CN109280909A - 具有生物活性的植入体表面处理方法 - Google Patents

具有生物活性的植入体表面处理方法 Download PDF

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CN109280909A
CN109280909A CN201811418422.5A CN201811418422A CN109280909A CN 109280909 A CN109280909 A CN 109280909A CN 201811418422 A CN201811418422 A CN 201811418422A CN 109280909 A CN109280909 A CN 109280909A
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implant surfaces
biologically active
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曾晨光
李少军
许羽冬
陈诗浩
杨习锋
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Guangzhou Sun Shing Biotech Co ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/06Titanium or titanium alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/32Phosphorus-containing materials, e.g. apatite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24CABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C11/00Selection of abrasive materials or additives for abrasive blasts
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C8/00Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/02Methods for coating medical devices

Abstract

本发明提供一种具有生物活性的植入体表面处理方法,先通过生物活性玻璃提高植入体表面的活性,再采用常规湿法在植入体表面植入磷离子溶液、钙离子溶液和磷酸钙溶液,最后提供适量的磷蒸气促使植入体表面生成低结晶的、具有生物活性的羟基磷灰石涂层。

Description

具有生物活性的植入体表面处理方法
技术领域
本发明涉及一种具有生物活性的植入体,可广泛应用于移植材料等生物材料。
背景技术
近年来,羟磷灰石已经广泛用作能够代替例如骨骼或牙齿等硬组织的人造生物材料。羟磷灰石是一种在化学上和晶体学上与构成人体骨骼和牙齿的矿物组分相同的材料。当移植到人体中时,羟磷灰石呈现出与周围细胞的高度生物相容性,并且在接合区处迅速与骨骼直接形成化学键。由钙离子、磷酸根离子和羟基离子构成的纯羟磷灰石晶体是一种化学计量晶体,具有杆状结构,并且具有高结晶度。另一方面,从骨骼或钙化软骨分离的生物晶体是具有低结晶度的非化学计量的羟磷灰石。为了形成羟磷灰石的结晶学性质类似于生物晶体的结晶膜,已经采取了使用磷酸钙溶液或模拟体液的各种方法。
存在一种使用磷酸钙溶液或模拟体液的方法,这是一种湿式涂覆方法。各种类型磷酸钙的制备或涂覆都是从磷酸钙离子溶液为原料。这些磷酸钙化合物可通过在多种条件下将钙离子和磷酸根离子混合于水溶液中来制备,但一般耗时过长,且生产量不高。
考虑到磷酸根离子解离常数较低,本发明提供一种表面处理方法,利用磷裂化器提供磷元素蒸气,与植入体表面进行碰撞,通过控制磷元素蒸气的流量,促使植入体表面生成低结晶的、具有生物活性的羟基磷灰石涂层。、
发明内容
本发明提供一种具有生物活性的植入体表面处理方法,包括以下步骤:
S1.将生物活性玻璃微粒作为喷砂介质,对植入体表面进行喷砂处理,处理完毕后清洗干燥待用,得到喷砂处理的植入体;
S2.将植入体浸入到含有钙离子和磷酸根离子的水溶液中,在常温下保持1-5h,取出;
S3.利用磷裂化器提供磷元素蒸气,与植入体表面进行碰撞,通过控制磷元素蒸气的流量,促使植入体表面生成低结晶的、具有生物活性的羟基磷灰石涂层。
优选地,所述植入体是金属,由钛或钛合金制成。
优选地,S1所述的生物活性玻璃微粒粒径尺寸为50-200nm。
生物活性玻璃(BG)可以是45S5生物玻璃或其它生物玻璃,可采用溶胶-凝胶法(sol-gel)制备,也可以采用高温熔融-淬冷-粉碎的方法制备,也可以直接购买生物玻璃微粉。
优选地,所述磷裂化器采用市售仪器,可将可商购的红磷转化为气相磷。
磷裂化器是已知的并且是可商购的仪器,用于将可商购的红磷(Pn)转化为高反应性气相磷的受控的且可复制的流。磷裂化器运行的基本阶段有红磷蒸发以形成白磷(P4),之后是P4裂化以形成反应性的P2。白磷蒸气可以冷凝和再蒸发,或者可以直接经由热裂化管在超过800℃的温度输送。
关于裂化源的进一步信息可以发现于F.A.Couon,G.Wilkinson,C.A.Murillo,MBochman,″AdvancedInorganicChemistry″,第6版,1999,John WileyandSons中。
优选地,S2所述钙离子和磷酸根离子的浓度均为0.1-2.0mol/L。
优选地,S3所述磷元素蒸气的流量为10-200sccm。
本发明的创新之处在于,先通过生物活性玻璃提高植入体表面的活性,再采用常规湿法在植入体表面植入磷离子溶液、钙离子溶液和磷酸钙溶液,考虑到磷酸根离子解离常数较低,提供适量的磷蒸气促使植入体表面生成低结晶的、具有生物活性的羟基磷灰石涂层。本项技术属于首次公开,未有现有技术披露。
具体实施方式
实施例1
一种具有生物活性的钛金属植入体表面处理方法,包括以下步骤:
S1.将生物活性玻璃微粒作为喷砂介质,对植入体表面进行喷砂处理,处理完毕后清洗干燥待用,得到喷砂处理的植入体;所述的生物活性玻璃微粒粒径尺寸为50nm;
S2.将植入体浸入到含有钙离子和磷酸根离子的水溶液中,在常温下保持1h,取出;所述钙离子和磷酸根离子的浓度均为0.1mol/L;
S3.利用磷裂化器提供磷元素蒸气,与植入体表面进行碰撞,通过控制磷元素蒸气的流量为10sccm,促使植入体表面生成低结晶的、具有生物活性的羟基磷灰石涂层。
本测试发现,本发明的获得的具有表面生物活性涂层的钛金属与常规湿法制备的钛金属相比,不仅提高了纯钛表面微弧氧化层的生物活性,并且耗时小、产量高。
实施例2
一种具有生物活性的钛金属植入体表面处理方法,包括以下步骤:
S1.将生物活性玻璃微粒作为喷砂介质,对植入体表面进行喷砂处理,处理完毕后清洗干燥待用,得到喷砂处理的植入体;所述的生物活性玻璃微粒粒径尺寸为100nm。
S2.将植入体浸入到含有钙离子和磷酸根离子的水溶液中,在常温下保持3h,取出;所述钙离子和磷酸根离子的浓度均为1.0mol/L;
S3.利用磷裂化器提供磷元素蒸气,与植入体表面进行碰撞,通过控制磷元素蒸气的流量为100sccm,促使植入体表面生成低结晶的、具有生物活性的羟基磷灰石涂层。
本测试发现,本发明的获得的具有表面生物活性涂层的钛金属与常规湿法制备的钛金属相比,不仅提高了纯钛表面微弧氧化层的生物活性,并且耗时小、产量高。
实施例3
一种具有生物活性的钛金属植入体表面处理方法,包括以下步骤:
S1.将生物活性玻璃微粒作为喷砂介质,对植入体表面进行喷砂处理,处理完毕后清洗干燥待用,得到喷砂处理的植入体;所述的生物活性玻璃微粒粒径尺寸为200nm。
S2.将植入体浸入到含有钙离子和磷酸根离子的水溶液中,在常温下保持5h,取出;所述钙离子和磷酸根离子的浓度均为2.0mol/L;
S3.利用磷裂化器提供磷元素蒸气,与植入体表面进行碰撞,通过控制磷元素蒸气的流量为200sccm,促使植入体表面生成低结晶的、具有生物活性的羟基磷灰石涂层。
本测试发现,本发明的获得的具有表面生物活性涂层的钛金属与常规湿法制备的钛金属相比,不仅提高了纯钛表面微弧氧化层的生物活性,并且耗时小、产量高。

Claims (6)

1.一种具有生物活性的植入体表面处理方法,其特征在于,包括以下步骤:
S1.将生物活性玻璃微粒作为喷砂介质,对植入体表面进行喷砂处理,处理完毕后清洗干燥待用,得到喷砂处理的植入体;
S2.将植入体浸入到含有钙离子和磷酸根离子的水溶液中,在常温下保持1-5h,取出;
S3.利用磷裂化器提供磷元素蒸气,与植入体表面进行碰撞,通过控制磷元素蒸气的流量,促使植入体表面生成低结晶的、具有生物活性的羟基磷灰石涂层。
2.根据权利要求1所述的一种具有生物活性的植入体表面处理方法,其特征在于,所述植入体是金属,由钛或钛合金制成。
3.根据权利要求1所述的一种具有生物活性的植入体表面处理方法,其特征在于,S1所述的生物活性玻璃微粒粒径尺寸为50-200nm。
4.根据权利要求1所述的一种具有生物活性的植入体表面处理方法,其特征在于,所述磷裂化器采用市售仪器,可将可商购的红磷转化为气相磷。
5.根据权利要求1所述的一种具有生物活性的植入体表面处理方法,其特征在于,S2所述钙离子和磷酸根离子的浓度均为0.1-2.0mol/L。
6.根据权利要求1所述的一种具有生物活性的植入体表面处理方法,其特征在于,S3所述磷元素蒸气的流量为10-200sccm。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1974876A (zh) * 2006-11-02 2007-06-06 华南理工大学 钛金属表面生物活性膜层及其喷砂-微弧氧化复合工艺
US20130042859A1 (en) * 2011-02-28 2013-02-21 Midori Renewables, Inc. Polymeric acid catalysts and uses thereof
CN107447193A (zh) * 2016-11-14 2017-12-08 深圳大学 一种黑磷薄膜及其制备方法
CN108042847A (zh) * 2017-12-11 2018-05-18 安徽理工大学 一种改善钛合金种植体表面生物仿生矿化能力的方法
CN108295307A (zh) * 2018-03-02 2018-07-20 中国医科大学附属口腔医院 一种骨植入用钙磷化合物-镁复合涂层及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1974876A (zh) * 2006-11-02 2007-06-06 华南理工大学 钛金属表面生物活性膜层及其喷砂-微弧氧化复合工艺
US20130042859A1 (en) * 2011-02-28 2013-02-21 Midori Renewables, Inc. Polymeric acid catalysts and uses thereof
CN107447193A (zh) * 2016-11-14 2017-12-08 深圳大学 一种黑磷薄膜及其制备方法
CN108042847A (zh) * 2017-12-11 2018-05-18 安徽理工大学 一种改善钛合金种植体表面生物仿生矿化能力的方法
CN108295307A (zh) * 2018-03-02 2018-07-20 中国医科大学附属口腔医院 一种骨植入用钙磷化合物-镁复合涂层及其制备方法

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