CN104940991A - Medical porous tantalum material for replacing dentary and preparation method thereof - Google Patents

Medical porous tantalum material for replacing dentary and preparation method thereof Download PDF

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CN104940991A
CN104940991A CN201510415672.3A CN201510415672A CN104940991A CN 104940991 A CN104940991 A CN 104940991A CN 201510415672 A CN201510415672 A CN 201510415672A CN 104940991 A CN104940991 A CN 104940991A
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vacuum
powder
speed
insulation
porous tantalum
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CN104940991B (en
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叶雷
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Chongqing Runze Pharmaceutical Co Ltd
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朱启东
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    • 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
    • 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
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

Provided are a medical porous tantalum material for replacing a dentary and a preparation method thereof. The preparation method comprises the steps that tantalum powder, polyving akohol and sodium bicarbonate are mixed to be mixed powder, the mixed powder is pressed into an organic foam body, molding, degreasing, sintering, cooling and heat treating are conducted on the mixed power, and then the medical porous tantalum material for replacing the dentary is obtained; the pressure adopted for pressing molding ranges from 50 MPa to 100 MPa, the pore diameter of the formed medical porous tantalum material ranges from 30 micrometers to 50 micrometers, and the degree of porosity ranges from 30% to 38%. According to the porous tantalum preparation method, a pure physical mold pressing method is adopted, the content of impurities in the final porous tantalum material is extremely low, and the biological compatibility and the biological safety are effectively improved; according to testing, the content of the impurities can be lower than 0.2%, the density of the material can reach 10.34-11.67 g/cm<3>, the degree of porosity can reach 30-38%, the pore diameter can reach 30-50 micrometers, the elasticity modulus can reach 4.5-6.0 GPa, the bending strength can reach 120-130 MPa, and the compressive strength can reach 100-140 MPa. The porous tantalum material is a medical implant material which is very suitable for being used for replacing the dentary.

Description

Medical porous tantalum material of a kind of alternative dentale and preparation method thereof
The present patent application is the divisional application of application number 201110296545.8, the applying date on 09 29th, 2011, denomination of invention " medical porous tantalum material of a kind of alternative dentale and preparation method thereof ".
Technical field
The present invention relates to a kind of porous medical metal implanted material and preparation method thereof, particularly relate to medical embedded porous tantalum material of a kind of alternative compact bone tissue and preparation method thereof.
Background technology
Porous medical metal implanted material has the downright bad and alternative compact bone tissue for the treatment of osseous tissue wound, bone formation purposes as important and special in dentale etc., and showing common this kind of material has porous metals rustless steel, porous metals titanium etc.As the porous embedded material that osseous tissue wound and bone formation necrosis therapeutic use, its porosity should reach 30 ~ 80%, and hole is preferably all communicated with and is uniformly distributed, or make it both consistent with the bone growth of human body as required, alleviate again the weight of material itself, implant with applicable human body and 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, to tantalum going deep into further as body implanting material cognition, the demand of people to human body implantation porous metals tantalum material becomes more and more urgent, 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 being uniformly distributed interconnected pore and adapting with human body, then 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 main processing method with powder sintering like that substantially, especially obtain porosity communication and equally distributed porous metal foam structure adopt the dipping of the metal dust slurry in powder sintering on Organic Foam Material after drying reburn and tie that to be called for short foam impregnation method in the majority.About powder sintered obtained porous metal material usually its Metal Mechanic Property be not very well, its main cause how technique arranges the problem of subsiding in the support of pore-forming medium and elimination relation, metal powder sintered process.And all there is no good solution in known bibliographical information and let alone nature.
Adopt metal powder sintered legal system to make the bibliographical information of porous tantalum seldom, particularly almost do not have by the porous tantalum powder sintering bibliographical information obtained for the purpose of medical embedded material use.Can reference be publication number be CN200510032174, title " three-dimensional through hole or some perforations are connected with each other porous metal foam and preparation method thereof " and CN200710152394, title " a kind of porous foam tungsten and preparation method thereof ".But its porous metals obtained or for filtering material use, or share for Aero-Space and other high-temperature field but not use as medical metal implanted material, moreover the porous metals processed also non-porous tantalum.
About porous tantalum, US5282861 discloses and is a kind ofly applied to cancellous bone implants, the perforate tantalum material of biological cells and tissues sensor and preparation thereof.This porous tantalum is made up of pure business tantalum, it carries out carbon skeleton that thermal degradation obtains for support with polyurethane precursor, this carbon skeleton is multiple dodecahedron, it is mesh-like structure in it, entirety spreads all over micropore, porosity can up to 98%, then by commercially pure tantalum by the methods combining of chemical vapour deposition, infiltration to carbon skeleton to form porous metals micro structure, referred to as chemical deposition.The tantalum layer thickness on its surface of porous tantalum material that this method obtains is between 40 ~ 60 μm; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight then accounts for about 1%.Document is recorded further, 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, mechanical property such as ductility, comprcssive strength, the bending strength etc. of its material have obvious weak point, and the follow-up processing to porous tantalum material itself can be had influence on, the cutting etc. of such as profiled member.Also all there is such deficiency in the product obtained in aforesaid metal powder sintered method equally.
Summary of the invention
The object of the present invention is to provide a kind of medical porous tantalum material being applicable to alternative dentale of good biocompatibility.
Another object of the present invention is to the preparation method that above-mentioned porous tantalum medical material is provided.
The object of the invention is to be realized by following technological means:
A medical porous tantalum material for alternative dentale, is characterized in that: be mixed into mixed-powder by tantalum powder and polyvinyl alcohol, sodium bicarbonate, more repressed molding, defat, sintering, cooling and heat treatment are obtained; Described compressing be that described mixed-powder is pressed in Organic Foam Material, its pressure is 50 ~ 100Mpa, and the medical porous tantalum material pore diameter of formation is 30 ~ 50 μm, and porosity is between 30 ~ 38%.
In the R&D process of medical porous tantalum material, syntheti c route is numerous, but inventor creatively proposes the fine and close medical porous tantalum embedded material adopting above-mentioned processing step to prepare, through its impurity content of test can lower than 0.2%, its biocompatibility and biological safety good, density can reach 10.34 ~ 11.67g/cm 3, porosity can reach 30 ~ 38%, and pore diameter can reach 30 ~ 50 μm; Elastic modelling quantity can reach 4.5 ~ 6.0Gpa, bending strength can reach 120 ~ 130Mpa, comprcssive strength can reach 100 ~ 140Mpa, and porous tantalum of the present invention is suitable for the medical embedded material of alternative dentale very much.
The present invention adopt Ta powder mean diameter 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 the effect of pore-creating simultaneously, and above-mentioned sodium bicarbonate plays pore-creating.Vacuum environment of the present invention preferably adopts vacuum to be 10 -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, hardness 50 ° ~ 80 °) polyurethane foam in.
In R&D process, inventor studies discovery further, if control bad in above-mentioned preparation, though the medical embedded material that is suitable for alternative dentale as mentioned above can be obtained but conforming product rate is not high: as difficult in powder pressing forming, after pressing part easily there is layering, uneven, defat rear section there will be the technical problems such as crackle.
In order to make molding in powder compaction process easier, thus 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 directly calculated by the situation of final porous tantalum material in volumn concentration in volumn concentration, the quality weighing of its correspondence is calculated) in above-mentioned mixed-powder weighs or according to the densimeter of respective substance, 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, the part idiosome that is more stable, that reduce easily appearance of idiosome in skimming processes is out of shape, aperture is uneven, thus improve yield rate, quality stability further, above-mentioned skimming processes is progressively warming up to 400 ~ 800 DEG C with the speed of 0.5 DEG C/min ~ 3 DEG C/min, passes into formed protective atmosphere and be incubated 60min ~ 240min with argon; Preferably further progressively be warming up to 400 ~ 800 DEG C with the speed of 2.5 ~ 3 DEG C/min, pass into argon and formed protective atmosphere and be incubated 150min ~ 240min.
The preparation method of the medical porous tantalum material of above-mentioned alternative dentale, die pressing sintering is adopted 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; Again described mixed-powder is pressed under 50 ~ 100Mpa molding in Organic Foam Material, defat, vacuum-sintering, cooling and heat treatment and obtains porous tantalum material.
The mean diameter of above-mentioned raw materials tantalum powder is less than 43 microns, oxygen content 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, hardness 50 ° ~ 80 °) polyurethane foam in.
In order to make pressing pressure in compacting embryo process even, not stratified, thus make final porous tantalum distribution of pores evenly, quality is more stable, the pressure adopted in above-mentioned pressing process is preferably 70 ~ 80Mpa; Be preferably in above-mentioned skimming processes and be progressively warming up to 400 ~ 800 DEG C with the speed of 0.5 DEG C/min ~ 3 DEG C/min; pass into argon and formed protective atmosphere and be incubated 60min ~ 240min; preferably further progressively be warming up to 400 ~ 800 DEG C with the speed of 2.5 ~ 3 DEG C/min; pass into argon and formed protective atmosphere and be incubated 150min ~ 240min; further preferably progressively be warming up to 400 ~ 800 DEG C with the speed of 2.5 DEG C/min, pass into argon and formed protective atmosphere and be incubated 220min.
The present invention's further feature is on the other hand: be not less than 10 in vacuum -4~ 10 -3pa, temperature 2000 ~ 2200 DEG C, the temperature retention time vacuum-sintering process of 1 ~ 5 hour obtains porous sintered body.Filling with inert gas protection vacuum protection can be replaced during sintering process insulation; Finally carry out vacuum annealing process, wherein vacuum annealing process refers to that after vacuum-sintering, continue maintenance temperature is in 1000 ~ 1250 DEG C, and temperature retention time 1 ~ 4 hour, vacuum is not less than 10 -4~ 10 -3pa.
Vacuum-sintering condition also includes: vacuum is not less than 10 -3pa, rises to 1200 DEG C ~ 1500 DEG C with the heating rate of 10 ~ 20 DEG C/min from room temperature, after insulation 1h ~ 2h; Again to be warming up to 2000 ~ 2200 DEG C lower than the heating rate of 20 DEG C/min, be at least incubated 2h ~ 4h.
Cooling condition after vacuum-sintering also includes: vacuum is not less than 10 -3pa, with not higher than 25 DEG C/min, is not less than 10 DEG C/min and gradually falls cooldown rate mode, and to sintered porous bodies segmentation cooling down to 800 DEG C, each section of temperature retention time 30min ~ 90min, then cools to room temperature with the furnace.
Vacuum annealing condition also includes: vacuum is not less than 10 -4pa, rises to 1000 ~ 1250 DEG C with the speed not higher than 30 DEG C/min, insulation 4h ~ 6h; Again with after first slow fast be not less than 5 DEG C/min but not higher than the cooldown rate sub-sectional cooling of 30 DEG C/min to room temperature, the temperature retention time of each section tapers off and is no more than in 1.5h ~ 3h and selects.
Further feature is on this basis: described ungrease treatment condition also includes: be progressively warming up to 600 ~ 800 DEG C, specifically pass into formation protective atmosphere with pure argon gas (99.9999%), 400 DEG C are risen to from room temperature with the speed of 1 ~ 3 DEG C/min, insulation 60 ~ 120min, 600 ~ 800 DEG C are risen to from 400 DEG C, insulation 180 ~ 240min with the speed of 1.5 ~ 2.5 DEG C/min; Described vacuum-sintering condition also includes: rise to 1200 ~ 1250 DEG C with the speed of 10 ~ 15 DEG C/min from room temperature, and insulation 30 ~ 60min, vacuum is 10 -4pa ~ 10 -3pa; Rise to 1500 DEG C with the speed of 10 ~ 20 DEG C/min, insulation 30 ~ 60min, vacuum is 10 -4pa ~ 10 -3pa, rises to 2000 ~ 2200 DEG C with the speed of 6 ~ 20 DEG C/min, and insulation 120 ~ 240min, vacuum is 10 -4pa ~ 10 -3pa; Cooling condition after vacuum-sintering also includes: vacuum is 10 -4pa ~ 10 -3pa; 1500 ~ 1600 DEG C are cooled to, insulation 30 ~ 60min with the speed of 10 ~ 20 DEG C/min; 1200 ~ 1250 DEG C are cooled to, insulation 60 ~ 90min with the speed of 12 ~ 20 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 10 ~ 20 DEG C/min; Described vacuum annealing condition also includes: rise to 1000 ~ 1250 DEG C with the speed of 15 ~ 30 DEG C/min, and insulation 240 ~ 480min, vacuum is 10 -4pa ~ 10 -3pa, then be cooled to 1000 DEG C with the speed of 5 ~ 10 DEG C/min, insulation 90 ~ 180min, vacuum is 10 -4pa ~ 10 -3pa; Be cooled to 800 DEG C with the speed of 10 ~ 20 DEG C/min, insulation 60 ~ 120min, vacuum is 10 -4pa; Be cooled to room temperature with the speed of 20 ~ 30 DEG C/min, vacuum is 10 -4pa ~ 10 -3pa.
