的抑菌合金的制备方法 - Google Patents
一种具有形状记忆功能的抑菌合金的制备方法 Download PDFInfo
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Abstract
本发明公开一种具有形状记忆功能的抑菌合金的制备方法，属于医用生物领域。本发明所述方法以金属钛粉、铌粉和银粉为原料，其中钛粉、铌粉和银粉按质量比71%～39%:26%～45%:3%～16%进行配比，称取，球磨，烘干后得到混合粉末；将混合粉末装入石墨模具中后，采用放电等离子烧结制备出具有抑菌性能的TiNbAg合金。本发明所制备出的TiNbAg合金不仅具有独特的形状记忆功能和优异的超弹性，而且植入后能有效释放出具有抑菌性能的Ag2+，该抑菌合金可以用于硬组织替换、牙科种植体以及脊柱矫正器等方面。
Description
技术领域
本发明涉及一种具有形状记忆功能的抑菌合金的制备方法，属于粉末冶金技术领域。
背景技术
据报道，在美国，每年因植入医疗器械而导致的病人多达100万例，感染者需要长期服用抗菌类药物，严重者需要二次手术，清除病灶，取出植入的医疗器械，给患者带来了极大的精神和经济压力。随着越来越多的耐药细菌的出现，对细菌感染的治疗愈发困难。20世纪90年代，日本钢铁企业研究开发出具有抗菌性能的含Ag不锈钢R304-AB，R430-AB，R430LN-AB等，对大肠杆菌的杀菌率均在99%以上，具有优异的抗菌性能。
目前医用不锈钢往往含有Ni，Co，Cr等毒性元素，并且其强度高。而钛合金以其较高的比强度、较低的弹性模量、优良的耐蚀性和生物相容性成为医用不锈钢之后理想的生物医用材料。然而Ti-6Al-4V及Ti-6Al-7Nb等α+β型钛合金不仅含有有毒元素Al和V等，而且易产生应力屏蔽，使植入物周围出现骨吸收，最终导致植入物松动或者断裂。无毒稳定元素如铌和钽等不仅具有良好的组织相容性，还能降低β相转变温度，增加两相区范围，提高钛合金的可加工性，而且可以提高其耐腐烛性。随着铌含量的提高，钛铌合金还有具有优异的超弹性，但不具备抑菌能力。
为了使钛合金具有抑菌能力，目前大多采用表面改性的方法，比如离子溅射、离子注入、喷涂或者激光熔敷等方法在钛合金表面制备一层含有抑菌元素的涂层。植入早期，涂层中的抑菌元素会快速释放，导致局部离子浓度过高，对细胞有毒害作用；植入中后期，在涂层失效后，钛合金易丧失抑菌能力。申请号为CN 107739886 A公布了一种用于骨科植入物的钛银合金及其制备方法，该方法制备的钛-银合金虽具有一定的抗菌性，但从扫描电镜照片可以看出，钛与银并未形成有效的钛银固溶体，植入易导致银的快速释放，难以具有长效的抗菌能力。
发明内容
本发明要解决的技术问题是：如何使Ti-Nb合金在具备超弹性的条件下，兼备长效的抗菌性能，为了达到上述目的，本发明采用一种具有形状记忆功能的抑菌合金，主要包括下列几个步骤：
（1）选用金属钛粉、铌粉和银粉作为原料，其中钛粉的质量百分比为：71%～39%；铌粉的质量百分比为：26%～45%；银粉的质量百分比：3%～16%，三种原料质量百分比之和为100%。
（2）将步骤（1）称取的粉末放入不锈钢球磨罐后，放入不锈钢磨球和无水乙醇，并将其抽真空，上述过程均在真空手套箱中完成；球磨后，进行烘干。
（3）在自制的石墨模具放入步骤（2）得到的混合粉末，用手预压后，置于放电等离子烧结炉中，烧结炉内部真空度抽至10-3~10-4Pa后，以100～150℃/min的升温速率升温至600～800℃，保温2～3min，然后以25～50℃/min的升温速率升温至950~1000℃，保温3~8min，过程中持续施加40～60MPa的轴向压力。烧结完成后，随炉冷却至室温后，获得TiNbAg合金。
优选的，本发明所述步骤（1）中钛粉的纯度≥99.5%，粒径为25μm；铌粉的纯度≥99.5%，粒径为12.5μm；银粉的纯度≥99.99%，粒径为45μm。
本发明所述步骤（2）中球磨过程的条件为：将原料放入不锈钢球磨罐中，放入不锈钢磨球和无水乙醇，并将其抽真空，其中，不锈钢球磨罐中的真空度为6～8Pa，不锈钢球磨罐在行星式球磨机上固定，以150～200r/min的转速球磨1h后；待罐体温度下降至室温后，将罐体再次抽真空至6～8Pa，再以300～400r/min的转速球磨8～10h。
本发明所述不锈钢磨球和原料的球料比为4:1～3:1，其中磨球质量比为大球：中球：小球=(2~3):(8~10):(15~20)。
本发明所述步骤（1）中烘干过程是在真空干燥箱中进行，干燥箱的真空度为6～8Pa，烘干温度为40～50℃。
本发明所述自制的石墨模具的结构为：圆柱状外体：Φ20.5mm×H25.5mm；圆形内腔：Φ15.5mm；堵头：Φ15.5mm×10mm，与石墨模具圆形内腔吻合。
本发明的有益效果：
（1）本发明所述Ti-Nb合金系医用β钛合金，具有较好的弹性和较大的弹性形变范围；采用机械球磨将钛、铌与银粉均匀混合，放电等离子烧结过程中银粉相加速向基体内扩散并均匀固溶在基体中，有效避免了银元素偏析，可以在不改变其超弹性的条件下，有效提高合金的抑菌能力。
（2）钛铌银合金不仅具有较好的弹性和较大的弹性形变范围，还具有较高的抑菌能力，可以用于硬组织替换、牙科种植体以及脊柱矫正器等方面。
附图说明
图1 本发明实施例1制备的具有形状记忆功能的抑菌合金的X射线衍射图谱。
图2 本发明实施例1制备的具有形状记忆功能的抑菌合金的表面形貌。
图3 本发明实施例1制备的具有形状记忆功能的抑菌合金的力学性能。
图4 本发明实施例1制备的具有形状记忆功能的抑菌合金的抗菌能力。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明，但本发明的保护范围并不限于所述内容。
实施例1
（1）选用金属钛粉、铌粉和银粉作为原料，其中钛粉的质量百分比为：60%；铌粉的质量百分比为：30%；银粉的质量百分比：10%，钛粉的纯度为99.5%，粒径为25μm；铌粉的纯度为99.5%，粒径为12.5μm；银粉的纯度为99.99%，粒径为45μm。
（2）将步骤（1）称取的粉末放入不锈钢球磨罐后，按照不锈钢磨球和原料的球料比为3:1放入不锈钢磨球，其中磨球质量比为大球:中球:小球=2:8:15，并加入适量无水乙醇，并将其抽真空至8Pa，上述过程均在真空手套箱中完成；不锈钢球磨罐在行星式球磨机上固定，以200r/min的转速球磨1h后；待罐体温度下降至室温后，将罐体再次抽真空至8Pa，再以400r/min的转速球磨10h后，进行烘干，其中干燥箱的真空度为8Pa，烘干温度为45℃。
（3）在自制的石墨模具（圆柱状外体：Φ20.5mm×H25.5mm；圆形内腔：Φ15.5mm；堵头：Φ15.5mm×10mm）放入步骤（2）得到的混合粉末，用手预压后，置于放电等离子烧结炉中，烧结炉内部真空度抽至10-4Pa后，以100℃/min的升温速率升温至800℃，保温3min，然后以25℃/min的升温速率升温至950℃，保温8min，过程中持续施加60MPa的轴向压力；烧结完成后，随炉冷却至室温后，获得TiNbAg合金。
图1为本实施例制备的具有形状记忆功能的抑菌合金的X射线衍射图谱，从图中可以看出，经过烧结后，铌无限固溶进钛中，而且钛与银发生反应形成钛银化合物，植入后可以有效避免银的快速释放，对细胞产生毒性。
图2为本实施例制备的具有形状记忆功能的抑菌合金的表面形貌，从图中可以看出，合金以针状β相为主，银的加入没有促进β相向α相转变，未改变合金的基础性能；为发现银在晶界处富集，说明在烧结过程中，银通过固溶进入钛的晶格中，形成大量的钛银化合物，避免银单质在植入后快速释放。
图3(a)所示为本实施例2制备的具有形状记忆功能的抑菌合金的弯曲变形量对形状回复率的影响；从图中可以发现，TiNbAg合金形状回复率随弯曲变形量的增加而逐渐降低；当合金弯曲变形量为2%时，其形状回复率为88.7%；当合金弯曲变形量提升到4%后，合金回复率急剧下降至65.2%以下。
图3(b)所示为TiNbAg合金弯曲变形次数对形状回复率的影响；道次弯曲变形量为3.5%和5.5%。从图中可以发现，道次弯曲变形量为3.5%时，合金前5次变形使得形状回复率呈现下降趋势；从第五次变形开始，随着弯曲变形次数的增加，变形回复率变化较小，而且超过10次变形后，合金依然呈现50%以上的形状回复率。当道次弯曲变形量为5.5%，由于较大的塑性变形，合金前5次变形使得形状回复率快速下降；从第5次至第8次形状回复率变化较小；在一定的形变范围内，TiNbAg合金具有一定的超弹性。
图4为本实施例制备的具有形状记忆功能的抑菌合金对大肠杆菌的抑菌能力，从图中可以看出，TiNbAg合金对大肠杆菌具有优异的抑菌能力。
实施例2
（1）选用金属钛粉、铌粉和银粉作为原料，其中钛粉的质量百分比为：71%；铌粉的质量百分比为：26%；银粉的质量百分比：3%；其中钛粉的纯度为99.5%，粒径为25μm；铌粉的纯度为99.5%，粒径为12.5μm；银粉的纯度为99.99%，粒径为45μm。
（2）将步骤（1）称取的粉末放入不锈钢球磨罐后，按照球料比为4:1放入不锈钢磨球，其中磨球质量比为大球：中球：小球=2:8:15，并加入适量无水乙醇，并将其抽真空至6Pa，上述过程均在真空手套箱中完成；将球磨罐在行星式球磨机上固定，以150r/min的转速球磨1h后；待罐体温度下降至室温后，将罐体再次抽真空至6Pa，再以300r/min的转速球磨0h后，进行烘干，其中干燥箱的真空度为6Pa，烘干温度为40℃。
（3）在自制的石墨模具（圆柱状外体：Φ20.5mm×H25.5mm；圆形内腔：Φ15.5mm；堵头：Φ15.5mm×10mm）放入步骤（2）得到的混合粉末，用手预压后，置于放电等离子烧结炉中，烧结炉内部真空度抽至10-3Pa后，以100℃/min的升温速率升温至600℃，保温2min，然后以25℃/min的升温速率升温至950℃，保温3min，过程中持续施加40MPa的轴向压力；烧结完成后，随炉冷却至室温后，获得TiNbAg合金。
本实施例制备得到的TiNbAg合金表面形貌和微观结构与实施例1相似，性能如表1所示。
表1抑菌合金的形状回复率及对大肠杆菌的抑菌能力
由表1可以看出， TiNbAg合金具有一定的超弹性，对大肠杆菌具有优异的抑菌能力。
实施例3
（1）选用金属钛粉、铌粉和银粉作为原料，其中钛粉的质量百分比为：50%；铌粉的质量百分比为：40%；银粉的质量百分比：10%，钛粉的纯度为99.5%，粒径为25μm；铌粉的纯度为99.5%，粒径为12.5μm；银粉的纯度为99.99%，粒径为45μm。
（2）将步骤（1）称取的粉末放入不锈钢球磨罐后，按照不锈钢磨球和原料的球料比为3:1放入不锈钢磨球，其中磨球质量比为大球：中球：小球=2:8:15，并加入适量无水乙醇，并将其抽真空至8Pa，上述过程均在真空手套箱中完成；不锈钢球磨罐在行星式球磨机上固定，以200r/min的转速球磨1h后；待罐体温度下降至室温后，将罐体再次抽真空至8Pa，再以400r/min的转速球磨10h后，进行烘干，其中干燥箱的真空度为8Pa，烘干温度为45℃。
