CN113230462A - 医用器件 - Google Patents
医用器件 Download PDFInfo
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- CN113230462A CN113230462A CN202110376269.XA CN202110376269A CN113230462A CN 113230462 A CN113230462 A CN 113230462A CN 202110376269 A CN202110376269 A CN 202110376269A CN 113230462 A CN113230462 A CN 113230462A
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Images
Classifications
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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Abstract
本发明涉及一种医用器件。该医用器件包括基体及包覆于所述基体的第一涂层，所述基体含有含量≥5wt％的金属元素X，所述第一涂层为所述金属元素X的单质金属层、所述金属元素X的合金层和所述金属元素X的金属陶瓷层中的至少一种，所述第一涂层中不含有镍或钴。该医用器件具有较好的使用安全性、可靠性及生物相容性，使得产品能够满足较大塑性变形的使用需求，在使用过程中具有良好的可靠性；特别是能满足在使用过程中存在较大塑性变形的医用植入器件等产品的需求。
Description
技术领域
本发明涉及医疗技术领域，特别是涉及一种医用器件。
背景技术
生物医用金属材料以其优良的力学性能、易加工性和可靠性在临床医学中获得了广泛的应用，其重要性与生物医用高分子材料并驾齐驱，在整个生物医用材料应用中占据非常重要的比例。医用金属材料的开发，重点在于不断提高使用的安全性、可靠性及生物相容性。
医用金属材料经过多年的临床应用，仍然存在许多问题，主要问题还是生物相容性。生物相容性即不引起生物体组织、血液等的不良反应。因金属材料中均含有较多的合金化元素，植入人体后，由于腐蚀、磨损等导致金属离子溶出，进而引发细胞及组织液的一些生物反应，如组织反应、血液反应和全身反应，表现为水肿、血栓栓塞、感染及肿瘤等现象。众所周知，镍离子除了对人体有很大毒性和过敏反应外，可能诱导有机体突变，甚至发生癌变。近几年研究发现，钴离子的释放也会引起细胞与组织的坏死、皮肤过敏反应等。目前市场临床应用中最广泛的医用金属承力植入材料，如不锈钢、钴合金、镍钛形状记忆合金等均含有镍合金元素；同时，占市场主导地位的心血管支架材料除了含有镍合金元素外，基体释放的钴离子也加剧了其生物安全性问题。
综上，在发展新型医用金属材料时必须严格控制其中的金属元素X，最好是少用或不用对人体产生毒性和过敏性较大的合金化元素。一般采用的提高生物安全性的技术方法包括合金化、提高耐蚀性、提高光洁度、表面涂层等。能从根本上解决问题的是合金化和表面涂层方法。因合金化方法需从成分设计考虑，经历合金熔炼、热处理及后加工等多道工序，周期长，投入大，风险高。植入物材料表面涂层技术是可以解决镍、钴离子溶出的一种有效方法。
发明内容
基于此，有必要提供一种具有较好的使用安全性、可靠性及生物相容性的医用器件。
一种医用器件，包括基体及包覆于所述基体的第一涂层，所述基体含有含量≥5wt％的金属元素X，所述第一涂层为所述金属元素X的单质金属层、所述金属元素X的合金层和所述金属元素X的金属陶瓷层中的至少一种，所述第一涂层中不含有镍或钴。
在其中一些实施例中，所述第一涂层为所述合金层和所述金属陶瓷层中的至少一种与所述单质金属层形成的叠层；
在所述第一涂层中，所述单质金属层为靠近所述基体的内层，所述合金层和所述金属陶瓷层中的至少一种为远离所述基体的外层。
在其中一些实施例中，当所述第一涂层为所述金属元素X的单质金属层时，所述单质金属层为经过钝化处理的金属涂层；或者
当所述第一涂层为所述单质金属层和所述金属陶瓷层形成的叠层时，所述单质金属层位于所述基体与所述金属陶瓷层之间；或者
当所述第一涂层为所述单质金属层和所述合金层形成的叠层时，所述单质金属层位于所述基体与所述合金层之间。
在其中一些实施例中，所述第一涂层与所述基体的自腐蚀电位差为100mV以内。
在其中一些实施例中，所述金属陶瓷层的材质为所述金属元素X的氧化物、碳化物、氮化物、硅化物和硼化物中的至少一种。
在其中一些实施例中，所述金属元素X为Cr、W、Mo及贵金属元素中的至少一种。
在其中一些实施例中，所述金属元素X在所述基体中的含量为7wt％～60wt％。
在其中一些实施例中，所述基体为能够发生塑性形变的基体。
在其中一些实施例中，所述基体的材质选自不锈钢、钴基合金、钛合金、贵金属合金或镍钛形状记忆合金。
在其中一些实施例中，所述金属元素X为Cr、W、Mo或Pt中的一种。
在其中一些实施例中，所述第一涂层含有所述金属陶瓷层，所述医用器件还包括设于所述金属陶瓷层上的第二涂层；
其中，所述金属陶瓷层为所述金属元素X的碳化物，所述第二涂层为碳层；或者
所述金属陶瓷层为所述金属元素X的硅化物，所述第二涂层为硅层。
在其中一些实施例中，所述医用器件的任意相邻两层不同材质的层结构之间的自腐蚀电位差为100mV以内。
在其中一些实施例中，所述单质金属层、所述合金层和所述金属陶瓷层的厚度为10nm～500nm。
在其中一些实施例中，所述金属元素X不为钛元素。
在其中一些实施例中，所述医用器件还包括设于所述第一涂层表面的药物活性层。
在其中一些实施例中，所述第一涂层形成有载药凹槽，所述药物活性层设于所述载药凹槽内。
本发明上述医用器件通过在基体上形成特定材质的第一涂层，且第一涂层含有在基体中含量≥5wt％的金属元素X，该金属元素X为除镍或钴之外的元素。如此基体上采用与基体具有相同金属元素X的第一涂层，一方面可避免涂层和基体的延展性能等性能差异大导致出现裂痕的问题，能够增强第一涂层与基体之间具有优异的结合力和延展性，使得产品能够满足较大塑性变形的使用需求，在使用过程中具有良好的可靠性；特别是能满足在使用过程中存在较大塑性变形的医用植入器件等产品的需求。另一方面包覆于基体的第一涂层不含有镍或钴，可以起到隔离或明显降低基体中含有的镍、钴等致敏致癌合金元素的溶出的效果，具有更好的使用安全性和生物相容性。
附图说明
图1为一实施方式的血管支架的结构示意图；
图2为对比例2制得的支架产品扩张后的扫描电镜图；
图3为对比例4制得的支架产品扩张后的扫描电镜图；
图4为对比例5制得的支架产品扩张后的扫描电镜图；
图5为对比例6制得的支架产品的扫描电镜图；
图6为对比例7制得的支架产品扩张至名义尺寸的扫描电镜图；
图7为对比例8制得的支架产品扩张至极限后扩尺寸的扫描电镜图；
图8为对比例9制得的支架产品模拟穿越后的扫描电镜图；
图9为实施例4制得的支架产品扩张至名义尺寸的扫描电镜图；
图10为实施例8制得的支架产品扩张至极限后扩尺寸的扫描电镜图。
具体实施方式
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。附图中给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
需要说明的是，当元件被称为“设于”另一个元件上，它可以直接在另一个元件上或者也可以存在居中的元件。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
在本发明的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
本发明一实施方式提供了一种医用器件，包括基体及包覆于基体的第一涂层。
基体含有含量≥5wt％的金属元素X。第一涂层为该金属元素X的单质金属层、该金属元素X的合金层和该金属元素X的金属陶瓷层中的至少一种。且第一涂层中不含有镍或钴，换言之，金属元素X不为镍或钴，且合金层中也不含有镍或钴。
本发明上述医用器件通过在基体上形成特定材质的第一涂层，且第一涂层含有在基体中含量≥5wt％的金属元素X，该金属元素X为除镍或钴之外的元素。如此基体上采用与基体具有相同金属元素X的第一涂层，一方面可避免涂层和基体的延展性能等性能差异大导致出现裂痕的问题，能够增强第一涂层与基体之间具有优异的结合力和延展性，使得产品能够满足较大塑性变形的使用需求，在使用过程中具有良好的可靠性；特别是能满足在使用过程中存在较大塑性变形的医用植入器件等产品的需求。另一方面包覆于基体的第一涂层不含有镍或钴，可以起到隔离或明显降低基体中含有的镍、钴等致敏致癌合金元素的溶出的效果，具有更好的使用安全性和生物相容性。
同时，第一涂层还提高了基体材料的耐腐蚀性能，进而能够在一定程度上延长医用器件的使用寿命，给临床应用带来极大便利。
在其中一些实施例中，医用器件为医用植入器件或医用介入器件。可理解，本发明上述医用器件特别适用于但不仅仅适用于在使用过程中存在较大塑性变形的医用植入器件，也可适用于医用介入器件等产品中。换言之，基体可为能够发生塑性形变的基体，但不限于能够发生塑性形变的基体。
值得说明的是，医用植入器件包括但不限于血管支架、冠脉支架、心脏瓣膜支架、心脏起搏器、静脉滤器和金属骨钉、金属骨板及人工关节等。医用介入器件包括但不限于血管内导管、导丝和管鞘及栓塞器材等。
以医用植入器件中的心血管支架为例，一般地，心血管支架在植入扩张过程中至少有30％的塑性变形量，在此过程中心血管支架上结合力和延展性不佳的涂层易发生大面积开裂或与基体剥离脱落。若涂层脱落，会导致血栓死亡等严重后果。要能够达到心血管支架压握植入后，涂层随基体发生大塑性变形后还能起到隔离或明显降低镍、钴等致敏致癌合金元素的溶出的效果，这就要求涂层与基体之间具有良好的延展性和结合力。经试验验证，本发明医用器件中涂层与基体之间满足了良好结合力要求，并实现了该目标。
本发明上述医用器件通过表面涂层的方法，有效减少镍、钴等致敏致癌合金元素的溶出，为医用器件特别是医用植入器件提供了一种最经济且有效地改善生物安全性的方法。
如上所述，第一涂层为该金属元素X的单质金属层、该金属元素X的合金层和该金属元素X的金属陶瓷层中的至少一种。故而第一涂层与基体之间可形成金属键、离子键、共价键或分子键，故而使得第一涂层与基体之间具有较好的结合力。例如单质金属层包覆于基体上时，其与基体之间可形成金属键。
在其中一些实施例中，金属元素X为铬(Cr)、钨(W)、钼(Mo)及贵金属元素中的至少一种。其中，贵金属元素包括金(Au)、银(Ag)、汞(Hg)、铂(Pt)、钯(Pd)、铱(lr)、铑(Rh)、钌(Ru)、锇(Os)。
进一步地，金属元素X不为钛元素。
可理解，在金属元素X不为镍或钴且在基体中含量≥5wt％的基础上，金属元素X在基体中的含量越高，理论上涂层与基体的结合力更优。例如，在其中一些实施例中，金属元素X在基体中的含量≥7wt％。在一些示例中，金属元素X在基体中的含量≥9wt％。
进一步考虑医用器件的基体的材质选择，进一步地，在一些示例中，金属元素X在基体中的含量为7wt％～60wt％，进一步地为9wt％～60wt％；更进一步为9wt％～40wt％，更进一步地，为9wt％～35wt％。
可理解，在一些实施例中，金属元素X的种类为至少两个。
在其中一些实施例中，第一涂层为该金属元素X的单质金属层。如此可对单质金属层进行钝化处理，得到经钝化处理的金属涂层，钝化处理可以提高纯金属功能涂层表面钝化膜的致密性，进而进一步提高单质金属层的表面耐蚀性。
可理解，可在自然条件下使单质金属层发生钝化，也可以通过硝酸溶液进行钝化处理。若单质金属层自然钝化的氧化层比较薄，为进一步提高涂层的耐蚀性，还可以通过硝酸溶液进行钝化处理：浸入40wt-60wt％硝酸溶液中进行钝化处理。进一步地，钝化条件为：钝化温度20℃-30℃，钝化时间30min-60min。
可理解，上述合金层可为包含金属元素X在内的至少两种金属形成的金属合金层。在一些示例中，合金层的金属元素选自Cr、W、Mo及贵金属元素中的至少两种。
在其中一些实施例中，第一涂层为金属元素X的合金层。
可理解，金属陶瓷层包括但不限于金属氧化物、金属碳化物、金属氮化物、金属硅化物和金属硼化物。在其中一些实施例中，上述金属陶瓷层的材质为上述金属元素X的氧化物、碳化物、氮化物、硅化物和硼化物中的至少一种。进一步地，上述金属陶瓷层的材质为上述金属元素X的氧化物、碳化物、氮化物和硅化物中的至少一种。
在其中一些实施例中，第一涂层为金属元素X的金属陶瓷层。
在其中一些实施例中，第一涂层为合金层和金属陶瓷层中的至少一种与单质金属层形成的叠层(或称为复合涂层)；在第一涂层中，单质金属层为靠近基体的内层，合金层和金属陶瓷层中的至少一种为远离基体的外层。由于单质金属层与基体之间具有更好的结合力，故而可提高第一涂层与基体的结合力。而利用延展性好的单质金属层作为内层或过渡层，可以显著提高复合涂层的延展性，在医用器件压握及扩张变形过程中，可以随基体承受较大的塑性变形，而不发生开裂失效。
进一步地，单质金属层与基体直接接触。如此第一涂层与基体之间通过优选的金属见进行结合，具有更好的结合力。
在一些示例中，第一涂层为单质金属层和金属陶瓷层形成的叠层，单质金属层位于基体与金属陶瓷层之间。
由于金属陶瓷层的强度和硬度高但延展性较差，故而金属陶瓷层设置在外层，在内层单质金属层保证良好的延展性的基础上，还可使第一涂层具备较高的强度和硬度，可以满足骨科植入器件的高硬度高耐磨要求。
在另一些示例中，第一涂层为单质金属层和合金层形成的叠层，单质金属层位于基体与合金层之间。如此单质金属层与基体之间，单质金属层与合金层之间均形成牢固的金属键，结合强度高，在保证优异结合力的同时，还能保证功能涂层具有良好的塑性变形能力。金属键没有方向性，受外力作用发生原子位置的相对移动时，结合键不会遭到破坏。
在另一些示例中，第一涂层也可为单质金属层、合金层及金属陶瓷层三者依次形成的叠层；在第一涂层中，单质金属层为内层，合金层为中间层，金属陶瓷层为外层。
可理解，在其他一些实施例中，第一涂层也可为合金层与金属陶瓷层形成的叠层，合金层位于基体与金属陶瓷层之间。
在其中一些实施例中，基体的材质选自不锈钢、钴基合金、钛合金、贵金属合金或镍钛形状记忆合金。可理解，基体可为含镍或钴的材质。进一步地，贵金属合金包含铂铬合金。钴基合金包括钴铬合金，例如L605，此时金属元素X可为Cr或W；还包括钴铬钼合金，例如MP35N和ASTM F75，此时金属元素X为Cr或Mo。
进一步地，基体的材质选自不锈钢、钴基合金、铂铬合金时，金属元素X可为Cr。可理解，可进一步根据基材的材质具体选择，选择其他种类元素作为金属元素X。
进一步地，基体的材质为L605、MP35N、316L或PtCr合金，本发明实施例或对比例所用各基材的元素组成如下表1所示。
表1
进一步地，基体的材质为L605合金，金属元素X为Cr或W。
进一步地，基体的材质为MP35N合金或钴铬钼合金ASTM F75，金属元素X为Cr或Mo；
进一步地，基体的材质为316L合金，金属元素X为Cr；
进一步地，基体的材质为PtCr合金，金属元素X为Cr或Pt。
换言之，基体的材质为L605、MP35N、316L或PtCr合金时，金属元素X都可以为Cr。
在其中一些实施例中，单质金属层、合金层和金属陶瓷层的厚度为10nm～500nm；进一步地，优选为10nm～300nm，更进一步地，优选为10nm～200nm。甚至更优选地，优选为10nm～100nm；且特别优选地，单质金属层、合金层和金属陶瓷层的厚度均为10nm～80nm，进一步为30nm～80nm。
通过优化各涂层的厚度选择，可以进一步保证第一涂层完整地包覆于基体的所有表面，无穿透性孔洞等缺陷，可有效避免基体中镍、钴等离子的释放。
且在第一涂层中作为内层与基体直接接触的涂层的厚度，可进一步优选为10nm～80nm；进一步为10nm～60nm；且特别优选地为10nm～50nm。
进一步地，第一涂层的总厚度在10nm～30nm，能完整包覆基体的较优最薄厚度，基体塑性大变形后能够包覆基体，有害离子溶出降低程度小。
进一步地，第一涂层的总厚度在30nm～100nm，与基体协调变形比较好，结合力及延展性好，基体塑性大变形后还能包覆住基体，有害离子溶出降低程度比总厚度在10nm～30nm(其他条件不变)好。
进一步地，第一涂层的总厚度在100nm～300nm，与基体协调变形最优，结合力及延展性最优，基体塑性大变形后还能完整包覆住基体，有害离子溶出降低程度最优。
进一步地，第一涂层的总厚度在300nm～500nm，涂层稍厚，基体塑性变形后易开裂，增加了有害离子溶出的倾向。
在其中一些实施例中，第一涂层中的任意涂层均为纳米涂层，纳米尺寸的功能涂层对基体材料具有活化催化作用，有利于进一步增强基体和涂层的界面间的结合力，有效解决医用器件在较大塑性变形时表面涂层脱落或大面积裂纹的问题。此外，相对微米级别涂层或更大尺寸涂层的医用植入器件，本发明表面的纳米涂层尺寸并没有显著增加而加剧心梗及血栓的发生率。且纳米涂层的致密度高，能够降低或有效避免致敏致癌的镍元素和钴元素的溶出或析出，作为医用植入器件的生物相容性和安全性更好，扩大了器械的适用人群范围。
本发明的技术人员经过研究发现，通过将医用器件的任意相邻两层不同材质的层结构之间的自腐蚀电位差控制在一个合理的范围内，可以进一步保证相邻两层涂层之间具有良好的结合力。与其他自腐蚀电位较高的保护性涂层比，可进一步较大程度地降低在开裂或脱落等可能发生的涂层失效模式下基体与涂层之间发生原电池效应的风险。其中，医用器件的任意相邻两层不同材质的层结构之间包括基体和与其直接接触的涂层之间，第一涂层为叠层时第一涂层内部任意相邻两层不同材质的层结构之间，以及后文中提及的第二涂层与第一涂层之间等。
优选地，医用器件的任意相邻两层不同材质的层结构之间的自腐蚀电位差在100mV以内；更优选地，医用器件的任意相邻两层不同材质的层结构之间的自腐蚀电位差在80mV以内；甚至更优选地，医用器件的任意相邻两层不同材质的层结构之间的自腐蚀电位差在60mV以内；且特别优选地，医用器件的任意相邻两层不同材质的层结构之间的自腐蚀电位差在50mV以内；最优选地，医用器件的任意相邻两层不同材质的层结构之间的自腐蚀电位差在30mV以内。
在其中一些实施例中，第一涂层含有金属陶瓷层。进一步地，医用器件还包括设于金属陶瓷层上的第二涂层。进一步地，金属陶瓷层为金属元素X的碳化物或金属元素X的硅化物，第二涂层为硅层。或者，进一步地，金属陶瓷层为金属元素X的碳化物，第二涂层为碳层。
如此通过在第一涂层上形成硅层或碳层作为第二涂层，一方面第二涂层与金属陶瓷层具有较好的结合力，另一方面可避免第二涂层中不含有金属元素，可避免金属陶瓷层中的微量金属元素的溶出。
进一步地，第二涂层的厚度为30nm～500nm。进一步地，第二涂层的厚度为30nm～200nm；进一步地，第二涂层的厚度为50nm～150nm；进一步地，第二涂层的厚度为50nm～100nm。
医用器件例如血管支架表面可光滑可粗糙，可带槽可不带槽，可带孔或不带孔，或可以包含但不仅限于其它任何可以载药的凹槽或微孔。在其中一些实施例中，第一涂层形成有载药凹槽，如图1所示的血管支架，其支架由一个或多个波杆组成，波杆由基体110和第一涂层120组成，第一涂层120上设有凹槽101。图1中(a)为波杆的示意图，(b)为波杆在A-A的截面示意图。
在其中一些实施例中，医用器件还包括设于第一涂层表面的药物活性层。进一步地，药物活性层可设于载药凹槽内。
进一步地，药物活性层中的药物包含治疗心脑血管疾病药物、肿瘤疾病药物、肠道疾病治疗药物、尿道疾病治疗药物等。进一步地，其中的药物包含但不限于紫杉醇(Paclitaxel)、多西紫杉醇(Docetaxel)、阿司匹林铜(Copper aspirinate)、他克莫司(Tacrolimus)、羟基喜树碱(Hydroxy camptothecin)、长春花碱(Vinblastine)、阿霉素(Doxorubicin)、雷帕霉素(Rapamycin)和雷帕霉素衍生物中的至少一种。
本发明一实施方式还提供了上述医用器件的制备方法，包括如下步骤：
提供基体；
在基体上形成包覆的第一涂层。
可理解，当第一涂层为单质金属层、合金层和金属陶瓷层中的至少两种时，通过分步形成。
如上所述，在其中一些实施例中，医用器件还包括第二涂层。
在其中一些实施例中，形成第一涂层和第二涂层的方法可为：物理气相沉积、热喷涂、脉冲激光薄膜沉积、磁控溅射沉积、蒸发镀、离子镀、化学镀、电化学镀、化学气相沉积、阳极氧化、离子注入与沉积、辉光放电等离子处理了等物理或化学的表面改性方法，或者原子层沉积、涂料涂装技术、陶瓷涂敷技术、化学转化膜技术、堆焊技术、着色染色技术、表面扩渗技术、喷焊堆焊、激光合金化技术等，也可以是一种或多种表面改性方法的组合。针对具有三维形状的医用植入器件的内、外表面或带槽的医用植入器件，为了实现表面涂层全包覆的涂层方法优选为原子层沉积及电化学镀，或者载物台及样品能旋转实现涂层全包覆的物理或化学的气相沉积方法。
在其中一些实施例中，在制备第一涂层前，可先对基体依次进行酸洗、电化学抛光和表面活化处理的步骤。其中酸洗的目的：去除表面切割碎屑、热影响层及污染物；电化学抛光的目的：去除氧化层，获得光亮、平整的表面，降低表面粗糙度，进而降低医用器件植入后的血栓风险及组织反应，获得符合支架设计要求的尺寸；表面活化处理的目的：去除支架表面钝化膜，暴露新鲜的基材。
在一些实施例中，基体为管状基体。以医用植入器件中的心血管支架为例，其制备方法包括如下步骤：
将基材形成管状件，将管状件切割形成波杆，在波杆上沉积第一涂层。
进一步地，该制备方法还可包括如下步骤：
在形成波杆之后且在沉积第一涂层之前，在波杆上挖凹槽。如此在挖凹槽后沉积第一涂层，且使第一涂层也形成凹槽，可用于载药。
在一些实施例中，该制备方法还可包括：在第一涂层上形成第二涂层的步骤。第一涂层形成有载药凹槽时，第二涂层在该位置也相应形成凹槽，以使最外层涂层也形成凹槽，用于载药。
上述医用器件的制备方法，能够获得三维的、内外表面全覆盖、厚度均匀且具有优良结合力的医用器件，该医用器件保证了血管支架及其它医用植入器件生物安全性，同时提高了耐腐蚀性，可用于血管支架等医用植入器件的制备，且可延长血管支架及其它医用植入器件在体内的使用寿命。
为了使本发明的目的、技术方案及优点更加简洁明了，本发明用以下具体实施例进行说明，但本发明绝非仅限于这些实施例。以下所描述的实施例仅为本发明较好的实施例，可用于描述本发明，不能理解为对本发明的范围的限制。应当指出的是，凡在本发明的精神和原则之内所做的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
一、制备实施例1～20的血管支架
将合金管状件基材依次进行切割、酸洗、热处理、抛光处理；
再对样品进行预处理、脱脂、酸洗、浸蚀活化处理等；
再通过电化学镀获得所需厚度的纳米尺寸的第一涂层；该电化学镀包含液相传质、电化学反应及电结晶，制得血管支架。电化学镀的条件如下：电流为0.05A、电镀时间为10min、搅拌速度为800rpm、温度为45℃。
实施例的血管支架的基体材料及第一涂层的材料如下表2所示：
表2
其中，实施例8中钝化处理的步骤为：将支架浸入50wt％硝酸溶液中，于温度25℃钝化处理时间50min。
实施例1～2和实施例4～5及实施例7的性能比较，如下表3所示：
表3
实施例21：带槽的血管支架
实施例21的血管支架与实施例1的血管支架基本相同，之间的区别在于，实施例21的血管支架所采用的基体上设有凹槽，相应形成的第一涂层上也设有凹槽。
表4
从图1和表4可知，本发明同样适用于带凹槽的血管支架，凹槽内均匀完整覆盖有第一涂层，并且支架极限扩张后功能涂层也无大面积裂纹脱落及开裂现象发生，耐腐蚀测试满足要求，且离子溶出及生物学实验结果优良。
实施例22：含第二功能涂层的心脏起搏器的植入电极
实施例22的植入电极与实施例14的血管支架的基体材料和第一涂层基本相同，之间的区别在于：实施例22的植入电极在MoSi2的外层上还设有硅层作为第二涂层。具体材料如下表5所示：
表5
实施例23：人工膝关节
实施例24：金属骨钉
| 金属骨钉 | 基体材料 | 第一涂层，厚度 |
| 实施例24 | 不锈钢316L | CrN,500nm |
对比例
对比例的血管支架的基体材料及第一涂层的材料如下表6所示：
表6
性能测试1支架在存在较大塑性变形使用过程中的延展性
功能涂层的分离与其材料本身的性能有关，界面处分离(如涂层脱落及大面积开裂)主要由功能涂层/基体之间的结合强度(即结合力)决定的。
按照标准的医疗器械植入流程，首先将血管支架压握在球囊上，在37℃的PBS溶液中模拟人体穿越三次后再用充盈器扩至支架的名义尺寸。针对本发明实施例的血管支架，在扩至支架的名义尺寸的基础上，再进一步用后扩球囊增大压力继续对支架进行后扩到达支架的极限后扩尺寸，在此极限条件下验证本发明的支架上涂层的结合性能。
对比例1～3中的NiTi合金为镍钛丝，制得的产品为镍钛丝编织产品，该产品具有超弹性但不具有塑性变形性能，其在植入过程中不发生塑性变形，因此对涂层结合力要求较低。进一步地，将对比例2制得的产品进行模拟植入，经验证在模拟植入过程后，该产品确实发生了涂层脱落现象，如图2所示的SEM图。从中可知，镍钛合金仅在弹性变形时就发生了涂层脱落现象。对比例1、对比例3与对比例2制得的产品性能类似，即其涂层与基体的结合力不佳。
通过对比例2和对比例4～8可知，Ti单质涂层及TiN复合涂层不适用于镍钛合金以外的L605、MP35N、316L及PtCr等要求基体能够发生塑性变形的材料表面，结合力较差。Ti合金元素在L605、MP35N、316L及PtCr作为杂质元素，其Ti合金含量低，不超过1％，其单质涂层或复合涂层在基体上的结合力差，在支架扩张后出现开裂甚至严重的涂层剥离。图3和图4分别为对比例4～5制得的血管支架在支架扩张至名义尺寸后出现开裂甚至严重的涂层剥离的SEM图。该实验结果也表明，当支架扩至名义尺寸，在相同的变形量条件下，涂层厚度越大，出现裂纹的倾向也增大。
图5为对比例6制得的支架产品的扫描电镜图；图6为对比例7制得的支架产品扩张至名义尺寸的扫描电镜图；图7为对比例8制得的支架产品扩张至极限后扩尺寸的扫描电镜图。从中可知，对比例6～8的支架产品中的基体不含有Ti合金元素，仅基体MP35N含有微量杂质元素Ti(<1％)，而涂层都为TiN；故而基体与涂层材料没有相同的合金元素，存在比较大的自腐蚀电位差，涂层结合力比较差。对比例6制得的支架未扩张，仅超声清洗就发现涂层大面积脱落。对比例7制得的支架后扩名义尺寸后涂层出现大面积剥落。对比例8制得的支架后扩后涂层出现大面积裂纹，有涂层脱落风险。支架植入后扩过程中，若涂层出现脱落将导致血栓死亡严重后果。
对比例9制得的支架还未发生塑性变形，仅超声清洗后，PBS模拟穿越后(即未进行名义尺寸扩张之前)涂层就已发现大面积破损，其SEM如图8所示。
实施例4制得的支架扩张至名义尺寸的表面形貌，如图9所示；实施例8制得的支架杆在拉直的极限扩张变形条件的表面形貌，如图10所示，涂层与基体依旧非常牢固地结合在一起，涂层没有出现裂纹或脱落，证明了本发明涂层与基体之间具有非常优异的结合力和延展性。由此说明，本发明制得的支架能够满足较大塑性变形的要求，可靠性优异。
性能测试2支架在模拟使用条件下的镍钴金属离子的溶出性能
利用原子发射光谱定量分析测试方法(ICP-MS)可以确定功能涂层能否有效去除、隔离或避免镍、钴致敏致癌合金元素的溶出。
对于以上的实施例制得的支架产品，取无涂层样品作为对照样，同时以无镍合金Biodur 108的镍离子溶出作为空白对照样。每个支架总表面积为12cm2，在50℃的PBS培养液中浸提1周后取浸提液，原子发射光谱定量分析测试结果ICP-MS测试浸提液中镍钴金属离子的含量，如表7所示。
表7
原子发射光谱定量分析测试ICP-MS离子溶出结果表明，本发明的血管支架上的涂层能有效减少镍、钴等有害离子的溶出，镍离子的降低可以达到ppm级别；特别对于L605、MP35N和ASTM F75这些钴基合金的血管植入支架，其钴离子的溶出降低幅度尤为明显。对于对比例1-3中的NiTi合金，第一涂层使得镍离子的溶出有所降低，另外，在溶液中还检测到了约0.02μg/mL的Ti离子，加剧了植入类医疗器械的生物安全性离子溶出的风险。
而对比例4～9的支架产品从提供的扫描电镜图可知其涂层已大量开裂或脱落，故而该涂层已经起不到阻挡有害离子溶出的作用，在此不再考察其镍钴金属离子的溶出性能及后续的耐腐蚀性。
对比例1～3的支架产品从扫描电镜图可知，也发生了一定程度的涂层脱落现象，即其涂层与基体的结合力不佳，故而其对镍离子的溶出的阻挡作用十分有限，因此后续不再考察其耐腐蚀电位。
实施例22与实施例14对比可知，第二涂层的存在进一步降低了支架在模拟使用条件下的镍钴金属离子的溶出。
性能测试3支架的耐腐蚀性
依据YYT 0695-2008小型植入器械腐蚀敏感性的循环动电位极化标准测试方法(ASTM F 2129-06)，试验条件为37℃，PBS溶液；按照TC的标准测试方法对以上各实施例进行耐腐蚀测试，无涂层支架样品作为对照样。得到的测试结果如表8所示。
表8
值得说明的是，表8中的自腐蚀电位是以支架样品为对象测试的，而支架样品是由基体及包覆在基体上的包覆涂层制得的，故而测得的自腐蚀电位可认为是基体上的最外层的涂层的自腐蚀电位。以L605无涂层和实施例1～8为例，表8中L605无涂层的自腐蚀电位即为基体的自腐蚀电位，表8中实施例1～8的自腐蚀电位即分别可认为是Cr2O3、CrN、CrC、Cr2O3、CrN、CrC、Cr、Cr(钝化处理)的自腐蚀电位，基于此可以获得支架样品任意相邻两层层结构之间的自腐蚀电位差。
血管支架及其它医用植入器件作为三类植入类医疗器械，必须具有优异的耐腐蚀性能，要求击穿电位应≥600mV，保护电位应≥300mV。测试结果表明，所有涂层样品支架的耐蚀性均优于无涂层支架对照样，满足击穿电位应≥600mV，保护电位应≥300mV的产品耐蚀性使用需求。表8中保护电位为“/”，表示为无穷大。
其中，根据实施例7和实施例8对比可知，第一涂层为单质金属层且作为外层时，将单质金属层经钝化处理后，支架产品的击穿电位从未经钝化处理之前的726mV提高到806mV。
对比例1～3与无涂层的NiTi合金的耐腐蚀性能相比，没有明显区别，即体现的即为基体的材质本身的性质，推测可能是涂层与基体结合力不佳，发生了一定的脱落现象导致。且，对比例1～3的涂层发生了一定的脱落现象，导致其无法起到有效隔离或明显降低基体中的镍离子溶出的作用。
性能测试4
对于以上各实施例，取实施例制得的样品进行了细胞毒、溶血及凝血生物学测试，以进一步确定功能涂层的生物安全性。
结果表明，实施例制得的支架样品均满足细胞存活率大于等于70％，溶血率<5％，凝血四项p>0.05的生物安全性要求。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
Claims (14)
1.一种医用器件，其特征在于，包括基体及包覆于所述基体的第一涂层，所述基体含有含量≥5wt％的金属元素X，所述第一涂层为所述金属元素X的单质金属层、所述金属元素X的合金层和所述金属元素X的金属陶瓷层中的至少一种，所述第一涂层中不含有镍或钴。
2.如权利要求1所述的医用器件，其特征在于，所述第一涂层为所述合金层和所述金属陶瓷层中的至少一种与所述单质金属层形成的叠层；
在所述第一涂层中，所述单质金属层为靠近所述基体的内层，所述合金层和所述金属陶瓷层中的至少一种为远离所述基体的外层。
3.如权利要求1所述的医用器件，其特征在于，当所述第一涂层为所述金属元素X的单质金属层时，所述单质金属层为经过钝化处理的金属涂层；或者
当所述第一涂层为所述单质金属层和所述金属陶瓷层形成的叠层时，所述单质金属层位于所述基体与所述金属陶瓷层之间；或者
当所述第一涂层为所述单质金属层和所述合金层形成的叠层时，所述单质金属层位于所述基体与所述合金层之间。
4.如权利要求1所述的医用器件，其特征在于，所述金属陶瓷层的材质为所述金属元素X的氧化物、碳化物、氮化物、硅化物和硼化物中的至少一种。
5.如权利要求1所述的医用器件，其特征在于，所述金属元素X为Cr、W、Mo及贵金属元素中的至少一种。
6.如权利要求1所述的医用器件，其特征在于，所述金属元素X在所述基体中的含量为7wt％～60wt％。
7.如权利要求1所述的医用器件，其特征在于，所述基体为能够发生塑性形变的基体；或者
所述基体的材质选自不锈钢、钴基合金、钛合金、贵金属合金或镍钛形状记忆合金。
8.如权利要求1所述的医用器件，其特征在于，所述金属元素X为Cr、W、Mo或Pt中的一种。
9.如权利要求1所述的医用器件，其特征在于，所述第一涂层含有所述金属陶瓷层，所述医用器件还包括设于所述金属陶瓷层上的第二涂层；
其中，所述金属陶瓷层为所述金属元素X的碳化物，所述第二涂层为碳层；或者
所述金属陶瓷层为所述金属元素X的硅化物，所述第二涂层为硅层。
10.如权利要求1至9任一项所述的医用器件，其特征在于，所述医用器件的任意相邻两层不同材质的层结构之间的自腐蚀电位差为100mV以内。
11.如权利要求1至9任一项所述的医用器件，其特征在于，所述单质金属层、所述合金层和所述金属陶瓷层的厚度为10nm～500nm。
12.如权利要求1至9任一项所述的医用器件，其特征在于，所述金属元素X不为钛元素。
13.如权利要求1至9任一项所述的医用器件，其特征在于，所述医用器件还包括设于所述第一涂层表面的药物活性层。
14.如权利要求13所述的医用器件，其特征在于，所述第一涂层形成有载药凹槽，所述药物活性层设于所述载药凹槽内。
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| WO2022214027A1 (zh) * | 2021-04-08 | 2022-10-13 | 上海微创医疗器械（集团）有限公司 | 医用器件 |
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