CN114164393A - 一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法及其应用 - Google Patents
一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法及其应用 Download PDFInfo
- Publication number
- CN114164393A CN114164393A CN202111331582.8A CN202111331582A CN114164393A CN 114164393 A CN114164393 A CN 114164393A CN 202111331582 A CN202111331582 A CN 202111331582A CN 114164393 A CN114164393 A CN 114164393A
- Authority
- CN
- China
- Prior art keywords
- titanium alloy
- alloy material
- spraying
- ball milling
- strontium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 42
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 36
- 239000000956 alloy Substances 0.000 title claims abstract description 25
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 18
- 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 title claims abstract description 18
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 18
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000005507 spraying Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000007750 plasma spraying Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 230000001954 sterilising effect Effects 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 8
- 238000005488 sandblasting Methods 0.000 claims abstract description 8
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000010431 corundum Substances 0.000 claims abstract description 4
- 239000004576 sand Substances 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 238000010146 3D printing Methods 0.000 claims description 13
- 239000011324 bead Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 10
- 210000000988 bone and bone Anatomy 0.000 description 24
- 230000007547 defect Effects 0.000 description 15
- 230000000844 anti-bacterial effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 239000007943 implant Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 230000001580 bacterial effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 208000015181 infectious disease Diseases 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 230000004663 cell proliferation Effects 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 230000011164 ossification Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000000316 bone substitute Substances 0.000 description 3
- 239000006285 cell suspension Substances 0.000 description 3
- 238000012258 culturing Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
- 238000001727 in vivo Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 210000000689 upper leg Anatomy 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241000283973 Oryctolagus cuniculus Species 0.000 description 2
- 108010087230 Sincalide Proteins 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000010609 cell counting kit-8 assay Methods 0.000 description 2
- 238000004113 cell culture Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010883 osseointegration Methods 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 208000018084 Bone neoplasm Diseases 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 201000003803 Inflammatory myofibroblastic tumor Diseases 0.000 description 1
- 206010068331 Inflammatory pseudotumour Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 241000283977 Oryctolagus Species 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 208000007720 Plasma Cell Granuloma Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000735 allogeneic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 210000004271 bone marrow stromal cell Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001516 cell proliferation assay Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000001804 debridement Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000004053 dental implant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 210000003414 extremity Anatomy 0.000 description 1
- 239000012091 fetal bovine serum Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 210000000265 leukocyte Anatomy 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000000440 neutrophil Anatomy 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 230000009818 osteogenic differentiation Effects 0.000 description 1
- 230000002188 osteogenic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 210000003625 skull Anatomy 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229960005322 streptomycin Drugs 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Transplantation (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Veterinary Medicine (AREA)
- Dermatology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Civil Engineering (AREA)
- Ceramic Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Dispersion Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
本发明申请属于材料制备技术领域，具体公开了一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法及其应用，包括以下步骤：(1)钛合金材料预处理：将钛合金片进行喷砂粗化处理；所用砂为46目棕刚玉Al2O3,喷砂后备用；(2)球磨与造粒；(3)大气等离子喷涂制备涂层：将预处理后的钛片夹装在金属圆筒上，使用等离子喷涂方法将步骤(2)中的复合粉喷涂到步骤(1)中的钛合金材料；喷涂过程中使用90rpm的转速进行喷涂；喷涂完成后自然冷却至室温，高压蒸汽灭菌法灭菌备用。本发明主要用于制备锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料，解决了现有技术中人工关节置换术中容易被感染的问题。
Description
技术领域
本发明属于材料制备技术领域，具体公开了一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法及其应用。
背景技术
感染、创伤、骨肿瘤所导致的大段骨缺损，其治疗修复一直是临床上所面临的难题。传统自体骨、同种异体骨、可降解人工骨或组织工程骨等因取骨量有限，缺乏足够力学强度而无法胜任大段及负重部位骨缺损修复的力学要求。
医用钛合金等金属骨替代材料具有满意的机械强度，但其弹性模量远高于人体骨骼，植入体内后易产生应力遮挡，以及后期松动。而且由于金属惰性，未经处理的钛合金表面骨整合能力差。长期在体内会出现一定程度的电解、腐蚀甚至炎性假瘤，导致内植物松动、失效。另外，钛合金钢板或假体植入体内后发生感染处理很棘手，由于内植物表面细菌生物膜的形成和阻隔，抗生素治疗往往无效，需要彻底去除内植物，彻底行清创翻修手术才能治愈感染。比如，人工关节置换术后的假体周围感染被称为“灾难性并发症”，给患者造成重大的身体、心理和经济负担。
发明内容
本发明的目的在于提供一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法及其应用，以解决现有技术中人工关节置换术中容易被感染的问题。
为了达到上述目的，本发明的技术方案为：一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法及其应用，包括以下步骤：
(1)钛合金材料预处理：将钛合金片进行喷砂粗化处理；所用砂为46目棕刚玉Al2O3,喷砂后备用；
(2)球磨与造粒：加入ZnO、HA和SrO质量占比0％-10％，将ZnO、HA和SrO混合制备成复合粉，球磨之后SrO/ZnO和HA充分混合，每个球磨罐放50g复合粉，75g球磨珠,向复合粉中加入无水乙醇溶解；使用球磨珠球磨，使用200目筛子过滤，烘干备用；
(3)大气等离子喷涂制备涂层：将预处理后的钛片夹装在金属圆筒上，使用等离子喷涂方法将步骤(2)中的复合粉喷涂到步骤(1)中的钛合金材料；喷涂过程中使用90rpm的转速进行喷涂；喷涂完成后自然冷却至室温，依次用无水乙醇和去离子水对涂层进行超声清洗，高压蒸汽灭菌法灭菌备用。
进一步，步骤(2)中球磨珠球磨时间为12min，转速380r/min；进行两次球磨过程。
进一步，步骤(3)等离子喷涂过程中通入Ar和H2，Ar流量为40slpm、H2流量为7slpm。
进一步，步骤(3)中金属圆筒的转速为90rpm；等离子喷涂参数：喷涂功率40kW、送粉率为30g min-1、喷涂距离为100mm。
进一步，可应用于制备3D打印多孔钛合金复合抗菌-促成骨·多功能表面活性涂层。
本技术方案的工作原理及有益效果在于：
(1)采用金属3D打印增材制造技术可以实现复杂外形植入体的快速定制，通过调整打印参数能精确控制微孔结构，包括形状、大小、孔隙率、空间走向等，从而获得最适合患者所需的个性化植入体。因此，基于患者的个体骨骼CAD设计并打印的个性化植入物能直接实现“假体-骨”的精准匹配或肿瘤骨替代，从而提高手术质量，缩短手术时间，降低手术相关并发症。
(2)针对普通钛合金材料弹性模量高、生物惰性、骨整合能力弱，以及缺乏表面抗菌性的缺点。本方案采用EBM金属3D打印技术快速制备具有合适孔径和孔隙率的个性化多孔钛合金(Ti6Al4V)实验材料，喷涂合适质量百分比的锶/纳米氧化锌/羟基磷灰石复合涂层进行表面修饰，赋予多孔钛合金抗菌能力，并提高其生物相容性和表面促成骨能力。最终实现符合人体的生物力学需求的多功能个性化骨缺损修复材料以及多功能个性化植入假体的快速设计、3D打印和涂层构建。
(3)本方案快速、有效制备3D打印多孔钛合金复合“抗菌-促成骨”多功能表面活性涂层材料，满足骨科临床对大段骨缺损、骨重建、骨替代的需求，同时进一步满足临床对骨长入和抗菌性的双重需求，如人工关节感染性翻修、牙科种植体、颅骨缺损、颌面外科骨缺损的修复提供了新的契机。该方案对于3D打印抗菌和促成骨多功能内植物的研发，提高生物力学性能和个性化定制效率，以及促进生物功能化纳米材料和3D打印先进制造技术的融合发展均有重要的理论意义和临床价值。
(4)纳米氧化锌具有广谱抗菌性，但是细胞相容性欠佳，而羟基磷灰石具有优良的生物相容性。因此，将氧化锌的抗菌性与羟基磷灰石的生物相容性结合在一起，以发挥两者更大的效能。
(5)为改善钛合金材料的生物惰性，增加成骨引导性和诱导性，多项研究获得了令人鼓舞的进展。以促成骨活性多肽和含BMP II等活性因子物质构建明胶缓释系统，随着多孔钛合金孔隙内明胶缓慢降解释放rhBMP II，复合材料MSCs的粘附、增殖及成骨分化指标(ALP、OC)均明显高于未复合组。尽管复合rhBMP II的明胶微球具有良好的缓释性能、生物安全性及成骨活性，但它与多孔钛合金表面结构之间并没有令人满意的粘合效果。而且对于医用钛合金类内植物，涉及高温灭菌消毒、包装、运输、储存等多道环节。在多孔钛合金表面复合多肽类和BMP II等成骨活性因子在具体操作过程繁琐，有严格的时限性等缺点，很大程度上限制了其在临床的应用。而在3D打印多孔钛合金表面采用高温大气等离子喷涂锶、纳米氧化锌、HA等无机金属和氧化物，有着耐高温消毒、一次性喷涂成型、存储时间长、无需使用前临时再浸泡处理等诸多优点。
(6)金属3D打印多孔钛合金表面采用等离子喷涂法成功构建具有抗菌、促成骨活性的Sr/nano-ZnO/HA复合涂层，通过掺入一定质量百分比的Sr修饰nano-ZnO/HA复合涂层，将纳米氧化锌的细胞毒性控制至可接受范围，增加其组织相容性和吸附成骨细胞的能力。创新构建了兼具抗菌性和促成骨能力的3D打印多孔钛合金内植物，弥补了医用钛合金(Ti6Al4V)的固有缺陷。
附图说明
本实施例中，图1是本发明一种利用等离子喷涂复合涂层修饰的多孔钛合金材料的制备方法制备产品在SEM观察下的30倍测试图；
图2是图1中产品在SEM观察下的500倍测试图；
图3是本发明中的细胞增殖测试图；
图4是本发明中的体外抗菌实验测试结果图；
图5是本发明中不同SrO质量占比制得的产品XRD测试图。
具体实施方式
下面通过具体实施方式进一步详细说明：
实施例基本如下所示，一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法，包括以下步骤：
(1)钛合金材料预处理：将钛合金片进行喷砂粗化处理(所用砂为46目棕刚玉，Al2O3),喷砂后立即进行喷涂。
(2)球磨与造粒：球磨与造粒：加入ZnO、HA和SrO质量占比0％-10％，将ZnO、HA和SrO混合制备成复合粉，球磨之后SrO/ZnO和HA充分混合，每个球磨罐放50g复合粉，75g球磨珠,向复合粉中加入无水乙醇溶解；使用球磨珠球磨，使用200目筛子过滤，烘干备用；适量无水乙醇溶解。球磨珠球磨12min，转速380r/min。两次球磨，200目筛子过滤，烘干备用。
(3)大气等离子喷涂制备涂层：将预处理后的钛片夹装在金属圆筒上，90rpm的转速进行喷涂。等离子喷涂参数：40功率(kW)、Ar流量(40slpm)、H2流量(7slpm)、送粉率(30gmin-1)、喷涂距离(100mm)。喷涂完成后自然冷却至室温，依次用无水乙醇和去离子水对涂层进行超声清洗1分钟得产品，高压蒸汽灭菌法灭菌备用。
本发明中的一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料，可应用于制备3D打印多孔钛合金复合抗菌-促成骨·多功能表面活性涂层。
nano-ZnO/HA复合涂层的表征
1、场发射扫描电子显微镜分析：对测试样品进行喷金处理后，采用场发射扫描电子显微镜(FE-SEM，德国Zeiss，SUPRA55)对涂层的表面形貌进行观察，结合图1和图2所示。
2、X射线衍射分析：利用X射线衍射仪分析涂层的物相组成。具体测试参数：电流为100mA，电压为40KV，Cu靶Ka辐射，特征波长λ＝0.154056nm，衍射角(2θ)，扫描范围为20°-80°，扫描速度为0.02°/s。测试结果结合图5所示。
Sr/nano-ZnO/HA复合涂层蛋白质吸附能力测定
每组取三个样品放入24孔培养板中37℃孵育2h后，PBS液清洗三次，加入500μL1％的十二烷基硫酸钠(SDS)溶液于孔中，放入摇床震荡1h以洗脱样品表面的蛋白。微量BCA试剂盒用来检测SDS溶液中的蛋白浓度。通过平均吸光值校准，以及蛋白标准品与其对应浓度绘制标准曲线。根据标准曲线计算出待测样品的蛋白浓度。
nano-ZnO/HA复合涂层以及采用掺锶修饰对细胞增值性的影响
设置nano-ZnO/HA组、Sr/nano-ZnO/HA组以及无任何涂层的空白组。采用小鼠成骨前体细胞系MC3T3-E1细胞对样品涂层的细胞增殖情况进行评估。
1、复苏细胞：实验将含有10％胎牛血清和1％双抗(链霉素和青霉素)的α-MEM培养液，在37℃恒温、5％CO2的细胞培养箱中进行培养。培养箱湿度为70％-80％。
2、细胞接种：对细胞进行培养分离，对细胞悬液进行稀释，得到所需浓度的细胞悬液，分别加入所在24孔板中，置于细胞培养箱中培养。
3、涂层表面细胞增殖：使用CCK-8试剂盒检测，在每个时间点每孔加入混匀好的细胞
培养液和CCK-8试剂。放入37℃避光孵育4h，在450nm波长下使用酶标仪测量吸光度。全过程避光操作。然后以空白组为对照组，计算另外两组相对于空白组的细胞增殖数目百分比。结合图3所示，从上图中可以看出，当锌比例不变，锶的比例增加时细胞增值率有略微增加。当锶的比例不变时随着锌的比例增加时细胞增殖率减小.E组与A、F组之间无统计学差异，E组与B、C、D、G、H相比P＜0.05有统计学意义。
Sr/nano-ZnO/HA复合涂层修饰的3D打印多孔钛合金体内抗菌性实验。
同体内成骨实验分为骨缺损组、空白组(纯3D打印件未含任何涂层)、nano-ZnO/HA组、RGD/nano-ZnO/HA共四组，在兔子双侧股骨外侧髁用医用电钻和直径6mm斯氏针制造骨缺损，直径6mm，深度10mm，将多孔钛合金柱形棒植入新西兰兔股骨外侧髁圆柱形骨缺损中。然后在每只兔子骨缺损处注入一定量的金葡菌。术后观察实验动物的饮食、活动情况；感染的临床症状(体温、伤口愈合情况、肢体肿胀情况)、血白细胞含量和中性粒细胞的比例。抑菌率评估：将植入物周围的股骨切块、碾碎，加入PBS缓冲液，离心后取上清液(含细菌)，将上清液涂布在细菌培养板上过夜培养，计数菌落数。结合图4所示，本实施例中复合涂层的体外抗菌性测试分八个试验组，1组为纯HA；2组为10％ZnO-HA；3组为10％ZnO-5％SrO-HA；4组为10％ZnO-10％SrO-HA；5组为10％ZnO-15％SrO-HA；6组为10％SrO-HA；7组为5％SrO-10％ZnO-HA；8组为5％SrO-10％ZnO-HA；体外抗菌实验(制成麦氏浊度为0.25的金黄色葡萄球菌悬液，将材料至于24孔板中，每孔加入1ml制备好的细菌悬液，放入37℃温箱孵育24小时，用取菌环蘸取10ul涂布于新鲜的琼脂培养基上，放入37°温箱孵育24小时，观察细菌生长情况。由图可知含有ZnO的各组细菌生长较少。
以上所述的仅是本发明的实施例，方案中公知的具体结构及特性等常识在此未作过多描述。应当指出，对于本领域的技术人员来说，在不脱离本发明结构的前提下，还可以作出若干变形和改进，这些也应该视为本发明的保护范围，这些都不会影响本发明实施的效果和专利的实用性。
Claims (5)
1.一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法，其特征在于，包括以下步骤：
(1)钛合金材料预处理：将钛合金片进行喷砂粗化处理；所用砂为46目棕刚玉Al2O3,喷砂后备用；
(2)球磨与造粒：加入ZnO、HA和SrO质量占比0％-10％，将ZnO、HA和SrO混合制备成复合粉，球磨之后SrO/ZnO和HA充分混合，每个球磨罐放50g复合粉，75g球磨珠,向复合粉中加入无水乙醇溶解；使用球磨珠球磨，使用200目筛子过滤，烘干备用；
(3)大气等离子喷涂制备涂层：将预处理后的钛片夹装在金属圆筒上，使用等离子喷涂方法将步骤(2)中的复合粉喷涂到步骤(1)中的钛合金材料；喷涂过程中使用90rpm的转速进行喷涂；喷涂完成后自然冷却至室温，依次用无水乙醇和去离子水对涂层进行超声清洗，高压蒸汽灭菌法灭菌备用。
2.根据权利要求1所述的一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法，其特征在于，步骤(2)中球磨珠球磨时间为12min，转速380r/min；进行两次球磨过程。
3.根据权利要求1所述的一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法，其特征在于，步骤(3)等离子喷涂过程中通入Ar和H2，Ar流量为40slpm、H2流量为7slpm。
4.根据权利要求1所述的一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法，其特征在于，步骤(3)中金属圆筒的转速为90rpm；等离子喷涂参数：喷涂功率40kW、送粉率为30g min-1、喷涂距离为100mm。
5.根据权利要求1-4任一项所述的一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的应用，其特征在于，可应用于制备3D打印多孔钛合金复合抗菌-促成骨·多功能表面活性涂层。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111331582.8A CN114164393A (zh) | 2021-11-11 | 2021-11-11 | 一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法及其应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111331582.8A CN114164393A (zh) | 2021-11-11 | 2021-11-11 | 一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法及其应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114164393A true CN114164393A (zh) | 2022-03-11 |
Family
ID=80478773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111331582.8A Pending CN114164393A (zh) | 2021-11-11 | 2021-11-11 | 一种锶/纳米氧化锌/羟基磷灰石复合涂层修饰的多孔钛合金材料的制备方法及其应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114164393A (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190275472A1 (en) * | 2018-03-12 | 2019-09-12 | Extremem, Inc. | Preparation method for composite porous structure and composite porous structure made thereby |
| CN113106519A (zh) * | 2021-04-02 | 2021-07-13 | 福建师范大学 | 一种制备ha梯度复合涂层材料的区带电泳与电泳沉积方法 |
-
2021
- 2021-11-11 CN CN202111331582.8A patent/CN114164393A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190275472A1 (en) * | 2018-03-12 | 2019-09-12 | Extremem, Inc. | Preparation method for composite porous structure and composite porous structure made thereby |
| CN113106519A (zh) * | 2021-04-02 | 2021-07-13 | 福建师范大学 | 一种制备ha梯度复合涂层材料的区带电泳与电泳沉积方法 |
Non-Patent Citations (3)
| Title |
|---|
| DONGXU KE ET AL.: "In Vitro Characterizations of Si4+ and Zn2+ Doped Plasma Sprayed Hydroxyapatite Coatings Using Osteoblast and Osteoclast Coculture", 《ACS BIOMATERIALS SCIENCE & ENGINEERING》, pages 1302 - 1310 * |
| YONG HUANG ET AL.: "Corrosion resistance and biocompatibility of SrHAp/ZnO composite implant coating on titanium", 《APPLIED SURFACE SCIENCE》, pages 353 - 358 * |
| 王成焘等: "《骨科植入物工程学》", 上海交通大学出版社, pages: 42 - 43 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhong et al. | 3D printing of metal–organic framework incorporated porous scaffolds to promote osteogenic differentiation and bone regeneration | |
| Diao et al. | 3D‐plotted beta‐tricalcium phosphate scaffolds with smaller pore sizes improve in vivo bone regeneration and biomechanical properties in a critical‐sized calvarial defect rat model | |
| Eliaz et al. | Calcium phosphate bioceramics: a review of their history, structure, properties, coating technologies and biomedical applications | |
| Zhu et al. | Advances in implant surface modifications to improve osseointegration | |
| Lin et al. | Orthopedic implant biomaterials with both osteogenic and anti-infection capacities and associated in vivo evaluation methods | |
| Wang et al. | Polyetheretherketone/nano-fluorohydroxyapatite composite with antimicrobial activity and osseointegration properties | |
| Wu et al. | 3D printed chitosan-gelatine hydrogel coating on titanium alloy surface as biological fixation interface of artificial joint prosthesis | |
| Dorozhkin | Medical application of calcium orthophosphate bioceramics | |
| Wang et al. | Fabrication of bioactive 3D printed porous titanium implants with Sr ion-incorporated zeolite coatings for bone ingrowth | |
| Kim et al. | A polycaprolactone/cuttlefish bone‐derived hydroxyapatite composite porous scaffold for bone tissue engineering | |
| Chen et al. | Nanohydroxyapatite/cellulose nanocrystals/silk fibroin ternary scaffolds for rat calvarial defect regeneration | |
| US20210121606A1 (en) | Ionic-doped composition methods and uses thereof | |
| Hu et al. | Porous biphasic calcium phosphate ceramics coated with nano-hydroxyapatite and seeded with mesenchymal stem cells for reconstruction of radius segmental defects in rabbits | |
| CN110559483A (zh) | 一种3d打印技术制备的松质骨仿生支架的设计与应用 | |
| CN107158465B (zh) | 一种骨支架复合材料的制备方法 | |
| Tang et al. | Mechanical strength, surface properties, cytocompatibility and antibacterial activity of nano zinc-magnesium silicate/polyetheretherketone biocomposites | |
| Liu et al. | Bioactive porous biocomposites coated magnesium alloy implant for bone rejuvenation using a fracture in rat model | |
| Hu et al. | Zn–Sr-sintered true bone ceramics enhance bone repair and regeneration | |
| CN106630997A (zh) | 骨骼修复用复合生物陶瓷的制备方法 | |
| CN114452441A (zh) | 一种颅骨修复聚醚醚酮材料及其制备方法 | |
| CN208243822U (zh) | 一种3d打印复合磁性金属支架 | |
| CN113521387A (zh) | 一种锶掺杂改性的天然羟基磷灰石支架材料的制备方法和应用 | |
| PL240725B1 (pl) | Biomateriał na bazie naturalnego polisacharydu-β-1,3-glukanu (kurdlanu) i ceramiki do zastosowań w inżynierii tkankowej kości oraz sposób jego otrzymywania | |
| PL240639B1 (pl) | Dwufazowy biomateriał na bazie kurdlanu oraz hydroksyapatytu (HAp) oraz sposób jego otrzymywania i jego zastosowanie do regeneracji ubytków chrzęstno-kostnych | |
| Kumar et al. | 3D-printed titanium alloys for orthopedic applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220311 |
|
| RJ01 | Rejection of invention patent application after publication |