（3）在自制的石墨模具（圆柱状外体：Φ20.5mm×H25.5mm；圆形内腔：Φ15.5mm；堵头：Φ15.5mm×10mm）放入步骤（2）得到的混合粉末，用手预压后，置于放电等离子烧结炉中，烧结炉内部真空度抽至10-4Pa后，以100℃/min的升温速率升温至800℃，保温3min，然后以25℃/min的升温速率升温至975℃，保温8min，过程中持续施加60MPa的轴向压力。烧结完成后，随炉冷却至室温后，获得TiNbAg合金。
本实施例制备得到的TiNbAg合金表面形貌和微观结构与实施例1相似，性能如表2所示。
表2抑菌合金的形状回复率及对大肠杆菌的抑菌能力
从表中可以看出，TiNbAg合金具有一定的超弹性，对大肠杆菌具有优异的抑菌能力。
实施例4
（1）选用金属钛粉、铌粉和银粉作为原料，其中钛粉的质量百分比为：40%；铌粉的质量百分比为：45%；银粉的质量百分比：15%，钛粉的纯度为99.5%，粒径为25μm；铌粉的纯度为99.5%，粒径为12.5μm；银粉的纯度为99.99%，粒径为45μm。
（2）将步骤（1）称取的粉末放入不锈钢球磨罐后，按照不锈钢磨球和原料的球料比为3:1放入不锈钢磨球，其中磨球质量比为大球：中球：小球=3:10:20，并加入适量无水乙醇，并将其抽真空至8Pa，上述过程均在真空手套箱中完成；不锈钢球磨罐在行星式球磨机上固定，以200r/min的转速球磨1h后；待罐体温度下降至室温后，将罐体再次抽真空至8Pa，再以400r/min的转速球磨10h后，进行烘干，其中干燥箱的真空度为8Pa，烘干温度为50℃。
（3）在自制的石墨模具（圆柱状外体：Φ20.5mm×H25.5mm；圆形内腔：Φ15.5mm；堵头：Φ15.5mm×10mm）放入步骤（2）得到的混合粉末，用手预压后，置于放电等离子烧结炉中，烧结炉内部真空度抽至10-4Pa后，以150℃/min的升温速率升温至800℃，保温3min，然后以50℃/min的升温速率升温至1000℃，保温8min，过程中持续施加50MPa的轴向压力；烧结完成后，随炉冷却至室温后，获得TiNbAg合金。
本实施例制备得到的TiNbAg合金表面形貌和微观结构与实施例1相似，性能如表3所示。
表3抑菌合金的形状回复率及对大肠杆菌的抑菌能力
从表中可以看出，TiNbAg合金具有一定的超弹性，对大肠杆菌具有优异的抑菌能力。
Claims (6)
1.一种具有形状记忆功能的抑菌合金的制备方法，其特征在于，包括以下步骤:
（1）选用金属钛粉、铌粉和银粉作为原料，其中钛粉的质量百分比为：39%～71%；铌粉的质量百分比为：26%～45%；银粉的质量百分比：3%～16%；
（2）将步骤（1）称取的粉末进行球磨混匀，烘干后备用；
（3）在自制的石墨模具中放入步骤（2）得到的混合粉末，用手预压后，置于放电等离子烧结炉中，烧结炉内部真空度抽至10-3~10-4Pa后，以100～150℃/min的升温速率升温至600～800℃，保温2～3min，然后以25～50℃/min的升温速率升温至950~1000℃，保温3~8min，过程中持续施加40～60MPa的轴向压力；烧结完成后，随炉冷却至室温后，获得TiNbAg合金。
2.根据权利要求1所述具有形状记忆功能的抑菌合金的制备方法，其特征在于：步骤（1）中钛粉的纯度≥99.5%，粒径为25μm；铌粉的纯度≥99.5%，粒径为12.5μm；银粉的纯度≥99.99%，粒径为45μm。
3.据权利要求1所述具有形状记忆功能的抑菌合金的制备方法，其特征在于：步骤（2）中球磨的具体过程为：将原料放入不锈钢球磨罐中，放入不锈钢磨球和无水乙醇，并将其抽真空，其中，不锈钢球磨罐中的真空度为6～8Pa，不锈钢球磨罐在行星式球磨机上固定，以150～200r/min的转速球磨1h后；待罐体温度下降至室温后，将罐体再次抽真空至6～8Pa，再以300～400r/min的转速球磨8～10h。
4.根据权利要求3所述具有形状记忆功能的抑菌合金的制备方法，其特征在于：所述不锈钢磨球和原料的球料比为4:1～3:1，其中磨球质量比为大球:中球:小球=(2~3):(8~10):(15~20)。
5.根据权利要求1所述的一种具有形状记忆功能的抑菌功能合金的制备方法，其特征在于：所述步骤（2）中烘干过程是在真空干燥箱中进行，干燥箱的真空度为6～8Pa，烘干温度为40～50℃。
6.根据权利要求1所述的一种具有形状记忆功能的抑菌功能合金的制备方法，其特征在于：所述自制的石墨模具的结构为，圆柱状外体：Φ20.5mm×H25.5mm；圆形内腔：Φ15.5mm；堵头：Φ15.5mm×10mm，与石墨模具圆形内腔吻合。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050254990A1 (en) * | 2004-04-02 | 2005-11-17 | Furukawa Techno Material Co., Ltd. | Super-elastic titanium alloy for living body |
| CN106834774A (zh) * | 2017-02-17 | 2017-06-13 | 南方科技大学 | 一种新型牙科用铌银合金及其制备方法 |
| US20170340777A1 (en) * | 2014-11-14 | 2017-11-30 | The Texas A&M University System | Shape Memory Alloy Orthopedic Implant |
| CN109055814A (zh) * | 2018-07-18 | 2018-12-21 | 昆明理工大学 | 一种医用抗菌钛合金的制备方法 |
| CN113166854A (zh) * | 2020-06-08 | 2021-07-23 | 南京江东工贸有限公司 | 一种金属材料及其制备方法与应用 |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050254990A1 (en) * | 2004-04-02 | 2005-11-17 | Furukawa Techno Material Co., Ltd. | Super-elastic titanium alloy for living body |
| US20170340777A1 (en) * | 2014-11-14 | 2017-11-30 | The Texas A&M University System | Shape Memory Alloy Orthopedic Implant |
| CN106834774A (zh) * | 2017-02-17 | 2017-06-13 | 南方科技大学 | 一种新型牙科用铌银合金及其制备方法 |
| CN109055814A (zh) * | 2018-07-18 | 2018-12-21 | 昆明理工大学 | 一种医用抗菌钛合金的制备方法 |
| CN113166854A (zh) * | 2020-06-08 | 2021-07-23 | 南京江东工贸有限公司 | 一种金属材料及其制备方法与应用 |
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