CN105862096A - Method for preparing FHA bioactive coating through electrical brush-plating-sintering method - Google Patents
Method for preparing FHA bioactive coating through electrical brush-plating-sintering method Download PDFInfo
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- CN105862096A CN105862096A CN201610389235.3A CN201610389235A CN105862096A CN 105862096 A CN105862096 A CN 105862096A CN 201610389235 A CN201610389235 A CN 201610389235A CN 105862096 A CN105862096 A CN 105862096A
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- Prior art keywords
- plating
- brush
- fha
- solution
- brush plating
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- 238000000034 method Methods 0.000 title claims abstract description 85
- 238000000576 coating method Methods 0.000 title claims abstract description 75
- 239000011248 coating agent Substances 0.000 title claims abstract description 61
- 238000005245 sintering Methods 0.000 title claims abstract description 28
- 230000000975 bioactive effect Effects 0.000 title abstract description 6
- 238000007747 plating Methods 0.000 claims abstract description 341
- 239000010936 titanium Substances 0.000 claims abstract description 98
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- 239000011159 matrix material Substances 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 151
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 55
- 239000000758 substrate Substances 0.000 claims description 55
- 239000012153 distilled water Substances 0.000 claims description 48
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 40
- 230000008569 process Effects 0.000 claims description 39
- 230000001680 brushing effect Effects 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- 230000005611 electricity Effects 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 150000003608 titanium Chemical class 0.000 claims description 21
- 230000003213 activating effect Effects 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 14
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 14
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 13
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 13
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 229920000742 Cotton Polymers 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- DWPRJUQFFDWYCE-UHFFFAOYSA-F [Ti+4].[Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Ti+4].[Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DWPRJUQFFDWYCE-UHFFFAOYSA-F 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 7
- 238000000151 deposition Methods 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- 238000003760 magnetic stirring Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000001652 electrophoretic deposition Methods 0.000 description 2
- 229910052587 fluorapatite Inorganic materials 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical class [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100001083 no cytotoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical class [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/04—Electroplating with moving electrodes
- C25D5/06—Brush or pad plating
-
- 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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic 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
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/08—Coatings comprising two or more layers
-
- 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
- A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction
Abstract
The invention discloses an FHA bioactive coating and a preparation method thereof. The structure of the coating is matrix/Ti/FHA, and the substitutive rate of F for OH in adopted FHA powder is 0.5. The preparation method includes the specific steps of preparation of an FHA plating solution; pretreatment of a matrix; electrical brush-plating of a titanium plating solution and electrical brush-plating of the FHA plating solution; sintering of the matrix obtained after electrical brush-plating of the titanium plating solution and electrical brush-plating of the FHA plating solution to obtain the target coating. The method has the advantages that the coating is of a coating structure in which mechanical performance and bio-compatibility are well matched, the deposition time is greatly shortened, and FHA is not decomposed; the utilization rate of the plating solutions is increased by multiple times to more than ten times, a redox reaction of the coating is promoted through increase of the content of metal ions in the plating solutions, the method can be used within wide current density and temperature ranges, the production cost is reduced, the production efficiency is improved, and the anti-corrosion performance of the coating and the adhesive force of the coating and the matrix are effectively improved.
Description
Technical field
The present invention relates to titanium alloy T i6A14V prepares on surface FHA bioactivity coatings, is coated with to strengthen FHA further
Layer adhesion, first plates one layer of pure titanium at matrix surface；Particularly by Brush Plating-sintering process at Ti6A14It is raw that V prepares on surface FHA
Thing active coating, coating structure is matrix/Ti/FHA；The side of FHA bioactivity coatings is prepared particularly to Brush Plating-sintering process
Method.
Background technology
Bioactive ceramic coating/titanium alloy composite material, has good Biofunctional, including sufficiently high intensity
And toughness, suitable elasticity and hardness, good resisting fatigue creep-resistant property and wear-resisting and self lubricity, excellent is corrosion-resistant
Property and good biocompatibility and good processability, and meet the medical device made with it and implant human body need
Has medicative condition.Artificial joint alternate material can be widely used as.
The substituted apatite of fluorine formed by the OH-in F-part substituted hydroxy apatite, is called for short FHA (Ca10(PO4)6
(OH)2-2xF2x 0≤x≤1);In human body fluid environment, FHA has the dissolubility lower than HA, has longer when retaining
Between.The HA heat stability of synthesis is bad, and sintering temperature can resolve into other phase, such as calcium phosphate (TCP higher than 900 DEG C;Ca3
(PO4)2).And the heat stability of FHA is better than HA, fluor-apatite (Ca5(PO4)3F) until 1400 DEG C are not decomposed, table is studied
Bright, the FHA no cytotoxicity of high F content.Therefore FHA is potential becomes excellent substitute material for human hard tissues.
Brush Plating-sintering process has simple to operate, and technique is flexible, and coating speed is fast, bond strength high.And
Can prepare uniform coating on complex-shaped surface, occupied ground is little, has broad application prospects.
For Mu Qian, the preparation method of FHA bioactive coating material has plasma spraying method, pulse-laser deposition, is coated with
Cover-the serial of methods such as sintering process.Plasma spraying method due to spraying temperature the highest, not only result in coating has the biggest
Thermal stress and the biggest porosity, FHA granule is it may happen that decompose；After quickly cooling, FHA often contains a large amount of amorphous phase,
Its speed dissolved in body fluid quickly, is unfavorable for implanting human body and the combination of osseous tissue.Pulse-laser deposition is applicable to preparation
Relatively thin coating, and bigger residual stress can be caused；Coating-sintering process will be through high temperature, and FHA is likely occurred decomposition.
These technology are not the most optimal for the preparation of FHA bioactive materials.And Brush Plating is the one of electro-deposition, compared to groove
Plating and electrophoretic deposition, its electric current density is much bigger, it is possible to obtain preferable coating at short notice, and simple to operate, technique
Flexibly, production prices are low.
Ti6A14V matrix surface Brush Plating-sintering process is prepared FHA bioactive coating material and is the most not yet appeared in the newspapers
Road.
Summary of the invention
In order to meet the demand of the preferable coating of preparation, embodiments provide a kind of Brush Plating-sintering process and prepare FHA
The method of bioactivity coatings, by Brush Electroplating Technique, at the titanium alloy-based surface pure titanium of Brush Plating to improve basal body binding force
Brush plating FHA bioactivity coatings again, and strengthen matrix and the adhesion of coating by air sintering, improve the corrosion resistant of coating
Erosion performance.
In order to realize foregoing invention purpose, the invention provides a kind of FHA bioactivity coatings, described coating structure is
Matrix/Ti/FHA, in FHA powder used, F is 0.5 to the Replacement rate of OH.
Described coating structure is Ti6A14V/Ti/FHA。
In order to goal of the invention is better achieved, present invention also offers the preparation method of a kind of FHA bioactivity coatings, institute
Stating preparation method uses Brush Plating-sintering process to prepare FHA bioactivity coatings, comprises the following steps that
(1) configuration of FHA plating solution；
(2) substrate pretreated；
(3) brush titanizing plating solution and Brush Plating FHA plating solution, controls the speed relatively of brushing plating voltage, the pH value of plating solution, and brush plating
Degree, in order to control structure and the thickness of coating.
(4) through step (3), the matrix sintering after brush titanizing plating solution and Brush Plating FHA plating solution is obtained target coating.
The configuration of described step (1) FHA plating solution, concretely comprises the following steps and is:
A, take titanium salt Ti (SO4)2200-300g, puts in the container filling 350-500ml distilled water and is completely dissolved, be configured to
Titanium salt solution；Use magnetic stirrer;
B, take citric acid 30-60g, ammonium sulfate 20-40g, add 300-400ml distilled water, magnetic stirring apparatus stirs and joins
Putting and stir, then regulation pH value is 2.2-2.5, is configured to compound complex agent；
C, taking 3-5g acetic acid as buffer agent, the compound complex agent adding the configuration of step B stirs, and then step A is configured
Titanium salt solution be poured slowly into, obtain solution one；
D, take 0.1-0.2g sodium lauryl sulphate and pour mix homogeneously in the solution one that step C obtains into as surfactant,
Obtain solution two；
E, to step D configuration solution two in add 24-40g sodium hypophosphite NaH2PO2, acutely stir with omnipotent mechanics blender
Mix 5-15 minute, be subsequently adding FHA powder, after being heated to 40-80 DEG C and continuing to stir 15-30min, obtain the dense plating solution of FHA；With
The dense plating solution of distilled water diluting FHA obtains FHA plating solution, and FHA powder concentration range in FHA plating solution is 0.125g/ml--
The pH value of 0.200g/ml, FHA plating solution is 3.5-7.5, and pH value hydrochloric acid regulates with the solution of ammonia volume ratio 2:1.
Described step (2) substrate pretreated, comprises the concrete steps that:
1. chemistry abatement processes: by Ti6A14V titanium alloy substrate deionized water cleans up, and dries and is placed in platter, uses
After absorbent cotton dips acetone wiping plating surface, then with deionized water rinsing, dry, to be plated；
2. electricity is clean processes:
At Ti6A14The clean liquid of brush plating electricity on V titanium alloy substrate, brush-plating technique is: electrode just connects, and brushing plating voltage 10-12V, during brush plating
Between 20-40S, with relative velocity 6-24m/min unidirectional brush plating on workpiece, clean with distilled water after brush plating；
The clean liquid of electricity includes following components: sodium hydroxide 20-30g/L, tertiary sodium phosphate 40-60g/L, sodium carbonate 20-25g/L, second
Acid 0.2-0.5g/L, sodium hypophosphite 0.2-0.5g/L, surplus is water；The pH value of the clean liquid of electricity is 11-13；
3. activation processing: in step 2. Ti after electricity processes only6A14First No. 1 activating solution of brush plating on V titanium alloy substrate, so
No. 3 activating solutions of rear brush plating,
No. 1 activating solution brush-plating technique of brush plating is: electrode reversal connection, brushing plating voltage 10-12V, brush plating time 20-40S, with relative velocity
6-24m/min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
No. 3 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 10-12V, brush plating time 20-40S, with relative velocity
6-24m/min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating.
Described step (3) brush titanizing plating solution and Brush Plating FHA plating solution, comprise the concrete steps that: selects conventional DC pulse
Brush Plating instrument, workpiece connects negative pole, and plated pen connects positive pole, and plated pen selects high-purity fine graphite, and outer layer covers absorbent cotton is in case during its plating
Directly contact with workpiece.
1. at the Ti after substrate pretreated6A14Brush plating titanium plating solution on V titanium alloy substrate, during brush plating, process conditions are electrode
Just connecing, brushing plating voltage 10-12V, brush plating time more than 30S, with the unidirectional brush plating of relative velocity 6m/min-24m/min, pH value is
3.5-6.5；Clean with distilled water after brush plating；
Titanium plating solution includes following components: Ti (SO4)2200-300g/L, citric acid 30-60g/L, ammonium sulfate 20-40g/L, acetic acid
3-5g/L, sodium lauryl sulphate trace 0.1-0.3g/, surplus are water；
2. at the Ti after step 1. brush plating titanium plating solution6A14Brush plating FHA plating solution on V titanium alloy substrate；During brush plating, process conditions are
Electrode just connects, brushing plating voltage 10-16V, brush plating time more than 30S, with the unidirectional brush plating of relative velocity 6m/min-24m/min, brush plating
After clean with distilled water.
Matrix sintering after brush titanizing plating solution and Brush Plating FHA plating solution is obtained by described step (4) through step (3)
Comprising the concrete steps that of target coating:
By the Ti after brush titanizing plating solution and Brush Plating FHA plating solution6A14V titanium alloy substrate is placed in resistance furnace and is sintered, and rises
Temperature speed is 5-15 DEG C/min, and sintering temperature is 450 DEG C-850 DEG C, and temperature retention time is 2-3h, and cooling rate is 1-10 DEG C/min,
It is cooled to 10-30 DEG C and obtains target coating.
Principle
Find out from the thermodynamic data relative analysis of titanium, be feasible from aqueous solution electrodeposition Titanium.Titanium is valence variation element,
The standard electrode potential of electrode reaction during different valence state:
Ti2++2e=Ti E0=-1.63v
Ti3++3e=Ti E0=-1.136v
TiO2++2H++4e=Ti+H2O E0=-0.882v
TiF2-+4e=Ti+6F- E0=-1.19v
We with compare from the manganese metal of aqueous solution electrodeposition, chromium, zinc:
Zn2++2e=Zn E0=-0.763v
ZnO2 2-+2e+2H2O=Zn+OH- E0=-1.216v
Cr3++3e=Cr E0=-0.74v
Mn2++2e=Mn E0=-1.186v
The numerical value being not difficult to find out titanium or titanium alloy from these thermodynamic datas is relatively, it is seen that from aqueous solution electrodeposition
Theoretical establishment.From the point of view of electrode reaction dynamic analysis, managing to increase hydrogen overpotential on titanium, electro-deposition is capable of.According to
Tal fibre Philippine side journey ηH=a+blg|i| calculates the overpotential of hydrogen, as long as occurring the current potential of liberation of hydrogen for Titanium than separating out
The current potential of Titanium is more negative, then titanium can separate out.Compared to chemical deposition, during electro-deposited alloy titanium, electrode surface state eliminates
The disadvantage that activity is big, also eliminates passivating film harm.
The technical scheme that the embodiment of the present invention provides has the benefit that the coating structure of the present invention is matrix/Ti/
FHA, first plates layer of metal titanium on matrix and can preferably improve the adhesion of FHA and matrix, and utilize heat treatment work
Skill forms the coating structure of mechanical property and biocompatibility matched well.The FHA prepared compared to electrophoretic deposition-sintering process is coated with
Layer and optimum combination power 10.6MPa of matrix, the inventive method coating increased with the adhesion of matrix, and sedimentation time
Significantly shorten.Compared to methods such as laser melting coating, thermal sprayings, the inventive method is unlikely to make FHA decompose；Compared to chemistry
The methods such as deposition and groove plating, the plating solution utilization rate of the inventive method improves several times to tens times, the metal ion content in plating solution
Increase the generation being conducive to coating oxidation reduction reaction.The method of the present invention can make in wider electric current density and temperature range
With, need not at ordinary times plating solution chemical examination is adjusted.Brush Plating FHA has not only widened manufacture of materials field, reduces production cost, carries
High production efficiency, and effectively improve the decay resistance of coating and coating and the adhesion strength of matrix, brushed by adjustment
Plating voltage, brush plating relative velocity, plating solution pH value and sintering temperature have obtained the good of coating mechanical property and bio-compatible performance
Coupling.
Detailed description of the invention
It is unfavorable for implanting human body and the combination of osseous tissue, and the problem that coating is weak with basal body binding force for current coating, this
Invention provides the preparation method of a kind of FHA bioactivity coatings.
Titanium sulfate: Ti (SO4)2CAS No.:13693-11-3 Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure CP
Citric acid CAS No.:77-92-9 lark prestige Science and Technology Ltd.
Ammonium sulfate: CAS No.:7783-20-2 Shanghai Aladdin biochemical technology limited company, chemical pure/analytical pure
Acetic acid: CAS No.:64-19-7 Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure
Sodium lauryl sulphate CAS No.:151-21-3 Shanghai Aladdin biochemical technology limited company, chemical pure
Sodium hypophosphite NaH2PO2: CAS No.7681-51-0 Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure CP
Acetone: CAS No.:67-64-1 Shenyang chemical reagent factory, analytical pure
Tertiary sodium phosphate: CAS No.:7601-54-9 Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure
No. 1 activating solution is sulfuric acid type Qingdao Peng Xuda Electronics Equipment Co., Ltd (Linyi Rui Tai sufacing company limited)
No. 3 activating solutions are Fructus Citri Limoniae acid type Qingdao Peng Xuda Electronics Equipment Co., Ltd (the auspicious safe limited public affairs of sufacing in Linyi
Department)
With reference to Zhou Hongming, Zeng Lin, easy painting etc..Electrophoretic deposition prepares BG/BG-FHA composite coating [J]. composite journal,
2011,06,002. use methods therein to prepare FHA powder:
1) calculate: Ca10(PO4)6[(OH)1-xFx]2(x value is 0,0.25,0.5,0.75,1)
2) solution preparation: Ca (NO3) 2 4H2O and 1mol/L (NH4) the 2HPO4 solution of preparation 1mol/L, corresponding corresponding x
The NH4F of value joins in rich P solution, and stirring makes the solid in a solution fully dissolve, instilled by strong aqua ammonia in each solution,
A solution Ph value is made to be about 11.
3) titration: richness P solution is dropwise added slowly in rich Ca solution, is stirred vigorously while titration, uses ammonia
Keeping the pH value of mixed liquor not less than 10.5, after reaction completely, mixed liquor is put and is continued stirring 2-24h at room temperature.
4) ageing: mixed liquor is stood 24h, pours out the supernatant, is placed in residual mixed liquor on heating furnace and is heated to boiling
Rise, until without obvious ammonia abnormal smells from the patient.
5) filter: residual mixed liquor is carried out distillation washing, until pH value is 7, finally filters with dehydrated alcohol.
6) it is dried: gained filter cake is placed in drying baker in 60 DEG C of dry 48h.
7) grind, sieve: being ground in grinding alms bowl by products therefrom, then sieving by 325 mesh sieve finally gives
Powder for brush plating.
Embodiment 1
1, FHA plating solution configuration:
1. titanium salt (titanium sulfate) Ti (SO is weighed4)2250g, puts into the titanium salt of weighing in the beaker filling 500ml distilled water and uses
Magnetic stirring apparatus individually dissolves 10min to being completely dissolved, and is configured to titanium salt solution；
2. take citric acid 50g, ammonium sulfate 30g, add 400ml distilled water and be placed on magnetic stirring apparatus the compound network of the configuration that stirs
Mixture, regulation pH value is 2.4, is configured to compound complex agent；
3. take 3g acetic acid to stir as buffer agent, the compound complex agent configured before addition, and slowly fallen by titanium salt solution
Enter, obtain solution one;
4. take 0.1g sodium lauryl sulphate and pour mix homogeneously in the solution one that 3. step obtains into as surfactant, obtain molten
Liquid two；
5. in the solution two that 4. step configures, add 24g sodium hypophosphite NaH2PO2, stir 10 points with omnipotent mechanics blender
Clock, is subsequently adding FHA powder 125g, is heated to 40 DEG C and continues to stir 30min, obtaining the dense plating solution of FHA；
6. being 0.125g/ml with the dense plating solution of distilled water diluting FHA to FHA powder concentration in the plating solution, solution ph is 5.5, molten
Liquid pH hydrochloric acid regulates with the solution of ammonia volume ratio 2:1.
2, substrate pretreated
1. chemistry abatement processes: by Ti6A14V titanium alloy substrate deionized water cleans up, and dries and is placed in platter, with de-
Fat cotton dips acetone wiping plating surface, removes surface and oil contaminant, corrosion, oxide layer and impurity, after acetone wiping, deionization
Water rinses, and dries, to be plated；
2. electricity is clean processes:
At Ti6A14On V titanium alloy substrate, the clean formula of liquid of brush plating electricity is: sodium hydroxide 25g/L, tertiary sodium phosphate 45g/L, carbonic acid
Sodium 20g/L, acetic acid 0.3g/L, sodium hypophosphite 0.2g/L, surplus is water；PH value 11.
Brush-plating technique is: electrode just connects, brushing plating voltage 12V, and brush plating time 30S, with relative velocity 14m/min on workpiece
Unidirectional brush plating, cleans with distilled water after brush plating.
3. activation processing: continue at Ti6A14No. 1 activating solution of brush plating on V titanium alloy substrate, brush-plating technique is: electrode reversal connection,
Brushing plating voltage 12V, brush plating time 30S, with relative velocity 14m/min unidirectional brush plating on workpiece, use distilled water after brush plating
Clean.Then at Ti6A14Continuing No. 3 activating solutions of brush plating on V titanium alloy substrate, brush-plating technique is: electrode reversal connection, brushing plating voltage
12V, brush plating time 30S, with relative velocity 14m/min unidirectional brush plating on workpiece, clean with distilled water after brush plating.
3, brush titanizing plating solution and Brush Plating FHA plating solution
Selecting conventional DC pulse Brush Plating instrument, negative pole connects workpiece, positive pole plated pen, and plated pen selects high-purity fine graphite, outer layer covers
Absorbent cotton is in case directly contacting with workpiece during its plating.
(1) at the Ti after substrate pretreated6A14Brush plating titanium plating solution on V titanium alloy substrate, titanium solution composition proportioning is: Ti
(SO4)2250g/L, citric acid 45g/L ammonium sulfate 20g/L, acetic acid 3g/L, sodium lauryl sulphate 0.1g/L, surplus is water；
During brush plating, process conditions are that electrode just connects, brushing plating voltage 10V, brush plating time 120S, with the unidirectional brush plating of relative velocity 14m/min,
PH value is 5, cleans with a large amount of distilled water after brush plating.
(2) Ti after brush plating titanium plating solution6A14The FHA plating solution of preparation in brush plating step 1, brush is continued on V titanium alloy substrate
During plating, process conditions are that electrode just connects, brushing plating voltage 12V, brush plating time more than 120S, with the unidirectional brush of relative velocity 14m/min
Plating, cleans with a large amount of distilled water after brush plating.
4, by the Ti after brush plating FHA plating solution6A14V titanium alloy substrate is placed in resistance furnace and is sintered heat treatment, and heat up speed
Degree is 5 DEG C/min, and sintering heat treatment temperature is 450 DEG C, and temperature retention time is 3h, and cooling rate is 1 DEG C/min, it is cooled to 20 DEG C
Obtain target coating.
Coating layer thickness is about 17 μm after tested；After almighty test machine analysis heat treatment, the adhesion of coating and matrix is
17.9MPa。
Embodiment 2
1, FHA plating solution configuration:
1. titanium salt (titanium sulfate) Ti (SO is weighed4)2250g, puts into the titanium salt of weighing in the beaker filling 500ml distilled water and uses
Magnetic stirring apparatus individually dissolves 10min to being completely dissolved, and is configured to titanium salt solution；
2. take citric acid 50g, ammonium sulfate 30g, add 400ml distilled water and be placed on magnetic stirring apparatus the compound network of the configuration that stirs
Mixture, regulation pH value is 2.4, is configured to compound complex agent；
3. take 3g acetic acid to stir as buffer agent, the compound complex agent configured before addition, and slowly fallen by titanium salt solution
Enter, obtain solution one;
4. take 0.1g sodium lauryl sulphate and pour mix homogeneously in the solution one that 3. step obtains into as surfactant, obtain molten
Liquid two；
5. in the solution two that 4. step configures, add 24g sodium hypophosphite NaH2PO2, stir 10 points with omnipotent mechanics blender
Clock, is subsequently adding FHA powder 150g, is heated to 40 DEG C and continues to stir 30min, obtaining the dense plating solution of FHA；
6. being 0.150g/ml with the dense plating solution of distilled water diluting FHA to FHA powder concentration in the plating solution, solution ph is 3.5, molten
Liquid pH hydrochloric acid regulates with the solution of ammonia volume ratio 2:1.
2, substrate pretreated
1. chemistry abatement processes: by Ti6A14V titanium alloy substrate deionized water cleans up, and dries and is placed in platter, with de-
Fat cotton dips acetone wiping plating surface, removes surface and oil contaminant, corrosion, oxide layer and impurity, after acetone wiping, deionization
Water rinses, and dries, to be plated；
2. electricity is clean processes:
At Ti6A14On V titanium alloy substrate, the clean formula of liquid of brush plating electricity is: sodium hydroxide 25g/L, tertiary sodium phosphate 45g/L, carbonic acid
Sodium 20g/L, acetic acid 0.3g/L, sodium hypophosphite 0.2g/L, surplus is water；PH value 11.
Brush-plating technique is: electrode just connects, brushing plating voltage 12V, and brush plating time 30S, with relative velocity 14m/min on workpiece
Unidirectional brush plating, cleans with distilled water after brush plating.
3. activation processing: continue at Ti6A14No. 1 activating solution of brush plating on V titanium alloy substrate, brush-plating technique is: electrode reversal connection,
Brushing plating voltage 12V, brush plating time 30S, with relative velocity 14m/min unidirectional brush plating on workpiece, use distilled water after brush plating
Clean.Then at Ti6A14Continuing No. 3 activating solutions of brush plating on V titanium alloy substrate, brush-plating technique is: electrode reversal connection, brushing plating voltage
12V, brush plating time 30S, with relative velocity 14m/min unidirectional brush plating on workpiece, clean with distilled water after brush plating.
3, brush titanizing plating solution and Brush Plating FHA plating solution
Selecting conventional DC pulse Brush Plating instrument, negative pole connects workpiece, positive pole plated pen, and plated pen selects high-purity fine graphite, outer layer covers
Absorbent cotton is in case directly contacting with workpiece during its plating.
(1) at the Ti after substrate pretreated6A14Brush plating titanium plating solution on V titanium alloy substrate, titanium solution composition proportioning is: Ti
(SO4)2200g/L, citric acid 30g/L ammonium sulfate 30g/L, acetic acid 5g/L, sodium lauryl sulphate 0.3g/L, surplus is water；
During brush plating, process conditions are that electrode just connects, brushing plating voltage 12V, brush plating time 120S, with the unidirectional brush plating of relative velocity 24m/min,
PH value is 3.5, cleans with a large amount of distilled water after brush plating.
(2) Ti after brush plating titanium plating solution6A14The FHA plating solution of preparation in brush plating step 1, brush is continued on V titanium alloy substrate
During plating, process conditions are that electrode just connects, brushing plating voltage 10V, brush plating time 100S, with the unidirectional brush plating of relative velocity 6m/min, brush plating
After with a large amount of distilled water clean.
4, by the Ti after brush plating FHA plating solution6A14V titanium alloy substrate is placed in resistance furnace and is sintered heat treatment, and heat up speed
Degree is 5 DEG C/min, and sintering heat treatment temperature is 650 DEG C, and temperature retention time is 3h, and cooling rate is 1 DEG C/min, it is cooled to 20 DEG C
Obtain target coating.
Coating layer thickness is about 33 μm after tested；After almighty test machine analysis heat treatment, the adhesion of coating and matrix is
25.6MPa。
Embodiment 3
1, FHA plating solution configuration:
1. titanium salt (titanium sulfate) Ti (SO is weighed4)2200g, puts into the titanium salt of weighing in the beaker filling 350ml distilled water and uses
Magnetic stirring apparatus individually dissolves 10min to being completely dissolved, and is configured to titanium salt solution；
2. take citric acid 60g, ammonium sulfate 20g, add 300ml distilled water and be placed on magnetic stirring apparatus the compound network of the configuration that stirs
Mixture, regulation pH value is 2.2, is configured to compound complex agent；
3. take 5g acetic acid to stir as buffer agent, the compound complex agent configured before addition, and slowly fallen by titanium salt solution
Enter, obtain solution one;
4. take 0.2g sodium lauryl sulphate and pour mix homogeneously in the solution one that 3. step obtains into as surfactant, obtain molten
Liquid two；
5. in the solution two that 4. step configures, add 40g sodium hypophosphite NaH2PO2, stir 15 points with omnipotent mechanics blender
Clock, is subsequently adding FHA powder 175g, is heated to 80 DEG C and continues to stir 15min, obtaining the dense plating solution of FHA；
6. being 0.175g/ml with the dense plating solution of distilled water diluting FHA to FHA powder concentration in the plating solution, solution ph is 7.5, molten
Liquid pH hydrochloric acid regulates with the solution of ammonia volume ratio 2:1.
2, substrate pretreated
1. chemistry abatement processes: by Ti6A14V titanium alloy substrate deionized water cleans up, and dries and is placed in platter, with de-
Fat cotton dips acetone wiping plating surface, removes surface and oil contaminant, corrosion, oxide layer and impurity, after acetone wiping, deionization
Water rinses, and dries, to be plated；
2. electricity is clean processes:
Electricity is clean to be processed: at Ti6A14On V titanium alloy substrate, the clean formula of liquid of brush plating electricity is: sodium hydroxide 30g/L, tertiary sodium phosphate
60g/L, sodium carbonate 25g/L, acetic acid 0.2g/L, sodium hypophosphite 0.5g/L, surplus is water；PH value 13.
Brush-plating technique is: electrode just connects, brushing plating voltage 10V, and brush plating time 40S, with relative velocity 24m/min on workpiece
Unidirectional brush plating, cleans with distilled water after brush plating.
3. activation processing: continue at Ti6A14No. 1 activating solution of brush plating on V titanium alloy substrate, brush-plating technique is: electrode reversal connection,
Brushing plating voltage 10V, brush plating time 40S are with relative velocity 6m/min unidirectional brush plating on workpiece, clear with distilled water after brush plating
Wash.Then at Ti6A14Continuing No. 3 activating solutions of brush plating on V titanium alloy substrate, brush-plating technique is: electrode reversal connection, brushing plating voltage 10V,
Brush plating time 40S, with relative velocity 24m/min unidirectional brush plating on workpiece, cleans with distilled water after brush plating.
3, brush titanizing plating solution and Brush Plating FHA plating solution
Selecting conventional DC pulse Brush Plating instrument, negative pole connects workpiece, positive pole plated pen, and plated pen selects high-purity fine graphite, outer layer covers
Absorbent cotton is in case directly contacting with workpiece during its plating.
(1) at the Ti after substrate pretreated6A14Brush plating titanium plating solution on V titanium alloy substrate, titanium solution composition proportioning is: Ti
(SO4)2300g/L, citric acid 60g/L ammonium sulfate 40g/L, acetic acid 4g/L, sodium lauryl sulphate 0.3g/L, surplus is water；
During brush plating, process conditions are that electrode just connects, brushing plating voltage 12V, brush plating time 70S, with the unidirectional brush plating of relative velocity 6m/min, PH
Value is 6.5, cleans with a large amount of distilled water after brush plating.
(2) Ti after brush plating titanium plating solution6A14The FHA plating solution of preparation in brush plating step 1, brush is continued on V titanium alloy substrate
During plating, process conditions are that electrode just connects, brushing plating voltage 16V, brush plating time more than 100S, with the unidirectional brush of relative velocity 24m/min
Plating, cleans with a large amount of distilled water after brush plating.
4, by the Ti after brush plating FHA plating solution6A14V titanium alloy substrate is placed in resistance furnace and is sintered heat treatment, and heat up speed
Degree is 15 DEG C/min, and sintering heat treatment temperature is 850 DEG C, and temperature retention time is 2h, and cooling rate is 10 DEG C/min, it is cooled to 30
DEG C obtain target coating.
Coating layer thickness is about 34 μm after tested；After almighty test machine analysis heat treatment, the adhesion of coating and matrix is
29MPa。
Embodiment 4
1, FHA plating solution configuration:
1. titanium salt (titanium sulfate) Ti (SO is weighed4)2250g, puts into the titanium salt of weighing in the beaker filling 500ml distilled water and uses
Magnetic stirring apparatus individually dissolves 10min to being completely dissolved, and is configured to titanium salt solution；
2. take citric acid 50g, ammonium sulfate 30g, add 400ml distilled water and be placed on magnetic stirring apparatus the compound network of the configuration that stirs
Mixture, regulation pH value is 2.4, is configured to compound complex agent；
3. take 3g acetic acid to stir as buffer agent, the compound complex agent configured before addition, and slowly fallen by titanium salt solution
Enter, obtain solution one;
4. take 0.1g sodium lauryl sulphate and pour mix homogeneously in the solution one that 3. step obtains into as surfactant, obtain molten
Liquid two；
5. in the solution two that 4. step configures, add 24g sodium hypophosphite NaH2PO2, stir 10 points with omnipotent mechanics blender
Clock, is subsequently adding FHA powder 200g, is heated to 40 DEG C and continues to stir 30min, obtaining the dense plating solution of FHA；
6. being 0.200g/ml with the dense plating solution of distilled water diluting FHA to FHA powder concentration in the plating solution, solution ph is 7.5, molten
Liquid pH hydrochloric acid regulates with the solution of ammonia volume ratio 2:1.
2, substrate pretreated
1. chemistry abatement processes: by Ti6A14V titanium alloy substrate deionized water cleans up, and dries and is placed in platter, with de-
Fat cotton dips acetone wiping plating surface, removes surface and oil contaminant, corrosion, oxide layer and impurity, after acetone wiping, deionization
Water rinses, and dries, to be plated；
2. electricity is clean processes:
At Ti6A14On V titanium alloy substrate, the clean formula of liquid of brush plating electricity is: sodium hydroxide 20-30g/L, tertiary sodium phosphate 40-60g/
L, sodium carbonate 20-25g/L, acetic acid 0.2-0.5g/L, sodium hypophosphite 0.2-0.5g/L, surplus is water；The pH value of the clean liquid of electricity is
11-13；
Electricity is clean to be processed: at Ti6A14On V titanium alloy substrate, the clean formula of liquid of brush plating electricity is: sodium hydroxide 25g/L, tertiary sodium phosphate
45g/L, sodium carbonate 20g/L, acetic acid 0.3g/L, sodium hypophosphite 0.2g/L, surplus is water；PH value 11.
Brush-plating technique is: electrode just connects, brushing plating voltage 12V, and brush plating time 30S, with relative velocity 14m/min on workpiece
Unidirectional brush plating, cleans with distilled water after brush plating.
3. activation processing: continue at Ti6A14No. 1 activating solution of brush plating on V titanium alloy substrate, brush-plating technique is: electrode reversal connection,
Brushing plating voltage 12V, brush plating time 30S, with relative velocity 14m/min unidirectional brush plating on workpiece, use distilled water after brush plating
Clean.Then at Ti6A14Continuing No. 3 activating solutions of brush plating on V titanium alloy substrate, brush-plating technique is: electrode reversal connection, brushing plating voltage
12V, brush plating time 30S, with relative velocity 14m/min unidirectional brush plating on workpiece, clean with distilled water after brush plating.
3, brush titanizing plating solution and Brush Plating FHA plating solution
Selecting conventional DC pulse Brush Plating instrument, negative pole connects workpiece, positive pole plated pen, and plated pen selects high-purity fine graphite, outer layer covers
Absorbent cotton is in case directly contacting with workpiece during its plating.
(1) at the Ti after substrate pretreated6A14Brush plating titanium plating solution on V titanium alloy substrate, titanium solution composition proportioning is: Ti
(SO4)2250g/L, citric acid 50g/L ammonium sulfate 35g/L, acetic acid 4g/L, sodium lauryl sulphate 0.1g/L, surplus is water；
During brush plating, process conditions are that electrode just connects, brushing plating voltage 12V, brush plating time 240S, with the unidirectional brush plating of relative velocity 18m/min,
PH value is 6, cleans with a large amount of distilled water after brush plating.
(2) Ti after brush plating titanium plating solution6A14The FHA plating solution of preparation in brush plating step 1, brush is continued on V titanium alloy substrate
During plating, process conditions are that electrode just connects, brushing plating voltage 12V, brush plating time more than 260S, with the unidirectional brush of relative velocity 20m/min
Plating, cleans with a large amount of distilled water after brush plating.
4, by the Ti after brush plating FHA plating solution6A14V titanium alloy substrate is placed in resistance furnace and is sintered heat treatment, and heat up speed
Degree is 5 DEG C/min, and sintering heat treatment temperature is 700 DEG C, and temperature retention time is 3h, and cooling rate is 1 DEG C/min, it is cooled to 20 DEG C
Obtain target coating.
Coating layer thickness is about 57 μm after tested；After almighty test machine analysis heat treatment, the adhesion of coating and matrix is
45MPa。
Comparative example 1
Laser melting coating, heat spraying method prepares FHA coating, basic step: the synthesis presoma containing FHA is coated in matrix table
Face, then make presoma be changed into FHA coating by the way of high temperature cladding.Temperature controls difficulty, and FHA is when matrix cladding step
Easily decompose.
Comparative example 2
Electrophoretic deposition-sintering process prepares FHA coating, basic step: prepare the deposition liquid containing FHA, matrix is placed in electrophoresis tank
Energising deposition, dislodger is anode, and matrix is negative electrode.FHA coating is prepared, this method sedimentation time by principle of oxidation and reduction
Long, the coating of preparation and the adhesion of matrix most preferably 10.6MPa, the utilization rate of plating solution is low, the most recyclable.
In sum, the bioactivity coatings that prepared by the inventive method Brush Plating-sintering process is compared to electrophoretic deposition-sintering
FHA coating prepared by method and optimum combination power 10.6MPa of matrix, the adhesion that improve FHA and matrix is up to 45MPa,
And utilize Technology for Heating Processing to form the coating structure of mechanical property and biocompatibility matched well, and sedimentation time is significantly
Shorten.Compared to methods such as laser melting coating, thermal sprayings, the inventive method is unlikely to make FHA decompose；Compared to chemical deposition
With the method such as groove plating, the plating solution utilization rate of the inventive method improves several times to tens times, and the metal ion content in plating solution increases
Be conducive to the generation of coating oxidation reduction reaction.The method of the present invention can use in wider electric current density and temperature range,
Need not at ordinary times plating solution chemical examination is adjusted.Brush Plating FHA has not only widened manufacture of materials field, reduces production cost, improves
Production efficiency.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (7)
1. a FHA bioactivity coatings, it is characterised in that described coating structure is matrix/Ti/FHA, the FHA applied
Powder F is 0.5 to the Replacement rate of OH.
FHA bioactivity coatings the most according to claim 1, it is characterised in that described coating structure is Ti6A14V/
Ti/FHA。
The preparation method of FHA bioactivity coatings the most according to claim 1 and 2, it is characterised in that described preparation method
Use Brush Plating-sintering process to prepare FHA bioactivity coatings, comprise the following steps that
(1) configuration of FHA plating solution；
(2) substrate pretreated；
(3) brush titanizing plating solution and Brush Plating FHA plating solution；
(4) through step (3), the matrix sintering after brush titanizing plating solution and Brush Plating FHA plating solution is obtained target coating.
4. according to the arbitrary described preparation method of claims 1-3, it is characterised in that described step (1) FHA plating solution
Configuration, concretely comprises the following steps:
A, take titanium salt titanium sulfate 200-300g, put in the container filling 350-500ml distilled water and be completely dissolved, be configured to titanium salt
Solution；
B, take citric acid 30-60g, ammonium sulfate 20-40g, add 300-400ml distilled water and stir, then regulation pH value is
2.2-2.5, it is configured to compound complex agent；
C, taking 3-5g acetic acid as buffer agent, the compound complex agent adding the configuration of step B stirs, and then step A is configured
Titanium salt solution be poured slowly into, obtain solution one；
D, take 0.1-0.2g sodium lauryl sulphate as surfactant, pour mix homogeneously in the solution one that step C obtains into,
Obtain solution two；
E, to step D configuration solution two in add 24-40g sodium hypophosphite NaH2PO2, stir 5-15 minute, be subsequently adding
FHA powder 125-200g, after being heated to 40-80 DEG C and continuing to stir 15-30min, obtains the dense plating solution of FHA；Use distilled water diluting
The dense plating solution of FHA obtains FHA plating solution, and FHA powder concentration range in FHA plating solution is 0.125g/ml--0.200g/ml, FHA plating
The pH value of liquid is 3.5-7.5, and pH value hydrochloric acid regulates with the solution of ammonia volume ratio 2:1.
5., according to the arbitrary described preparation method of claims 1-4, it is characterized in that, described step (2) substrate pretreated,
Comprise the concrete steps that:
1. chemistry abatement processes: by Ti6A14V titanium alloy substrate deionized water cleans up, and dries and is placed in platter, with de-
After fat cotton dips acetone wiping plating surface, then with deionized water rinsing, dry, to be plated；
2. electricity is clean processes:
At Ti6A14The clean liquid of brush plating electricity on V titanium alloy substrate, brush-plating technique is: electrode just connects, and brushing plating voltage 10-12V, during brush plating
Between 20-40S, with relative velocity 6-24m/min unidirectional brush plating on workpiece, clean with distilled water after brush plating；
The clean liquid of electricity includes following components: sodium hydroxide 20-30g/L, tertiary sodium phosphate 40-60g/L, sodium carbonate 20-25g/L, second
Acid 0.2-0.5g/L, sodium hypophosphite 0.2-0.5g/L, surplus is water；The pH value of the clean liquid of electricity is 11-13；
3. activation processing: in step 2. Ti after electricity processes only6A14First No. 1 activating solution of brush plating on V titanium alloy substrate, then
No. 3 activating solutions of brush plating,
No. 1 activating solution brush-plating technique of brush plating is: electrode reversal connection, brushing plating voltage 10-12V, brush plating time 20-40S, with relative velocity
6-24m/min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating；
No. 3 activating solution brush-plating techniques of brush plating are: electrode reversal connection, brushing plating voltage 10-12V, brush plating time 20-40S, with relative velocity
6-24m/min is unidirectional brush plating on workpiece, cleans with distilled water after brush plating.
6., according to the arbitrary described preparation method of claims 1-5, it is characterized in that, described step (3) brush titanizing plating solution
And Brush Plating FHA plating solution, comprise the concrete steps that:
1. at the Ti after substrate pretreated6A14Brush plating titanium plating solution on V titanium alloy substrate, during brush plating process conditions be electrode just
Connecing, brushing plating voltage 10-12V, brush plating time more than 30S, with the unidirectional brush plating of relative velocity 6m/min-24m/min, plating solution pH value is
3.5-6.5；Clean with distilled water after brush plating；
Titanium plating solution includes following components: Ti (SO4)2200-300g/L, citric acid 30-60g/L, ammonium sulfate 20-40g/L, acetic acid
3-5g/L, sodium lauryl sulphate trace 0.1-0.3g/, surplus are water；
2. at the Ti after step 1. brush plating titanium plating solution6A14Brush plating FHA plating solution on V titanium alloy substrate；During brush plating, process conditions are
Electrode just connects, brushing plating voltage 10-16V, brush plating time more than 30S, with the unidirectional brush plating of relative velocity 6m/min-24m/min, brush plating
After clean with distilled water.
7. according to the arbitrary described preparation method of claims 1-6, it is characterized in that, described step (4) will through step (3)
Matrix after brush titanizing plating solution and Brush Plating FHA plating solution sinters and obtains comprising the concrete steps that of target coating:
By the Ti after brush titanizing plating solution and Brush Plating FHA plating solution6A14V titanium alloy substrate is placed in resistance furnace and is sintered, and rises
Temperature speed is 5-15 DEG C/min, and sintering temperature is 450 DEG C-850 DEG C, and temperature retention time is 2-3h, and cooling rate is 1-10 DEG C/min,
It is cooled to 10-30 DEG C and obtains target coating.
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| CN106514039A (en) * | 2016-11-03 | 2017-03-22 | 华北水利水电大学 | Copper-tin-titanium brazing filler metal and preparation method thereof |
| CN106514039B (en) * | 2016-11-03 | 2019-03-08 | 华北水利水电大学 | A kind of copper and tin titanium solder and preparation method thereof |
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| CN110029383B (en) * | 2019-03-15 | 2020-08-18 | 浙江工贸职业技术学院 | Degradable zinc-copper foam biological material |
| CN110607545A (en) * | 2019-09-20 | 2019-12-24 | 天津大学 | Electrochemical additive manufacturing method of antibacterial fluorinated hydroxyapatite bionic cicada wing patterned surface |
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