CN114717542A - 光催化和光热双重机制抗菌的碗状钛合金表面改性方法 - Google Patents
光催化和光热双重机制抗菌的碗状钛合金表面改性方法 Download PDFInfo
- Publication number
- CN114717542A CN114717542A CN202210351948.6A CN202210351948A CN114717542A CN 114717542 A CN114717542 A CN 114717542A CN 202210351948 A CN202210351948 A CN 202210351948A CN 114717542 A CN114717542 A CN 114717542A
- Authority
- CN
- China
- Prior art keywords
- titanium
- titanium alloy
- bowl
- polymer
- photocatalysis
- 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.)
- Granted
Links
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 62
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 16
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 16
- 238000002715 modification method Methods 0.000 title claims abstract description 10
- 230000003115 biocidal effect Effects 0.000 title claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229920000642 polymer Polymers 0.000 claims abstract description 66
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000010936 titanium Substances 0.000 claims abstract description 60
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 40
- 239000004005 microsphere Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 15
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000005498 polishing Methods 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims abstract description 4
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- 238000007348 radical reaction Methods 0.000 claims abstract description 3
- 150000003254 radicals Chemical class 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 230000009977 dual effect Effects 0.000 claims description 11
- 230000007246 mechanism Effects 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004528 spin coating Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 26
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- OYZDSTHSJLIZOU-UHFFFAOYSA-N [Fe].[Nb].[Zr].[Ti] Chemical compound [Fe].[Nb].[Zr].[Ti] OYZDSTHSJLIZOU-UHFFFAOYSA-N 0.000 description 9
- 238000005286 illumination Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229920000361 Poly(styrene)-block-poly(ethylene glycol) Polymers 0.000 description 5
- 239000007943 implant Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000592 Ferroniobium Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 210000002449 bone cell Anatomy 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 102400001284 Vessel dilator Human genes 0.000 description 1
- 108010090012 atrial natriuretic factor prohormone (31-67) Proteins 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000008499 blood brain barrier function Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000001218 blood-brain barrier Anatomy 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 210000004394 hip joint Anatomy 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000003910 polypeptide antibiotic agent Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
- C23C18/1216—Metal oxides
-
- 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
- A61L27/34—Macromolecular materials
-
- 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
-
- 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
-
- 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
- A61L27/56—Porous materials, e.g. foams or sponges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- A61L2300/404—Biocides, antimicrobial agents, antiseptic 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
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
-
- 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
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Transplantation (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Materials For Medical Uses (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种碗状钛合金表面改性方法，步骤如下：一、将样品清洗打磨抛光；二、通过可控自由基反应合成不同分子量的嵌段聚合物；三、将嵌段聚合物分散在乙醇/四氢呋喃的混合溶剂中，加入钛酸四丁酯溶液经水解反应后，离心收集二氧化钛前驱体/聚合物微球；四、将核壳结构的二氧化钛前驱体/聚合物微球旋涂在钛及钛合金表面，烧结后医用钛及钛合金表面就具有碗状结构。得到的钛及钛合金表面，具有高效的光催化和光热性能，且突破二氧化钛吸收紫外光的局限性，在红外光的辐照下具有优异的抗菌性能，相比金属基体表面抗菌率达100％。
Description
技术领域
本发明属于材料表面改性领域，涉及一种对医用钛合金表面改性的方法，通过在钛合金表面碗状结构的改性以获得优异的生物学性能和抗菌性能。
背景技术
钛及钛合金具有优异的力学性能、生物相容性、耐腐蚀性、易加工成形、无磁性无毒等优点，其制造的人造骨头、髋关节、以及血管扩张器、夹板、假体、紧固螺钉等上百种金属植入物在临床应用中都获得较好反馈，使其成为目前医学临床中较理想的植入物材料。但是钛及钛合金植入物在临床中，常出现由于金属表面生物惰性引起的免疫炎症反应和在植入过程中植入物的局部细菌感染等问题，所以钛及钛合金表面抗菌功能化改性成为研究热点。
现有技术中，对于钛合金植入物的抗菌功能化的改性主要借助于表面负载抗菌离子，或者在其表面制备抗菌性的聚合物涂层，达到抗菌的目的。例如中国专利CN 103014646A公布了一种兼具成骨及抗菌性能的钛表面改性方法，该发明采用等离子体浸没离子注入处理工艺将银离子和钙离子共注入钛合金材料表面，使得钛合金表面兼具促成骨和抗菌性能。但是此类方法有明显的缺点，负载抗菌离子虽然可以降低感染风险，但往往也会引发全身毒副作用，人体组织液相当于无限稀释植入物表面负载的抗菌离子，在体液循环下将抗菌性的金属离子带往人体各处，甚至突破血脑屏障造成危险。中国专利CN107137762A公布了一种医用钛或钛合金表面抗菌涂层的构建方法，将聚合物和抗菌肽做成涂层固化在金属基体表面，此发明可以显著提高金属植入物的抗菌性能，但是可能有聚合物涂层存在降解快，抗菌性不足的问题。
因此虽然现有技术存在对钛合金及其表面的抗菌性能的研究和改进，但是还是存在一些不足，例如引发的毒副作用对人体感染的风险以及抗菌涂层化学稳定性不足导致抗菌性能下降的问题。因此有必要提出一种抗菌性能稳定以及良好的生物相容性的钛合金表面改性方法。
发明内容
为了克服现有技术的上述缺点与不足,本发明的目的在于提供一种医用钛及钛合金表面光催化和光热双重机制抗菌的纳米结构表面改性的方法。该方法通过使用富含C和N元素的聚合物作为模板，与钛酸四丁酯发生水解反应，生成二氧化钛前驱体微球，在钛及钛合金表面涂覆后烧结，在钛及钛合金表面得到纳米碗状结构的二氧化钛涂层。具有碗状结构的样品表面在近红外光的照射下，发生光催化和光热反应，释放ROS离子和局部热量，使金属植入物具有抗菌性能。
表面的纳米碗状结构在效果上，相比普通的金属基体表面，不仅具有长效抗菌性,还有良好的生物相容性，可促骨细胞增殖和黏附。
本发明提供了一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，包括以下步骤：
(1)试样预处理：将纯钛或钛合金试样进行机械研磨、抛光，然后依次浸入丙酮、酒精和去离子水中分别进行超声清洗各5min，然后吹干待用；
(2)聚合物合成：将嵌段聚合物原料通过可控自由基反应合成，根据投料比和反应时间的不同，加入0.1～1％的链引发剂，制备不同分子量的两嵌段聚合物，冻干备用；
(3)将上述两嵌段聚合物分散在乙醇/四氢呋喃的混合溶剂中，挥发掉四氢呋喃，加入钛酸四丁酯溶液和100μL的盐酸，搅拌一段时间后，离心收集核壳结构的二氧化钛前驱体/聚合物微球，转移至定量的乙醇溶液中备用；
(4)将核壳结构的二氧化钛前驱体/聚合物微球旋涂在钛及钛合金表面，分别在氮气氛和空气中烧结一段时间，自然冷却后最终得到具有碗状结构表面的钛及钛合金。
在一个优选的实施例中，上述方法，所述步骤(2)中使用的嵌段聚合物可以是两嵌段也可以是三嵌段聚合物。
在一个优选的实施例中，上述方法中，所述步骤(2)所述嵌段聚合物富含碳和氮元素，且在乙醇溶剂中自组装成球。
在一个优选的实施例中，上述方法中，所述步骤(1)中钛合金为钛锆铌铁合金。
在一个优选的实施例中，上述方法中，所述步骤(1)中纯钛及钛合金为片状试样，研磨面为平面，试样尺寸可根据需要调节。
在一个优选的实施例中，上述方法中，所述步骤(2)中选择的聚合物必须含有丰富的碳和氮元素，聚合物种类可以根据需要选择，反应时间为12～48h，单体投料比为1：50～1：200。
在一个优选的实施例中，上述方法中，所述步骤(3)中两嵌段聚合物的用量浓度是0.5～2.0mg/mL，钛酸四丁酯的用量根据聚合物的浓度用量为0.1～2mL/mL，搅拌时间为6～48h，离心速度为5000～8000rpm。
在一个优选的实施例中，上述方法中，所述步骤(4)中在钛及钛合金表面旋涂的二氧化钛前驱体/聚合物微球的浓度为0.5～2mg/mL，旋涂量根据钛及钛合金的表面积用量为50～1000μL/cm2，旋涂次数为1～4次。
在一个优选的实施例中，上述方法中，氮气烧结的温度为400～600℃，时间为1～3h，空气中烧结的温度为400～600℃，时间为1～2h。
本发明的有益效果：
(1)本发明发明的碗状表面结构改性方法，操作简单快捷，制备时间短，加工效率高，成本低，可适用范围广，可以快速高效地在钛及钛合金样品表面制备碗状结构的二氧化钛涂层，具有实用推广价值。
(2)本发明创造性的将聚合物自组装成球和钛及钛合金的表面改性结合起来，为未来钛及钛合金表面多孔结构和涂层功能化的改性方法提供思路和理论基础。
(3)采用本发明在钛及钛合金表面制备的纳米碗状二氧化钛涂层，在近红外光照下半小时，相比金属基体表面，碗状表面可以100％抗菌，且可一直重复使用，抗菌性不会改变，在抗菌的同时，促成骨细胞增殖和黏附的效果明显，有利于骨愈合。
附图说明
附图1是本发明在钛及钛合金表面制备碗状结构表面的流程示意图；
附图2是两嵌段聚合和二氧化钛前驱体制备的核壳结构微球的扫描电镜图；
附图3是钛合金表面制备碗状结构的扫描电镜图；
附图4是钛合金试样经红外光照半小时的表面温度变化统计图；
附图5是钛合金试样经红外光照半小时后抗菌率统计图；
附图6是为钛合金试样经抗菌实验后的平板菌落图。
具体实施方式
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的模块或具有相同或类似功能的模块。下面通过参考附图描述的实施例是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。
在本说明书的描述中，参考术语“一个实施例”、“另一个实施例”等的描述意指结合该实施例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
本发明在钛及钛合金表面制备碗状结构表面的流程示意图，如附图1所示。流程包括：
聚合物合成→制备得到二氧化钛前驱体/聚合物微球→旋涂预处理的钛及钛合金表面→烧结得到具有碗状结构表面的钛及钛合金。
具体地：聚合物原料置于乙醇中，添加链引发剂，优选还包括催化剂，反应得到两嵌段聚合物；将上述产物置于四氢呋喃和乙醇混合溶液中，挥发四氢呋喃溶剂，加入钛酸四丁酯、盐酸和的水，反应得到核壳结构的二氧化钛前驱体/聚合物微球，然后涂布，烧结，得到最终碗状结构表面的钛及钛合金。
具体地，下面阐述具体实施例中在钛锆铌铁合金表面制备碗状结构的工艺。
实施例1：使用聚苯乙烯-聚乙烯吡啶(PS-P4VP)作为聚合物模板在钛锆铌铁合金表面制备碗状结构
现采用上述装置对长×宽×厚为10×10×1mm的钛锆铌铁合金试样进行试验，其操作步骤如下：
(1)钛锆铌铁合金试样预处理：将钛锆铌铁合金试样进行机械研磨、抛光，然后依次浸入丙酮、酒精和去离子水中分别进行超声清洗各5min，然后吹干待用；
(2)PS-P4VP两嵌段聚合物合成：将3.75mL的4-乙烯吡啶(4VP)置于5mL乙醇中，添加0.1g链引发剂和0.01g催化剂，在油浴70℃条件下反应24h，用石油醚和乙醇反复沉降，最后乙醇清洗保存待用，将聚合物P4VP和苯乙烯单体按1：200的投料比置于甲醇溶液中，在油浴70℃条件下反应48h，最终得到两嵌段聚合物PS-P4VP；
(3)将2mg/mL的PS-P4VP置于3mL四氢呋喃和2mL的乙醇混合溶液中，慢慢挥发四氢呋喃溶剂，再加入200μL钛酸四丁酯、100μL的盐酸和100μL的水，反应24h后得到核壳结构的二氧化钛前驱体/聚合物微球(如图2)。
(4)将50μL的二氧化钛前驱体/聚合物微球旋涂在钛锆铌铁合金表面，重复两次，放于550℃氮气中烧结2h，再置于450℃的空气中烧结1h，最终在钛锆铌铁合金表面得到碗状结构(如图3)。
经上述处理，在钛锆铌铁合金试样表面制备了碗径约100nm的碗状二氧化钛涂层，富含C和N元素的碗状二氧化钛涂层可以较小二氧化钛的禁带宽度，使其表面可以高效利用近红外光，而不是在长期照射下对人体有害的紫外光。在近红外光半小时内的光照下，钛锆铌铁金属表面和钛锆铌铁碗状表面的温度有较大差异，碗状表面可以更高效的折射近红外光，使表面局部温度达到52℃(如图4)。在近红外光的半小时的光照下，本发明的钛锆铌铁合金表面制备碗状结构，对于金黄色葡萄球菌和大肠杆菌的抗菌率达到100％，而钛锆铌铁金属基体表面只有30％左右(如图5和6)。
实施例2：使用PS-P4VP作为聚合物模板在纯钛表面制备碗状结构
现采用上述装置对长×宽×厚为10×10×1mm的纯钛试样进行试验，其操作步骤如下：
(1)纯钛试样预处理：将纯钛试样进行机械研磨、抛光，然后依次浸入丙酮、酒精和去离子水中分别进行超声清洗各5min，然后吹干待用；
(2)PS-P4VP两嵌段聚合物合成：将6.5mL的4-乙烯吡啶(4VP)置于10mL乙醇中，添加0.1g链引发剂和0.01g催化剂，在油浴70℃条件下反应48h，用石油醚和乙醇反复沉降，最后乙醇清洗保存待用，将聚合物P4VP和苯乙烯单体按1：100的投料比置于甲醇溶液中，在油浴70℃条件下反应48h，最终得到两嵌段聚合物PS-P4VP；
(3)将1mg/mL的PS-P4VP置于2mL四氢呋喃和6mL的乙醇混合溶液中，慢慢挥发四氢呋喃溶剂，再加入400μL钛酸四丁酯、200μL的盐酸和200μL的水，反应48h后得到核壳结构的二氧化钛前驱体/聚合物微球。
(4)将100μL的二氧化钛前驱体/聚合物微球旋涂在纯钛表面，放于550℃氮气中烧结2h，再置于450℃的空气中烧结1h，最终在钛锆铌铁合金表面得到碗状结构。
经上述处理，在纯钛试样表面制备了碗径200nm的碗状二氧化钛涂层，富含C和N元素的碗状二氧化钛涂层可以较小二氧化钛的禁带宽度，使其表面可以高效利用近红外光，而不是在长期照射下对人体有害的紫外光。在近红外光半小时内的光照下，纯钛表面和纯钛碗状表面的温度有较大差异，碗状表面可以更高效的折射近红外光，使表面局部温度达到50℃。在30min的近红外光光照下，对于金黄色葡萄球菌和大肠杆菌的抗菌率达到100％。
实施例3：使用聚苯乙烯-聚乙二醇(PS-PEG)作为聚合物模板在纯钛表面制备碗状结构
现采用上述装置对长×宽×厚为10×10×1mm的纯钛试样进行试验，其操作步骤如下：
(1)纯钛试样预处理：将纯钛试样进行机械研磨、抛光，然后依次浸入丙酮、酒精和去离子水中分别进行超声清洗各5min，然后吹干待用；
(2)PS-PEG两嵌段聚合物合成：将5.0mL的乙二醇置于10mL乙醇中，添加0.1g链引发剂和0.01g催化剂，在油浴70℃条件下反应48h，用石油醚和乙醇反复沉降，最后乙醇清洗保存待用，将聚合物PEG和苯乙烯单体按1：200的投料比置于甲醇溶液中，在油浴70℃条件下反应48h，最终得到两嵌段聚合物PS-PEG；
(3)将1mg/mL的PS-PEG置于2mL四氢呋喃和3mL的乙醇混合溶液中，慢慢挥发四氢呋喃溶剂，再加入100μL钛酸四丁酯、100μL的盐酸和100μL的水，反应48h后得到核壳结构的二氧化钛前驱体/聚合物微球。
(4)将50μL的二氧化钛前驱体/聚合物微球旋涂在纯钛表面，重复旋涂3次，放于550℃氮气中烧结2h，再置于450℃的空气中烧结1h，最终在纯钛表面得到碗状结构。
经上述处理，在纯钛试样表面制备了碗径200nm的碗状二氧化钛涂层。在近红外光半小时内的光照下，纯钛表面和纯钛碗状表面的温度有较大差异，碗状表面可以更高效的折射近红外光，使表面局部温度达到50℃。在30min的近红外光光照下，对于金黄色葡萄球菌和大肠杆菌的抗菌率达到100％。
显然，上述实施例仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而这些属于本发明的精神所引伸出的显而易见的变化或变动仍处于本发明的保护范围之中。
Claims (10)
1.一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，其特征在于：包括以下步骤：
(1)试样预处理：将纯钛或钛合金试样进行机械研磨、抛光，然后依次浸入丙酮、酒精和去离子水中分别进行超声清洗各5min，然后吹干待用；
(2)聚合物合成：将嵌段聚合物原料通过可控自由基反应合成，根据投料比和反应时间的不同，加入0.1～1％的链引发剂，制备不同分子量的两嵌段聚合物，冻干备用；
(3)将上述两嵌段聚合物分散在乙醇/四氢呋喃的混合溶剂中，慢慢挥发掉四氢呋喃，加入钛酸四丁酯溶液和100μL的盐酸，搅拌一段时间后，离心收集核壳结构的二氧化钛前驱体/聚合物微球，转移至定量的乙醇溶液中备用；
(4)将核壳结构的二氧化钛前驱体/聚合物微球旋涂在钛及钛合金表面，分别在氮气氛和空气中烧结一段时间，自然冷却后最终得到具有碗状结构表面的钛及钛合金。
2.根据权利要求1所述的一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，其特征在于：所述步骤(1)中钛及钛合金为片状试样，研磨面为平面，可根据需要改变试样尺寸。
3.根据权利要求1所述的一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，其特征在于：所述步骤(2)中使用的嵌段聚合物原料可以是两嵌段也可以是三嵌段聚合物。
4.根据权利要求3所述的一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，其特征在于：所述嵌段聚合物原料富含碳和氮元素，且在乙醇溶剂中自组装成球。
5.根据权利要求1所述的一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，其特征在于：所述步骤(2)中制备的所述两嵌段聚合物的分子量在5000～20000。
6.根据权利要求1所述的一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，所述步骤(2)中聚合物反应时间为12～48h，反应温度为50～80℃，单体投料比为1：50～1：400。
7.根据权利要求1所述的一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，其特征在于：所述步骤(3)中两嵌段聚合物的用量浓度是0.5～2.0mg/mL，钛酸四丁酯的用量根据聚合物的浓度用量为0.1～2mL/mL。
8.根据权利要求1所述的一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，其特征在于：所述步骤(4)中在钛及钛合金表面旋涂的二氧化钛前驱体/聚合物微球的浓度为0.5～2mg/mL。
9.根据权利要求1所述的一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，其特征在于：所述步骤(4)中微球旋涂量根据钛及钛合金的表面积用量为50～1000μL/cm2，旋涂次数为1～4次。
10.根据权利要求1所述的一种具有光催化和光热双重机制抗菌的碗状钛合金表面改性方法，其特征在于：所述步骤(4)中氮气烧结的温度为400～600℃，时间为1～3h，空气中烧结的温度为400～600℃，时间为1～2h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210351948.6A CN114717542B (zh) | 2022-04-02 | 2022-04-02 | 光催化和光热双重机制抗菌的碗状钛合金表面改性方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210351948.6A CN114717542B (zh) | 2022-04-02 | 2022-04-02 | 光催化和光热双重机制抗菌的碗状钛合金表面改性方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114717542A true CN114717542A (zh) | 2022-07-08 |
| CN114717542B CN114717542B (zh) | 2024-05-03 |
Family
ID=82241594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210351948.6A Active CN114717542B (zh) | 2022-04-02 | 2022-04-02 | 光催化和光热双重机制抗菌的碗状钛合金表面改性方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114717542B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114481015A (zh) * | 2021-12-20 | 2022-05-13 | 安徽理工大学 | 一种富含CaTiO3的纳米晶β型钛合金的制备方法、制得的钛合金 |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0959042A (ja) * | 1995-06-14 | 1997-03-04 | Toto Ltd | 防曇性コーティングを備えた透明基材 |
| DE19747816A1 (de) * | 1997-10-29 | 1999-05-06 | Univ Ulm | Nanostrukturierung von Oberflächen |
| WO2002087339A1 (en) * | 2001-04-30 | 2002-11-07 | Ak Properties, Inc. | Antimicrobial powder coated metal sheet |
| JP2004344688A (ja) * | 2003-05-19 | 2004-12-09 | Asahi Kasei Chemicals Corp | 塗布用シ−ト |
| US20050224779A1 (en) * | 2003-12-11 | 2005-10-13 | Wang Zhong L | Large scale patterned growth of aligned one-dimensional nanostructures |
| JP2007289629A (ja) * | 2006-03-25 | 2007-11-08 | Soga:Kk | 抗菌コーティング剤およびその施用方法ならびにそのコーティングを施した物 |
| CN102100926A (zh) * | 2010-06-21 | 2011-06-22 | 浙江工业大学 | 一种医用钛或钛合金表面活化改性方法 |
| CN102275983A (zh) * | 2011-07-18 | 2011-12-14 | 北京科技大学 | 一种二氧化钛碗状颗粒或哑铃形中空颗粒及其制备方法 |
| US20120059240A1 (en) * | 2008-06-24 | 2012-03-08 | Massachusetts Institute Of Technology | Method for preparation of micellar hybrid nanoparticles for therapeutic and diagnostic applications and compositions thereof |
| CN105529404A (zh) * | 2015-12-21 | 2016-04-27 | 吉林大学 | 一种具有二维纳米碗阵列陷光结构的有机太阳能电池及其制备方法 |
| CN106629747A (zh) * | 2017-01-20 | 2017-05-10 | 中国科学院宁波材料技术与工程研究所 | 一种空心碗状二氧化硅纳米颗粒及其制备方法和应用 |
| WO2017160242A1 (en) * | 2016-03-14 | 2017-09-21 | Chulalongkorn University | Titanium dioxide catalyst supported on polymer film or membrane substrate and preparation method thereof |
| CN110917349A (zh) * | 2019-12-11 | 2020-03-27 | 南京师范大学 | 一种碗状isp复合功能性纳米粒子及其制备方法和应用 |
| CN112593231A (zh) * | 2020-12-16 | 2021-04-02 | 北京航空航天大学 | 一种纯钛或钛合金表面制备含Ag抗菌颗粒的方法 |
| KR102240107B1 (ko) * | 2019-11-06 | 2021-04-15 | 한국과학기술원 | 그릇 형태의 메조다공성 나노입자, 이의 제조방법 및 이를 포함하는 이차전지용 음극물질 |
| US20210403338A1 (en) * | 2020-06-24 | 2021-12-30 | Nanchang University | Dual light-responsive zinc oxide and preparation method thereof as well as photosensitive coating with antibacterial/osteogenic properties |
-
2022
- 2022-04-02 CN CN202210351948.6A patent/CN114717542B/zh active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0959042A (ja) * | 1995-06-14 | 1997-03-04 | Toto Ltd | 防曇性コーティングを備えた透明基材 |
| DE19747816A1 (de) * | 1997-10-29 | 1999-05-06 | Univ Ulm | Nanostrukturierung von Oberflächen |
| WO2002087339A1 (en) * | 2001-04-30 | 2002-11-07 | Ak Properties, Inc. | Antimicrobial powder coated metal sheet |
| JP2004344688A (ja) * | 2003-05-19 | 2004-12-09 | Asahi Kasei Chemicals Corp | 塗布用シ−ト |
| US20050224779A1 (en) * | 2003-12-11 | 2005-10-13 | Wang Zhong L | Large scale patterned growth of aligned one-dimensional nanostructures |
| JP2007289629A (ja) * | 2006-03-25 | 2007-11-08 | Soga:Kk | 抗菌コーティング剤およびその施用方法ならびにそのコーティングを施した物 |
| US20120059240A1 (en) * | 2008-06-24 | 2012-03-08 | Massachusetts Institute Of Technology | Method for preparation of micellar hybrid nanoparticles for therapeutic and diagnostic applications and compositions thereof |
| CN102100926A (zh) * | 2010-06-21 | 2011-06-22 | 浙江工业大学 | 一种医用钛或钛合金表面活化改性方法 |
| CN102275983A (zh) * | 2011-07-18 | 2011-12-14 | 北京科技大学 | 一种二氧化钛碗状颗粒或哑铃形中空颗粒及其制备方法 |
| CN105529404A (zh) * | 2015-12-21 | 2016-04-27 | 吉林大学 | 一种具有二维纳米碗阵列陷光结构的有机太阳能电池及其制备方法 |
| WO2017160242A1 (en) * | 2016-03-14 | 2017-09-21 | Chulalongkorn University | Titanium dioxide catalyst supported on polymer film or membrane substrate and preparation method thereof |
| CN106629747A (zh) * | 2017-01-20 | 2017-05-10 | 中国科学院宁波材料技术与工程研究所 | 一种空心碗状二氧化硅纳米颗粒及其制备方法和应用 |
| KR102240107B1 (ko) * | 2019-11-06 | 2021-04-15 | 한국과학기술원 | 그릇 형태의 메조다공성 나노입자, 이의 제조방법 및 이를 포함하는 이차전지용 음극물질 |
| CN110917349A (zh) * | 2019-12-11 | 2020-03-27 | 南京师范大学 | 一种碗状isp复合功能性纳米粒子及其制备方法和应用 |
| US20210403338A1 (en) * | 2020-06-24 | 2021-12-30 | Nanchang University | Dual light-responsive zinc oxide and preparation method thereof as well as photosensitive coating with antibacterial/osteogenic properties |
| CN112593231A (zh) * | 2020-12-16 | 2021-04-02 | 北京航空航天大学 | 一种纯钛或钛合金表面制备含Ag抗菌颗粒的方法 |
Non-Patent Citations (2)
| Title |
|---|
| YAYUAN LI ET AL.: "Carbon and nitrogen co-doped bowl-like Au/TiO2 nanostructures with tunable size for enhanced visible-light-driven photocatalysis", 《APPLIED SURFACE SCIENCE》, 26 March 2018 (2018-03-26), pages 350 - 358, XP085383092, DOI: 10.1016/j.apsusc.2018.03.187 * |
| 李贞子等: "《黑色二氧化钛可见光催化材料的制备与应用》", 上海交通大学出版社, pages: 145 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114481015A (zh) * | 2021-12-20 | 2022-05-13 | 安徽理工大学 | 一种富含CaTiO3的纳米晶β型钛合金的制备方法、制得的钛合金 |
| CN114481015B (zh) * | 2021-12-20 | 2023-10-03 | 安徽理工大学 | 一种富含CaTiO3的纳米晶β型钛合金的制备方法、制得的钛合金 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114717542B (zh) | 2024-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113527748B (zh) | 一种聚醚醚酮表面改性方法及改性得到的聚醚醚酮及其应用 | |
| US20130045266A1 (en) | Method for preparing polymeric biomaterials having immobilized drug delivery system comprising bioactive molecules loaded particle carrier | |
| CN1836743A (zh) | 多孔、分层、三维空间多级结构的组织支架材料及其制备方法 | |
| KR100791512B1 (ko) | 나노구조로 이루어진 하이브리드형 조직재생용 멤브레인과스캐폴드 및 그들의 제조방법 | |
| CN114717542A (zh) | 光催化和光热双重机制抗菌的碗状钛合金表面改性方法 | |
| CN1944529A (zh) | 可生物降解的二氧化硅/聚乳酸纳米复合材料的制备方法 | |
| CN113546221B (zh) | 一种镁基复合材料及其制备方法和应用 | |
| CN112402693A (zh) | 一种表面具有促成骨涂层的骨科植入器械及制备方法 | |
| Bretcanu et al. | Biodegradable polymer coated 45S5 Bioglassderived glass-ceramic scaffolds for bone tissue engineering | |
| CN115350334B (zh) | 一种聚酰亚胺基复合气凝胶材料的制备方法、产品及应用 | |
| CN114377196B (zh) | 一种兼具生物活性和抗菌的涂层及其应用 | |
| CN1222326C (zh) | 一种由线型聚氨酯嵌段共聚物组成的医用薄膜及其生产方法 | |
| Lai et al. | Comparative evaluation of the biocompatible and physical–chemical properties of poly (lactide-co-glycolide) and polydopamine as coating materials for bacterial cellulose | |
| TW201720472A (zh) | 一種兼具抗菌及促進細胞生長特性之表面改質牙材及其製備方法 | |
| CN109205581B (zh) | 一种具有光热协同抗菌性能的复合羟基磷灰石粉末的制备方法 | |
| CN110801536B (zh) | 一种有机包裹的磁纳米粒子复合骨支架及其制备方法 | |
| CN110551180A (zh) | 一种具有响应效应的多功能植入体及其制备方法与应用 | |
| CN1216653C (zh) | 一种用于引导组织再生的复合膜制备方法 | |
| Wang et al. | A study on PLGA sustained release icariin/titanium dioxide nanotube composite coating. | |
| CN1314462C (zh) | 纳米结构化可降解生物医用复合材料及其制备方法 | |
| Li et al. | Synthesis and characterization of core-shell hydroxyapatite/chitosan biocomposite nanospheres | |
| CN112516386A (zh) | 聚乳酸-多巴胺-二氧化硅纤维膜及其制备方法 | |
| Mochizuki et al. | Crystallinity control of apatite through Ca‐EDTA complexes and porous composites with PLGA | |
| Bhat et al. | Polymer/silica Composites Fabricated by Sol-Gel Technique for Medical Applications. | |
| CN112745142A (zh) | 具有抗菌功能的石墨烯/磷酸钙陶瓷复合支架及制备方法 |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240205 Address after: Room 301, Building 21, Beihang Science and Technology Park, No. 77 Aerospace Road, Mashan Street, High tech Zone, Yantai City, Shandong Province, China, 264035 Applicant after: Lidong New Materials Technology (Shandong) Co.,Ltd. Country or region after: China Address before: 410000 1004, building F1, Lugu enterprise Plaza, Changsha high tech Development Zone, Hunan Province Applicant before: Hunan Lidong Technology Co.,Ltd. Country or region before: China |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |