CN102796899B - Preparation method of medical porous metal implanting material - Google Patents
Preparation method of medical porous metal implanting material Download PDFInfo
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- CN102796899B CN102796899B CN201110296596.0A CN201110296596A CN102796899B CN 102796899 B CN102796899 B CN 102796899B CN 201110296596 A CN201110296596 A CN 201110296596A CN 102796899 B CN102796899 B CN 102796899B
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000011812 mixed powder Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 229910052786 argon Inorganic materials 0.000 claims abstract description 12
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 9
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 9
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 9
- 239000012188 paraffin wax Substances 0.000 claims abstract description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000005469 granulation Methods 0.000 claims abstract description 6
- 230000003179 granulation Effects 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 5
- 239000001923 methylcellulose Substances 0.000 claims abstract description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 5
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims abstract description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 3
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 3
- 239000004202 carbamide Substances 0.000 claims abstract description 3
- 235000013877 carbamide Nutrition 0.000 claims abstract description 3
- 235000010981 methylcellulose Nutrition 0.000 claims abstract description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011780 sodium chloride Substances 0.000 claims abstract description 3
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 3
- 239000008117 stearic acid Substances 0.000 claims abstract description 3
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 3
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 3
- 238000010792 warming Methods 0.000 claims description 47
- 238000009413 insulation Methods 0.000 claims description 29
- 239000011148 porous material Substances 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000007943 implant Substances 0.000 claims description 11
- 238000001746 injection moulding Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 abstract description 51
- 210000000988 bone and bone Anatomy 0.000 abstract description 8
- 238000005238 degreasing Methods 0.000 abstract 2
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 11
- 210000001519 tissue Anatomy 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000006262 metallic foam Substances 0.000 description 2
- 230000017074 necrotic cell death Effects 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Veterinary Medicine (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method of a medical porous metal implanting material. The preparation method comprises the steps of: mixing tantalum powder, pore-forming agent and forming agent to mixed powder; and carrying out granulation, mould-injection forming, demoulding, degreasing, sintering and heat treatment to obtain the medical porous metal implanting material which is used for replacing tooth bone tissues, wherein the pore-forming agent comprises one or more of sodium bicarbonate, urea, sodium chloride, methylcellulose and ethyl cellulose; the forming agent comprises one or more of polyvinyl alcohol, stearic acid, zinc stearate, paraffin and synthetic rubber; and the degreasing process comprises the steps of: gradually raising the temperature to 400-800 DEG C at a speed of 0.5-3 DEG C/min, introducing in argon to form protection atmosphere and holding the temperature for 60-240min. According to the preparation method provided by the invention, the sintering and heat treatment steps are effectively improved, so that the mechanical property of a prepared porous tantalum material is greatly improved and the porous tantalum material is particularly suitable for serving as a medical implanting material for replacing the tooth bone tissues of human body.
Description
Technical field
The present invention relates to a kind of preparation method of medical metal implanted material, especially relate to a kind of preparation method of medical porous metal implant material.
Background technology
Porous medical metal implanted material has treatment osseous tissue wound, bone formation necrosis and alternative compact bone tissue as important and special purposes such as dentales, and existing this common class material has porous metals rustless steel, porous metals titanium etc.Porous embedded material as osseous tissue wound and the use of bone formation necrosis therapeutic, its porosity should reach 30～80%, and hole is preferably all communicated with and is uniformly distributed, or make it as required both consistent with the bone growth of human body, alleviate again the weight of material itself, to be applicable to human body, implanted use.
And refractory metals tantalum, because it has outstanding biocompatibility, its porous material is expected to the conventional medical metallic biomaterial such as aforementioned as an alternative.Due to metal tantalum to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, tantalum is goed deep into as the further of body implanting material cognition, and people implant and become more and more urgent by the demand of porous metals tantalum material human body, also more and more higher to its requirement.Wherein, as the medical embedded metal tantalum of porous, if can have the very high physical and mechanical properties that is uniformly distributed interconnected pore and adapts with human body, it is expected to as a kind of novel osseous tissue substitution material.
As medical embedded porous metal material just as porous metal material be to take powder sintering as main processing method like that substantially, in particular for obtain porosity communication and equally distributed porous metal foam structure adopt metal dust slurry in the powder sintering dipping on Organic Foam Material afterwards the dry knot that reburns to be called for short foam impregnation method in the majority.About powder sintered obtained porous metal material conventionally its Metal Mechanic Property be not fine, its main cause is the problem of subsiding how arranging in technique in the support of pore-forming medium and elimination relation, metal powder sintered process.And in known bibliographical information, all there is no good solution and laissez-faire nature.
Adopt bibliographical information that metal powder sintered legal system makes porous tantalum seldom, particularly take and obtain medical embedded material and almost do not have with the porous tantalum powder sintering bibliographical information that is object.Can reference be that publication number is CN200510032174, title " three-dimensional through hole or part hole porous metal foam connected with each other and preparation method thereof " and CN200710152394, title " a kind of porous foam tungsten and preparation method thereof ".Yet porous metals that it obtains or for filtering material use, or share for Aero-Space and other high-temperature field but not use as medical metal implanted material, moreover also non-porous tantalum of the porous metals of processing.
About porous tantalum, US5282861 discloses a kind of perforate tantalum material and preparation thereof that is applied to spongy bone implant, cell and organizes sensor.This porous tantalum is made by pure business tantalum, it take polyurethane precursor, and to carry out the carbon skeleton that thermal degradation obtains be support, this carbon skeleton is multiple dodecahedron, it in it, is mesh-like structure, integral body spreads all over micropore, porosity can be up to 98%, then the method by chemical vapour deposition, infiltration is attached on carbon skeleton to form porous metals micro structure, referred to as chemical deposition by commercially pure tantalum.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtains is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight accounts for 1% left and right.Document is further recorded, the comprcssive strength 50～70MPa of this porous material, elastic modelling quantity 2.5～3.5GPa, tensile strength 63MPa, amount of plastic deformation 15%.But using it as compact bone tissue as the porous tantalum of the medical embedded materials such as dentale, the mechanical property of its material has obvious weak point as ductility, comprcssive strength, bending strength etc., and can have influence on the follow-up processing to porous tantalum material itself, such as cutting of profiled member etc.Also all there is such deficiency in the same product obtaining in aforesaid metal powder sintered method.
Summary of the invention
The object of the present invention is to provide the preparation method of the medical porous metal implant material that a kind of biocompatibility and mechanical property are good.
The object of the invention is to realize by following technological means:
A kind of preparation method of medical porous metal implant material, tantalum powder and pore creating material, forming agent are mixed into mixed-powder, then through pelletize, be injected into mould molding, the demoulding, defat, sintering and heat treatment and make the medical porous metal implant material that substitutes dentale tissue; It is characterized in that: described pore creating material is one or more in sodium bicarbonate, carbamide, sodium chloride, methylcellulose, ethyl cellulose, described forming agent is one or more in polyvinyl alcohol, stearic acid, zinc stearate, paraffin, synthetic rubber; Described skimming processes is that the speed with 0.5 ℃/min～3 ℃/min is progressively warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 60min～240min, and described sintering step is that vacuum is 10
-4pa～10
-3pa, with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 120～240min, with stove, be chilled to 200～300 ℃, with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 120～360min; Described heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, is incubated 240～480min with 10～20 ℃/min, then is chilled to 400 ℃, is incubated 120～300min with 2～5 ℃/min, then cools to room temperature with the furnace.
In the R&D process of medical porous tantalum material, syntheti c route is numerous, but inventor has creatively proposed to adopt above-mentioned processing step to prepare fine and close medical porous tantalum embedded material, the above-mentioned Technology for Heating Processing particularly adopting, has eliminated fully internal stress, has made the toughness of organizing more evenly, greatly improved prepared porous tantalum material of porous tantalum material; Above-mentioned sintering processes technique, makes idiosome become heater, more even, thorough thereby sintering obtains.
For the porous tantalum material porosity of the alternative dentale tissue that makes to make suitable so that biocompatibility excellent, improve the mechanical property of its material simultaneously, above-mentioned granulation process is to be that 450～650 ℃, operating pressure are under 12～15MPa, described mixed-powder to be a granulated into particle diameter not higher than the circular granular of 20 μ m in operating temperature, and the temperature that described circular granular is injected into mould is that 380～540 ℃, pressure are 72～90MPa.
The mean diameter of the Ta powder that the present invention adopts is less than 43 microns, oxygen content and is less than 0.1% ，Wei commercially available prod; Above-mentioned pore creating material, forming agent are also commercially available prod.It is 10 that vacuum environment of the present invention preferably adopts vacuum
-4pa～10
-3the vacuum condition of Pa.
In R&D process, inventor further studies discovery, if control bad in above-mentioned preparation, though can make and be suitable for as mentioned above substituting the medical embedded material of dentale but conforming product rate is not high: as difficult in powder pressing forming, be prone to layering, inhomogeneous in compacting rear section, defat rear section there will be the technical problems such as crackle.
In order to make in powder compaction process molding easier, thereby raising yield rate, finished product hole uniformity, make preparation process more stable, in above-mentioned mixed-powder, the consumption of forming agent is 5～10%, the consumption of pore creating material is 20～30%, surplus is tantalum powder, in volumn concentration, (in volumn concentration, be the unit of directly calculating by the situation of final porous tantalum material, in above-mentioned mixed-powder weighs or according to the densimeter of respective substance, calculate its corresponding quality weighing), more preferably forming agent is that paraffin accounts for 7～9%, pore creating material is that ethyl cellulose accounts for 26～29%, surplus is tantalum powder, further be preferably paraffin and account for 8%, ethyl cellulose accounts for 27%, surplus is tantalum powder, all in volumn concentration, above-mentioned demould time is preferably 6～9S, more preferably 7S.
In order to make in skimming processes idiosome more stable, reduce the part idiosome distortion being prone to, aperture is inhomogeneous, thereby further improve yield rate, quality of production stability, in the preparation of the porous tantalum material of above-mentioned alternative dentale tissue, skimming processes is preferably progressively warming up to 400～800 ℃ with the speed of 2.5～3 ℃/min, with argon, pass into and form protective atmosphere and be incubated 150min～240min, further preferably with the speed of 2.5 ℃/min, be progressively warming up to 400～800 ℃, with argon, pass into and form protective atmosphere and be incubated 220min, most preferably, above-mentioned defat is that the speed with 1～3 ℃/min rises to 400 ℃ from room temperature, insulation 60～120min, speed with 1.5～2.5 ℃/min rises to 600～800 ℃ from 400 ℃, insulation 180～240min, the preferred temperature of above-mentioned granulation process is that 510～535 ℃, operating pressure are the circular granular that under 13MPa, described mixed-powder is a granulated into particle diameter 10～20 μ m (more preferably 13 μ m), by the injection molding temperature of described circular granular, is that 465～490 ℃, pressure are 83～85MPa.
For make idiosome sintering obtain more evenly, thorough, make the medical porous tantalum strength of materials that makes higher, it is 10 that above-mentioned sintering step is preferably vacuum
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, be incubated 220～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 250～320min; Further being preferably vacuum is 10
-4pa～10
-3pa, is warming up to 1800 ℃, is incubated 200min, with stove, is chilled to 200～300 ℃ with 13 ℃/min, then is warming up to 1800 ℃, insulation 230min with 17 ℃/min, with 7 ℃/min, is warming up to 2000～2200 ℃, insulation 300min.
Better in order to eliminate more fully internal stress, the toughness of material, above-mentioned heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, is incubated 260～320min with 15 ℃/min, then is chilled to 400 ℃, insulation 120min with 3 ℃/min, then is cooled to room temperature with 18 ℃/min～23 ℃/min.
Cooling condition after above-mentioned vacuum-sintering also includes: vacuum is not less than 10
-3pa, with not higher than 25 ℃/min, is not less than 10 ℃/min and gradually falls cooldown rate mode, and to sintered porous bodies segmentation cooling down to 800 ℃, each section of temperature retention time 30min～90min, then cools to room temperature with the furnace.
Preferably, the cooling condition after above-mentioned vacuum-sintering is: vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, is incubated 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, is incubated 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling.
The character of metal tantalum and niobium is extremely similar, and said method is equally also applicable to the preparation of medical porous niobium material.
Preparation methods for porous metal materials of the present invention has adopted injection moulding, makes the content of impurity in final porous tantalum material extremely low, has effectively improved biocompatibility and biological safety; Optimization of process conditions to pelletize of the present invention, injection moulding, defat, sintering and annealing steps, make that yield rate is high, finished product aperture uniformity is better, make that preparation process is more stable, quality stability good, effectively eliminated thermal stress, made organizing of porous tantalum material more even, with the mechanical property that further improves porous tantalum, be all improved as intensity, toughness simultaneously.The above-mentioned Technology for Heating Processing particularly adopting, has eliminated fully internal stress, has made the toughness of organizing more evenly, greatly improved prepared porous tantalum material of porous tantalum material; Above-mentioned sintering processes technique, makes idiosome become heater, more even, thorough thereby sintering obtains.As everyone knows, the qualification rate of product, production stability are determined by manual operation factor and process route itself determines, manual operation can be tending towards normal level in high standardization after all, therefore quality of production stability is mainly determined by technique own, its product qualified rate of preparation technology of the present invention is high, production is stable, and conforming product rate is up to 93.0%～95.0%.Porous tantalum finished product even pore distribution and connection that the present invention makes, good biocompatibility.For the porous tantalum material of the alternative dentale tissue making, through its impurity content of test can be lower than 0.2%, density reachable 11.67～13.34g/cm
3, porosity can reach 20～30%, and pore diameter can reach 12～25 μ m, elastic modelling quantity can reach that 6.0～7.0Gpa, percentage elongation reach 14.0～15.0%, bending strength can reach 160～180Mpa, comprcssive strength can reach 115～130Mpa.
The specific embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, person skilled in art can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1: take paraffin, mean diameter and be less than 43 microns of oxygen contents and be less than 0.1% tantalum powder and ethyl cellulose and be mixed into mixed-powder, wherein paraffin accounts for 8%, ethyl cellulose accounts for 27%, tantalum powder accounts for 65%, all in volumn concentration.Pelletize: be that 510～520 ℃, operating pressure are under 12～13MPa, described mixed-powder to be a granulated into the circular granular of particle diameter 10～13 μ m in operating temperature.Injection moulding: the temperature that described circular granular is injected into mould is that 465～490 ℃, pressure are 83～85MPa.Demould time: 6～7S.Ungrease treatment: vacuum 10
-4pa, rises to 400 ℃ with the speed of 1～3 ℃/min from room temperature, is incubated 60～120min, with the speed of 1.5～2.5 ℃/min, rises to 600～800 ℃ from 400 ℃, is incubated 180～240min.Vacuum-sintering: vacuum is 10
-4pa～10
-3pa; with 13 ℃/min, be warming up to 1800 ℃, be incubated 200min, with stove, be chilled to 200～300 ℃, then be warming up to 1800 ℃, insulation 230min with 17 ℃/min, with 7 ℃/min, be warming up to 2000～2200 ℃, insulation 300min; the protection of sintering process applying argon gas, heat treatment: vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, is incubated 260～320min with 15 ℃/min, then is chilled to 400 ℃, insulation 120min with 3 ℃/min, then is cooled to room temperature with 18 ℃/min～23 ℃/min, removes surface dirt and dirt after taking out product, makes porous tantalum finished product.
Inventor detects the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 12.54g/cm
3, porosity 25%, hole average diameter 23 μ m, elastic modelling quantity 6.7GPa, percentage elongation 14.8%, bending strength 172MPa, comprcssive strength 125MPa.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
Embodiment 2: weighing polyvinyl alcohol, mean diameter are less than 43 microns of oxygen contents and are less than 0.1% tantalum powder and sodium bicarbonate and are mixed into mixed-powder, and wherein polyvinyl alcohol accounts for 6%, sodium bicarbonate accounts for 29%, tantalum powder accounts for 65%, all in volumn concentration.Pelletize: be that 450 ℃, operating pressure are under 15MPa, described mixed-powder to be a granulated into the circular granular of particle diameter 20 μ m in operating temperature.Injection moulding: the temperature that described circular granular is injected into mould is that 540 ℃, pressure are 90MPa.Demould time: 9S.Ungrease treatment: vacuum 10
-4pa, is warming up to 400 ℃, insulation 60min with the heating rate of 1 ℃/min from room temperature; Heating rate with 2.5 ℃/min is warming up to 800 ℃, temperature retention time 180 minutes from 400 ℃ again.Vacuum-sintering: sintering step: vacuum is 10
-4pa, is warming up to 1800 ℃, is incubated 240min, with stove, is chilled to 200～300 ℃ with 20 ℃/min, then is warming up to 1500 ℃, insulation 180min with 10 ℃/min, with 10 ℃/min, is warming up to 2000～2200 ℃, insulation 360min; After taking out product, remove surface dirt and dirt, heat treatment step: vacuum is 10
-3pa, is warming up to 800～900 ℃, insulation 480min with 10 ℃/min, then is chilled to 400 ℃, insulation 300min with 2 ℃/min, then cools to room temperature with the furnace.The sample making carries out conventional post processing again and obtains porous tantalum finished product.
Inventor detects the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 11.74g/cm
3, porosity 30%, hole average diameter 24 μ m, elastic modelling quantity 6.1GPa, percentage elongation 14.2%, bending strength 163MPa, comprcssive strength 117MPa.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
Embodiment 3: take zinc stearate, mean diameter and be less than 43 microns of oxygen contents and be less than 0.1% tantalum powder and methylcellulose and be mixed into mixed-powder, wherein zinc stearate accounts for 10%, methylcellulose accounts for 23%, tantalum powder accounts for 67%, all in volumn concentration.Pelletize: be that 650 ℃, operating pressure are under 12MPa, described mixed-powder to be a granulated into the circular granular of particle diameter 10 μ m in operating temperature.Injection moulding: the temperature that described circular granular is injected into mould is that 380 ℃, pressure are 72MPa.Demould time: 6S.Ungrease treatment: vacuum 10
-4pa, is warming up to 400 ℃, insulation 120min with the heating rate of 3 ℃/min from room temperature; Heating rate with 1.5 ℃/min is warming up to 750 ℃, temperature retention time 240 minutes from 400 ℃ again; Sintering: vacuum is 10
-3pa, is warming up to 1500 ℃, is incubated 120min, with stove, is chilled to 200～300 ℃ with 10 ℃/min, then is warming up to 1800 ℃, insulation 240min with 20 ℃/min, with 5 ℃/min, is warming up to 2000～2200 ℃, insulation 120min; Heat treatment step: vacuum is 10
-4pa, is warming up to 800～900 ℃, insulation 240min with 20 ℃/min, then is chilled to 400 ℃, insulation 120min with 5 ℃/min, then cools to room temperature with the furnace, removes product surface dust and dirt, makes porous tantalum finished product.
Inventor detects the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 13.30g/cm
3, porosity 20%, hole average diameter 20 μ m, elastic modelling quantity 7.0GPa, percentage elongation 14.85%, bending strength 178MPa, comprcssive strength 122MPa.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
Embodiment 4: a kind of porous tantalum, it is less than with particle diameter the ta powder that 43 μ m, oxygen content are less than 0.1%, polyvinyl alcohol and sodium bicarbonate mixed powder are raw material, then process and make through pelletize, injection moulding, the demoulding, ungrease treatment, vacuum-sintering, vacuum annealing.
Wherein, polyvinyl alcohol accounts for 7%, sodium bicarbonate accounts for 20%, ta powder accounts for 73%, in volumn concentration;
Pelletize: be that 520 ℃, operating pressure are under 14MPa, described mixed-powder to be a granulated into the circular granular of particle diameter 16 μ m in operating temperature;
Injection moulding and the demoulding: the temperature that described circular granular is injected into mould is that 468 ℃, pressure are 76MPa.Demould time: 8S;
Subsequently mixed-powder is put into nonoxidizing atmosphere stove and be warming up to 800 ℃ with certain heating rate, protective atmosphere is that 99.999% argon carries out ungrease treatment, its before heating up, first pass into pure argon gas at least 30min to get rid of furnace air, temperature control process: the speed with 1.5 ℃/min rises to 400 ℃ from room temperature, insulation 88min, argon intake 0.5L/min; Speed with 2.0 ℃/min rises to 800 ℃, insulation 195min, argon intake 1L/min from 400 ℃; Powered-down again, the sample furnace cooling after defat, argon intake 1L/min, until close argon while being cooled to room temperature;
For the sample after ungrease treatment, with tungsten device, be placed in fine vacuum high temperature sintering furnace with certain heating rate intensification vacuum-sintering, before heating up, the vacuum of sintering furnace at least will reach 10
-4pa, is warming up to 1750 ℃, is incubated 220min, with stove, is chilled to 200～300 ℃ with 16 ℃/min, then is warming up to 1600 ℃, insulation 195min with 13 ℃/min, with 7 ℃/min, is warming up to 2000～2200 ℃, insulation 224min;
Sintering is complete, and vacuum is 10
-3pa, is cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; Speed with 12 ℃/min is cooled to 1200 ℃, insulation 60min; Speed with 10 ℃/min is cooled to 800 ℃, then furnace cooling;
For the cooled sample of vacuum-sintering, with corundum container, be placed in vacuum annealing furnace and heat up and carry out stress relief annealing processing with certain heating rate, the vacuum before heating up in annealing furnace at least will reach 10
-4pa, is warming up to 800～900 ℃, insulation 385min with 17 ℃/min, then is chilled to 400 ℃, insulation 260min with 3.5 ℃/min, then with 19 ℃/min, is cooled to room temperature, makes medical porous tantalum material.
Inventor detects the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 12.87g/cm
3, porosity 23%, hole average diameter 20 μ m, elastic modelling quantity 6.5GPa, bending strength 174MPa, comprcssive strength 123MPa.Through long-term test, this preparation technology's conforming product rate is up to 94.0%.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
In the method providing at above-described embodiment 4, we can also do other selections to wherein each kind of condition can obtain porous tantalum of the present invention equally, below all the other steps with embodiment 4.
The above-mentioned porous tantalum finished product making detects by preceding method, and its impurity content can be lower than 0.2%, density reachable 11.67～13.34g/cm
3, porosity can reach 20～30%, and pore diameter can reach 12～25 μ m, elastic modelling quantity can reach that 6.0～7.0Gpa, percentage elongation reach 14.0～15.0%, bending strength can reach 160～180Mpa, comprcssive strength can reach 115～130Mpa.Make porous tantalum and be applicable to the medical embedded material of human body dentale tissue as an alternative.
Claims (10)
1. the preparation method of a medical porous metal implant material, tantalum powder and pore creating material, forming agent are mixed into mixed-powder, then through pelletize, be injected into mould molding, the demoulding, defat, sintering and heat treatment and make the medical porous metal implant material that substitutes dentale tissue; It is characterized in that: described pore creating material is one or more in sodium bicarbonate, carbamide, sodium chloride, methylcellulose, ethyl cellulose, described forming agent is one or more in polyvinyl alcohol, stearic acid, zinc stearate, paraffin, synthetic rubber; Described skimming processes is that the speed with 0.5 ℃/min～3 ℃/min is progressively warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 60min～240min; Described sintering step is that vacuum is 10
-4pa～10
-3pa, with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 120～240min, with stove, be chilled to 200～300 ℃, with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 120～360min; Described heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, is incubated 240～480min with 10～20 ℃/min, then is chilled to 400 ℃, is incubated 120～300min with 2～5 ℃/min, then cools to room temperature with the furnace.
2. preparation method as claimed in claim 1, it is characterized in that: described granulation process is to be that 450～650 ℃, operating pressure are under 12～15MPa, described mixed-powder to be a granulated into particle diameter not higher than the circular granular of 20 μ m in operating temperature, the temperature that described circular granular is injected into mould is that 380～540 ℃, pressure are 72～90MPa.
3. preparation method as claimed in claim 1 or 2, is characterized in that: in described mixed-powder, the consumption of forming agent is 5～10%, the consumption of pore creating material is 20～30%, surplus is tantalum powder, in volumn concentration; Described demould time is 6～9S.
4. preparation method as claimed in claim 3, is characterized in that: described forming agent is that paraffin accounts for 7～9%, pore creating material is that ethyl cellulose accounts for 26～29%, surplus is tantalum powder, all in volumn concentration.
5. preparation method as claimed in claim 4, is characterized in that: described paraffin accounts for 8%, ethyl cellulose accounts for 27%, surplus is tantalum powder, all in volumn concentration; Described demould time is 7S.
6. preparation method as claimed in claim 1 or 2, it is characterized in that: in the preparation of the medical porous metal implant material of described alternative dentale tissue, skimming processes is that speed with 1～3 ℃/min rises to 400 ℃ from room temperature, insulation 60～120min, with the speed of 1.5～2.5 ℃/min, rise to 600～800 ℃ from 400 ℃, be incubated 180～240min; The temperature of described granulation process is that 510～535 ℃, operating pressure are under 13MPa, described mixed-powder to be a granulated into the circular granular of particle diameter 10～20 μ m, by the injection molding temperature of described circular granular, is that 465～490 ℃, pressure are 83～85MPa.
7. preparation method as claimed in claim 4, it is characterized in that: in the preparation of the medical porous metal implant material of described alternative dentale tissue, skimming processes is that speed with 1～3 ℃/min rises to 400 ℃ from room temperature, insulation 60～120min, with the speed of 1.5～2.5 ℃/min, rise to 600～800 ℃ from 400 ℃, be incubated 180～240min; The temperature of described granulation process is that 510～535 ℃, operating pressure are under 13MPa, described mixed-powder to be a granulated into the circular granular of particle diameter 10～20 μ m, by the injection molding temperature of described circular granular, is that 465～490 ℃, pressure are 83～85MPa.
8. preparation method as claimed in claim 3, is characterized in that: described sintering step is that vacuum is 10
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, be incubated 220～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 250～320min.
9. preparation method as claimed in claim 7, is characterized in that: described sintering step is that vacuum is 10
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, be incubated 220～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 250～320min.
10. preparation method as claimed in claim 8 or 9, is characterized in that: described heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, is incubated 260～320min with 15 ℃/min, then is chilled to 400 ℃, insulation 120min with 3 ℃/min, then is cooled to room temperature with 18 ℃/min～23 ℃/min.
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| 泡沫浸渍法制备的多孔铌基生物材料及性能;节云峰等;《稀有金属材料与工程》;20101130;第39卷(第11期);第2015-2017页 * |
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