CN113577384A - Preparation method of biological ceramic surface coated active organic matter implant - Google Patents
Preparation method of biological ceramic surface coated active organic matter implant Download PDFInfo
- Publication number
- CN113577384A CN113577384A CN202110472624.3A CN202110472624A CN113577384A CN 113577384 A CN113577384 A CN 113577384A CN 202110472624 A CN202110472624 A CN 202110472624A CN 113577384 A CN113577384 A CN 113577384A
- Authority
- CN
- China
- Prior art keywords
- ceramic
- implant
- support
- blank
- preparing
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 55
- 239000007943 implant Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000005416 organic matter Substances 0.000 title claims description 10
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000005238 degreasing Methods 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 230000000975 bioactive effect Effects 0.000 claims abstract description 11
- 238000010146 3D printing Methods 0.000 claims abstract description 10
- 230000001939 inductive effect Effects 0.000 claims abstract description 3
- 230000008467 tissue growth Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- 210000000988 bone and bone Anatomy 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003462 bioceramic Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000000016 photochemical curing Methods 0.000 claims description 11
- 238000001723 curing Methods 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 5
- 239000000378 calcium silicate Substances 0.000 claims description 5
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 5
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000017 hydrogel Substances 0.000 claims description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000008055 phosphate buffer solution Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229920002674 hyaluronan Polymers 0.000 claims description 3
- 229960003160 hyaluronic acid Drugs 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007639 printing Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 3
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 210000004748 cultured cell Anatomy 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 238000005516 engineering process Methods 0.000 description 9
- 230000010261 cell growth Effects 0.000 description 4
- 239000001963 growth medium Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 108010087230 Sincalide Proteins 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 238000010609 cell counting kit-8 assay Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- FWBHETKCLVMNFS-UHFFFAOYSA-N 4',6-Diamino-2-phenylindol Chemical compound C1=CC(C(=N)N)=CC=C1C1=CC2=CC=C(C(N)=N)C=C2N1 FWBHETKCLVMNFS-UHFFFAOYSA-N 0.000 description 2
- 230000024245 cell differentiation Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 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
- 239000000126 substance Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 238000001516 cell proliferation assay Methods 0.000 description 1
- 239000006285 cell suspension Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
Images
Classifications
-
- 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
- A61L27/10—Ceramics or glasses
-
- 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
- A61L27/12—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
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- 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
- A61L27/58—Materials at least partially resorbable by the body
-
- 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
- A61L31/026—Ceramic or ceramic-like structures, e.g. glasses
-
- 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
-
- 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
- A61L31/10—Macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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
- A61L31/146—Porous materials, e.g. foams or sponges
-
- 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
- A61L31/148—Materials at least partially resorbable by the body
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/06—Coatings containing a mixture of two or more compounds
-
- 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
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Heart & Thoracic Surgery (AREA)
- Vascular Medicine (AREA)
- Surgery (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a preparation method of an implant body with a biological ceramic surface coated with active organic matters, belonging to the field of medical combination. The invention comprises the following steps: preparing a ceramic blank by a 3D printing mode, adhering a material capable of inducing tissue growth on the surface of the ceramic blank by using uncured ceramic slurry on the surface of the ceramic blank, then carrying out secondary curing under ultraviolet light to obtain a support blank with a coating, degreasing and sintering the support blank to finally obtain a ceramic support with mechanical strength, then coating a bioactive material prefabricated in advance on the surface of the support, and curing by using ultraviolet light to finally obtain the medical implant support with a porous structure.
Description
Technical Field
The invention belongs to the field of medical combination, and particularly relates to a preparation method of an implant with a biological ceramic surface coated with active organic matters.
Technical Field
In recent years, 3D printing technology has been developed rapidly, and its figure can be seen in all walks of life. The 3D printing technology is applied to bone repair, so that some defects existing in the traditional bone grafting can be avoided, and a series of materials which can be used for repairing bone defects are brought. Such as metallic materials, bioceramic materials, polymeric materials, composite materials, etc. The materials can be customized individually by using a 3D printing technology, and can be well matched with the form of a biological bone. In addition, the production of complex porous structures, such as porous structures, can be realized by utilizing a 3D printing technology, which is beneficial to the transportation of nutrients and the growth of cell tissues and has important significance for bone repair.
While these materials may meet certain requirements for repair of bone defects, they are deficient in other respects. The metal material has excellent mechanical property and can bear larger force, but the metal material has poor biocompatibility as an implant, and can cause the problems of corrosion, metal ion precipitation and the like after being in a body fluid environment of a human body for a long time, thereby causing damage to the human body. In addition, the elastic modulus of the metal cannot be matched with human bones, so that stress shielding is easily caused, and the implant is loosened. PLA (polylactic acid), GelMA (methacrylic acid acylated hydrogel), HA (chitosan), hyaluronic acid and the like which are widely applied in high polymer materials have good biodegradability. Unfortunately, the excessively fast degradation rate, low strength, limits its use in the field of bone repair.
The bioceramic is a commonly used structural ceramic, has excellent mechanical property, wear resistance and chemical stability, is prepared from zirconium oxide, calcium silicate, tricalcium phosphate and hydroxyapatite, and has good biocompatibility, so that the bioceramic is widely applied to biology and medicine. However, the biological activity of bioceramics is relatively low compared to organic implants. The organic matter implant material with good biological activity can realize cell growth into organic matter, and in the process of bone implantation, the organic matter can simulate cartilage tissue, thereby realizing bionic bone structurally.
In addition, compared with the traditional manufacturing method, the 3D printing technology has the advantages of fast production and personalized customization; photocuring molding technology is the most common ceramic 3D printing technology at present. The design of complex structures is realized by drawing three-dimensional models through a computer, and the design of pore size and porosity can also be realized aiming at the porous structure required in the interior of the biological implant. The complex porous structure can meet the regeneration of tissues. According to the technology, photosensitive resin and ceramic powder are mixed, a complex porous structure is printed by utilizing the characteristic of curing under a specific light wave, and the support with mechanical strength is obtained through subsequent degreasing and sintering.
Disclosure of Invention
The invention provides a preparation method of an implant body with a biological ceramic surface coated with active organic matters, the implant support obtained by the preparation method not only retains the excellent mechanical property of a ceramic material, but also can effectively improve the biological activity of the implant through a surface coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing an implant body with a bioceramic surface coated with active organic matters comprises the following steps: preparing a ceramic blank by a 3D printing mode, adhering a material capable of inducing tissue growth on the surface of the ceramic blank by using uncured ceramic slurry on the surface of the ceramic blank, then carrying out secondary curing under ultraviolet light to obtain a support blank with a coating, degreasing and sintering the support blank to finally obtain a ceramic support with mechanical strength, then coating a bioactive material prefabricated in advance on the surface of the support, and curing by using ultraviolet light to finally obtain the medical implant support with a porous structure.
The method specifically comprises the following steps:
step 1, modeling: drawing a three-dimensional model of the porous scaffold by using three-dimensional software, wherein the stored format is STL;
step 2, slurry preparation: mixing photosensitive resin, bioactive ceramics and a dispersing agent, wherein the mass ratio of the ceramic powder to the resin is (1-4): 1, the mass of the dispersing agent is 1-3% of the total mass of the slurry, and the slurry is stirred for 30 minutes in vacuum at the stirring speed of 1000-1200rpm until the slurry is uniform;
step 3, preparing a blank: importing the STL-format file obtained in the step 1 into a DLP photocuring printer, adding the slurry obtained in the step 2, and preparing a porous ceramic support blank;
and step 5, degreasing and sintering: heating, degreasing and sintering the ceramic support obtained in the step 4, and cooling the ceramic support to room temperature;
step 6, preparing a surface coating material: dissolving a material to be coated into a phosphate buffer solution, heating to 70-90 ℃ to fully dissolve the material, then adding a photoinitiator, and finally cooling to room temperature to obtain the required coating material;
and 7, adhering surface coating materials: and (3) putting the ceramic support obtained in the step (5) into the surface coating material solution prepared in the step (6), soaking for 5 minutes, taking out, exposing and curing the ceramic support, and repeatedly soaking and curing for multiple times as required to obtain the implant.
In the above steps, the bioactive ceramic in step 2 is at least one of calcium silicate, zirconium oxide, tricalcium phosphate, hydroxyapatite and calcium phosphate, and is combined according to actual requirements; the particle size of the bioactive ceramic powder is 50nm-200 mu m; the photosensitive resin is acrylate, and the reaction wavelength is 405 nm; the dispersing agent is sodium polyacrylate;
in the step 3, the thickness of the DLP photocuring printing layer is 20-100 mu m, and the exposure time is 5-20 s;
the adhesive coating material in the step 4 comprises at least one of magnesium oxide, zinc oxide, copper oxide, silicon dioxide, strontium phosphate, lithium chloride, manganese oxide and hydroxyapatite; the particle size of the adhesive coating powder is 10nm-10000 nm; the secondary photocuring exposure time is 30-300s, and the light source wavelength is 350-450 nm;
in the step 5, degreasing and sintering are carried out by adopting a powder embedding method, powder of a surface adhesion material is covered on the green body for degreasing and sintering, and the temperature and technological parameters of degreasing and sintering are as follows: the degreasing process comprises the following steps: heating to 350-plus-material temperature of 500 ℃ and preserving heat for 3-5 hours, then continuing to heat to 80-1050 ℃ and preserving heat for 3-5 hours, wherein the sintering process is as follows: heating to 1100-1500 deg.C, and maintaining for 1-2 hr at a temperature raising rate of 0.5-2 deg.C/min;
in the step 6, the coating material is at least one of methacryloylated hydrogel (GelMA), photocured hyaluronic acid and methacryloylated polycaprolactone; the proportion of the coating material to the phosphate buffer solution photoinitiator is 1 g: 30g of: 1g of a compound;
the wavelength of the exposure in step 7 is 350-450nm, and the exposure time is 30-300 s.
The implant prepared by the method can be used as a bracket for culturing cells, so that the cells can be cultured on the bracket, and can also be used as a bracket of bone filler and a bone nail.
The size of the implant prepared by the method is 100-2000 mu m, and the porosity is 20-85%.
Has the advantages that: the invention provides a preparation method of a biological ceramic surface coated active organic matter implant, compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, by utilizing a photocuring 3D printing technology, the prepared implant can meet the requirements of a macroscopic porous structure, and has a controllable shape, pore size and pore shape;
(2) the biological ceramic material used by the invention has excellent biocompatibility, and part of the material is beneficial to the proliferation and differentiation of cells in the degradation process;
(3) the adhesion layer material used in the invention has positive effect on the growth and differentiation of cells, and the part of material can fill part of micropores after sintering, thus realizing the improvement of the mechanical property of the implant;
(4) the coating material used by the invention is an organic coating, and the coating material can realize internal cell growth and can be degraded, thereby providing an important basis for the growth of fixed cells after being implanted into a body.
Drawings
FIG. 1 is a flow chart of a method of making an embodiment of the present invention;
FIG. 2 is a physical diagram of a blank of a 3D-printed calcium silicate ceramic porous scaffold in an embodiment of the invention;
FIG. 3 is a diagram of a calcium silicate ceramic stent blank adhered with nano-magnesia in an embodiment of the invention;
FIG. 4 is a pictorial representation of a stent having a bioactive substance coated on its surface in an embodiment of the present invention;
FIG. 5 is a schematic representation of the staining of adherent cells on an implant with DAPI in an embodiment of the present invention;
FIG. 6 is a graph showing the results of detecting the activity of MC3T3-E1 cells using CCK-8 in the present example.
Detailed Description
The invention is further illustrated with reference to the accompanying drawings and specific examples:
example 1
As shown in fig. 1, a method for preparing a bioceramic implant with active organic matter coated on the surface is realized by the following steps:
step 1, modeling: drawing a porous support by using Magics software, and storing in a format of SLT;
step 2, slurry preparation: adding 70g of photosensitive resin, 100g of bioactive ceramic and 3g of dispersing agent into a vacuum stirrer, and stirring for 30min at the rotating speed of 1200 rpm;
step 3, preparing a blank: importing the STL-format file obtained in the step (1) into a DLP photocuring printer, adding the slurry obtained in the step (2), wherein the printing layer is 40 mu m thick, the exposure time is 8s, and the obtained ceramic blank is shown in figure 2;
and 5, degreasing and sintering: putting the ceramic support obtained in the step 4 into a crucible, burying the ceramic support by using nano magnesium oxide powder, heating to 450 ℃ and preserving heat for 3 hours, heating to 900 ℃ and preserving heat for 5 hours after completion, finally heating to 1300 ℃ and preserving heat for 1 hour, wherein the heating rate is 0.5 ℃/min, and the obtained support is kept for later use after furnace cooling to room temperature, and is shown in fig. 4;
step 6, preparing a surface coating material: adding 1g GelMA into 30ml PBS, heating to 80 ℃, stirring to be completely melted, cooling to room temperature, and adding 1ml photoinitiator;
and 7, adhering surface coating materials: and (3) putting the ceramic support obtained in the step (5) into the coating solution prepared in the step (6), soaking for 5 minutes, exposing for 5 minutes under light waves with the wavelength of 405nm, and repeating the step for 3 times to obtain the implant shown in fig. 4.
Implant cell biocompatibility experiment
Cell adhesion experiments: the implant was sterilized and placed in a 24-well plate, and then cells were seeded onto the implant (cell concentration 10)4Pieces/ml) was inoculated to 1ml, cultured in an incubator at 37 ℃ for 4 days, stained with DAPI after completion of the culture, and observed using a confocal microscope to obtain an image as shown in fig. 5, showing that the implantation was performedThe body has good biocompatibility to MC3T3-E1 cells, the growth state of the cells is good, and the growth of the cells is facilitated.
CCK-8 cell proliferation assay: the scaffolds were sterilized and placed in 24-well plates, each plate inoculated with 1ml of MC3T3-E1 cell suspension (cell concentration 10)4One/ml), then adding 1ml of culture medium, placing the mixture into an incubator for culture, adding the culture medium containing 10% of CCK-8 into a 24-well plate after culturing for 1d, 4d and 7d respectively, placing the culture medium into the 24-well plate, incubating for 2 hours, transferring the culture medium into a 96-well plate, and measuring the numerical value of each well by using an enzyme-labeling instrument at the wavelength of 450nm, wherein the result is shown in figure 6, GelMA hydrogel is adhered to the surface of the porous implant, and the hydrogel and the scaffold have good adhesion effect and are not easy to fall off.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present application, and these modifications and improvements should also be considered as the protection scope of the present invention.
Claims (10)
1. A preparation method of a biological ceramic surface coating active organic matter implant is characterized by comprising the following steps: preparing a ceramic blank by a 3D printing mode, adhering a material capable of inducing tissue growth on the surface of the ceramic blank by using uncured ceramic slurry on the surface of the ceramic blank, then carrying out secondary curing under ultraviolet light to obtain a support blank with a coating, degreasing and sintering the support blank to finally obtain a ceramic support with mechanical strength, then coating a bioactive material prefabricated in advance on the surface of the support, and curing by using ultraviolet light to finally obtain the medical implant support with a porous structure.
2. The method for preparing the bioceramic surface-coated active organic matter implant according to claim 1, wherein the method specifically comprises the following steps:
step 1, modeling: drawing a three-dimensional model of the porous scaffold by using three-dimensional software, wherein the stored format is STL;
step 2, slurry preparation: mixing photosensitive resin, bioactive ceramics and a dispersing agent, wherein the mass ratio of the ceramic powder to the resin is (1-4): 1, the mass of the dispersing agent is 1-3% of the total mass of the slurry, and the slurry is stirred for 30 minutes in vacuum at the stirring speed of 1000-1200rpm until the slurry is uniform;
step 3, preparing a blank: importing the STL-format file obtained in the step 1 into a DLP photocuring printer, adding the slurry obtained in the step 2, and preparing a porous ceramic support blank;
step 4, adhering surface materials: putting the ceramic blank support obtained in the step 3 into powder adhered with the coating material, stirring until the surface of the ceramic blank support is uniformly adhered, and then carrying out secondary photocuring;
and step 5, degreasing and sintering: heating, degreasing and sintering the ceramic support obtained in the step 4, and cooling the ceramic support to room temperature;
step 6, preparing a surface coating material: dissolving a material to be coated into a phosphate buffer solution, heating to 70-90 ℃ to fully dissolve the material, then adding a photoinitiator, and finally cooling to room temperature to obtain the required coating material;
and 7, adhering surface coating materials: and (3) putting the ceramic support obtained in the step (5) into the surface coating material solution prepared in the step (6), soaking for 5 minutes, taking out, exposing and curing the ceramic support, and repeatedly soaking and curing for multiple times as required to obtain the implant.
3. The method for preparing a bio-ceramic implant with a surface coated with active organic compounds according to claim 2, wherein the bio-active ceramic in step 2 is at least one of calcium silicate, zirconium oxide, tricalcium phosphate, hydroxyapatite and calcium phosphate, and the particle size of the bio-active ceramic powder is 50nm to 200 μm; the photosensitive resin is acrylate; the dispersant is at least one of sodium polyacrylate and polyethylene glycol.
4. The method for preparing a bioceramic surface-coated active organic implant according to claim 2, wherein the DLP photocuring printing in step 3 is in a layer thickness of 20-100 μm and the exposure time is 5-20 s.
5. The method for preparing a bioceramic surface-coated active organic implant according to claim 2, wherein the adhesion coating material in step 4 comprises at least one of magnesium oxide, zinc oxide, copper oxide, silicon dioxide, strontium phosphate, lithium chloride, manganese oxide, and hydroxyapatite; the particle size of the adhesive coating material powder is 10nm-10000 nm; the secondary photocuring exposure time is 30-300s, and the light source wavelength is 350-450 nm.
6. The method for preparing the implant body with the bioceramic surface coated with the active organic matter as claimed in claim 2, wherein the step 5 comprises degreasing and sintering by a powder embedding method, and the temperature process parameters of degreasing and sintering are as follows: the degreasing process comprises the following steps: heating to 350-plus-material temperature of 500 ℃ and preserving heat for 3-5 hours, then continuing to heat to 80-1050 ℃ and preserving heat for 3-5 hours, wherein the sintering process is as follows: heating to 1100 ℃ and 1500 ℃ for 1-2 hours, and controlling the heating rate at 0.5-2 ℃/min.
7. The method for preparing a bioceramic surface-coated active organic implant according to claim 2, wherein the coating material in step 6 is at least one of methacryloylated hydrogel (GelMA), photo-cured hyaluronic acid, and methacryloylated polycaprolactone; the proportion of the coating material, the phosphate buffer solution and the photoinitiator is 1 g: 30 ml: 1g of the total weight of the composition.
8. The method as claimed in claim 2, wherein the exposure wavelength in step 7 is 350-450nm, and the exposure time is 30-300 s.
9. Implant prepared by the method according to any of claims 1 to 9, characterized in that the implant has a pore size of 100 μm and a porosity of 20% to 85%.
10. The implant of claim 9 as a scaffold for cultured cells or as a bone filler and bone peg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110472624.3A CN113577384A (en) | 2021-04-29 | 2021-04-29 | Preparation method of biological ceramic surface coated active organic matter implant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110472624.3A CN113577384A (en) | 2021-04-29 | 2021-04-29 | Preparation method of biological ceramic surface coated active organic matter implant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113577384A true CN113577384A (en) | 2021-11-02 |
Family
ID=78242958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110472624.3A Pending CN113577384A (en) | 2021-04-29 | 2021-04-29 | Preparation method of biological ceramic surface coated active organic matter implant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113577384A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115432999A (en) * | 2022-09-05 | 2022-12-06 | 聊城大学 | Ceramic reinforced and toughened through inside and outside and preparation method thereof |
-
2021
- 2021-04-29 CN CN202110472624.3A patent/CN113577384A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115432999A (en) * | 2022-09-05 | 2022-12-06 | 聊城大学 | Ceramic reinforced and toughened through inside and outside and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Feng et al. | Application of 3D printing technology in bone tissue engineering: a review | |
| Kashte et al. | Artificial bone via bone tissue engineering: current scenario and challenges | |
| Kerativitayanan et al. | Nanoengineered osteoinductive and elastomeric scaffolds for bone tissue engineering | |
| Miranda et al. | Three-dimensional culture of rat BMMSCs in a porous chitosan-gelatin scaffold: A promising association for bone tissue engineering in oral reconstruction | |
| CN111973811B (en) | Zinc-containing artificial bone and preparation method thereof | |
| Daghrery et al. | A highly ordered, nanostructured fluorinated CaP‐coated melt electrowritten scaffold for periodontal tissue regeneration | |
| US9969971B2 (en) | Calcium-containing structures and methods of making and using the same | |
| Qian et al. | Promoting bone regeneration of calcium phosphate cement by addition of PLGA microspheres and zinc silicate via synergistic effect of in-situ pore generation, bioactive ion stimulation and macrophage immunomodulation | |
| Han et al. | BMP-2 and hMSC dual delivery onto 3D printed PLA-Biogel scaffold for critical-size bone defect regeneration in rabbit tibia | |
| Fazeli et al. | 3D-printed PCL scaffolds coated with nanobioceramics enhance osteogenic differentiation of stem cells | |
| Yang et al. | Self-adhesive hydrogel biomimetic periosteum to promote critical-size bone defect repair via synergistic osteogenesis and angiogenesis | |
| Shumilova et al. | Porous 3D implants of degradable poly‐3‐hydroxybutyrate used to enhance regeneration of rat cranial defect | |
| Gouveia et al. | In-vitro mechanical and biological evaluation of novel zirconia reinforced bioglass scaffolds for bone repair | |
| Kargozar et al. | Synergistic combination of bioactive glasses and polymers for enhanced bone tissue regeneration | |
| Qian et al. | Novel strategy to accelerate bone regeneration of calcium phosphate cement by incorporating 3D plotted poly (lactic‐co‐glycolic acid) network and bioactive wollastonite | |
| CN101185772B (en) | Human body hard tissue filling renovation material containing calcium citrate | |
| Leng et al. | Material-based therapy for bone nonunion | |
| Al-Zubaidi et al. | Improvements in clinical durability from functional biomimetic metallic dental implants | |
| Zhou et al. | Additive manufacturing of bioceramic implants for restoration bone engineering: Technologies, advances, and future perspectives | |
| Zhang et al. | An anti-bacterial porous shape memory self-adaptive stiffened polymer for alveolar bone regeneration after tooth extraction | |
| CN112430086A (en) | Preparation method of medical implant coated on surface of biological ceramic | |
| Islam et al. | Excellency of hydroxyapatite composite scaffolds for bone tissue engineering | |
| CN113577384A (en) | Preparation method of biological ceramic surface coated active organic matter implant | |
| Mei et al. | 3D-printed mesoporous bioactive glass/GelMA biomimetic scaffolds for osteogenic/cementogenic differentiation of periodontal ligament cells | |
| Zhao et al. | Promotion of bone formation and antibacterial properties of titanium coated with porous Si/Ag-doped titanium dioxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |