CN116585536A - Zinc-based medical material containing metal/zinc phosphate composite coating and preparation method and application thereof - Google Patents
Zinc-based medical material containing metal/zinc phosphate composite coating and preparation method and application thereof Download PDFInfo
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- CN116585536A CN116585536A CN202310427212.7A CN202310427212A CN116585536A CN 116585536 A CN116585536 A CN 116585536A CN 202310427212 A CN202310427212 A CN 202310427212A CN 116585536 A CN116585536 A CN 116585536A
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- zinc
- metal
- zinc phosphate
- composite coating
- medical material
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 title claims abstract description 97
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims abstract description 97
- 239000002184 metal Substances 0.000 title claims abstract description 86
- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 239000011701 zinc Substances 0.000 title claims abstract description 85
- 239000011248 coating agent Substances 0.000 title claims abstract description 84
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000012567 medical material Substances 0.000 title claims abstract description 30
- 229910001463 metal phosphate Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 238000000151 deposition Methods 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000000956 alloy Substances 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 31
- 150000002500 ions Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 16
- 230000008021 deposition Effects 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 17
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000007943 implant Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010884 ion-beam technique Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 description 60
- 238000005260 corrosion Methods 0.000 description 60
- 239000010410 layer Substances 0.000 description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- 238000006731 degradation reaction Methods 0.000 description 13
- 229910000398 iron phosphate Inorganic materials 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 229910000733 Li alloy Inorganic materials 0.000 description 11
- 238000010586 diagram Methods 0.000 description 11
- 239000001989 lithium alloy Substances 0.000 description 11
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 description 11
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 7
- 238000000635 electron micrograph Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [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 4
- 230000009894 physiological stress Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001727 in vivo Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 210000002449 bone cell Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007739 conversion coating Methods 0.000 description 2
- 231100000135 cytotoxicity Toxicity 0.000 description 2
- 230000003013 cytotoxicity Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 102000036675 Myoglobin Human genes 0.000 description 1
- 108010062374 Myoglobin Proteins 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 201000010934 exostosis Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 201000010930 hyperostosis Diseases 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000007737 ion beam deposition Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010883 osseointegration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 208000037816 tissue injury Diseases 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- -1 vapor deposition Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/086—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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- 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
- A61L2300/112—Phosphorus-containing compounds, e.g. phosphates, phosphonates
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Epidemiology (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Biomedical Technology (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a zinc-based medical material containing a metal/zinc phosphate composite coating and a preparation method and application thereof, wherein the composite coating consists of a substrate zinc-based alloy, a middle metal layer and an uppermost zinc phosphate coating, the coatings are tightly combined, the metal layer is prepared on the surface of a zinc substrate by an ion deposition method, and then the zinc phosphate composite coating is prepared on the basis of the metal layer by a chemical method. The coating also has good biodegradability and biocompatibility, so that the coating is more suitable for being used as a biodegradable material implanted into a human body.
Description
Technical Field
The invention belongs to the technical field of medical degradable zinc alloy materials, and particularly relates to a zinc-based medical material containing a metal/zinc phosphate composite coating, and a preparation method and application thereof.
Background
At present, biomedical metal materials are the most widely applied inert materials such as stainless steel, titanium alloy, cobalt-based alloy and the like, and have great problems in clinical application, such as nondegradable materials, and the materials need to be taken out through secondary operation; toxic ions are generated, and the human body is greatly affected. Biodegradable metal means that the metal can be slowly degraded in vivo, and degradation products can not cause serious host reaction, and can be completely dissolved and absorbed without residue after helping tissue healing. Therefore, the research and development of the degradable metal material have wide application prospect.
Zinc alloys have become a research hotspot in the field of degradable metals in recent years due to their unique physiological functions and moderate corrosion degradation rates. But its mechanical properties, corrosion resistance, biocompatibility, etc. remain important issues to be addressed in the application of zinc as a degradable metal implant. In recent years, many researches on alloying and surface modification of zinc have been carried out, which improve the mechanical, corrosion-resistant and biological properties of zinc to a certain extent and make great contribution to the application of zinc as biodegradable metal.
The biomedical implant material is implanted into a human body, and the speed of no toxicity and corrosion degradation rate is critical. The zinc addition is too high to causeThe corrosion products gather to cause local corrosion phenomena, which are not beneficial to the mechanical integrity of the implant; at the same time, zn is easy to be caused in the degradation process 2+ Excessive release results in vitro cytotoxicity and delayed in vivo osseointegration. Alloying and surface modification treatments of zinc are viable alternatives to effectively address these deficiencies.
The main zinc metal degradable alloying systems currently in main flow are: zn-Mg, zn-Fe, zn-Cu, zn-Li, and the like; the current common research methods for alloy surface modification include ion deposition, surface coating, vapor deposition, chemical heat treatment and the like. The patent 202110789515.4 discloses a zinc phosphate chemical conversion coating on the surface of a zinc alloy, a preparation method and application thereof, wherein the zinc phosphate chemical conversion coating is obtained by directly immersing a zinc alloy substrate in curing liquid for chemical conversion treatment, the preparation process is complex, a single-layer coating is formed, the prepared single-layer coating has poor adhesive force, and the zinc phosphate is directly prepared on the surface of a zinc substrate and is not completely covered, so that more pores and cracks exist, and local corrosion can occur during corrosion.
Disclosure of Invention
Aiming at the defects of the prior art, the first aim of the invention is to provide a zinc-based medical material containing a metal/zinc phosphate (ZnP) composite coating, wherein the zinc-based medical material is provided with the metal/zinc phosphate composite coating on the surface of a zinc matrix, and the composite coating has excellent biocompatibility and excellent film-based binding force with a zinc-based alloy substrate, can improve the corrosion resistance of a zinc-alloy biodegradable material, and realizes uniform corrosion and controllable corrosion rate.
The second object of the invention is to provide a method for preparing a zinc-based medical material containing a metal/zinc phosphate composite coating.
A third object of the present invention is to provide the use of a zinc-based medical material comprising a metal/zinc phosphate composite coating.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a zinc-based medical material containing a metal/zinc phosphate composite coating, which consists of a zinc-based alloy substrate and a metal/zinc phosphate composite coating arranged on the surface of the zinc-based alloy substrate, wherein the metal/zinc phosphate composite coating is sequentially provided with a metal layer and a zinc phosphate coating from bottom to top, and the metal in the metal layer is selected from one of Fe, cu, sn, ti, preferably one of Fe, cu and Ti.
According to the zinc-based medical material provided by the invention, the metal layer is firstly arranged on the surface of the zinc-based alloy substrate as the intermediate layer, and the inventor finds that the metal layer can effectively regulate and control the corrosion speed and the uneven corrosion problem of the biodegradable zinc-based alloy in the human environment, so that the biodegradable zinc-based material is degraded in the human body at a proper speed. The zinc phosphate coating on the surface layer not only has good biodegradability, but also has a structure similar to that of hydroxyapatite, and the latter is a main component of human bone, so that the zinc phosphate coating has good biocompatibility and capability of promoting adhesion, proliferation and differentiation of bone cells, and is expected to be used for bionic deposition of degradable zinc metal. The single coating has low adhesion capability and poor adhesive force, and the zinc phosphate is directly prepared on the surface of the zinc substrate, but does not completely cover, so that more pores and cracks exist, and local corrosion can occur during corrosion. The adhesive capacity of the prepared composite coating can be improved, the prepared zinc phosphate coating is more uniform and compact, the corrosion of electrolyte to a zinc matrix is effectively prevented, the corrosion of zinc alloy is more uniform, and the zinc alloy has better performance than that of the single coating.
In a preferred embodiment, the zinc-based alloy substrate is a zinc alloy, preferably a zinc-lithium alloy.
Further preferably, the mass fraction of lithium in the zinc-lithium alloy is 0.1 to 2%.
The inventor finds that the zinc-lithium alloy has good biocompatibility and cell compatibility, can enhance the cell activity, and also has proper degradation rate.
Preferably, the thickness of the metal layer is 3-7 μm, preferably 5 μm; the thickness of the zinc phosphate is 10-15 mu m, preferably 12 mu m.
The inventor finds that the thickness of the metal layer and the zinc phosphate composite coating needs to be effectively controlled, and if the thickness is too thick, the corrosion resistance of a sample can be affected due to the increase of residual stress; the thickness is too thin, which may cause the problems of poor adhesive force, easy falling off, non-compactness and the like.
Preferably, the metal in the metal layer is selected from Fe.
The inventor finds that when the metal layer is Fe, zinc phosphate can be more uniformly covered on the surface of the zinc-based alloy substrate, so that zinc alloy corrosion is more uniform, and iron has good biological safety, is a trace element necessary for a human body, is a required component of cells, and is a component of hemoglobin, myoglobin and various enzymes.
Preferably, the metal layer is prepared by ion deposition.
The inventor finds that the degradation performance of the finally obtained biodegradable zinc-based material is optimal by adopting an ion deposition method, because the ion deposition process is an unbalanced process, the implanted element is not limited by a diffusion coefficient, a solid solubility and a balance phase diagram, no interface is formed between the implanted layer and the matrix, metallurgical bonding can be formed, and the bonding strength and the adhesiveness between the implanted layer and the matrix are high. Meanwhile, high-energy ions are forcedly injected into the surface of the workpiece, so that a large number of interstitial atoms, vacancies and dislocation are generated, the surface is reinforced, and the fatigue life is prolonged. Ion deposition is performed under high vacuum and at a lower process temperature, so that the workpiece does not undergo oxidation decarburization and no significant dimensional change.
Preferably, the zinc phosphate coating is prepared by a chemical method.
The inventor finds that the metal layer is prepared by adopting an ion deposition method and then the zinc phosphate composite coating is prepared by adopting a chemical method, so that the film layer binding force is ensured to be good, the thickness of the film layer can be increased, and the long-time service life of the sample in a human body can be met without carrying out subsequent treatment on the sample.
The invention relates to a preparation method of a zinc-based medical material containing a metal/zinc phosphate composite coating, which adopts an ion deposition method to arrange a metal layer on the surface of a zinc-based alloy substrate, then the zinc-based alloy substrate provided with the metal layer is soaked in a zinc phosphate solution, and the zinc-based medical material containing the metal/zinc phosphate composite coating is obtained after reaction.
According to the preferred scheme, the zinc-based alloy substrate is firstly polished and polished, then is respectively ultrasonically cleaned for more than 10min by acetone and absolute ethyl alcohol, and is dried by a blower. By this pretreatment, all zinc substrate surfaces were cleaned and dried.
Preferably, the ion deposition method comprises the following steps: the metal source with purity more than or equal to 99% is used as an arc source, and the pressure of a vacuum chamber in the magnetic filtering cathode vacuum arc deposition equipment is controlled to be 3.0-4.0x10 before the deposition of the magnetic filtering cathode vacuum arc ion beam -3 Pa; when the magnetic filtration cathode vacuum arc deposition is carried out, the arc starting current is controlled to be 130-140A, the duty ratio is controlled to be 50-80%, the deposition is carried out by adopting-800V, -600V, -400V and-200V in sequence, each negative pressure point is deposited for 20-40 s, and then after the deposition of-200V is completed, the deposition is carried out for 10-15 min when the negative pressure is-100V.
Further preferably, the ion deposition method adopts a magnetic filtration cathode vacuum arc technology (FCVA), the arcing current is controlled to be 130-140A, the duty ratio is 50-80%, and each negative pressure point is deposited for 20-30 s when the ion deposition method is carried out at-800V, -600V, -400V and-200V.
The inventor finds that the performance of the metal film obtained by adopting the magnetic filtration cathode vacuum arc ion beam deposition (FCVA) technology is better, because the types of particles are screened by a magnetic field before being deposited on the alloy, the components which damage the quality of the film layer are removed, so that the film layer formed on the alloy has uniform and stable structure, high density and less number of various defects; under the action of a magnetic field formed by externally applying negative bias, the charged high-energy ions generate a certain degree of bombardment sputtering action on the alloy substrate, so that the combination of a film-base interface is stable and is not easy to fall off; the ionization rate of the target material is very high, the deposition film forming rate is fast, and the working efficiency is very high; the deposition temperature is relatively low, and the change of the structural property of the substrate caused by overhigh temperature in the working process is avoided.
In a preferred scheme, the zinc phosphate solution is obtained by the following steps: zn (NO) 3 ) 2 ·6H 2 O、Ca 3 (NO 3 ) 2 ·4H 2 O、NaH 2 PO 4 Adding the mixture into water, mixing to obtain a mixed solution, and then adopting 2.5-3.5M NaOH to adjust the pH of the mixed solution to 2.5-3.5 to obtain a zinc phosphate solution, wherein Zn (NO 3 ) 2 ·6H 2 The concentration of O is 12.5-13.5 g/L, ca 3 (NO 3 ) 2 ·4H 2 The concentration of O is 9.5-10.5 g/L, naH 2 PO 4 The concentration of (2) is 21-22 g/L;
in a preferred scheme, the reaction temperature is 35-45 ℃ and the reaction time is 1-3 h.
In the invention, the zinc phosphate coating prepared by adopting a chemical method has small solubility in a neutral environment, stable chemical property and stable existence in a physiological environment of a human body with the pH value of 7.35-7.45. The zinc phosphate coating can isolate the contact between the metal substrate and body fluid, and avoid Cl in physiological environment - And the corrosion of water to the substrate has good corrosion resistance. At the same time, the main inorganic phase Zn of the zinc phosphate coating 3 (PO 4 )·4H 2 O is a potential biological material. Phosphate in zinc phosphate coating can promote Ca in physiological environment 2+ By chemical action, the zinc phosphate is converted into hydroxyapatite.
In the invention, after the metal layer is arranged on the surface of the zinc-based alloy substrate by adopting an ion deposition method, the zinc-based alloy substrate provided with the metal layer is only soaked in the zinc phosphate solution, so that the uniform zinc phosphate coating which completely covers the zinc-based alloy substrate can be obtained.
The zinc phosphate coating prepared on the surface of the zinc-based alloy by adopting the hydrothermal method has a compact and uniform structure, can obviously slow down the corrosion degradation rate of zinc, and has good biocompatibility and antibacterial capability.
The invention also provides application of the zinc-based medical material containing the metal/zinc phosphate composite coating, and the zinc-based medical material is used as a biomedical metal implantation material.
Principle and advantages
(1) The key problems of zinc and zinc alloys as biodegradable metals are their mechanical properties, corrosion resistance and biocompatibility. The mechanical property of pure zinc can not reach the standard of biomedical implant materials, and the strength and corrosion rate of the zinc-based alloy obtained through alloying treatment are improved greatly. Zinc-based degradable metals also have the problem of uneven corrosion degradation, which is easy to cause the early failure of the implant; the release of surface excess zinc ions can also cause cytotoxicity. The problem of uneven corrosion can be solved by the surface modification technology, the degradation behavior can be regulated and controlled, and the biocompatibility can be improved.
(2) Physiological stress is an important component of metabolism of human body, is closely related to bone tissue reconstruction, blood circulation, body fluid flow and the like, and plays an important role in the healing process of bone tissue injury. During service, the implant device will inevitably be subjected to physiological stress, which is believed to affect the degradation behavior of the material and thus the service behavior of the implant device (e.g., resulting in a service life of the device that is less than expected). The pure metal film layer has the characteristics of good plasticity and toughness, and different metals have different potential differences, so that the effect of physiological stress can be effectively resisted, and the degradation speed of zinc and zinc alloy in human bodies can be improved. And the pure metal film layer can realize uniform corrosion in a human body, so that the damage of premature failure of the implant material caused by mechanical property loss due to non-uniform corrosion can be avoided, and the implant material can meet the long-term service effect of the human body. (3) The inventor finds that the metal/zinc phosphate composite coating is prepared on the surfaces of zinc and zinc alloy through a large number of experiments, and finally the biodegradable zinc-based material has the most suitable degradation rate in a human body and excellent biocompatibility and corrosion resistance. Zinc phosphate has not only good biodegradability but also a structure similar to that of hydroxyapatite, which is a main component of human bone, so that zinc phosphate has good biocompatibility and capability of promoting adhesion, proliferation and differentiation of bone cells.
(4) The metal layer is prepared by adopting an ion deposition method, and the ion deposition is used as a surface treatment process, so that a new alloy layer can be formed on the surface, the surface state is changed, and the problem of the bonding strength between the coating prepared by other processes and the substrate is solved. The zinc phosphate composite coating prepared by the chemical method is prepared on the basis of the ion deposition metal layer, so that the film layer binding force is good, the thickness of the film layer can be increased, the film layer binding force and the adhesion capability are improved, and deformation is not easy to generate. The coating is uniform and compact, has less number of various defects, has good stability, shows uniform corrosion degradation modes, is beneficial to avoiding the problem of early fracture failure in the service process of the zinc-based degradable implant, and can meet the long-time service life in a human body.
In summary, the preparation of the metal/zinc phosphate composite coating on the surface of the zinc-based medical material disclosed by the invention has the following advantages:
(1) The proper surface treatment process selected by the invention does not cause any pollution to the environment and does not introduce any elements harmful to human bodies. The metal layer is prepared on the zinc-based alloy by ion deposition and the zinc phosphate composite coating is prepared by a chemical method, so that not only can the controlled decomposition of the zinc-based alloy under uniform corrosion be realized, but also the biocompatibility can be improved.
(2) The pure metal film layer has the characteristic of good plastic toughness. Can effectively resist physiological stress. And the pure metal film layer can realize uniform corrosion in a human body, and the different metal film layers have different potential differences and different corrosion rates, so that the corrosion rate of the zinc-based alloy can be regulated and controlled. The adhesion capability of the prepared zinc phosphate coating can be improved, the prepared zinc phosphate coating is more uniform and compact, and the corrosion of electrolyte to a zinc matrix is effectively prevented, so that the corrosion of zinc alloy is more uniform.
(3) Compared with other ion deposition methods, the magnetic filtration cathode vacuum arc technology (FCVA) of the preferred scheme of the invention has high equipment atom ionization rate, and the magnetic filtration device is arranged, so that large particles are greatly reduced during film formation, and the compactness and uniformity of the film can be improved. The technology has the advantages of green environmental protection, no pollution to the ecological environment, high deposition rate, large-area deposition and the like, and has very wide application value in the field of human implantation materials.
(4) The chemical method for preparing the zinc phosphate coating has the advantages of simple process, less working procedures, low cost and easy realization of large-area film formation. The zinc phosphate coating has good corrosion resistance and biocompatibility. Phosphate in zinc phosphate coating can promote Ca in physiological environment 2+ By chemical action, the zinc phosphate is converted into hydroxyapatite. It can participate in metabolism in vivo, has stimulation or induction effect on hyperostosis, can promote repair of defective tissue, and shows bioactivity.
In a word, the metal/zinc phosphate composite coating prepared on the surface of the zinc-based medical material can obviously improve the corrosion resistance and biocompatibility of the biodegradable zinc alloy, has proper degradation rate, and can be applied to degradable biomedical materials.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIG. 1 is a physical view of a zinc-lithium alloy substrate with an uncoated surface of example 1.
FIG. 2 is a physical diagram of the surface of example 1 after the iron/zinc phosphate composite coating is prepared.
FIG. 3 is an electron micrograph of a zinc-lithium alloy matrix with an uncoated surface of example 1.
FIG. 4 is a surface electron micrograph of the surface of example 1 after having prepared an iron/zinc phosphate composite coating.
FIG. 5 is a side cross-sectional electron micrograph of the surface of example 1 after preparing an iron/zinc phosphate composite coating.
FIG. 6 is an XRD comparison of the surface preparation of the iron/zinc phosphate composite coating of example 1 with a substrate.
FIG. 7 is a graph showing the polarization of the surface-prepared iron/zinc phosphate composite coating of example 1 and a substrate in Hanks' solution.
Fig. 8 is a schematic structural diagram of a composite coating prepared from the zinc-based medical material of example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Example 1:
(a) The Zn-0.5Li alloy is biologically degraded as a substrate, and the magnetic Filtration Cathode Vacuum Arc (FCVA) technology is adopted, and the pressure of a vacuum chamber in the magnetic filtration cathode vacuum arc deposition equipment is controlled to be 3.0 multiplied by 10 before the deposition of the magnetic filtration cathode vacuum arc -3 Pa; when the magnetic filtration cathode vacuum arc deposition is carried out, the arc starting current is controlled to be 135A, the duty ratio is 50%, the deposition is carried out by adopting-800V, -600V, -400V and-200V, each negative pressure point is deposited for 30s, and after the deposition of-200V is completed, the deposition is carried out for 10min when the negative pressure is-100V; the biodegradable zinc-lithium alloy with a layer of pure Fe film on the surface, which has compact and uniform structure and good binding force, is obtained.
(b) The preparation process of the zinc phosphate solution comprises the following steps: 6.5g Zn (NO) was weighed out with a balance 3 ) 2 ·6H 2 O、5gCa 3 (NO 3 ) 2 ·4H 2 O、10.75g NaH 2 PO 4 The sample was poured into a 500ml beaker of water and stirred with a glass rod, followed by adjusting the pH of the solution to 3 with 3M NaOH to prepare a zinc phosphate solution. And (3) soaking the zinc-lithium alloy with the surface provided with the pure iron film layer in zinc phosphate solution, and then putting the zinc-lithium alloy into a heat-collecting magnetic stirrer together for heating in water bath at 40 ℃ for 2 hours to prepare the zinc phosphate coating.
FIG. 1 is a physical view of a zinc-lithium alloy substrate with an uncoated surface of example 1. FIG. 2 is a physical diagram of the surface of example 1 after the iron/zinc phosphate composite coating is prepared. FIG. 3 is an electron micrograph of a zinc-lithium alloy matrix with an uncoated surface of example 1. FIG. 4 is a surface electron micrograph of the surface of example 1 after preparation of an iron/zinc phosphate composite coating, in which dense petaloid zinc phosphate is visible. FIG. 5 is a side cross-sectional electron micrograph of the surface of example 1 after preparing a composite iron/zinc phosphate coating, which is seen to be about 17 μm thick and about 5 μm thick as a metal layer. FIG. 6 is an XRD comparison of the surface preparation of the iron/zinc phosphate composite coating of example 1 with a substrate. From these figures, it can be seen that the zinc phosphate coating in example 1 of the present invention has been successfully prepared on the surface of the zinc-lithium alloy, and the zinc phosphate coating has a relatively uniform distribution and a relatively compact structure. The preparation process is reliable.
FIG. 7 is a graph showing the polarization of the surface-prepared iron/zinc phosphate composite coating of example 1 and a substrate in Hanks' solution. Curve fitting it by origin software to obtain corrosion potential E of substrate corr Corrosion current density I at-1.016V corr 15.21. Mu.A/cm 2 Thereby calculating the corrosion rate R c 0.187mm/year; corrosion potential E of iron/zinc phosphate composite coating corr The corrosion current density I is increased to-0.45V corr Reduced to 0.60 mu A/cm 2 Thereby calculating the corrosion rate R c The reduction is 0.035mm/year. It is known that higher corrosion potential means lower corrosion tendency, and the samples of the iron/zinc phosphate composite coating prepared by ion deposition and chemical method have higher corrosion potential, lower corrosion current density and low corrosion rate, which indicates that the corrosion resistance is improved. The metal film and the zinc phosphate layer are prepared on the surface of the substrate, so that the corrosive liquid and the substrate can be separated, and the possibility of pitting is reduced, so that the composite coating of the iron/zinc phosphate prepared on the surface has better corrosion resistance.
Example 2:
other conditions were identical to example 1 except that ion-deposited Fe was replaced with ion-deposited Cu.
The thickness of the film layer was found to be about 17.5 μm by the side film layer diagram. The corrosion rate R can be obtained by Tafil curve calculation c The drop was 0.032mm/year.
Example 3:
other conditions were identical to those of example 1, except that ion-deposited Fe was replaced with ion-deposited Sn.
The thickness of the film layer was found to be about 17.3 μm by the side film layer diagram. The corrosion rate R can be obtained by Tafil curve calculation c Reduced to 0.026mm/year.
Example 4:
other conditions were identical to example 1 except that ion-deposited Fe was replaced with ion-deposited Ti.
The thickness of the film layer was found to be about 17.2 μm by the side film layer diagram. The corrosion rate R can be obtained by Tafil curve calculation c Reduced to 0.033mm/year.
Example 5:
other conditions were consistent with example 1 except that the arc starting current was controlled to 130A during the magnetic filter cathode vacuum arc deposition.
The thickness of the film layer was found to be about 17.4 μm by the side film layer diagram. The corrosion rate R can be obtained by Tafil curve calculation c Reduced to 0.030mm/year.
Example 6:
other conditions were identical to example 1 except that the magnetic filtration cathodic vacuum arc deposition time was 15min.
The thickness of the film layer was found to be about 17.8 μm by the side film layer diagram. The corrosion rate R can be obtained by Tafil curve calculation c Reduced to 0.036mm/year.
Example 7:
other conditions were the same as in example 1 except that the water bath was heated in the zinc phosphate solution for 1h.
The thickness of the film layer was found to be about 17.4 μm by the side film layer diagram. The corrosion rate R can be obtained by Tafil curve calculation c Reduced to 0.033mm/year.
Example 8:
other conditions were identical to example 1, except that the water bath was heated in the zinc phosphate solution for 3 hours.
The thickness of the film layer was found to be about 17.7 μm by the side film layer diagram. The corrosion rate R can be obtained by Tafil curve calculation c Reduced to 0.031mm/year.
Comparative example 1:
other conditions were identical to example 1 except that the zinc phosphate coating was prepared directly on the zinc substrate without preparing the metal layer.
As can be seen from the side surface layer diagramThe thickness of the film was about 12.5 μm. The corrosion rate R can be obtained by Tafil curve calculation c Reduced to 0.015mm/year.
Comparative example 2:
other conditions were the same as in example 1 except that the metal layer was prepared to have a thickness of 1. Mu.m.
The thickness of the film layer was about 13.5. Mu.m, as seen from the side film layer diagram. The corrosion rate R can be obtained by Tafil curve calculation c Reduced to 0.029mm/year.
It will be understood by those skilled in the art that the foregoing examples are merely illustrative of the present invention in further detail and that the present invention is not limited to the above-described embodiments, and that various modifications and variations may be made on the basis of the examples under the above-described guidance of the present invention, and that such modifications or variations fall within the scope of the present invention. The scope of the invention is defined by the claims and their equivalents.
Claims (10)
1. A zinc-based medical material comprising a metal/zinc phosphate composite coating, characterized in that: the zinc-based medical material consists of a zinc-based alloy substrate and a metal/zinc phosphate composite coating arranged on the surface of the zinc-based alloy substrate, wherein the metal/zinc phosphate composite coating is sequentially provided with a metal layer and a zinc phosphate coating from bottom to top, and the metal in the metal layer is selected from one of Fe, cu, sn, ti.
2. A zinc-based medical material comprising a metal/zinc phosphate composite coating according to claim 1, wherein: the zinc-based alloy substrate is zinc alloy.
3. A zinc-based medical material comprising a metal/zinc phosphate composite coating according to claim 1, wherein: the thickness of the metal layer is 3-7 mu m, and the thickness of the zinc phosphate is 10-15 mu m.
4. A zinc-based medical material comprising a metal/zinc phosphate composite coating according to claim 1 or 3, characterized in that: the metal in the metal layer is selected from Fe.
5. A zinc-based medical material comprising a metal/zinc phosphate composite coating according to claim 1 or 3, characterized in that: the metal layer is prepared by an ion deposition method; the zinc phosphate coating is prepared by a chemical method.
6. A zinc-based medical material comprising a metal/zinc phosphate composite coating according to any one of claims 1 to 5, characterized in that: and (3) arranging a metal layer on the surface of the zinc-based alloy substrate by adopting an ion deposition method, and then soaking the zinc-based alloy substrate provided with the metal layer in a zinc phosphate solution for reaction to obtain the zinc-based medical material containing the metal/zinc phosphate composite coating.
7. A zinc-based medical material comprising a metal/zinc phosphate composite coating according to claim 6, wherein: the zinc-based alloy substrate is firstly ground and polished, then is respectively ultrasonically cleaned by acetone and absolute ethyl alcohol for more than 10 minutes, and is dried by a blower.
8. A zinc-based medical material comprising a metal/zinc phosphate composite coating according to claim 6, wherein: the ion deposition method comprises the following steps: the metal source with purity more than or equal to 99% is used as an arc source, and the pressure of a vacuum chamber in the magnetic filtering cathode vacuum arc deposition equipment is controlled to be 3.0-4.0x10 before the deposition of the magnetic filtering cathode vacuum arc ion beam -3 Pa; when the magnetic filtration cathode vacuum arc deposition is carried out, the arc starting current is controlled to be 130-140A, the duty ratio is controlled to be 50-80%, the deposition is carried out by adopting-800V, -600V, -400V and-200V in sequence, each negative pressure point is deposited for 20-40 s, and then after the deposition of-200V is completed, the deposition is carried out for 10-15 min when the negative pressure is-100V.
9. A zinc-based medical material comprising a metal/zinc phosphate composite coating according to claim 8, wherein: the process for obtaining the zinc phosphate solution comprises the following steps: zn (NO) 3 ) 2 ·6H 2 O、Ca 3 (NO 3 ) 2 ·4H 2 O、NaH 2 PO 4 Adding the mixture into water, mixing to obtain a mixed solution, and then adopting 2.5-3.5M NaOH to adjust the pH of the mixed solution to 2.5-3.5 to obtain a zinc phosphate solution, wherein Zn (NO 3 ) 2 ·6H 2 The concentration of O is 12.5-13.5 g/L, ca 3 (NO 3 ) 2 ·4H 2 The concentration of O is 9.5-10.5 g/L, naH 2 PO 4 The concentration of (2) is 21-22 g/L;
the reaction temperature is 35-45 ℃, and the reaction time is 1-3 h.
10. Use of a zinc-based medical material comprising a metal/zinc phosphate composite coating according to any one of claims 1 to 5, characterized in that: the zinc-based medical material is used as a biomedical metal implant material.
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