CN107374784B - 一种基于高分子聚合物增材制造的多孔植入物的制备方法 - Google Patents
一种基于高分子聚合物增材制造的多孔植入物的制备方法 Download PDFInfo
- Publication number
- CN107374784B CN107374784B CN201710448052.9A CN201710448052A CN107374784B CN 107374784 B CN107374784 B CN 107374784B CN 201710448052 A CN201710448052 A CN 201710448052A CN 107374784 B CN107374784 B CN 107374784B
- Authority
- CN
- China
- Prior art keywords
- molecular polymer
- porous implant
- high molecular
- additive manufacturing
- metal
- 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.)
- Expired - Fee Related
Links
- 239000007943 implant Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 239000000654 additive Substances 0.000 title claims abstract description 32
- 230000000996 additive effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052715 tantalum Inorganic materials 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000004677 Nylon Substances 0.000 claims description 11
- 229920001778 nylon Polymers 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 6
- -1 Polyethylene Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 229920002530 polyetherether ketone Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 238000007740 vapor deposition Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002071 nanotube Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000004626 polylactic acid Substances 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 15
- 239000002086 nanomaterial Substances 0.000 abstract description 11
- 238000004663 powder metallurgy Methods 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract 1
- 238000007709 nanocrystallization Methods 0.000 abstract 1
- 238000000110 selective laser sintering Methods 0.000 description 6
- 229960001701 chloroform Drugs 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000002449 bone cell Anatomy 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/28—Bones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/3094—Designing or manufacturing processes
- A61F2/30942—Designing or manufacturing processes for designing or making customized prostheses, e.g. using templates, CT or NMR scans, finite-element analysis or CAD-CAM techniques
-
- 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
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
-
- 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
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/3094—Designing or manufacturing processes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/28—Bones
- A61F2002/2835—Bone graft implants for filling a bony defect or an endoprosthesis cavity, e.g. by synthetic material or biological material
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
- A61F2/30771—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth applied in original prostheses, e.g. holes or grooves
- A61F2002/30772—Apertures or holes, e.g. of circular cross section
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/3094—Designing or manufacturing processes
- A61F2002/30985—Designing or manufacturing processes using three dimensional printing [3DP]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00011—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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/08—Methods for forming porous structures using a negative form which is filled and then removed by pyrolysis or dissolution
-
- 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
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Animal Behavior & Ethology (AREA)
- Engineering & Computer Science (AREA)
- Cardiology (AREA)
- Dermatology (AREA)
- Heart & Thoracic Surgery (AREA)
- Biomedical Technology (AREA)
- Vascular Medicine (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Geometry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
- Prostheses (AREA)
Abstract
本发明提供一种基于高分子聚合物增材制造的多孔植入物的制备方法，包括如下步骤：使用增材制造方法制备具有梯度微观结构的多孔植入物模型的高分子聚合物负型模具；将金属粉与粘结剂混合均匀后压制高分子聚合物负型模具中，然后置入有机溶剂中去除高分子聚合物负型模具，得到初步的金属多孔植入物；将其置入真空高温炉中并利用化学气相沉积法在植入物表面沉积金属涂层进一步增强植入物的强度；最后将金属多孔植入物置入电解液中进行阳极氧化处理，得到具有表面纳米结构的定制化金属多孔植入物。该方法将增材制造与粉末冶金技术相结合，解决了孔隙尺寸及分布不可控的问题，且实现了表面结构的纳米化开辟具有宏微纳结构的多孔植入物制备的新途径。
Description
技术领域
本发明涉及一种基于增材制造的多孔植入物的制备方法，改方法属于生物增材制造(3D打印)领域，可应用于生物医疗领域。
背景技术
传统的粉末冶金-造孔剂法是制备金属生物医用支架最有效的方法，可以制备不同孔隙水平，支架的多孔结构是由造孔剂的种类、尺寸和形态来决定，内部的微观孔隙结构分布不均匀且不易控制和定制化制备。增材制造技术对于制造个性化植入物具有无可比拟的优势，能对定制化的微观结构进行制备。
目前的多孔植入物不具有可控宏微观一体化结构和纳米化结构：合理的设计宏观和微观的一体化结构能够减少多孔植入物的应力问题，增强其力学性能；纳米结构不仅有利于体内骨细胞的粘附、还能促进骨细胞的再生和分化，提高植入物的生物相容性。增材制造技术能够实现多孔植入物的微观梯度结构的控制制造，阳极氧化技术能够形成纳米结构。因此，如何解决多孔植入物微观仿生梯度结构不可控及无纳米结构的问题，制备出生物相容性和力学性能俱佳的多孔植入物是其应用于临床的关键问题之一。
传统的多孔金属植入物的制造方法主要包括：有机泡沫浸渍法、造孔剂-粉末烧结法、气相沉积法。但这些工艺可控性差，难以实现对植入物宏观结构的个性化和微观仿生梯度孔隙结构的主动控制，而且无法成形纳米结构，此外工艺制备流程复杂、投资大、生产成本高。
发明内容
为了克服多孔植入物支架微观梯度结构不可控及不能形成纳米结构等不足，本发明的目的在于提供一种基于增材制造的多孔植入物的制备方法，该方法将增材制造技术、粉末冶金技术、化学气相技术和阳极氧化技术相结合，可实现微观梯度结构可控成形，并形成纳米结构利于细胞活动，提高多孔植入物的生物相容性，有望开辟多孔支架制备的新途径，对于促进多孔植入物的临床应用具有重要意义。
为达到上述目的，本发明采用了以下技术方案：
一种基于高分子聚合物增材制造的多孔植入物的制备方法，包括如下的步骤：
1)使用增材制造方法制备具有梯度微观结构的多孔植入物模型的高分子聚合物负型模具；
2)将金属粉与粘结剂混合均匀后压制到步骤1)中制得的高分子聚合物负型模具中；
3)将步骤2)中金属粉与高分子聚合物负型模具一同置入有机溶剂中去除高分子聚合物负型模具，得到初步的金属多孔植入物；
4)将步骤3)制得的初步的金属多孔植入物置入真空高温炉中增强金属多孔植入物的强度；
5)将步骤4)中制得的金属多孔植入物利用化学气相沉积法在植入物表面沉积金属涂层进一步增强强度；
6)将步骤5)中制得的金属多孔植入物置入电解液中进行阳极氧化处理，得到表面具有金属氧化物纳米管的定制化金属多孔植入物。
本发明的进一步的改进在于，步骤1)中，高分子聚合物负型模具的材料为聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚丙烯晴(AS\ABS)、尼龙(PA)、有机玻璃亚克力(PMMA)、聚碳酸酯(PC)、聚氨酯(PU)、硅橡胶、聚己内酯(PCL)、聚乳酸(PLA)、聚醚醚酮(PEEK)、环氧树脂、聚乙烯醇(PVA)中的至少一种以及碳纤维、石墨烯、单壁及多壁碳纳米管与以上材料的复合材料。
本发明的进一步的改进在于，步骤1)中，所用的增材制造方法为光固化成形(SLA)、熔融沉积成形(FDM)、激光选区烧结(SLS)、3DP中的至少一种。
本发明的进一步的改进在于，步骤2)中，金属粉为钽、钛铌或铍等高熔点金属，金属粉的粒径范围0.1-200μm。
本发明的进一步的改进在于，步骤2)中，粘结剂为乙醇、甘油、聚乙烯醇(PVA)中的至少一种。
本发明的进一步的改进在于，步骤2)中，压制金属粉的压力为1MPa-1000Mpa。
本发明的进一步的改进在于，步骤3)中，溶剂为水、三氯甲烷、甲醇、丙酮、环己酮、苯酚、甲酸、二甲基甲酰胺、苯、乙醚、乙醇、乙二醇中的至少一种。
本发明的进一步的改进在于，步骤4)中，真空烧结的真空度需≥5×10-2Pa。
本发明的进一步的改进在于，步骤4)中，烧结工艺参数为：先使升温2℃～30℃/h，从室温升至150℃～600℃，然后保温0.5～5小时；再以2℃～30℃/h升至300℃～800℃，保温0.5～5小时；最后以40℃～200℃/h升至1100℃～1600℃，保温2～5小时；保温后关闭电炉电源，自然降至室温取出。
本发明的进一步的改进在于，步骤5)中，利用气相沉积的方法在多孔植入物支架表面沉积金属涂层，反应温度为500-2000℃，涂层厚度为10-500μm，反应气氛为氢气。
本发明的进一步的改进在于，步骤6)中，阳极为金属植入物，阴极为石墨棒、铂片，两电极间距为0.5-15cm，电解液为氢氟酸(0.05mol/L-5mol/L)和硫酸(2mol/L-18.4mol/L)的乙二醇溶液、水溶液、无水甘油溶液，，电压0.1-300V，阳极氧化时间10s-4h，反应温度为10-300℃。
本发明技术与现有技术相比具有如下优点：
1.本发明将增材制造技术与粉末冶金-造孔剂法以及阳极氧化技术相结合，能够实现对多孔植入物微观梯度结构的成形控制以及表面纳米结构的制备。
2.制备的多孔植入物具有纳米结构，利于细胞活动，提高植入物的生物相容性。
具体实施方式
本发明所述一种基于高分子聚合物增材制造的多孔植入物的制备方法，包括增材制造技术、粉末冶金技术、化学气相技术和阳极氧化技术四个环节：
所述制备方法使用增材制造方法制备具有梯度微观结构的多孔植入物模型的高分子聚合物负型模具。
所述制备方法制备的高分子聚合物负型模具的材料为聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚丙烯晴(AS\ABS)、尼龙(PA)、有机玻璃亚克力(PMMA)、聚碳酸酯(PC)、聚氨酯(PU)、硅橡胶、聚己内酯(PCL)、聚乳酸(PLA)、聚醚醚酮(PEEK)、环氧树脂、聚乙烯醇(PVA)中的至少一种以及碳纤维、石墨烯、单壁及多壁碳纳米管与以上材料的复合材料。
所述制备方法制备高分子聚合物负型模具的增材制造方法为光固化成形(SLA)、熔融沉积成形(FDM)、激光选区烧结(SLS)、3DP中的至少一种。
所述制备方法将金属粉与粘结剂混合均匀后压制到高分子聚合物负型模具中。
所述制备方法使用金属粉为钽、钛铌或铍等高熔点金属，金属粉的粒径范围0.1-200μm。
所述混合金属粉使用的粘结剂为乙醇、甘油、聚乙烯醇(PVA)中的至少一种。
所述压制金属粉的压力为1MPa-1000MPa。
所述制备方法将金属粉与高分子聚合物负型模具一同置入有机溶剂中去除高分子聚合物负型模具，得到初步的金属多孔植入物。
所述溶解高分子聚合物负型磨具的溶剂为水、三氯甲烷、甲醇、丙酮、环己酮、苯酚、甲酸、二甲基甲酰胺、苯、乙醚、乙醇、乙二醇中的至少一种。
所述制备方法将制得的初步的金属多孔植入物置入真空高温炉中增强金属多孔植入物的强度；
所述真空烧结的真空度需≥5×10-2Pa。
所述烧结工艺参数为：先使升温2℃～30℃/h，从室温升至150℃～600℃，然后保温0.5～5小时；再以2℃～30℃/h升至300℃～800℃，保温0.5～5小时；最后以40℃～200℃/h升至1100℃～1600℃，保温2～5小时；保温后关闭电炉电源，自然降至室温取出。
所述制备方法将制得的金属多孔植入物利用化学气相沉积法在植入物表面沉积金属涂层进一步增强强度。
所述利用化学气相沉积方法孔植入物支架表面沉积金属涂层，反应温度为500-2000℃，涂层厚度为10-500μm，反应气氛为氢气。
所述制备方法将制得的金属多孔植入物置入电解液中进行阳极氧化处理，得到表面具有金属氧化物纳米管的定制化金属多孔植入物。
所述阳极氧化处理的阳极为金属植入物，阴极为石墨棒、铂片，两电极间距为0.5-15cm，电解液为氢氟酸(0.05mol/L-5mol/L)和硫酸(2mol/L-18.4mol/L)的乙二醇溶液、水溶液、无水甘油溶液，，电压0.1-300V，阳极氧化时间10s-4h，反应温度为10-300℃。
实施例
一种基于高分子聚合物增材制造的多孔植入物的制备方法，包括增材制造技术、粉末冶金技术、化学气相技术和阳极氧化技术四个环节：
以尼龙作为高分子聚合物模具通过增材制造、粉末冶金及阳极氧化制备具有微纳结构的多孔钽植入物为例。首先使用选区激光烧结(SLS)制备已设计好的具有微观梯度结构的多孔钽植入物模型的负型尼龙模具。然后将钽粉与粘结剂混合压制入尼龙模具中，置于三氯甲烷溶液中溶解尼龙，得到初步多孔钽植入物，真空烧结去除粘结剂、增强多孔钽植入物的强度，再利用气相沉积的方法在多孔钽表面沉积钽涂层，最后置入电解液中进行阳极氧化处理，得到表面具有氧化钽纳米管的定制化多孔钽植入物。
使用选区激光烧结法制备负型尼龙模具，将钽粉与粘结剂混合均匀，控制压力降钽粉压制入尼龙模具中，置入三氯甲烷绕那个月中溶解尼龙，获得初步的多孔钽支架，置入真空高温炉中，按照烧结工艺进行升温、保温和降温进行烧结增强强度，利用气相沉积的方法在多孔钽植入物表面沉积钽涂层，及控制反应温度、钽涂层厚度和反应气氛。最后置入电解液中进行阳极氧化处理，阳极为多孔钽支架，阴极为石墨棒电解液为氢氟酸和硫酸的混合溶液，控制电极间距反应电压、阳极氧化时间、反应温度。
Claims (8)
1.一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于，包括如下的步骤：
1)使用增材制造方法制备具有梯度微观结构的多孔植入物模型的高分子聚合物负型模具；高分子聚合物负型模具的材料为聚乙烯PE、聚丙烯PP、聚苯乙烯PS、聚丙烯晴AS\ABS、尼龙PA、有机玻璃亚克力PMMA、聚碳酸酯PC、聚氨酯PU、硅橡胶、聚己内酯PCL、聚乳酸PLA、聚醚醚酮PEEK、环氧树脂、聚乙烯醇PVA中的至少一种以及碳纤维、石墨烯、单壁及多壁碳纳米管与以上材料的复合材料；所用的增材制造方法为光固化成形SLA、熔融沉积成形FDM、激光选区烧结SLS、3DP中的至少一种；
2)将金属粉与粘结剂混合均匀后压制到步骤1)中制得的高分子聚合物负型模具中；
3)将步骤2)中金属粉与高分子聚合物负型模具一同置入有机溶剂中去除高分子聚合物负型模具，得到初步的金属多孔植入物；
4)利用粉末冶金-造孔剂法，将步骤3)制得的初步的金属多孔植入物置入真空高温炉中增强金属多孔植入物的强度；
5)将步骤4)中制得的金属多孔植入物利用化学气相沉积法在植入物表面沉积金属涂层进一步增强强度；
6)将步骤5)中制得的金属多孔植入物置入电解液中进行阳极氧化处理，得到表面具有金属氧化物纳米管的定制化金属多孔植入物。
2.根据权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤2)中，金属粉为钽、钛铌或铍高熔点金属，金属粉的粒径范围0.1-200μm，粘结剂为乙醇、甘油、聚乙烯醇PVA中的至少一种。
3.权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤2)中，压制金属粉的压力为1MPa-1000Mpa。
4.权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤3)中，溶剂为水、三氯甲烷、甲醇、丙酮、环己酮、苯酚、甲酸、二甲基甲酰胺、苯、乙醚、乙醇、乙二醇中的至少一种。
5.根据权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤4)中，真空烧结的真空度需≥5×10-2Pa。
6.根据权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤4)中，烧结工艺参数为：先使升温2℃-30℃/h，从室温升至150℃-600℃，然后保温0.5-5小时；再以2℃-30℃/h升至300℃-800℃，保温0.5-5小时；最后以40℃-200℃/h升至1100℃-1600℃，保温2-5小时；保温后关闭电炉电源，自然降至室温取出。
7.根据权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤5)中，利用气相沉积的方法在多孔植入物支架表面沉积金属涂层，反应温度为500-2000℃，涂层厚度为10-500μm，反应气氛为氢气。
8.根据权利要求1所述的一种基于高分子聚合物增材制造的多孔植入物的制备方法，其特征在于：步骤6)中，阳极为金属植入物，阴极为石墨棒、铂片，两电极间距为0.5-15cm，电解液为0.05mol/L-5mol/L氢氟酸和2mol/L-18.4mol/L硫酸的乙二醇溶液、水溶液、无水甘油溶液，电压0.1-300V，阳极氧化时间10s-4h，反应温度为10-300℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710448052.9A CN107374784B (zh) | 2017-06-14 | 2017-06-14 | 一种基于高分子聚合物增材制造的多孔植入物的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710448052.9A CN107374784B (zh) | 2017-06-14 | 2017-06-14 | 一种基于高分子聚合物增材制造的多孔植入物的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107374784A CN107374784A (zh) | 2017-11-24 |
| CN107374784B true CN107374784B (zh) | 2019-12-24 |
Family
ID=60332962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710448052.9A Expired - Fee Related CN107374784B (zh) | 2017-06-14 | 2017-06-14 | 一种基于高分子聚合物增材制造的多孔植入物的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107374784B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112809004B (zh) * | 2020-12-18 | 2022-12-30 | 广东省科学院新材料研究所 | 多孔功能结构及其制备方法 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0126467D0 (en) * | 2001-11-03 | 2002-01-02 | Accentus Plc | Deposition of coatings on substrates |
| US6865810B2 (en) * | 2002-06-27 | 2005-03-15 | Scimed Life Systems, Inc. | Methods of making medical devices |
| US7635447B2 (en) * | 2006-02-17 | 2009-12-22 | Biomet Manufacturing Corp. | Method and apparatus for forming porous metal implants |
| CN101884811A (zh) * | 2009-05-15 | 2010-11-17 | 上海交通大学医学院附属新华医院 | 一种具有生物活性和抗感染作用的梯度多孔β-TCP的骨移植材料及其制备方法和应用 |
| CN102335742B (zh) * | 2011-11-04 | 2013-01-30 | 北京科技大学 | 一种复杂形状生物医用多孔钛钼合金植入体的制备方法 |
| CN103285426A (zh) * | 2012-02-23 | 2013-09-11 | 湖南迈迪科新材有限公司 | 一种羟基磷灰石内嵌氧化钛纳米管复合涂层及其制备方法 |
| CN106421904B (zh) * | 2016-09-19 | 2019-07-23 | 西安交通大学 | 一种凝胶注模3d打印及电解还原制备多孔植入物的方法 |
-
2017
- 2017-06-14 CN CN201710448052.9A patent/CN107374784B/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN107374784A (zh) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110204778B (zh) | 一种具有梯度孔结构的聚合物发泡材料的制备方法 | |
| CN107199671B (zh) | 具有微纳复合结构的超疏水表面的微注射成型模具及其微注射成型方法 | |
| CN106466494B (zh) | 一种多孔材料及制备方法 | |
| TWI495183B (zh) | 電極薄膜之製備方法 | |
| CN106421904A (zh) | 一种凝胶注模3d打印及电解还原制备多孔植入物的方法 | |
| CN110950651A (zh) | 一种基于墨水直书写3d打印技术制备多级多孔陶瓷的方法 | |
| Soares et al. | Additive manufacturing of electrochemical energy storage systems electrodes | |
| CN107374784B (zh) | 一种基于高分子聚合物增材制造的多孔植入物的制备方法 | |
| You et al. | Structural and functional applications of 3D-printed graphene-based architectures | |
| Uddin et al. | Recent progress on synthesis of 3D graphene, properties, and emerging applications | |
| CN101217197B (zh) | 固体氧化物燃料电池连续梯度阳极的制备方法 | |
| CN106467939B (zh) | 一种多级孔金属制备方法 | |
| CN114226755A (zh) | 金属-陶瓷复合点阵制造方法及金属-陶瓷复合点阵结构 | |
| CN106563808B (zh) | 一种被动中耳植入装置及其制备方法 | |
| CN113331991A (zh) | 一种具有多尺度通道网络的预血管化生物结构体的制备方法 | |
| JP2008229869A (ja) | 連続インプリント用ロール状モールドおよびその製造方法 | |
| CN109608684B (zh) | 一种三维形状细菌纤维素及其制备方法与应用 | |
| CN107706354A (zh) | 一种沉积基体及其制备方法 | |
| JP2012195600A (ja) | インプリント用ロール状モールドおよびその製造方法 | |
| CN103120808A (zh) | 一种三维软体支架的制备方法 | |
| CN107320220B (zh) | 一种基于陶瓷增材制造的多孔植入物的制备方法 | |
| Lu et al. | Novel methods to fabricate macroporous 3D carbon scaffolds and ordered surface mesopores on carbon filaments | |
| KR101808410B1 (ko) | 니켈 나노튜브의 제조방법 | |
| KR101952581B1 (ko) | 다공성 구조체의 제조방법 | |
| CN108478862B (zh) | 羟基磷灰石陶瓷/石墨烯复合骨组织替换材料及其制备 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191224 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |