CN102796900B - Medical porous metal material and preparation method thereof - Google Patents
Medical porous metal material and preparation method thereof Download PDFInfo
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- CN102796900B CN102796900B CN201110298000.0A CN201110298000A CN102796900B CN 102796900 B CN102796900 B CN 102796900B CN 201110298000 A CN201110298000 A CN 201110298000A CN 102796900 B CN102796900 B CN 102796900B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007769 metal material Substances 0.000 title claims abstract description 18
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 66
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 50
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 45
- 238000005245 sintering Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 27
- 239000011812 mixed powder Substances 0.000 claims abstract description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 27
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 25
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 238000009413 insulation Methods 0.000 claims description 54
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 46
- 238000010792 warming Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- 229910052786 argon Inorganic materials 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 14
- 238000000465 moulding Methods 0.000 claims description 12
- 239000011496 polyurethane foam Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 239000006261 foam material Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000007723 die pressing method Methods 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000011218 segmentation Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 abstract description 10
- 239000006260 foam Substances 0.000 abstract description 3
- 238000005238 degreasing Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 15
- 229910052758 niobium Inorganic materials 0.000 description 12
- 239000010955 niobium Substances 0.000 description 12
- 229920005830 Polyurethane Foam Polymers 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 210000000988 bone and bone Anatomy 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 2
- 239000006262 metallic foam Substances 0.000 description 2
- 230000017074 necrotic cell death Effects 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000006467 substitution reaction Methods 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
- 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
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000002245 particle Substances 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
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000003870 refractory metal Substances 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
- WTKKCYNZRWIVKL-UHFFFAOYSA-N tantalum Chemical compound [Ta+5] WTKKCYNZRWIVKL-UHFFFAOYSA-N 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
-
- 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
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
-
- 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
-
- 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
-
- 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
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
-
- 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
-
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- 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
- B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Organic Chemistry (AREA)
- Dermatology (AREA)
- Veterinary Medicine (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a medical porous metal material for replacing dentale and a preparation method of the medical porous metal material. The preparation method of the medical porous metal material comprises the following steps of: mixing tantalum powder with polyvinyl alcohol and sodium bicarbonate to form mixed powder, and then pressing the mixed powder in an organic foam under the pressure of 50-100 MPa; and carrying out the steps of forming, degreasing, sintering, cooling and heat processing to obtain the medical porous metal material; in the step of heat processing, the vacuum degree is 10 to the power of -4 Pa to 10 to the power of -3 Pa, the temperature is raised to 800-900 DEG C at a speed of 10-20 DEG C per minute and is preserved for 240-480 minutes, then the temperature is reduced to 400 DEG C at a speed of 2-5 DEG C per minute and is preserved for 120-300 minutes, and then furnace cooling is carried out till room temperature; and the formed porous tantalum material has the pore diameter of 10-25 microns, the porosity degree of 25-35%, the elastic modulus of 6.0-7.0 Gpa and the elongation percentage of 14-15%.
Description
Technical field
The present invention relates to a kind of medical porous metal implant material and preparation method thereof, particularly relate to medical porous metal implant material of a kind of alternative compact bone tissue and preparation method thereof.
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 teeth, and existing this common class material has porous metals rustless steel, porous metals titanium etc.As the porous embedded material of 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, implanted use to be applicable to human body.
And refractory metals tantalum/niobium, 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/niobium to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, further the going deep into as body implanting material cognition to tantalum/niobium, to human body, implantation becomes more and more urgent by the demand of porous metals tantalum/niobium material to people, also more and more higher to its requirement.Wherein, as the medical embedded metal tantalum/niobium 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 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 metal powder sintered legal system to make the bibliographical information of porous tantalum/niobium little, particularly to obtain medical embedded material with almost not having as porous tantalum/niobium powder sintering process bibliographical information of 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 ".But its porous metals that obtain 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/niobium 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 up of pure business tantalum, it carries out carbon skeleton that thermal degradation obtains as support take polyurethane precursor, this carbon skeleton is multiple dodecahedron, it in it, is mesh-like structure, entirety spreads all over micropore, porosity can be up to 98%, then commercially pure tantalum is attached on carbon skeleton to form porous metals micro structure, referred to as chemical deposition by the method for chemical vapour deposition, infiltration.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 tooth, the mechanical property of its material is obvious weak point as ductility has, and can have influence on the follow-up processing to porous tantalum material itself, the cutting of such as 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 a kind of medical porous metal material that is applicable to substitute dentale of good toughness.
Another object of the present invention is to provide the preparation method of above-mentioned medical porous metal material.
The object of the invention is to realize by following technological means:
A kind of medical porous metal material, it is characterized in that: be mixed into mixed-powder by tantalum powder and polyvinyl alcohol, sodium bicarbonate, then molding in described mixed-powder being pressed into Organic Foam Material under 50～100Mpa, defat, sintering, cooling and heat treatment step makes; Described heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 240～480min with 10～20 ℃/min, then is chilled to 400 ℃, insulation 120～300min with 2～5 ℃/min, then cools to room temperature with the furnace; The medical porous tantalum material pore diameter forming is 10～25 μ m, porosity between 25～35%, elastic modelling quantity is 6.0～7.0Gpa, percentage elongation 14～15%.
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; Through its impurity content of test can be lower than 0.2%, its biocompatibility and biological safety good, density reachable 10.84～12.50g/cm
3, porosity can reach 25～35%, and pore diameter can reach 10～25 μ m; Elastic modelling quantity can reach that 6.0～7.0Gpa, percentage elongation 14～15%, bending strength can reach 120～130Mpa, comprcssive strength can reach 100～140MPa, and porous tantalum of the present invention is suitable for substituting the medical embedded material of dentale very much.
The mean diameter of the Ta powder that the present invention adopts is less than 43 microns, oxygen content is less than 0.1%, is commercially available prod; Above-mentioned polyvinyl alcohol, sodium bicarbonate are also commercially available prod.Above-mentioned polyvinyl alcohol mainly plays molding effect but it also possesses pore-creating effect simultaneously, and above-mentioned sodium bicarbonate plays pore-creating effect.It is 10 that vacuum environment of the present invention preferably adopts vacuum
-4pa～10
-3the vacuum condition of Pa.Above-mentioned Organic Foam Material optimization polyurethane foam, more preferably aperture 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °, and (most preferably aperture is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness) polyurethane foam in.
In R&D process, inventor further studies discovery, if control bad in above-mentioned preparation, though can make be suitable for as mentioned above substitute dentale medical embedded material conforming product rate is not high, the stability of technique is not ideal enough, affect its industrial-scale production: as powder pressing forming difficulty, 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 polyvinyl alcohol is 5～10%, the consumption of sodium bicarbonate is 20～30%, surplus is tantalum powder, (be the unit of directly calculating by the situation of final porous tantalum material in volumn concentration in volumn concentration, in above-mentioned mixed-powder weighs or according to the densimeter of respective substance, calculate its corresponding quality weighing), more preferably polyvinyl alcohol accounts for 7～9%, sodium bicarbonate accounts for 26～29%, surplus is tantalum powder, pressure in above-mentioned compressing process is preferably 70～80Mpa.
In order to make in skimming processes, idiosome is more stable, minimizing is prone to the distortion of part idiosome, aperture inhomogeneous, thereby further improve yield rate, quality stability, above-mentioned skimming processes is to be progressively warming up to 400～800 ℃ with the speed of 0.5 ℃/min～3 ℃/min, passes into and forms protective atmosphere and be incubated 60min～240min with argon; Further preferably progressively be warming up to 400～800 ℃ with the speed of 2.5～3 ℃/min, pass into and form protective atmosphere and be incubated 150min～240min with argon.
The preparation method of above-mentioned medical porous metal material, adopt die pressing sintering to form, its feature is to be mixed into mixed powder with tantalum powder and polyvinyl alcohol, sodium bicarbonate powder, wherein the consumption of polyvinyl alcohol accounts for 5～10%, the consumption of sodium bicarbonate accounts for 20～30%, surplus is tantalum powder, in volumn concentration; Molding in described mixed-powder being pressed into Organic Foam Material under 50～100Mpa again, defat, vacuum-sintering, cooling and heat treatment make porous tantalum material; Described heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 240～480min with 10～20 ℃/min, then is chilled to 400 ℃, insulation 120～300min with 2～5 ℃/min, is then chilled to room temperature with stove.
The mean diameter of above-mentioned raw materials tantalum powder is less than 43 microns, oxygen content and is less than 0.1%; Above-mentioned mixed powder is preferably that polyvinyl alcohol accounts for 7～9%, sodium bicarbonate accounts for 26～29%, surplus is tantalum powder, is further preferably that polyvinyl alcohol accounts for 8%, sodium bicarbonate accounts for 27%, surplus is tantalum powder, in volumn concentration.Above-mentioned Organic Foam Material optimization polyurethane foam, more preferably aperture 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °, and (most preferably aperture is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness) polyurethane foam in.
In order to make in compacting embryo process processed pressing pressure even, not stratified, thereby make that final porous tantalum distribution of pores is more even, quality is more stable, the pressure adopting in above-mentioned pressing process is preferably 70～80Mpa; In above-mentioned skimming processes, be preferably with the speed of 0.5 ℃/min～3 ℃/min and be progressively warming up to 400～800 ℃; pass into and form protective atmosphere and be incubated 60min～240min with argon; further preferably progressively be warming up to 400～800 ℃ with the speed of 2.5～3 ℃/min; pass into and form protective atmosphere and be incubated 150min～240min with argon; further preferably progressively be warming up to 400～800 ℃ with the speed of 2.5 ℃/min, pass into and form protective atmosphere and be incubated 220min with argon.
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 ℃, insulation 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.
Vacuum-sintering condition of the present invention includes: vacuum 10
-3pa, rises to 1200 ℃～1500 ℃ with the heating rate of 10～20 ℃/min from room temperature, after insulation 1h～2h; To be warming up to 2000～2200 ℃ lower than the heating rate of 20 ℃/min, be at least incubated 2h～4h again.
Cooling condition after 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.
Further feature is on this basis: described ungrease treatment condition also includes: be progressively warming up to 600～800 ℃, specifically pass into formation protective atmosphere with pure argon gas (99.9999%), 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 ℃, insulation 180～240min from 400 ℃; Described vacuum-sintering condition also includes: the speed with 10～15 ℃/min rises to 1200～1250 ℃ from room temperature, insulation 30～60min, and vacuum is 10
-4pa～10
-3pa; Rise to 1500 ℃ with the speed of 10～20 ℃/min, insulation 30～60min, vacuum is 10
-4pa～10
-3pa, rises to 2000～2200 ℃ with the speed of 6～20 ℃/min, insulation 120～240min, and vacuum is 10
-4pa～10
-3pa; Cooling condition after vacuum-sintering also includes: vacuum is 10
-4pa～10
-3pa; Be cooled to 1500～1600 ℃ with the speed of 10～20 ℃/min, insulation 30～60min; Be cooled to 1200～1250 ℃ with the speed of 12～20 ℃/min, insulation 60～90min; Be cooled to 800 ℃ with the speed of 10～20 ℃/min, then furnace cooling; Described vacuum annealing condition is: vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 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.
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.
Porous tantalum preparation method of the present invention has adopted pure physics die pressing, makes the content of impurity in final porous tantalum material extremely low, has effectively improved biocompatibility and biological safety; The optimization of process conditions of, defat compressing to the present invention, 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 eliminate thermal stress, made organizing of porous tantalum material more even, effectively improve the mechanical property of porous tantalum, particularly its toughness is greatly enhanced, density is also effectively controlled, makes its comfort as dentale substitution material good simultaneously, preparation technology of the present invention make product qualified rate high, produce stablely, conforming product rate can be up to 93%.Porous tantalum finished product even pore distribution and connection that the present invention makes, good biocompatibility, through its impurity content of test can be lower than 0.2%, density reachable 10.84～12.50g/cm
3, porosity can reach 25～35%, and pore diameter can reach 10～25 μ m; Elastic modelling quantity can reach that 6.0～7.0Gpa, percentage elongation can reach 14%～15%, bending strength can reach 120～130Mpa, comprcssive strength can reach 100～140Mpa, and porous tantalum of the present invention is suitable for substituting the medical embedded material of dentale very much.
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: 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, wherein polyvinyl alcohol accounts for 8%, sodium bicarbonate accounts for 27%, tantalum powder accounts for 65%, all in volumn concentration.Compressing: above-mentioned mixed-powder is added and in injection moulding machine, under 70Mpa, is pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10
-4pa, take argon as protective atmosphere, be warming up to 400 ℃, insulation 110min with the heating rate of 0.6 ℃/min from room temperature; Be warming up to 700 ℃, temperature retention time 190 minutes with the heating rate of 1.5 ℃/min from 400 ℃ again.Vacuum-sintering: sintering in vacuum drying oven, 2000 ℃ of sintering temperatures, are incubated 2 hours, vacuum 10
-4pa, the protection of sintering process applying argon gas, removes surface dirt and dirt after taking-up product, then carries out conventional cooling processing.Heat treatment: be that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 260～320min with 15 ℃/min, then is chilled to 400 ℃, insulation 120min with 3 ℃/min, is cooled to room temperature with 18～23 ℃/min.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 12.50g/cm
3, porosity 25%, hole average diameter 22 μ m, elastic modelling quantity 6.5Gpa, percentage elongation be 14.5%, bending strength 130MPa, comprcssive strength 135MPa.
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, wherein polyvinyl alcohol accounts for 9%, sodium bicarbonate accounts for 23%, tantalum powder accounts for 68%, all in volumn concentration.Compressing: above-mentioned mixed-powder is added and in injection moulding machine, under 80Mpa, is pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10
-4pa, take argon as protective atmosphere, be warming up to 400 ℃, insulation 100min with the heating rate of 1.5 ℃/min from room temperature.Vacuum-sintering: sintering in vacuum drying oven, 2100 ℃ of sintering temperatures, are incubated 4 hours, vacuum 10
-4pa, the protection of sintering process applying argon gas, removes surface dirt and dirt after taking-up product, then carries out conventional cooling processing.Heat treatment: be that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 240min with 10 ℃/min, then is chilled to 400 ℃, insulation 300min with 5 ℃/min, cools to room temperature with the furnace.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 10.83g/cm
3, porosity 35%, percentage elongation is 14%, hole average diameter 10 μ m, elastic modelling quantity 6.2GPa, bending strength 122MPa, comprcssive strength 113MPa.
Embodiment 3: 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, wherein polyvinyl alcohol accounts for 6%, sodium bicarbonate accounts for 28%, tantalum powder accounts for 66%, all in volumn concentration.Compressing: above-mentioned mixed-powder is added and in injection moulding machine, under 66Mpa, is pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10
-4pa, take argon as protective atmosphere, be warming up to 700 ℃, insulation 200min with the heating rate of 3 ℃/min from room temperature.Vacuum-sintering: sintering in vacuum drying oven, 2150 ℃ of sintering temperatures, are incubated 2 hours, vacuum 10
-4pa, the protection of sintering process applying argon gas, cooling coming out of the stove, removes product surface dust and dirt, carries out conventional cold treatment.Heat treatment: be that vacuum is 10
-4pa, is warming up to 800～900 ℃, insulation 480min with 20 ℃/min, then is chilled to 400 ℃, insulation 120min with 2 ℃/min, cools to room temperature with the furnace.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 11.17g/cm
3, porosity 33%, hole average diameter 20 μ m, elastic modelling quantity 7.0GPa, percentage elongation is 15%, bending strength 120MPa, comprcssive strength 130MPa.
Embodiment 4: weighing polyvinyl alcohol, mean diameter are less than 43 microns of oxygen contents and are less than 0.1% niobium powder and sodium bicarbonate and are mixed into mixed-powder, wherein polyvinyl alcohol accounts for 5%, sodium bicarbonate accounts for 20%, niobium powder accounts for 75%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm in injection moulding machine under 96Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10
-4pa, take argon as protective atmosphere, be warming up to 550 ℃, insulation 240min with the heating rate of 2.5 ℃/min from room temperature.Vacuum-sintering: low vacuum is in 10
-4pa～10
-3pa, 2000～2200 ℃ of temperature, temperature retention time 1～5 hour, applying argon gas or other inert gas shieldings when sintering process insulation, to obtain porous material; Conventional cooling processing.Heat treatment: be that vacuum is 10
-3pa, is warming up to 800～900 ℃, insulation 300min with 13 ℃/min, then is chilled to 400 ℃, insulation 150min with 4 ℃/min, cools to room temperature with the furnace.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous niobium finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 6.02g/cm
3, porosity 30%, hole average diameter 24 μ m, elastic modelling quantity 2.8GPa, percentage elongation is 14.8%, bending strength 88MPa, comprcssive strength 78MPa.
Embodiment 5: 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%, and polyvinyl alcohol and sodium bicarbonate mixed powder are raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, polyvinyl alcohol accounts for 10%, sodium bicarbonate accounts for 30%, ta powder accounts for 60%, in volumn concentration;
Compressing: raw material mixed-powder is added and in injection moulding machine, under 56Mpa, is pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding;
After compressing, 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 heat up before first pass into pure argon gas at least 30min with get rid of furnace air, temperature control process: the speed with 1.8 ℃/min rises to 400 ℃ from room temperature, insulation 76min, argon intake 0.5L/min; Speed with 2.5 ℃/min rises to 800 ℃, insulation 215min, 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;
Be placed in and in fine vacuum high temperature sintering furnace, be warming up to 2200 ℃ with certain heating rate and carry out vacuum-sintering with tungsten device for the sample after ungrease treatment, before heating up, the vacuum of sintering furnace at least will reach 10
-4pa, rises to 1200 ℃ with the speed of 10～15 ℃/min from room temperature, insulation 30min, and vacuum is 10
-4pa; Rise to 1500 ℃ with the speed of 10 ℃/min, insulation 30min, vacuum is 10
-4pa～10
-3pa; Rise to 2200 ℃ with the speed of 6 ℃/min, insulation 120min, vacuum is 10
-3pa; Sintering is complete, and vacuum is 10
-3pa, is cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; Be cooled to 1200 ℃ with the speed of 12 ℃/min, insulation 60min; Be cooled to 800 ℃ with the speed of 10 ℃/min, then furnace cooling;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with corundum container and be warming up to 800 ℃ with certain heating rate and carry out stress relief annealing processing, the vacuum before heating up in annealing furnace at least will reach 10
-4pa is that vacuum is 10
-3pa, is warming up to 800 ℃, insulation 270min with 18 ℃/min, then is chilled to 400 ℃, insulation 130min with 3 ℃/min, cools to room temperature with the furnace.Finally carry out conventional post processing and make porous tantalum.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 12.34g/cm
3, porosity 26%, hole average diameter 17 μ m, elastic modelling quantity 6.8GPa, percentage elongation is 15%, bending strength 122MPa, comprcssive strength 135MPa.This preparation technology's product qualification rate reaching 92.55%.
In the method providing at above-described embodiment 5, we can also do other to wherein each kind of condition and select can obtain equally porous tantalum of the present invention or porous niobium.
Gained porous tantalum or porous niobium finished product are pressed preceding method and are detected:
| Embodiment | 6 | 7 | 8 |
| Density (g/cm 3) | 12.00 | 11.34 | 5.57 |
| Porosity (%) | 28 | 32 | 35 |
| (μ m) in aperture | 20 | 25 | 18 |
| Elastic modelling quantity (GPa) | 6.5 | 6.9 | 3.2 |
| Bending strength (MPa) | 122 | 130 | 78 |
| Comprcssive strength (MPa) | 115 | 130 | 73 |
| Percentage elongation (%) | 14.86 | 14.21 | 14.55 |
Claims (10)
1. a medical porous metal material, it is characterized in that: be mixed into mixed-powder by tantalum powder and polyvinyl alcohol, sodium bicarbonate, then molding in described mixed-powder being pressed into Organic Foam Material under 50～100Mpa, defat, sintering, cooling and heat treatment step makes; Described heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 240～480min with 10～20 ℃/min, then is chilled to 400 ℃, insulation 120～300min with 2～5 ℃/min, then cools to room temperature with the furnace; The medical porous tantalum material pore diameter forming is 10～25 μ m, porosity between 25～35%, elastic modelling quantity is 6.0～7.0Gpa, percentage elongation 14～15%.
2. medical porous metal material as claimed in claim 1, is characterized in that: in described mixed-powder, the consumption of polyvinyl alcohol is 5～10%, the consumption of sodium bicarbonate is 20～30%, surplus is tantalum powder, in volumn concentration; Described Organic Foam Material is aperture 0.56～0.72mm, density 0.025g/cm
3, hardness 50
0～80
0polyurethane foam.
3. medical porous metal material as claimed in claim 2, is characterized in that: in described mixed-powder, polyvinyl alcohol accounts for 7～9%, sodium bicarbonate accounts for 26～29%, surplus is tantalum powder; Pressure in described compressing process is preferably 70～80Mpa.
4. the medical porous metal material as described in claim 1,2 or 3, is characterized in that: described skimming processes is to be progressively warming up to 400～800 ℃ with the speed of 0.5 ℃/min～3 ℃/min, passes into and forms protective atmosphere and be incubated 60min～240min with argon.
5. the preparation method of a medical porous metal material, adopt die pressing sintering to form, its feature is: be mixed into mixed powder with tantalum powder and polyvinyl alcohol, sodium bicarbonate powder, wherein the consumption of polyvinyl alcohol accounts for 5～10%, the consumption of sodium bicarbonate accounts for 20～30%, surplus is tantalum powder, in volumn concentration; Under 50～100Mpa, being pressed into aperture is 0.56～0.72mm again, density 0.025g/cm
3, hardness 50
0～80
0polyurethane foam in molding, defat, vacuum-sintering, cooling and heat treatment make porous tantalum material; Described heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 240～480min with 10～20 ℃/min, then is chilled to 400 ℃, insulation 120～300min with 2～5 ℃/min, is then chilled to room temperature with stove.
6. preparation method as claimed in claim 5, is characterized in that: the mean diameter of described Ta powder is less than 43 microns, oxygen content and is less than 0.1%; Described mixed powder is preferably that polyvinyl alcohol accounts for 7～9%, sodium bicarbonate accounts for 26～29%, surplus is tantalum powder, in volumn concentration.
7. preparation method as claimed in claim 6, is characterized in that: described mixed powder is preferably that polyvinyl alcohol accounts for 8%, sodium bicarbonate accounts for 27%, surplus is tantalum powder, in volumn concentration.
8. the preparation method as described in claim 5,6 or 7, is characterized in that: the pressure adopting in described pressing process is preferably 70～80Mpa; Described heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 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.
9. preparation method as claimed in claim 8, is characterized in that: in described skimming processes, be preferably with the speed of 0.5 ℃/min～3 ℃/min and be progressively warming up to 400～800 ℃, pass into and form protective atmosphere and be incubated 60min～240min with argon;
Described vacuum-sintering condition includes: vacuum 10
-3pa, rises to 1200 ℃～1500 ℃ with the heating rate of 10～20 ℃/min from room temperature, after insulation 1h～2h; To be warming up to 2000～2200 ℃ lower than the heating rate of 20 ℃/min, be at least incubated 2h～4h again;
Cooling condition after described 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.
10. preparation method as claimed in claim 5, it is characterized in that: described ungrease treatment is: be progressively warming up to 600～800 ℃, specifically pass into formation protective atmosphere with pure argon gas (99.9999%), 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 ℃, insulation 180～240min from 400 ℃; Described vacuum-sintering is: the speed with 10～15 ℃/min rises to 1200～1250 ℃ from room temperature, insulation 30～60min, and vacuum is 10
-4pa～10
-3pa; Rise to 1500 ℃ with the speed of 10～20 ℃/min, insulation 30～60min, vacuum is 10
-4pa～10
-3pa, rises to 2000～2200 ℃ with the speed of 6～20 ℃/min, insulation 120～240min, and vacuum is 10
-4pa～10
-3pa; Being cooled to after vacuum-sintering: vacuum is 10
-4pa～10
-3pa; Be cooled to 1500～1600 ℃ with the speed of 10～20 ℃/min, insulation 30～60min; Be cooled to 1200～1250 ℃ with the speed of 12～20 ℃/min, insulation 60～90min; Be cooled to 800 ℃ with the speed of 10～20 ℃/min, then furnace cooling; Described vacuum annealing condition is: vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 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 * |
| 烧结温度对泡沫铌力学性能及微观组织的影响;节云峰等;《中国有色金属学报》;20101031;第20卷(第10期);第2014-2018页 * |
| 节云峰等.泡沫浸渍法制备的多孔铌基生物材料及性能.《稀有金属材料与工程》.2010,第39卷(第11期),第2014-2018页. |
| 节云峰等.烧结温度对泡沫铌力学性能及微观组织的影响.《中国有色金属学报》.2010,第20卷(第10期),第2015-2017页. |
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