CN106245091A - Composite titania material and its preparation method and application - Google Patents
Composite titania material and its preparation method and application Download PDFInfo
- Publication number
- CN106245091A CN106245091A CN201610594250.1A CN201610594250A CN106245091A CN 106245091 A CN106245091 A CN 106245091A CN 201610594250 A CN201610594250 A CN 201610594250A CN 106245091 A CN106245091 A CN 106245091A
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- CN
- China
- Prior art keywords
- preparation
- composite titania
- electrolyte
- deionized water
- alcohol
- 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.)
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 61
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 239000003792 electrolyte Substances 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- 239000008367 deionised water Substances 0.000 claims description 46
- 229910021641 deionized water Inorganic materials 0.000 claims description 46
- 230000003647 oxidation Effects 0.000 claims description 43
- 238000007254 oxidation reaction Methods 0.000 claims description 43
- 229910021389 graphene Inorganic materials 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 239000002028 Biomass Substances 0.000 claims description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 235000021110 pickles Nutrition 0.000 claims description 21
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000002096 quantum dot Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000004070 electrodeposition Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229960004756 ethanol Drugs 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000003519 biomedical and dental material Substances 0.000 claims description 2
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 206010061218 Inflammation Diseases 0.000 abstract description 3
- 230000004663 cell proliferation Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 210000002449 bone cell Anatomy 0.000 abstract 1
- 239000010408 film Substances 0.000 description 41
- 239000002071 nanotube Substances 0.000 description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 17
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000000956 alloy Substances 0.000 description 17
- 239000010936 titanium Substances 0.000 description 17
- 229910052719 titanium Inorganic materials 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 238000004506 ultrasonic cleaning Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000005498 polishing Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 229920005610 lignin Polymers 0.000 description 6
- 230000001582 osteoblastic effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000002062 proliferating effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 239000005445 natural material Substances 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 201000010814 Synostosis Diseases 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000476 body water Anatomy 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- BVBRZOLXXOIMQG-UHFFFAOYSA-N fluoroborane Chemical compound FB BVBRZOLXXOIMQG-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000002188 osteogenic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- 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
- A61L27/306—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
- A61L27/50—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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/106—Halogens or compounds thereof, e.g. iodine, chlorite
-
- 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
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/108—Elemental carbon, e.g. charcoal
-
- 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
- A61L2300/41—Anti-inflammatory agents, e.g. NSAIDs
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
-
- 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)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dermatology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Biomedical Technology (AREA)
- Dispersion Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of composite titania material and its preparation method and application, and described composite titania material at least includes titanium dioxide and adulterate fluorine on the titanium dioxide or carbon, or doped with fluorine and carbon simultaneously.Composite titania material good biocompatibility of the present invention, the most also has anti-inflammation and promotes the effect of bone cell proliferation, having the strongest applicability, be also used as catalysis material simultaneously.
Description
Technical field
The present invention relates to a kind of composite titania material and its preparation method and application.
Background technology
Titanium or titanium alloy has high specific strength, highly corrosion resistant and excellent biocompatibility, is widely used by clinic
For implants such as orthopaedics, dentistry and angiocarpy brackets.But the passivation state titanium dioxide film that its surface grows naturally makes it present
Biologically inert, it is impossible to form effective chemistry synostosis with surrounding bony tissue.Therefore, by changing the knot of passive state oxide-film
Structure: include compactness, roughness, porous or three-dimensional order titania nanotube, and chemical composition can make it convert
For active oxidation film, not only can retain the mechanical property that titanium material is excellent, and can change according to specific clinical application demand
Kind relevant nature, such as character such as biocompatibility, Integrated implant ability, bacterial-infection resistings, is of great immediate significance to clinic.
Through retrieval to prior art, find titanium oxide film layer is carried out the element dopings such as ferrum, sulfur, nitrogen, carbon, fluorine/
Codope has been used in photocatalysis field.ZL200610030924.1 discloses a kind of with titanium carbide as raw material, through anodic oxygen
The method changing the carbon doping Nano-titania Porous Films of preparation, thin film has high photoelectric activity.
ZL201510570653.8 discloses one and utilizes primary reconstruction electrodeposition technology by Graphene and TiO2Nano-tube array is multiple
Closing the method making electrode material, the heat-conductivity conducting performance of electrode is better than single quasiconductor TiO2Nanotube.
ZL200910156957.4 discloses a kind of anodizing and prepares the TiO of sulfur-fluorin-doped2Nanotube.
ZL200910156958.9 discloses a kind of chemical vapour deposition technique and prepares the TiO of fluoro-boron codope2Nanotube.
ZL200910156958.9 discloses a kind of anodizing and prepares the TiO of ferrum-nitrogen-fluorin-doped2Nanotube, codope has
Cooperative effect can improve the photocatalysis performance of titanium dioxide further.
Biological field has strict selectivity to doped chemical, adulterates or compound element must be nontoxic, and have life
The thing compatibility, the carbon in the present invention and fluorine element, there is anti-inflammation, promote cell proliferation mineralising, improve osteogenic
Effect.Build titanium dioxide different structure at titanium alloy surface, carry out fluorine carbon doping, can be applicable to medical embedded material field,
It is also used as catalysis material.
Summary of the invention
It is an object of the invention to provide composite titania material and its preparation method and application, the system of this compound system
Preparation Method control is strong, can prepare smooth titanium deoxid film, porous silica titanium film and three-dimensional order titania nanotube
Array, has the excellent properties improving cell adhesion, promoting Oesteoblast growth, is also used as catalysis material simultaneously, increase
Add light-catalysed effect.
The first aspect of the invention is to disclose a kind of composite titania material, and described composite titania material is extremely
Include titanium dioxide and adulterate fluorine on the titanium dioxide or carbon, or doped with fluorine and carbon simultaneously less.
Further, the content of described fluorine is less than or equal to 15%.
Another aspect of the present invention is to provide the preparation method of a kind of composite titania material, at least includes following step
Rapid:
(1) electrolyte quota: preparation electrolyte；
(2) anodized: employing titanium alloy is anode, the electrolyte Anodic Oxidation prepared in step (1) processes；
(3) post processing: the titanium alloy processed by step 3 Anodic Oxidation carries out heat treatment.
Heat-treating methods uses general metal heating processing technology, including heating, is incubated and cools down.
Further, described step (2) Anodic Oxidation also includes pretreatment before processing: polished by titanium alloy, immerses acid
Washing liquid is cleaned, rinses, be dried.
Further, in described step (2), pretreatment also includes any one in techniques below feature or multinomial:
1) described pickle is HF, HNO3With the mixed liquor of deionized water, HF, HNO3It is 1～4 with deionized water volume ratio:
1.5～6:50～200；
2) pickling time is 10～50s；
3) concrete grammar rinsed is to rinse with deionized water, dehydrated alcohol successively.
Further, in described step (1), the compound method of electrolyte includes:
1) by HF, H3PO4Add in deionized water water, stirring, obtain basic electrolyte；
2) in basic electrolyte, alcohol or carbon source or both mixture are added.
Further, described alcohol in methanol, ethanol or ethylene glycol any one or multiple.
Further, when described step (1) is added alcohol, the mixing that in described electrolyte, alcohol forms with deionized water
In solvent, the concentration of HF is (0.1～1.0) wt%, H3PO4Concentration be (0.1～3) mol/L, described alcohol and the body of deionized water
Long-pending ratio is 0～7:1～3；
Or when adding carbon source in described step (1), in described electrolyte, the concentration of HF is (0.1～1.0) wt%, institute
State H3PO4Concentration be (0.1～3) mol/L, described carbon source is (0～5) g/L；
Or when described step (1) is added alcohol and carbon source, the mixing that in described electrolyte, alcohol forms with deionized water
In solvent, the concentration of HF is (0.1～1.0) wt%, H3PO4Concentration be (0.1～3) mol/L, described carbon source is (0～5) g/L,
The volume ratio of described alcohol and deionized water is 0～7:1～3；.
Further, described carbon source is selected from biomass derived Carbonaceous mesophase or graphene oxide or graphene oxide
Any one in the aqueous solution of quantum dot.
Described biomass derived Carbonaceous mesophase prepares gained according to the method in patent of invention CN 1421477A.
Concrete, in embodiment, biomass derived Carbonaceous mesophase used uses following method to prepare.
Preparation process:
1) with biomass resource material granule, aldehydes matter and concentrated sulphuric acid as reaction raw materials, carry out at 100～300 DEG C
Modified-reaction, obtains modified-reaction product；
2) by step 1) in gained modified-reaction product add water agitator treating, filtering drying, obtain powder body material；
3) by step 2) in the powder body material heat treatment or the microwave treatment at 100～400 DEG C that obtain, can obtain described
Biomass derived Carbonaceous mesophase.
Further, step 1) in, the mean diameter of described biomass resource material granule is at below 1cm；More preferably, institute
State the mean diameter of biomass resource material granule less than 1mm.It is also preferred that the left step 1) response time be 0.3～3h.
Further, step 1) in, described biomass resource material granule accounts for 14～80wt.%, aldehydes matter account for 14～
65wt.%, concentrated sulphuric acid account for 1.8～25wt.%；More preferably, described biomass resource material granule accounts for 40～75wt%, phenolic material
Matter accounts for 20～50wt.%, and concentrated sulphuric acid accounts for 2～15wt.%.
Biomass resource material be selected from following any one or more: containing in the natural polymer such as cellulose, lignin
The natural material of at least one and/or its garbage；Described natural material and/or each analog derivative of garbage；Cellulose
Or each analog derivative of lignin and mixture thereof.
Described biomass resource material is selected from one or more in following material: timber, wood flour, straw, rice husk, water
Marc, fruit core, leaf, frumentum epidermis, waste paper, waste wood wood, straw, lignin sulfur hydrochlorate, alkali lignin etc..
It is also preferred that the left described aldehydes matter is phenol.
It is also preferred that the left step 3) in time of heat treatment or microwave treatment be 0.5～3h.Microwave can use the moderate heat of microwave oven
Above wave band.
Use said method, be prepared for respectively with timber, wood flour, straw, rice husk, marc, fruit core, leaf, frumentum table
Skin, waste paper, waste wood wood, straw, lignin sulfur hydrochlorate, alkali lignin are the biomass derived carbonaceous mesophase of biomass resource material
Phase.
Further, in described step (2), applying voltage is 5～60V, and the response time is 0.05～6h.
Further, described step carries out heat treatment in (3), and temperature is 450～550 DEG C, and the time is 1～3h, and atmosphere is
Noble gas argon or nitrogen.
Further, also include that step (4) carries out negative electrode electro-deposition or dipping to titanium alloy.
Further, described negative electrode electro-deposition includes any one or two kinds in techniques below feature；
1) alcoholic solution that electrolyte is the derived carbonaceous mesophase of biomass that negative electrode electro-deposition uses, described biomass derived
The concentration of Carbonaceous mesophase is 0.1～5g/L, or graphene oxide water solution or graphene oxide quantum dot is water-soluble
Liquid, described graphene oxide or graphene oxide quantum dot concentration are 0.1～1g/L；
2) negative electrode electro-deposition voltage scan range is-1.5V～0.1V, and sweep speed is 10～100mV/s, sedimentation time
It is 5～120min.
Further, the alcoholic solution that solution is the derived carbonaceous mesophase of biomass that described dipping uses, described biology
The concentration of the derived carbonaceous mesophase of matter is 0.1～5g/L, or graphene oxide water solution or graphene oxide quantum dot
Aqueous solution, described graphene oxide or graphene oxide quantum dot concentration are 0.1～1g/L, and the time is 1～5h.
Another aspect of the present invention there is provided the above-mentioned composite titania material purposes as bio-medical material.
Another aspect of the present invention there is provided the above-mentioned composite titania material embedded material as skeletal system
Purposes.
Another aspect of the present invention there is provided the above-mentioned composite titania material purposes as catalysis material.
The beneficial effects of the present invention is: the advantage that the preparation method control of the present invention is strong, technique is simple and convenient to operate
Smooth titanium deoxid film, porous silica titanium film and three-dimensional order titanium dioxide that uniform quality, Fluorin doped carbon are compound can be prepared
Titanium nanotube.Composite titania material of the present invention is used to have anti-inflammation and promote the work of cell proliferation mineralising
With, good biocompatibility, the present invention can also be used as catalysis material simultaneously, can increase photocatalysis performance.
Accompanying drawing explanation
The smooth TiO of Fluorin doped of preparation in Fig. 1 (a) and Fig. 1 (b): present example 12The SEM figure of thin film.
The smooth TiO of Fluorin doped of preparation in Fig. 2: present example 12The energy spectrogram of thin film.
The compound porous TiO of Fluorin doped carbon of preparation in Fig. 3 (a): present example 22Thin film SEM schemes.
The compound porous TiO of Fluorin doped carbon of preparation in Fig. 3 (b): present example 22The side SEM figure of nanotube.
The compound porous TiO of Fluorin doped carbon of preparation in Fig. 4: present example 22The energy spectrogram of thin film.
The Fluorin doped orderly TiO of carbon complex three-dimensional of preparation in Fig. 5 (a): present example 32The surface SEM figure of nanotube.
The Fluorin doped orderly TiO of carbon complex three-dimensional of preparation in Fig. 5 (b): present example 32The side SEM figure of nanotube.
The Fluorin doped orderly TiO of carbon complex three-dimensional of preparation in Fig. 6: present example 32The energy spectrogram of nanotube.
The Fluorin doped orderly TiO of carbon complex three-dimensional of preparation in Fig. 7: present example 42The SEM figure of nanotube.
The Fluorin doped orderly TiO of carbon complex three-dimensional of preparation in Fig. 8: present example 52The SEM figure of nanotube.
The Fluorin doped three-dimensional order TiO of preparation in Fig. 9 (a): present example 62The surface SEM figure of nanotube.
The Fluorin doped three-dimensional order TiO of preparation in Fig. 9 (b): present example 62Nanotube side SEM schemes.
Osteoblastic proliferative conditions test after Figure 10 (a): three days, wherein No. 1 sample is TiO2Nanotube, No. 2 samples
For carbon doping TiO2Nanotube (specially embodiment 9), No. 3 samples are Fluorin doped TiO2Nanotube (specially embodiment 6), No. 4
Sample is Fluorin doped carbon composite Ti O2Nanotube (specially embodiment 3).
Sample in Figure 10 (b): Figure 10 (a) is the test of osteoblastic proliferative conditions after five days.
Sample in Figure 10 (c): Figure 10 (a) is the test of osteoblastic proliferative conditions after seven days.
Figure 11: show that blank group in example, Fluorin doped (embodiment 1), carbon doping (embodiment 4) and Fluorin doped carbon are multiple
Close (embodiment 2) obtained TiO2The photocatalysis performance design sketch of film.
Detailed description of the invention
Before further describing the specific embodiment of the invention, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiments；It is also understood that the term used in the embodiment of the present invention is specific concrete in order to describe
Embodiment rather than in order to limit the scope of the invention.The test method of unreceipted actual conditions in the following example,
Generally according to normal condition, or according to the condition proposed by each manufacturer.
When embodiment provides numerical range, it should be appreciated that unless the present invention is otherwise noted, two ends of each numerical range
Between point and two end points, any one numerical value all can be selected for.Unless otherwise defined, in the present invention use all technology and
The same meaning that scientific terminology and those skilled in the art of the present technique are generally understood that.Except in embodiment use concrete grammar, equipment,
Outside material, according to those skilled in the art's grasp to prior art and the record of the present invention, it is also possible to use and this
Any method, equipment and the material of the prior art that the method described in inventive embodiments, equipment, material are similar or equivalent comes real
The existing present invention.
The smooth titanium deoxid film of Fluorin doped is prepared in embodiment 1 anodic oxidation
Using composite electrolyte (containing ethanol) to carry out anodic oxidation, to prepare smooth titanium deoxid film step as follows:
(1) titanium alloy T i-Zr pretreatment: polished smooth by alloy, immerses in pickle, chemical polishing 10s, after use successively
Deionized water, dehydrated alcohol rinse, standby after drying up；Wherein said pickle is HF, HNO3With the mixed liquor of deionized water, body
Long-pending ratio is 1:1.5:50；
(2) electrolyte is prepared: by a certain amount of HF, H3PO4It is dissolved in 20mL deionized water and 10mL dehydrated alcohol
0.1mol/L H3PO4, the mixed solution of 0.8wt%HF, as electrolyte；
(3) anodic oxidation: pretreated titanium sheet as negative electrode, is placed in electrolyte in (2) carries out as anode, platinized platinum
Anodic oxidation, uses DC source, and voltage is 60V, and the response time is 0.5h；
(4) after reaction terminates, sample is taken out, dry up after deionized water ultrasonic cleaning, obtain sample 1；
(5) heat treatment: sample 1 is carried out 520 DEG C of heat treatments, atmosphere is argon, and the time is 2.5h, obtains sample 2.
The SEM photograph of prepared sample 2 is shown in Fig. 1.By Fig. 1 (a) and Fig. 1 (b) it will be seen that Titanium base pattern clearly may be used
Seeing, film surface is covered (Fig. 1 (b)) by even compact thin layer；Energy spectrum composition analysis shows, film layer can contain 8.68at% fluorine element
(see Fig. 2).
Result above shows, adds ethanol and can prepare the smooth titanium deoxid film of Fluorin doped in basic electrolyte.
The compound porous titanium deoxid film of Fluorin doped carbon is prepared in embodiment 2 anodic oxidation
Using composite electrolyte (containing ethanol and carbon source) to carry out anodic oxidation, to prepare porous titanium dioxide thin-film step as follows:
(1) medical titanium alloy Ti-35Nb-5Ta-7Zr pretreatment: polished smooth by alloy, immerses in pickle, and chemistry is thrown
Light 20s, after successively with deionized water, dehydrated alcohol rinses, the most standby after drying up；Wherein said pickle is HF, HNO3With go from
The mixed liquor of sub-water, volume ratio is 2:3:100；
(2) electrolyte is prepared: 1. a certain amount of biomass derived Carbonaceous mesophase is dissolved in 90mL dehydrated alcohol, stirs molten
Solve solution a；2. by a certain amount of HF, H3PO4It is dissolved in 10.1mL deionized water obtaining solution b；After 3. solution a, b being mixed
Concentration is 2.0g/L Carbonaceous mesophase, 1.9mol/L H3PO4, the solution of 0.5wt%HF, as electrolyte.
(3) anodic oxidation: pretreated alloy as negative electrode, is placed in electrolyte in (2) carries out as anode, platinized platinum
Anodic oxidation, uses DC source, and voltage is 15V, and the response time is 4h；
(4) after reaction terminates, sample is taken out, dry up after deionized water ultrasonic cleaning, obtain sample 1；
(5) heat treatment: sample 1 is carried out 480 DEG C of heat treatments, atmosphere is argon, and the time is 2.9h, obtains sample 2.
The SEM photograph of prepared sample 2 is shown in Fig. 3 (a) and Fig. 3 (b).By Fig. 3 it will be seen that Titanium base surface is by uniformly
Porous membrane covers (Fig. 3 (b)), has certain thickness；Energy spectrum composition analysis result shows, film layer carbon containing 6.9at%, fluorine-containing
30at% (see Fig. 4).
Result above shows, adds ethanol and Carbonaceous mesophase can be prepared Fluorin doped carbon and be combined many in basic electrolyte
Porous titanium dioxide film.
The Fluorin doped orderly titania nanotube of carbon complex three-dimensional is prepared in embodiment 3 anodic oxidation
Use composite electrolyte (containing methanol and carbon source) to carry out anodic oxidation and prepare three-dimensional order titania nanotube step
Rapid as follows:
(1) medical titanium alloy Ti-12Mo-6Zr-2Fe pretreatment: polished smooth by alloy sheet, immerses in pickle, chemistry
Polishing 26s, after successively with deionized water, dehydrated alcohol rinses, the most standby after drying up；Wherein said pickle is HF, HNO3With go
The mixed liquor of ionized water, volume ratio is 2:1.8:100；
(2) electrolyte is prepared: 1. a certain amount of biomass derived Carbonaceous mesophase being dissolved in 80mL methanol, stirring and dissolving obtains
Solution a；2. by a certain amount of HF, H3PO4It is dissolved in 20mL deionized water obtaining solution b；3. obtaining concentration after solution a, b being mixed is
5g/L mesophase, 2.5mol/L H3PO4, the solution of 0.7wt%HF, as electrolyte；
(3) anodic oxidation: pretreated alloy as negative electrode, is placed in electrolyte in (2) carries out as anode, platinized platinum
Anodic oxidation, uses DC source, and voltage is 30V, and the response time is 1.5h；
(4) after reaction terminates, sample is taken out, dry up after deionized water ultrasonic cleaning, obtain sample 1；
(5) heat treatment: sample 1 is carried out 500 DEG C of heat treatments, atmosphere is argon, and the time is 1.2h, obtains sample 2.
The SEM photograph of prepared sample 2 is shown in Fig. 5 (a) and Fig. 5 (b).As shown in Figure 5 a, film layer is made up of nanotube, caliber
50～60nm, wall thickness about 15nm；Side amplification (Fig. 5 (b)) is it will be seen that this nanotube is three-dimensional order shape, and pipe range is about
300nm；Energy spectrum composition analysis display film layer is simultaneously containing fluorine element and carbon (Fig. 6), fluorine-containing 15at%.
Result above shows, in basic electrolyte, interpolation methanol and Carbonaceous mesophase can prepare three that Fluorin doped carbon is compound
Tie up orderly titania nanotube.
Embodiment 4 anodic oxidations-cathodic electrodeposition prepares the orderly titania nanotube of carbon complex three-dimensional
Use basic electrolyte to carry out anodic oxidation and cathodic electrodeposition prepares three-dimensional order titania nanotube step
Rapid as follows:
(1) medical titanium alloy Ti-12Mo-6Zr-2Fe pretreatment: polished smooth by alloy sheet, immerses in pickle, chemistry
Polishing 40s, after successively with deionized water, dehydrated alcohol rinses, the most standby after drying up；Wherein said pickle is HF, HNO3With go
The mixed liquor of ionized water, volume ratio is 3:4.5:160；
(2) electrolyte is prepared: by a certain amount of HF, H3PO4Be dissolved in 100mL deionized water concentration be 1.5mol/
LH3PO4, the solution of 0.75wt%HF is as electrolyte；
(3) anodic oxidation: pretreated alloy sheet as negative electrode, is placed in electrolyte in (2) enters as anode, platinized platinum
Row anodic oxidation, uses DC source, and voltage is 20V, and the response time is 3h；
(4) after reaction terminates, sample is taken out, dry up after deionized water ultrasonic cleaning, obtain sample 1；
(5) sample 1 being carried out 550 DEG C of heat treatments, atmosphere is argon, and the time is 2.5h, obtains sample 2；
(6) sample 2 is placed in 0.9mg/mL graphene oxide quantum dot solution, carries out negative electrode electro-deposition, voltage scanning
Scope is-1.5V～0.1V, and sweep speed is 50mV/s, and sedimentation time is 15min, after having deposited by sample take out, go from
Dry up after sub-water ultrasonic cleaning, obtain sample 3.
The SEM photograph of prepared sample 3 is shown in Fig. 7.As seen from the figure, film surface is typical titania nanotube shape
Looks, visible flake graphite alkene between tube and tube, illustrate that adding cathodic electrodeposition by anodic oxidation can prepare the dioxy that carbon is compound
Change titanium nanotube.
Embodiment 5 anodic oxidations-infusion process prepares carbon titanium dioxide nanotube
Use basic electrolyte to carry out anodic oxidation and dipping self-assembly method prepares three-dimensional order titania nanotube step
Rapid as follows:
(1) medical titanium alloy Ti-15Mo-3Nb-0.3O pretreatment: polished smooth by alloy sheet, immerses in pickle, changes
Optical polishing 50s, after successively with deionized water, dehydrated alcohol rinses, the most standby after drying up；Wherein said pickle is HF, HNO3With
The mixed liquor of deionized water, volume ratio is 1.5:2.6:90；
(2) electrolyte is prepared: by a certain amount of HF, H3PO4Being dissolved in 100mL deionized water, obtaining concentration is 0.8mol/
LH3PO4, the solution of 0.4wt%HF, as electrolyte.
(3) anodic oxidation: pretreated alloy sheet as negative electrode, is placed in electrolyte in (2) enters as anode, platinized platinum
Row anodic oxidation, uses DC source, and voltage is 55V, and the response time is 1h；
(4) after reaction terminates, sample is taken out, dry up after deionized water ultrasonic cleaning, obtain sample 1；
(5) sample 1 being carried out 540 DEG C of heat treatments, atmosphere is argon, and the time is 2h, obtains sample 2；
(6) sample 2 is immersed in the graphene oxide dispersion of 0.1mg/mL, carry out impregnating self-assembling reaction, during dipping
Between be 5h, after having reacted by sample take out, go to dry up after deionized water ultrasonic cleaning, obtain sample 3.
The SEM photograph of prepared sample 3 is shown in Fig. 8.It can be seen that film surface is typical nano titania
Tubular looks, visible flake graphite alkene between tube and tube, illustrate to prepare carbon be combined two by anodic oxidation and dipping self-assembly method
Titanium oxide nanotubes.
Fluorin doped three-dimensional order titania nanotube is prepared in embodiment 6 anodic oxidation
Use basic electrolyte (containing ethylene glycol) to carry out anodic oxidation and heat treatment prepares three-dimensional order Fluorin doped titanium dioxide
Titanium nanotube step is as follows:
(1) medical titanium alloy Ti-13Nb-13Zr pretreatment: polished smooth by alloy sheet, immerses in pickle, and chemistry is thrown
Light 15s, after successively with deionized water, dehydrated alcohol rinses, the most standby after drying up；Wherein said pickle is HF, HNO3With go from
The mixed liquor of sub-water, volume ratio is 2.5:3.6:160；
(2) electrolyte is prepared: by a certain amount of HF, H3PO4It is dissolved in 70mL ethylene glycol and 30mL deionized water, obtains dense
Degree is 0.2mol/L H3PO4, the alcohol water mixed solution of 0.1wt.%HF, as electrolyte.
(3) anodic oxidation: pretreated alloy sheet as negative electrode, is placed in electrolyte in (2) enters as anode, platinized platinum
Row anodic oxidation, uses DC source, and voltage is 40V, and the time is 6h；
(4) after reaction terminates, sample is taken out, dry up after deionized water ultrasonic cleaning, obtain sample 1；
(5) heat treatment: sample 1 is carried out 500 DEG C of heat treatments, atmosphere is argon, and the time is 3h, obtains sample 2.
The surface topography of prepared sample 2 is titania nanotube (see Fig. 9)；Energy spectrum composition analysis display film layer contains
9.34at.% fluorine, illustrates to prepare the titania nanotube of Fluorin doped by interpolation ethylene glycol in electrolyte.
The smooth titanium oxide film layer of Fluorin doped is prepared in embodiment 7 anodic oxidation
Use basic electrolyte (containing methanol and ethanol) to carry out anodic oxidation and heat treatment combined method prepares smooth titanium dioxide
Titanium film layer step is as follows:
(1) medical titanium alloy Ti-6Al-4V pretreatment: polished smooth by alloy sheet, immerses in pickle, chemical polishing,
30s, after successively with deionized water, dehydrated alcohol rinses, the most standby after drying up；Wherein said pickle is HF, HNO3And deionization
The mixed liquor of water, volume ratio is 3.5:5.6:180；
(2) electrolyte is prepared: by a certain amount of HF, H3PO4Be dissolved in 2mL methanol and 8mL dehydrated alcohol mixed liquor and
Obtaining concentration in 90mL deionized water is 1mol/L H3PO4, the alcohol water mixed solution of 0.5wt%HF, as electrolyte.
(3) anodic oxidation: pretreated alloy sheet as negative electrode, is placed in electrolyte in (2) enters as anode, platinized platinum
Row anodic oxidation, uses DC source, and voltage is 5V, and the time is 0.05h；
(4) after reaction terminates, sample is taken out, dry up after deionized water ultrasonic cleaning, obtain sample 1；
(5) heat treatment: sample 1 is carried out 450 DEG C of heat treatments, atmosphere is argon, and the time is 1h, obtains sample 2.
The surface topography of prepared sample 2 is smooth titanium oxide film layer (class Fig. 4)；Energy spectrum composition analysis display film
Layer fluorine Han 6.34at%, illustrates to prepare the smooth titanium dioxide film of Fluorin doped by interpolation methanol and ethanol in electrolyte
Layer.
The smooth titanium oxide film layer of carbon doping is prepared in embodiment 8 anodic oxidation
Use basic electrolyte (carbonaceous sources) to carry out anodic oxidation and heat treatment prepares the smooth titanium oxide film layer of carbon doping
Step is as follows:
(1) medical titanium alloy Ti-6Al-7Nb pretreatment: polished smooth by alloy, immerses in pickle, chemical polishing
35s, after successively with deionized water, dehydrated alcohol rinses, the most standby after drying up；Wherein said pickle is HF, HNO3And deionization
The mixed liquor of water, volume ratio is 3.2:5.2:170；
(2) electrolyte is prepared: respectively by a certain amount of graphene oxide, HF and H3PO4It is dissolved in 100mL deionized water,
It is 2.0g/L graphene oxide to concentration, 2mol/L H3PO4, the mixed solution of 1wt.%HF, as electrolyte.
(3) anodic oxidation: pretreated alloy as negative electrode, is placed in electrolyte in (2) carries out as anode, platinized platinum
Anodic oxidation, uses DC source, and voltage is 25V, and the time is 2.5h；
(4) after reaction terminates, sample is taken out, dry up after deionized water ultrasonic cleaning, obtain sample 1；
(5) heat treatment: sample 1 is carried out 540 DEG C of heat treatments, atmosphere is argon, and the time is 2h, obtains sample 2.
The surface topography of prepared sample 2 is smooth titanium oxide film layer (class Fig. 2)；Energy spectrum composition analysis display film
Layer carbon Han 4.69at%, illustrates to prepare the smooth titanium oxide film layer of carbon doping by interpolation graphene oxide in electrolyte.
Carbon doping three-dimensional order titania nanotube is prepared in embodiment 9 anodic oxidation
Use basic electrolyte (carbonaceous sources) to carry out anodic oxidation and heat treatment prepares carbon doping three-dimensional order titanium dioxide
Nanotube step is as follows:
(1) medical titanium alloy Ti-6Al-7Nb pretreatment: polished smooth by alloy, immerses in pickle, chemical polishing
45s, after successively with deionized water, dehydrated alcohol rinses, the most standby after drying up；Wherein said pickle is HF, HNO3And deionization
The mixed liquor of water, volume ratio is 2.8:2:90；
(2) electrolyte is prepared: respectively by aqueous solution, HF and H of a certain amount of graphene oxide quantum dot3PO4It is dissolved in
In 100mL deionized water, obtain the graphene oxide quantum dot that concentration is 3.3g/L, 3mol/L H3PO4, the mixing of 0.6wt%HF
Solution, as electrolyte.
(3) anodic oxidation: pretreated alloy as negative electrode, is placed in electrolyte in (2) carries out as anode, platinized platinum
Anodic oxidation, uses DC source, and voltage is 48V, and the time is 5h；
(4) after reaction terminates, sample is taken out, dry up after deionized water ultrasonic cleaning, obtain sample 1；
(5) heat treatment: sample 1 is carried out 470 DEG C of heat treatments, atmosphere is argon, and the time is 1.5h, obtains sample 2.
The surface topography of prepared sample 2 is three-dimensional order titania nanotube (class Fig. 9)；Energy spectrum composition analysis shows
Show film layer carbon Han 5.60at%, illustrate to prepare carbon doping three-dimensional order titanium dioxide by interpolation graphene oxide in electrolyte
Titanium nanotube.
Embodiment 10 osteoblastic proliferation situation
Such as Figure 10 (a), 10 (b), 10 (c) shows the blank group (TiO the most not adulterated2Film) with above example in fluorine
Compound (embodiment 3) the obtained TiO of doping (embodiment 6), carbon doping (embodiment 9) and Fluorin doped carbon2Film is respectively at three days, five days
And the osteoblastic proliferation situation of seven days.As seen from the figure, prolongation over time, the light absorption value OD of each group is gradually increased, aobvious
Show that cell number increases, show that Fluorin doped carbon is combined the titanium dioxide film of different topology structure and can promote osteoblastic propagation,
There is good cell compatibility.
Embodiment 11 catalysis material is applied
With the blank group (TiO the most not adulterated2Film) and Fluorin doped (embodiment 1), carbon doping (embodiment 4) and Fluorin doped
Carbon is combined (embodiment 2) obtained TiO2Film degradation of phenol under visible light.Photocatalysis light source is 300W high pressure xenon lamp, and xenon lamp passes through
Condensed water cooling in quartz double-jacket.Light-catalyzed reaction instrument is tested, TiO will be covered with2Film, Fluorin doped, carbon are mixed
Miscellaneous and Fluorin doped carbon composite Ti O2The titanium sheet of film is vertically put in the phenol solution that 50mL mass concentration is 10mg/L.At the beginning of reaction
During the beginning, first phenol solution magnetic agitation 30min in the dark state being had ensured that, reactant reaches absorption at catalyst surface flat
Weighing apparatus.Then illumination 360min, sampling and testing.Always with magnetic agitation in Photocatalytic Degradation Process.The concentration of Phenol in Aqueous Solution,
With hplc determination, flowing is methanol aqueous solution (methanol: water=7:3 (V/V), flow velocity is 1mL/min) mutually, and phenol is maximum
Ultraviolet detection absorbing wavelength is 270nm.The palliating degradation degree of phenol is calculated according to concentration.
As seen from Figure 11, fluorine, carbon doping can significantly improve the photocatalysis performance of material, and Fluorin doped carbon is compound can be carried further
Photocatalysis performance for material.
The above, only presently preferred embodiments of the present invention, not any formal and substantial to present invention restriction,
It should be pointed out that, for those skilled in the art, on the premise of without departing from the inventive method, also can make
Some improvement and supplement, these improve and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, make when available disclosed above technology contents a little more
The equivalent variations moved, modify and develop, is the Equivalent embodiments of the present invention；Meanwhile, all substantial technological pair according to the present invention
The change of any equivalent variations that above-described embodiment is made, modify and develop, all still fall within the scope of technical scheme
In.
Claims (17)
1. a composite titania material, it is characterised in that described composite titania material at least include titanium dioxide with
And adulterate fluorine on the titanium dioxide or carbon, or doped with fluorine and carbon simultaneously.
The preparation method of composite titania material the most according to claim 1, it is characterised in that the content of described fluorine is little
In equal to 15%.
3. the preparation method of a composite titania material, it is characterised in that at least comprise the following steps:
(1) electrolyte quota: preparation electrolyte；
(2) anodized: employing titanium alloy is anode, the electrolyte Anodic Oxidation prepared in step (1) processes；
(3) post processing: the titanium alloy that step (2) Anodic Oxidation processed is carried out heat treatment.
The preparation method of composite titania material the most according to claim 3, it is characterised in that in described step (2)
Also include pretreatment before anodized: polished by titanium alloy, immerse in pickle and clean, rinse, be dried.
The preparation method of composite titania material the most according to claim 4, it is characterised in that in described step (2)
Pretreatment also includes any one in techniques below feature or multinomial:
1) described pickle is HF, HNO3With the mixed liquor of deionized water, HF, HNO3It is 1～4:1.5 with deionized water volume ratio
～6:50～200；
2) pickling time is 10～50s；
3) concrete grammar rinsed is to rinse with deionized water, dehydrated alcohol successively.
The preparation method of composite titania material the most according to claim 3, it is characterised in that in described step (1)
The compound method of electrolyte comprises the following steps:
1) by HF, H3PO4Add in deionized water, stirring, obtain basic electrolyte；
2) in basic electrolyte, alcohol or carbon source or both mixture are added.
The preparation method of composite titania material the most according to claim 6, it is characterised in that described alcohol is selected from first
In alcohol, ethanol or ethylene glycol any one or multiple.
The preparation method of composite titania material the most according to claim 7, it is characterised in that
When adding alcohol in the described step (1), alcohol and HF dense in the mixed solvent of the composition of deionized water in described electrolyte
Degree is (0.1～1.0) wt%, H3PO4Concentration be (0.1～3) mol/L, the volume ratio of described alcohol and deionized water is 0～7:1
～3；
Or when adding carbon source in described step (1), in described electrolyte, the concentration of HF is (0.1～1.0) wt%, described
H3PO4Concentration be (0.1～3) mol/L, described carbon source is (0～5) g/L；
Or when described step (1) is added alcohol and carbon source, the mixed solvent that in described electrolyte, alcohol forms with deionized water
The concentration of middle HF is (0.1～1.0) wt%, H3PO4Concentration be (0.1～3) mol/L, described carbon source is (0～5) g/L, described
The volume ratio of alcohol and deionized water is 0～7:1～3.
9. according to the preparation method of claim 6 composite titania material, it is characterised in that described carbon source is spread out selected from biomass
Any one in the aqueous solution of raw Carbonaceous mesophase or graphene oxide or graphene oxide quantum dot.
The preparation method of composite titania material the most according to claim 3, it is characterised in that in described step (2)
Applying voltage is 5～60V, and the response time is 0.05～6h.
The preparation method of 11. composite titania materials according to claim 3, it is characterised in that in described step (3)
Carrying out heat treatment, temperature is 450～550 DEG C, and the time is 1～3h, and atmosphere is noble gas argon or nitrogen.
The preparation method of 12. composite titania materials according to claim 3, it is characterised in that also include step (4)
Titanium alloy is carried out negative electrode electro-deposition or dipping.
The preparation method of 13. composite titania materials according to claim 12, it is characterised in that described negative electrode electricity sinks
Amass any one or two kinds included in techniques below feature；
1) alcoholic solution that negative electrode electro-deposition uses electrolyte to be the derived carbonaceous mesophase of biomass, in described biomass derived carbonaceous
Between the concentration of phase be 0.1～5g/L, or graphene oxide water solution or the aqueous solution of graphene oxide quantum dot, described
Graphene oxide or graphene oxide quantum dot concentration are 0.1～1g/L；
2) negative electrode electro-deposition voltage scan range is-1.5V～0.1V, and sweep speed is 10～100mV/s, sedimentation time be 5～
120min。
The preparation method of 14. composite titania materials according to claim 12, it is characterised in that described dipping uses
The alcoholic solution that solution is the derived carbonaceous mesophase of biomass, the concentration of described biomass derived Carbonaceous mesophase is 0.1～5g/
L, or graphene oxide water solution or the aqueous solution of graphene oxide quantum dot, described graphene oxide or oxidation stone
Ink alkene quantum dot concentration is 0.1～1g/L；, the time is 1～5h.
15. according to the composite titania material described in claim 1-14 any one as the purposes of bio-medical material.
16. according to the composite titania material described in claim 1-14 any one as the embedded material of skeletal system.
17. according to the composite titania material described in claim 1-14 any one as the purposes of catalysis material.
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| CN109183123B (en) * | 2018-07-16 | 2020-07-24 | 西安理工大学 | Titanium and titanium alloy anodic oxidation method in graphene/graphene oxide electrolyte |
| CN109183123A (en) * | 2018-07-16 | 2019-01-11 | 西安理工大学 | Titanium or titanium alloy anode oxidation method in graphene/graphene oxide electrolyte |
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| CN111155159A (en) * | 2020-01-16 | 2020-05-15 | 广东安特齿科有限公司 | Anodic oxidation liquid and coloring method of implant abutment |
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| CN113101947A (en) * | 2021-03-22 | 2021-07-13 | 华南理工大学 | Silver sulfide-reduced graphene oxide-titanium dioxide composite material and preparation method and application thereof |
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