CN113248249B - 溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法 - Google Patents

溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法 Download PDF

Info

Publication number
CN113248249B
CN113248249B CN202110677606.9A CN202110677606A CN113248249B CN 113248249 B CN113248249 B CN 113248249B CN 202110677606 A CN202110677606 A CN 202110677606A CN 113248249 B CN113248249 B CN 113248249B
Authority
CN
China
Prior art keywords
titanium alloy
solution
preparing
sol
substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110677606.9A
Other languages
English (en)
Other versions
CN113248249A (zh
Inventor
朱剑熹
韩斐
沈沁雪
朱勇
罗浩
郭斌
刘宇奇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiangya Hospital of Central South University
Original Assignee
Xiangya Hospital of Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiangya Hospital of Central South University filed Critical Xiangya Hospital of Central South University
Priority to CN202110677606.9A priority Critical patent/CN113248249B/zh
Publication of CN113248249A publication Critical patent/CN113248249A/zh
Application granted granted Critical
Publication of CN113248249B publication Critical patent/CN113248249B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
    • 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
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • 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
    • A61L27/303—Carbon
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/624—Sol-gel processing
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1229—Composition of the substrate
    • C23C18/1241—Metallic substrates
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Public Health (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Structural Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

一种溶胶‑凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法，通过溶胶‑凝胶法在医用钛合金表面制备羟基磷灰石生物陶瓷材料，并在传统的羟基磷灰石生物陶瓷涂层中掺入了氧化石墨烯以提高其耐腐蚀性能，进一步的，发明人系统地研究了氧化石墨烯的掺杂量对羟基磷灰石生物陶瓷材料耐腐蚀性能地影响，当掺入量为溶胶中P2O5的6.3%时，可使羟基磷灰石生物陶瓷涂层的自腐蚀电流降低至5.28*10‑3μA/cm2。

Description

溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法
技术领域
本发明涉及生物陶瓷材料领域，具体涉及一种溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法。
背景技术
生物医用材料是指和生物系统相作用，用以诊断、治疗修复或替代机体中的组织、器官或增进其功能的材料。可分为医用金属材料、医用高分子材料、医用陶瓷材料等，其中金属材料占有很大的比重，特别是骨科产品。生物陶瓷羟基磷灰石与人体骨中无机物磷灰石的晶体结构相同，因其无毒、生物相容性好，是骨的理想替代物。但是，生物陶瓷羟基磷灰石的强度低、韧性差，限制了其作为硬组织植入材料的用途。与此同时，由于钛合金与人体骨骼接近，对人体组织具有良好的生物相容性、无毒副作用，具有其他材料无法比拟的优势。因此，结合两者优势的钛合金生物陶瓷羟基磷灰石材料得到了广泛的应用。然而，由于生物医用材料长时间存在于复杂的人体环境中，对其耐腐蚀性能是极大的考验。因此，如何提高钛合金生物陶瓷羟基磷灰石材料的耐腐蚀性能是本领域急需解决的问题。
发明内容
针对现有技术存在的问题，本发明旨在提供一种溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法，该方法通过溶胶-凝胶法在医用钛合金表面制备含有氧化石墨烯的羟基磷灰石生物陶瓷材料，提高了传统羟基磷灰石涂层的耐腐蚀性能。
一种溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法，包括以下步骤：
A.以钛合金为衬底材料，将钛合金切割成合适大小；
B.对衬底进行预处理，预处理包括脱脂、酸洗、清洗和烘干；
C.制备阳极氧化层；
D.制备溶胶：按照钙磷比=1.67分别配置Ca(NO3)2·4H2O和P2O5的乙醇溶液，陈化12-15h，配置氧化石墨烯乙醇分散液并与P2O5的乙醇溶液混合，然后将混合溶液缓慢滴加至Ca(NO3)2·4H2O的乙醇溶液中，用氨水调节至pH=8，磁力搅拌30-40min，然后室温陈化20-24h；
E.制备羟基磷灰石生物陶瓷：把钛合金衬底放置于匀胶机上，将溶胶滴加在衬底表面，以1200-1500r/min的旋涂速度转动30-45s，然后把衬底放置到60-80℃的真空干燥箱中干燥30-60min，而后取出置于马弗炉中400-450℃下保温120-150min，得到羟基磷灰石生物陶瓷涂层。
进一步地，所述钛合金为医用钛合金。
进一步地，所述脱脂选用浓度为15-20%的碳酸氢钠溶液。
进一步地，所述酸洗选用浓度为10-15%的盐酸溶液。
进一步地，所述清洗处理为无水乙醇超声清洗。
进一步地，所述氧化石墨烯的质量为P2O5的2.5%-9.0%。
进一步地，所述氧化石墨烯的质量为P2O5的6.3%。
进一步地，所述步骤A中将钛合金切割成15×15*2mm的基片。
进一步地，所述步骤C具体为：采用直流电源装置提供25-30V阳极氧化电压，以1.5-2.0mol/L H3PO4溶液和1.2 -2.0wt% NH4F溶液为电解质溶液，在钛合金表面阳极氧化100-120min，氧化过程中始终施加磁力搅拌，最后以15-20℃/min的升温速率加热到300-400℃热处理2-2.5h，构建阳极氧化层。
本发明通过溶胶-凝胶法在医用钛合金表面制备羟基磷灰石生物陶瓷材料，并在传统的羟基磷灰石生物陶瓷涂层中掺入了氧化石墨烯以提高其耐腐蚀性能，进一步的，发明人系统地研究了氧化石墨烯的掺杂量对羟基磷灰石生物陶瓷材料耐腐蚀性能地影响，当掺入量为溶胶中P2O5的6.3%时，可使羟基磷灰石生物陶瓷涂层的自腐蚀电流降低至5.28*10-3μA/cm2。
具体实施方式
下面通过具体实施例来验证本发明的技术效果，但是本发明的实施方式不局限于此。
实施例1
一种溶胶-凝胶法制备羟基磷灰石生物陶瓷的方法，包括以下步骤：
A.以钛合金为衬底材料，将钛合金切割成15×15*2mm的基片；
B.对衬底进行预处理，预处理包括脱脂、酸洗、清洗和烘干，其中脱脂选用浓度为15%的碳酸氢钠溶液，酸洗选用浓度为10%的盐酸溶液，清洗处理为无水乙醇超声清洗；
C.制备阳极氧化层：采用直流电源装置提供25V阳极氧化电压，以1.5mol/L H3PO4溶液和1.2 wt% NH4F溶液为电解质溶液，在钛合金表面阳极氧化100min，氧化过程中始终施加磁力搅拌，最后以15℃/min的升温速率加热到300℃热处理2h，构建阳极氧化层；
D.制备溶胶：按照钙磷比=1.67分别配置Ca(NO3)2·4H2O和P2O5的乙醇溶液，陈化12h。配置氧化石墨烯乙醇分散液并与P2O5的乙醇溶液混合，然后将混合溶液缓慢滴加至Ca(NO3)2·4H2O的乙醇溶液中，用氨水调节至pH=8，磁力搅拌40min，然后室温陈化20h，其中氧化石墨烯的质量为P2O5的2.5wt%。
E.制备羟基磷灰石生物陶瓷：把钛合金衬底放置于匀胶机上，将溶胶滴加在衬底表面，以1200r/min的旋涂速度转动30s，然后把衬底放置到60℃的真空干燥箱中干燥30min，而后取出置于马弗炉中400℃下保温120min，得到羟基磷灰石生物陶瓷涂层。
实施例2
一种溶胶-凝胶法制备羟基磷灰石生物陶瓷的方法，包括以下步骤：
A.以钛合金为衬底材料，将钛合金切割成15×15*2mm的基片；
B.对衬底进行预处理，预处理包括脱脂、酸洗、清洗和烘干，其中脱脂选用浓度为15%的碳酸氢钠溶液，酸洗选用浓度为10%的盐酸溶液，清洗处理为无水乙醇超声清洗；
C.制备阳极氧化层：采用直流电源装置提供25V阳极氧化电压，以1.5mol/L H3PO4溶液和1.2 wt% NH4F溶液为电解质溶液，在钛合金表面阳极氧化100min，氧化过程中始终施加磁力搅拌，最后以15℃/min的升温速率加热到300℃热处理2h，构建阳极氧化层；
D.制备溶胶：按照钙磷比=1.67分别配置Ca(NO3)2·4H2O和P2O5的乙醇溶液，陈化12h。配置氧化石墨烯乙醇分散液并与P2O5的乙醇溶液混合，然后将混合溶液缓慢滴加至Ca(NO3)2·4H2O的乙醇溶液中，用氨水调节至pH=8，磁力搅拌40min，然后室温陈化20h，其中氧化石墨烯的质量为P2O5的3.2wt%。
E.制备羟基磷灰石生物陶瓷：把钛合金衬底放置于匀胶机上，将溶胶滴加在衬底表面，以1200r/min的旋涂速度转动30s，然后把衬底放置到60℃的真空干燥箱中干燥30min，而后取出置于马弗炉中400℃下保温120min，得到羟基磷灰石生物陶瓷涂层。
实施例3
一种溶胶-凝胶法制备羟基磷灰石生物陶瓷的方法，包括以下步骤：
A.以钛合金为衬底材料，将钛合金切割成15×15*2mm的基片；
B.对衬底进行预处理，预处理包括脱脂、酸洗、清洗和烘干，其中脱脂选用浓度为15%的碳酸氢钠溶液，酸洗选用浓度为10%的盐酸溶液，清洗处理为无水乙醇超声清洗；
C.制备阳极氧化层：采用直流电源装置提供25V阳极氧化电压，以1.5mol/L H3PO4溶液和1.2 wt% NH4F溶液为电解质溶液，在钛合金表面阳极氧化100min，氧化过程中始终施加磁力搅拌，最后以15℃/min的升温速率加热到300℃热处理2h，构建阳极氧化层；
D.制备溶胶：按照钙磷比=1.67分别配置Ca(NO3)2·4H2O和P2O5的乙醇溶液，陈化12h。配置氧化石墨烯乙醇分散液并与P2O5的乙醇溶液混合，然后将混合溶液缓慢滴加至Ca(NO3)2·4H2O的乙醇溶液中，用氨水调节至pH=8，磁力搅拌40min，然后室温陈化20h，其中氧化石墨烯的质量为P2O5的5.0wt%。
E.制备羟基磷灰石生物陶瓷：把钛合金衬底放置于匀胶机上，将溶胶滴加在衬底表面，以1200r/min的旋涂速度转动30s，然后把衬底放置到60℃的真空干燥箱中干燥30min，而后取出置于马弗炉中400℃下保温120min，得到羟基磷灰石生物陶瓷涂层。
实施例4
一种溶胶-凝胶法制备羟基磷灰石生物陶瓷的方法，包括以下步骤：
A.以钛合金为衬底材料，将钛合金切割成15×15*2mm的基片；
B.对衬底进行预处理，预处理包括脱脂、酸洗、清洗和烘干，其中脱脂选用浓度为15%的碳酸氢钠溶液，酸洗选用浓度为10%的盐酸溶液，清洗处理为无水乙醇超声清洗；
C.制备阳极氧化层：采用直流电源装置提供25V阳极氧化电压，以1.5mol/L H3PO4溶液和1.2 wt% NH4F溶液为电解质溶液，在钛合金表面阳极氧化100min，氧化过程中始终施加磁力搅拌，最后以15℃/min的升温速率加热到300℃热处理2h，构建阳极氧化层；
D.制备溶胶：按照钙磷比=1.67分别配置Ca(NO3)2·4H2O和P2O5的乙醇溶液，陈化12h。配置氧化石墨烯乙醇分散液并与P2O5的乙醇溶液混合，然后将混合溶液缓慢滴加至Ca(NO3)2·4H2O的乙醇溶液中，用氨水调节至pH=8，磁力搅拌40min，然后室温陈化20h，其中氧化石墨烯的质量为P2O5的6.3wt%。
E.制备羟基磷灰石生物陶瓷：把钛合金衬底放置于匀胶机上，将溶胶滴加在衬底表面，以1200r/min的旋涂速度转动30s，然后把衬底放置到60℃的真空干燥箱中干燥30min，而后取出置于马弗炉中400℃下保温120min，得到羟基磷灰石生物陶瓷涂层。
实施例5
一种溶胶-凝胶法制备羟基磷灰石生物陶瓷的方法，包括以下步骤：
A.以钛合金为衬底材料，将钛合金切割成15×15*2mm的基片；
B.对衬底进行预处理，预处理包括脱脂、酸洗、清洗和烘干，其中脱脂选用浓度为15%的碳酸氢钠溶液，酸洗选用浓度为10%的盐酸溶液，清洗处理为无水乙醇超声清洗；
C.制备阳极氧化层：采用直流电源装置提供25V阳极氧化电压，以1.5mol/L H3PO4溶液和1.2 wt% NH4F溶液为电解质溶液，在钛合金表面阳极氧化100min，氧化过程中始终施加磁力搅拌，最后以15℃/min的升温速率加热到300℃热处理2h，构建阳极氧化层；
D.制备溶胶：按照钙磷比=1.67分别配置Ca(NO3)2·4H2O和P2O5的乙醇溶液，陈化12h。配置氧化石墨烯乙醇分散液并与P2O5的乙醇溶液混合，然后将混合溶液缓慢滴加至Ca(NO3)2·4H2O的乙醇溶液中，用氨水调节至pH=8，磁力搅拌40min，然后室温陈化20h，其中氧化石墨烯的质量为P2O5的7.8wt%。
E.制备羟基磷灰石生物陶瓷：把钛合金衬底放置于匀胶机上，将溶胶滴加在衬底表面，以1200r/min的旋涂速度转动30s，然后把衬底放置到60℃的真空干燥箱中干燥30min，而后取出置于马弗炉中400℃下保温120min，得到羟基磷灰石生物陶瓷涂层。
实施例6
一种溶胶-凝胶法制备羟基磷灰石生物陶瓷的方法，包括以下步骤：
A.以钛合金为衬底材料，将钛合金切割成15×15*2mm的基片；
B.对衬底进行预处理，预处理包括脱脂、酸洗、清洗和烘干，其中脱脂选用浓度为15%的碳酸氢钠溶液，酸洗选用浓度为10%的盐酸溶液，清洗处理为无水乙醇超声清洗；
C.制备阳极氧化层：采用直流电源装置提供25V阳极氧化电压，以1.5mol/L H3PO4溶液和1.2 wt% NH4F溶液为电解质溶液，在钛合金表面阳极氧化100min，氧化过程中始终施加磁力搅拌，最后以15℃/min的升温速率加热到300℃热处理2h，构建阳极氧化层；
D.制备溶胶：按照钙磷比=1.67分别配置Ca(NO3)2·4H2O和P2O5的乙醇溶液，陈化12h。配置氧化石墨烯乙醇分散液并与P2O5的乙醇溶液混合，然后将混合溶液缓慢滴加至Ca(NO3)2·4H2O的乙醇溶液中，用氨水调节至pH=8，磁力搅拌40min，然后室温陈化20h，其中氧化石墨烯的质量为P2O5的9.0wt%。
E.制备羟基磷灰石生物陶瓷：把钛合金衬底放置于匀胶机上，将溶胶滴加在衬底表面，以1200r/min的旋涂速度转动30s，然后把衬底放置到60℃的真空干燥箱中干燥30min，而后取出置于马弗炉中400℃下保温120min，得到羟基磷灰石生物陶瓷涂层。
对比例1
一种溶胶-凝胶法制备羟基磷灰石生物陶瓷的方法，包括以下步骤：
A.以钛合金为衬底材料，将钛合金切割成15×15*2mm的基片；
B.对衬底进行预处理，预处理包括脱脂、酸洗、清洗和烘干，其中脱脂选用浓度为15%的碳酸氢钠溶液，酸洗选用浓度为10%的盐酸溶液，清洗处理为无水乙醇超声清洗；
C.制备阳极氧化层：采用直流电源装置提供25V阳极氧化电压，以1.5mol/L H3PO4溶液和1.2 wt% NH4F溶液为电解质溶液，在钛合金表面阳极氧化100min，氧化过程中始终施加磁力搅拌，最后以15℃/min的升温速率加热到300℃热处理2h，构建阳极氧化层；
D.制备溶胶：按照钙磷比=1.67分别配置Ca(NO3)2·4H2O和P2O5的乙醇溶液，陈化12h。然后将P2O5的乙醇溶液混合溶液缓慢滴加至Ca(NO3)2·4H2O的乙醇溶液中，用氨水调节至pH=8，磁力搅拌40min，然后室温陈化20h。
E.制备羟基磷灰石生物陶瓷：把钛合金衬底放置于匀胶机上，将溶胶滴加在衬底表面，以1200r/min的旋涂速度转动30s，然后把衬底放置到60℃的真空干燥箱中干燥30min，而后取出置于马弗炉中400℃下保温120min，得到羟基磷灰石生物陶瓷涂层。
对实施例1-6以及对比例1中的实验样品在SBF溶液中进行电化学腐蚀实验以评定其耐腐蚀性能，并以未进行羟基磷灰石涂层处理的钛合金（该钛合金包括阳极氧化层）作为空白对照组，并且，空白对照组进行与实施例相同的前处理工艺。各实验样品的自腐蚀电流密度如表1所示。
表1 各实验样品的自腐蚀电流
编号 自腐蚀电流密度μA/cm<sup>2</sup>
实施例1 1.73*10<sup>-2</sup>
实施例2 1.65*10<sup>-2</sup>
实施例3 9.11*10<sup>-3</sup>
实施例4 5.28*10<sup>-3</sup>
实施例5 8.49*10<sup>-3</sup>
实施例6 1.03*10<sup>-2</sup>
对比例1 1.96*10<sup>-2</sup>
空白对照组 3.92*10<sup>-2</sup>
从表1可以看出，在表面制备羟基磷灰石生物陶瓷涂层有利于提高钛合金的耐腐蚀性能，在羟基磷灰石生物陶瓷涂层中掺入氧化石墨烯，可以进一步提高其耐腐蚀性能，在本发明的研究范围内，最高可将自腐蚀电流降低至5.28*10-3μA/cm2。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。

Claims (8)

1.一种溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法，包括以下步骤：
A.以钛合金为衬底材料，将钛合金切割成合适大小；
B.对衬底进行预处理，预处理包括脱脂、酸洗、清洗和烘干；
C.制备阳极氧化层；
D.制备溶胶：按照钙磷比=1.67分别配置Ca(NO3)2·4H2O和P2O5的乙醇溶液，陈化12-15h，配置氧化石墨烯乙醇分散液并与P2O5的乙醇溶液混合，然后将混合溶液缓慢滴加至Ca(NO3)2·4H2O的乙醇溶液中，用氨水调节至pH=8，磁力搅拌30-40min，然后室温陈化20-24h，所述氧化石墨烯的质量为P2O5的2.5%-9.0%；
E.制备羟基磷灰石生物陶瓷：把钛合金衬底放置于匀胶机上，将溶胶滴加在衬底表面，以1200-1500r/min的旋涂速度转动30-45s，然后把衬底放置到60-80℃的真空干燥箱中干燥30-60min，而后取出置于马弗炉中400-450℃下保温120-150min，得到羟基磷灰石生物陶瓷涂层。
2.一种如权利要求1所述的方法，其特征在于：所述钛合金为医用钛合金。
3.一种如权利要求1所述的方法，其特征在于：所述脱脂选用浓度为15-20%的碳酸氢钠溶液。
4.一种如权利要求1所述的方法，其特征在于：所述酸洗选用浓度为10-15%的盐酸溶液。
5.一种如权利要求1所述的方法，其特征在于：所述清洗处理为无水乙醇超声清洗。
6.一种如权利要求1所述的方法，其特征在于，所述氧化石墨烯的质量为P2O5的6.3%。
7.一种如权利要求1所述的方法，其特征在于，所述步骤A中将钛合金切割成15×15*2mm的基片。
8.一种如权利要求1所述的方法，其特征在于，所述步骤C具体为：采用直流电源装置提供25-30V阳极氧化电压，以1.5-2.0mol/L H3PO4溶液和1.2 -2.0wt% NH4F溶液为电解质溶液，在钛合金表面阳极氧化100-120min，氧化过程中始终施加磁力搅拌，最后以15-20℃/min的升温速率加热到300-400℃热处理2-2.5h，构建阳极氧化层。
CN202110677606.9A 2021-06-18 2021-06-18 溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法 Active CN113248249B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110677606.9A CN113248249B (zh) 2021-06-18 2021-06-18 溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110677606.9A CN113248249B (zh) 2021-06-18 2021-06-18 溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法

Publications (2)

Publication Number Publication Date
CN113248249A CN113248249A (zh) 2021-08-13
CN113248249B true CN113248249B (zh) 2021-09-21

Family

ID=77188750

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110677606.9A Active CN113248249B (zh) 2021-06-18 2021-06-18 溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法

Country Status (1)

Country Link
CN (1) CN113248249B (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113913805B (zh) * 2021-10-20 2023-08-22 中南大学湘雅医院 一种冷喷涂改性层及其应用
CN115216774B (zh) * 2022-05-27 2023-10-20 北京化工大学 一种生物活性离子掺杂羟基磷灰石钛合金表面涂层及其制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Growth and electrochemical stability of self-organized TiO2 nanotubes on Ti-2 grade and orthopedic Ti6Al4V alloy for biomedical application;Mariana Rossi de Souza等;《RevistaMateria》;20141231;第19卷(第1期);第53-60页 *
n Vitro Electrochemical Behavior of Sol-Gel Derived Hydroxyapatite/Graphene Oxide Composite Coatings on 316L SS for Biomedical Applications;Arul Xavier Stango Sebastin等;《ChemistrySelect》;20201231(第5期);第12140-12147页 *
镁表面制备羟基磷灰石涂层方法研究;王燕等;《科学技术与工程》;20130331;第13卷(第9期);第2470-2473页 *

Also Published As

Publication number Publication date
CN113248249A (zh) 2021-08-13

Similar Documents

Publication Publication Date Title
CN113248249B (zh) 溶胶-凝胶法制备钛合金表面羟基磷灰石生物陶瓷的方法
CN100423794C (zh) 活性生物压电陶瓷涂层及在钛基体表面制备该涂层的方法
CN101302638A (zh) 一种纳米hap涂层/镁合金复合生物材料的制备方法
CN104726921A (zh) 二氧化钛/含锶氟羟基磷灰石生物活性纳米复合涂层及其制备方法和应用
Qiao et al. Composite coatings of lanthanum-doped fluor-hydroxyapatite and a layer of strontium titanate nanotubes: fabrication, bio-corrosion resistance, cytocompatibility and osteogenic differentiation
CN104947097A (zh) 一种纯钛表面磷酸氢钙微纳米纤维转化膜的制备方法
CN109680266A (zh) 一种在钛合金表面制备钽原子掺杂的生物活性陶瓷涂层及其制备方法
CN101385873A (zh) 纳米羟基磷灰石生物复合涂层的制备方法
CN113082290B (zh) 一种具有生物活性和抗菌性能的氧化锌涂层-羟基磷灰石涂层、制备方法及用途
CN102039408A (zh) 多孔钛表面制备具有生物活性陶瓷涂层的方法
CN107998445A (zh) 一种表面修饰多孔钽生物材料及其制备方法
CN109911873B (zh) 一种钛种植体表面组装纳米级羟基磷灰石的方法
CN105862096B (zh) 一种fha生物活性涂层的制备方法
CN108004527A (zh) 一种用于镁合金材料的锌掺杂羟基磷灰石涂层的制备方法
Sandrini et al. Apatite formation and cellular response of a novel bioactive titanium
CN101565824A (zh) 紫外光照射提高钛及其合金表面生物活性的方法
CN112121227A (zh) 一种钛金属表面钛酸锶/锶羟基磷灰石医用复合涂层的制备方法
CN104846371A (zh) 一种在医用镁合金表面制备分子筛涂层的方法
CN103628112A (zh) 一种钛基氧化钛氯化银复合涂层材料的制备方法
CN107338425A (zh) 一种钛表面含锶磷酸盐生物活性转化膜的制备方法
CN109778160A (zh) 医用镁合金植入体用处理剂及其使用方法
CN102691087A (zh) 一种提高医用β型钛合金表面生物活性的表面处理方法
CN105220202B (zh) 一种钛基三维多孔二氧化钛氧化层的制备方法
CN108103551B (zh) 一种促进微弧氧化膜层中羟基磷灰石结晶的方法
CN105420786A (zh) 一种钛表面纳米硅钛酸钠/二氧化钛生物涂层的制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant