CN110975006A - 一种钛合金基体表面ha涂层的制备方法 - Google Patents

一种钛合金基体表面ha涂层的制备方法 Download PDF

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CN110975006A
CN110975006A CN201911356348.3A CN201911356348A CN110975006A CN 110975006 A CN110975006 A CN 110975006A CN 201911356348 A CN201911356348 A CN 201911356348A CN 110975006 A CN110975006 A CN 110975006A
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张朝勇
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
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    • A61L27/06—Titanium or titanium alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412—Tissue-regenerating or healing or proliferative agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

本发明公开了一种钛合金基体表面HA涂层的制备方法，属于生物医用材料领域，包括以下步骤：对钛合金基体表面进行预处理；将喷涂粉末采用激光熔覆喷涂在处理好的钛合金基体表面，所述喷涂粉末包括混合粉末和钛粉，所述混合粉末包括羟基磷灰石粉末和碳酸钙粉末；将喷涂好的钛合金基体放入碱液中进行电极化处理。本发明可有效提高HA的含量，从而提高涂层的生物活性。

Description

一种钛合金基体表面HA涂层的制备方法
技术领域
本发明涉及一种钛合金基体表面HA涂层的制备方法，属于生物医用材料领域。
背景技术
钛及钛合金因其优良的综合力学性能与加工性能，在较早时期就被人们将其作为人体硬组织的修复和骨科植入物的材料。然而，当纯金属或其金属合金植入到体内后，由于体内环境具有一定的腐蚀性，因此金属植入物表面氧化膜会受到影响和破坏，光鲜的金属表面会暴露于体液中，金属材料释放出大量的金属离子到体液中，释放出的金属离子导致各种对人体健康有害的现象产生，如金属过敏、肉芽肿瘤，甚至肝癌。为了更好地制备出理想的植入物假体，根据临床的需要，在金属表面制备涂层，一方面保留金属优良的力学性能，另一方面发挥陶瓷涂层的生物相容性。
羟基磷灰石(HA)涂层作为一种生物活性陶瓷涂层，在植入物植入人体以后，HA涂层会与人体骨组织相互作用，从而形成骨性结合。HA涂层由于其成分与人体骨成分相似，并且具有优良的生物活性以及无毒、无害、不致癌等优点，同时对骨组织具有良好的诱导生长作用，因此成为了骨科植入物最主要的制作材料。
激光熔覆作为表面改性技术得到了快速的发展，其作为一种表面改性技术已广泛应用于航空、航海，化学工业级生物医学装置，而制备的生物陶瓷涂层孔隙率小，硬度高。但是激光熔覆在制备过程中的高温使得HA分解以及生产杂质相，导致涂层生物活性降低。
发明内容
本发明是提供一种钛合金基体表面HA涂层的制备方法，可有效提高HA的含量，从而提高涂层的生物活性。
为达到上述目的，本发明所采用的技术方案是：一种钛合金基体表面HA涂层的制备方法，包括以下步骤：对钛合金基体表面进行预处理；将喷涂粉末采用激光熔覆喷涂在处理好的钛合金基体表面，所述喷涂粉末包括混合粉末和钛粉，所述混合粉末包括羟基磷灰石粉末和碳酸钙粉末；将喷涂好的钛合金基体放入碱液中进行电极化处理。
优选地，所述预处理包括以下步骤：对钛合金基体表面进行打磨；对打磨好的钛合金基体进行清洗并烘干。
优选地，所述混合粉末中羟基磷灰石粉末、碳酸钙粉末的质量比为4:1。
优选地，所述钛粉与混合粉末的质量比为1：1。
优选地，所述激光熔覆喷涂包括以下步骤：在清洗好的钛合金基体上先铺一层钛粉，再将混合粉末铺在钛粉上，所述喷涂粉末总厚度为1mm；使用激光器对铺设好的喷涂粉末进行激光熔覆喷涂，激光器功率为600w~1200w，扫描速度3.8~11.2mm/s，使用氩气为保护气体。
优选地，所述电极化处理包括以下步骤：将喷涂好的钛合金基体与恒流直流电源的阳极相连，以钛片作阴极；将所述钛合金基体和钛片同时置于碱液中，并接通恒流直流电源，加载电压为80V，极化处理3min。
优选地，所述碱液为1mol/L的NaOH溶液。
本发明通过采用激光熔覆的方法对钛合金基体表面进行喷涂后，再将喷涂好的钛合金基体进行电极化处理，可有效将HA杂质相转化为HA，有效提高HA含量，，从而提高涂层的生物活性。
附图说明
图1为本发明实施例提供的一种钛合金基体表面HA涂层的制备方法的流程示意图；
图2为本发明实施例中未加入电极化处理和加入电极化处理后HA衍射峰强度对比图。
具体实施方式
为了更好的理解本发明的实质，下面结合具体实施例和附图对本发明作进一步的阐述。
本发明适用于生物医用材料领域，尤其适用于医用植入物涂层的制备，具体包括以下步骤：
步骤1：对钛合金基体表面进行预处理。
对钛合金基体表面进行打磨后，采用蒸馏水超声震荡清洗并烘干，辐射灭菌后放置备用。超声震荡清洗的温度为50℃，超声波工作频率为20~30KHz之间。
步骤2:将喷涂粉末采用激光熔覆喷涂在处理好的钛合金基体表面。喷涂粉末包括混合粉末和钛粉，混合粉末包括羟基磷灰石粉末和碳酸钙粉末。混合粉末中羟基磷灰石粉末、碳酸钙粉末的质量比优选为4:1。钛粉与混合粉末的质量比为1：1。
在清洗好的钛合金基体上先铺一层钛粉，再将混合粉末铺在钛粉上，喷涂粉末总厚度为1mm。采用底层钛粉，再铺设混合粉末可提高HA 涂层与钛合金基体的结合度。
使用激光器对铺设好的喷涂粉末进行激光熔覆喷涂，激光器功率为600w~1200w，扫描速度3.8~11.2mm/s，使用氩气为保护气体。
步骤3：将喷涂好的钛合金基体放入碱液中进行电极化处理。
如图2所示，由于激光熔覆过程中，HA会产生一定的杂质相，因此通过采用电极化处理使得杂质相向HA相转变，以提高HA含量，从而提高涂层的生物活性。杂质主要为磷酸四钙（TTCP）。未经过电极化处理的HA涂层如图2中a所示，经过电极化处理后，表面HA的含量升高，医用植入物具有更好的生物活性。
1）将喷涂好的钛合金基体与恒流直流电源的阳极相连，以钛片作阴极；
2）将钛合金基体和钛片同时置于1mol/L的NaOH溶液中，并接通恒流直流电源，加载电压为80V，极化处理3min。
应当指出，虽然通过上述实施方式对本发明进行了描述，然而本发明还可有其它多种实施方式。在不脱离本发明精神和范围的前提下，熟悉本领域的技术人员显然可以对本发明做出各种相应的改变和变形，但这些改变和变形都应当属于本发明所附权利要求及其等效物所保护的范围内。

Claims (7)

1.一种钛合金基体表面HA涂层的制备方法，其特征在于，包括以下步骤：
对钛合金基体表面进行预处理；
将喷涂粉末采用激光熔覆喷涂在处理好的钛合金基体表面，所述喷涂粉末包括混合粉末和钛粉，所述混合粉末包括羟基磷灰石粉末和碳酸钙粉末；
将喷涂好的钛合金基体放入碱液中进行电极化处理。
2.根据权利要求1所述钛合金基体表面HA涂层的制备方法，其特征在于：所述预处理包括以下步骤：
对钛合金基体表面进行打磨；
对打磨好的钛合金基体进行清洗并烘干。
3.根据权利要求1所述钛合金基体表面HA涂层的制备方法，其特征在于：所述混合粉末中羟基磷灰石粉末、碳酸钙粉末的质量比为4:1。
4.根据权利要求3所述钛合金基体表面HA涂层的制备方法，其特征在于：所述钛粉与混合粉末的质量比为1：1。
5.根据权利要求1所述钛合金基体表面HA涂层的制备方法，其特征在于：所述激光熔覆喷涂包括以下步骤：
在清洗好的钛合金基体上先铺一层钛粉，再将混合粉末铺在钛粉上，所述喷涂粉末总厚度为1mm；
使用激光器对铺设好的喷涂粉末进行激光熔覆喷涂，激光器功率为600w~1200w，扫描速度3.8~11.2mm/s，使用氩气为保护气体。
6.根据权利要求1所述钛合金基体表面HA涂层的制备方法，其特征在于：所述电极化处理包括以下步骤：
将喷涂好的钛合金基体与恒流直流电源的阳极相连，以钛片作阴极；
将所述钛合金基体和钛片同时置于碱液中，并接通恒流直流电源，加载电压为80V，极化处理3min。
7.根据权利要求6所述钛合金基体表面HA涂层的制备方法，其特征在于：所述碱液为1mol/L的NaOH溶液。
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