Porous tantalum preparation method of the present invention have employed pure physical abrasion method, makes the content of impurity in final porous tantalum material extremely low, effectively improves 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, make porous tantalum materials microstructure evenly, all be improved with the mechanical property such as intensity, the toughness that improve porous tantalum further simultaneously, preparation technology of the present invention makes that product qualified rate is high, administration measure, and conforming product rate can up to 95%.The porous tantalum finished product even pore distribution that the present invention obtains and being communicated with, good biocompatibility, through test its impurity content can lower than 0.2%, density can reach 10.34 ~ 11.67g/cm 3, porosity can reach 30 ~ 38%, and pore diameter can reach 30 ~ 50 μm; Elastic modelling quantity can reach 4.5 ~ 6.0Gpa, bending strength can reach 120 ~ 130Mpa, comprcssive strength can reach 100 ~ 140Mpa, and porous tantalum of the present invention is suitable for the medical embedded material of alternative dentale very much.
Detailed description of the invention
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that 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 according to the invention described above content to the present invention.
A kind of medical porous tantalum material of alternative dentale specifically selects that polyvinyl alcohol is forming agent, sodium bicarbonate is pore creating material, be less than 43 microns with mean diameter, the oxygen content tantalum powder that is less than 0.1% is mixed into mixed powder, under 50 ~ 100Mpa, mixed-powder is pressed into molding in Organic Foam Material, then obtains through defat, sintering, cooling and heat treatment.Formed porous tantalum after testing porosity between 30 ~ 38%, pore diameter 30 ~ 50 μm.
More particularly, above-mentioned porous tantalum is that the polyvinyl alcohol of 5 ~ 10% (in volumn concentrations), the sodium bicarbonate of 20 ~ 30% (in volumn concentrations) and the tantalum powder of surplus are mixed into mixed powder, puts it in injection moulding machine and is pressed into molding in polyurethane foam; Be placed in tungsten device again to put into the special atmosphere oven that pure argon gas (99.9999%) passes into formation and be progressively warming up to uniform temperature, and insulation carries out ungrease treatment to remove pore creating material, forming agent and polyurethane foam, wherein before intensification, first pass into argon to get rid of furnace air, the sample furnace cooling after defat; Sample after ungrease treatment is placed in fine vacuum high temperature sintering furnace with tungsten device and is progressively warming up to 2000 ~ 2200 DEG C; temperature retention time carries out vacuum-sintering in 1 ~ 5 hour; before heating up, the vacuum of sintering furnace at least will reach proper level; sample furnace cooling after vacuum-sintering; keep certain vacuum in cooling procedure or by certain cooldown rate sub-sectional cooling to keep uniform temperature in reasonable time, filling with inert gas can be adopted in insulating process as protective atmosphere.With corundum container, vacuum annealing furnace is placed in for the cooled sample of vacuum-sintering progressively heat up, be incubated and carry out stress relief annealing process; the vacuum that maintenance before heating up in annealing furnace is certain; sample furnace cooling after vacuum annealing process; also keep certain vacuum in cooling procedure or by certain cooldown rate sub-sectional cooling to keep uniform temperature in reasonable time; filling with inert gas can be adopted in insulating process as protective atmosphere, finally carry out conventional post processing and obtain porous tantalum.
For ungrease treatment, be placed in tungsten crucible to put into atmosphere furnace and heat up with certain heating rate, it first passed into argon or other noble gases to get rid of furnace air before intensification, temperature control process rises to certain temperature with suitable heating rate from room temperature, insulation, then heat up, be incubated.Vacuum-sintering process is carried out for the sample after ungrease treatment, it is placed in tungsten device the most high sintering temperature being warming up to tantalum with certain heating rate in fine vacuum high temperature sintering furnace carry out vacuum-sintering, before intensification, sintering furnace keeps certain vacuum, such as 1200 DEG C ~ 1250 DEG C are warming up to certain heating rate, insulation, keeps vacuum; Be warming up to such as 1250 DEG C ~ 1500 DEG C again with certain heating rate, insulation, then be warming up to the most high sintering temperature of such as tantalum with certain heating rate, insulation, keep vacuum; Sinter complete, keep vacuum, be cooled to such as 1500 DEG C ~ 1600 DEG C with certain rate of temperature fall, insulation, then be cooled to such as 1200 DEG C ~ 1250 DEG C with certain rate of temperature fall, insulation, also be cooled to such as 800 DEG C with certain rate of temperature fall, then furnace cooling.Vacuum annealing process is carried out for the cooled sample of vacuum-sintering, it is placed in vacuum annealing furnace with corundum container be warming up to such as 1000 DEG C ~ 1250 DEG C with certain heating rate and carry out stress relief annealing process, maintenance vacuum before heating up in annealing furnace, 1000 DEG C ~ 1250 DEG C are risen to from room temperature with certain heating rate, insulation, keeps vacuum; Such as 1000 DEG C are cooled to again, insulation with certain rate of temperature fall; Such as 800 DEG C are cooled to again, insulation with certain rate of temperature fall; Also with certain rate of temperature fall cooling room temperature.Finally carry out conventional post processing and obtain porous tantalum.
Inventor adopts metal powder sintered method mainly based on physical abrasion method, has done a large amount of theory analysises and experimental verification, obtain porous tantalum product through its impurity content of test can lower than 0.2%, density can reach 10.34 ~ 11.67g/cm 3, porosity can reach 30 ~ 38%, and pore diameter can reach 30 ~ 50 μm; Elastic modelling quantity can reach 4.5 ~ 6.0Gpa, bending strength can reach 120 ~ 130Mpa, comprcssive strength can reach 100 ~ 140Mpa.
Embodiment 1: weighing polyvinyl alcohol, mean diameter be less than 43 microns of oxygen contents be less than 0.1% tantalum powder and sodium bicarbonate be mixed into mixed-powder, wherein polyvinyl alcohol accounts for 8%, sodium bicarbonate accounts for 27%, tantalum powder accounts for 65%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is pressed into polyurethane foam (aperture 0.48 ~ 0.89mm, density 0.015g/cm in injection moulding machine under 80Mpa 3~ 0.035g/cm 3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10 -4pa, with the heating rate of 2.5 DEG C/min from room temperature to 400 DEG C, insulation 100min; 700 DEG C are warming up to from 400 DEG C again, temperature retention time 220 minutes with the heating rate of 2 DEG C/min.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 2000 DEG C, is incubated 2 hours, vacuum 10 -4pa, sintering process applying argon gas is protected, and removes surface dirt and dirt after taking out product, and obtained sample 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 10.84g/cm 3, porosity 35%, pore mean diameters 30 μm, elastic modelling quantity 5.5GPa, bending strength 130MPa, comprcssive strength 140MPa.
Embodiment 2: weighing polyvinyl alcohol, mean diameter be less than 43 microns of oxygen contents be less than 0.1% tantalum powder and sodium bicarbonate be mixed into mixed-powder, wherein polyvinyl alcohol accounts for 6%, sodium bicarbonate accounts for 29%, tantalum powder accounts for 65%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine that to be pressed into aperture under 70Mpa be 0.56 ~ 0.72mm, density 0.025g/cm 3, molding in the polyurethane foam that hardness is 50 ° ~ 80 °.Ungrease treatment: vacuum 10 -4pa, with the heating rate of 1 DEG C/min from room temperature to 400 DEG C, insulation 60min; 800 DEG C are warming up to from 400 DEG C again, temperature retention time 180 minutes with the heating rate of 2.5 DEG C/min.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 2100 DEG C, is incubated 4 hours, vacuum 10 -4pa, sintering process applying argon gas is protected, and removes surface dirt and dirt after taking out product, and obtained sample 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 10.34g/cm 3, porosity 38%, pore mean diameters 32 μm, elastic modelling quantity 4.5GPa, bending strength 123MPa, comprcssive strength 110MPa.
Embodiment 3: weighing polyvinyl alcohol, mean diameter be less than 43 microns of oxygen contents be less than 0.1% tantalum powder and sodium bicarbonate be mixed into mixed-powder, wherein polyvinyl alcohol accounts for 10%, sodium bicarbonate accounts for 23%, tantalum powder accounts for 67%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine that to be pressed into aperture under 52Mpa be 0.56 ~ 0.72mm, density 0.025g/cm 3, molding in the polyurethane foam that hardness is 50 ° ~ 80 °.Ungrease treatment: vacuum 10 -4pa, with the heating rate of 3 DEG C/min from room temperature to 400 DEG C, insulation 120min; 750 DEG C are warming up to from 400 DEG C again, temperature retention time 240 minutes with the heating rate of 1.5 DEG C/min.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 2200 DEG C, is incubated 2.5 hours, vacuum 10 -3pa, sintering process applying argon gas is protected, and cooling is come out of the stove, and removes product surface dust and dirt, and obtained sample 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 10.67g/cm 3, porosity 36%, pore mean diameters 34 μm, elastic modelling quantity 6.0GPa, bending strength 128MPa, comprcssive strength 100MPa.
Embodiment 4: weighing polyvinyl alcohol, mean diameter be less than 43 microns of oxygen contents be less than 0.1% tantalum powder and sodium bicarbonate be mixed into mixed-powder, wherein polyvinyl alcohol accounts for 5%, sodium bicarbonate accounts for 30%, tantalum powder accounts for 65%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine that to be pressed into aperture under 96Mpa be 0.56 ~ 0.72mm, density 0.025g/cm 3, molding in the polyurethane foam that hardness is 50 ° ~ 80 °.Ungrease treatment: vacuum 10 -4pa, with the heating rate of 2 DEG C/min from room temperature to 400 DEG C, insulation 80min; 800 DEG C are warming up to from 400 DEG C again, temperature retention time 190 minutes with the heating rate of 1.5 DEG C/min.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 2150 DEG C, is incubated 2 hours, vacuum 10 -4pa, sintering process applying argon gas is protected, and cooling is come out of the stove, and removes product surface dust and dirt, and obtained sample 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 11.17g/cm 3, porosity 33%, pore mean diameters 40 μm, elastic modelling quantity 4.5GPa, bending strength 120MPa, comprcssive strength 135MPa.
Embodiment 5: a kind of porous tantalum, it is less than 43 μm, the oxygen content ta powder that is less than 0.1% with particle diameter, and polyvinyl alcohol and sodium bicarbonate mixed powder are raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing are obtained.
Wherein, polyvinyl alcohol accounts for 7%, sodium bicarbonate accounts for 20%, ta powder accounts for 73%, in volumn concentration;
Compressing: raw material mixed-powder to be added in injection moulding machine that under 65Mpa, be pressed into aperture be 0.56 ~ 0.72mm, density 0.025g/cm 3, molding in the polyurethane foam that hardness is 50 ° ~ 80 °;
Ungrease treatment: under inert gas shielding atmosphere or vacuum 10 -4~ 10 -3pa, is warming up to 400 DEG C ~ 800 DEG C with 2.5 ~ 3 DEG C/min, is that protective atmosphere, temperature retention time 150 ~ 240 minutes are with removing polyvinyl alcohol wherein and sodium bicarbonate with argon;
Vacuum-sintering: low vacuum is in 10 -4pa ~ 10 -3pa, temperature 2000 ~ 2200 DEG C, temperature retention time 1 ~ 5 hour, applying argon gas or other inert gas shieldings during sintering process insulation, to obtain porous material;
Vacuum annealing: continue to keep temperature to be in 1000 ~ 1250 DEG C, temperature retention time 1 ~ 4 hour after vacuum-sintering, vacuum is 10 -4~ 10 -3pa, to carry out stress relief annealing process; Obtained sample 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 10.34g/cm 3, porosity 38%, pore mean diameters 39 μm, elastic modelling quantity 4.9GPa, bending strength 122MPa, comprcssive strength 134MPa.
Embodiment 6: a kind of porous tantalum, it is less than 43 μm, the oxygen content ta powder that is less than 0.1% with particle diameter, and polyvinyl alcohol and sodium bicarbonate mixed powder are raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing are obtained.
Wherein, polyvinyl alcohol accounts for 7%, sodium bicarbonate accounts for 20%, ta powder accounts for 73%, in volumn concentration;
Compressing: raw material mixed-powder to be added in injection moulding machine that under 65Mpa, be pressed into aperture be 0.56 ~ 0.72mm, density 0.025g/cm 3, molding in the polyurethane foam that hardness is 50 ° ~ 80 °;
After compressing, mixed-powder is put into nonoxidizing atmosphere stove and be warming up to 800 DEG C with certain heating rate, protective atmosphere is that 99.999% argon carries out ungrease treatment, its intensification before first pass into pure argon gas at least 30min to get rid of furnace air, temperature control process: rise to 400 DEG C from room temperature with the speed of 1.5 DEG C/min, insulation 88min, argon intake 0.5L/min; 800 DEG C are risen to from 400 DEG C, insulation 195min, argon intake 1L/min with the speed of 2.0 DEG C/min; Powered-down again, the sample furnace cooling after defat, argon intake 1L/min, until close argon when being cooled to room temperature;
To be placed in tungsten device for the sample after ungrease treatment and to be warming up to 2200 DEG C with certain heating rate in fine vacuum high temperature sintering furnace and to carry out vacuum-sintering, before heating up, the vacuum of sintering furnace at least will reach 10 -4pa, rises to 1200 DEG C with the speed of 10 ~ 15 DEG C/min from room temperature, and insulation 30min, vacuum is 10 -4pa; Rise to 1500 DEG C with the speed of 10 DEG C/min, insulation 30min, vacuum is 10 -4pa ~ 10 -3pa; Rise to 2200 DEG C with the speed of 6 DEG C/min, insulation 120min, vacuum is 10 -3pa; Sinter complete, vacuum is 10 -3pa, is cooled to 1600 DEG C with the speed of 10 ~ 15 DEG C/min, insulation 30min; 1200 DEG C are cooled to, insulation 60min with the speed of 12 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 10 DEG C/min;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with corundum container to be warming up to 1250 DEG C with certain heating rate and to carry out stress relief annealing process, the vacuum before heating up in annealing furnace at least will reach 10 -4pa, rises to 1250 DEG C with the speed of 15 DEG C/min from room temperature, and insulation 240min, vacuum is 10 -4pa ~ 10 -3pa; Be cooled to 1000 DEG C with the speed of 5 DEG C/min again, insulation 180min, vacuum is 10 -4pa ~ 10 -3pa; Be cooled to 800 DEG C with the speed of 10 DEG C/min, insulation 120min, vacuum is 10 -4pa; Be cooled to room temperature with the speed of 20 DEG C/min, vacuum is 10 -4pa.Finally carry out conventional post processing and obtain porous tantalum.
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 11.67g/cm 3, porosity 30%, pore mean diameters 50 μm, elastic modelling quantity 5.8GPa, bending strength 127MPa, comprcssive strength 133MPa.This preparation technology's conforming product rate is up to 93.4%.
In the method that above-described embodiment 6 provides, we can also do other selections to wherein each kind of condition can obtain porous tantalum of the present invention equally.
Gained porous tantalum finished product is pressed preceding method and is detected:
Embodiment 7 8 9 10 11 12 13
Density (g/cm 3) 11.34 10.34 10.67 11.67 11.17 11.0 10.50
Porosity (%) 32 38 36 30 33 34 37
Aperture (μm) 44 50 48 35 37 30 40
Elastic modelling quantity (GPa) 4.7 4.3 4.9 5.8 5.5 6.0 5.2
Bending strength (MPa) 120 122 125 128 124 130 121
Comprcssive strength (MPa) 123 100 115 118 128 140 135

Claims (4)

1. the medical porous tantalum material of an alternative dentale, die pressing sintering is adopted to form, it is characterized in that: 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, be pressed into aperture is again 0.56 ~ 0.72mm, density 0.025g/cm 3, hardness 50 0~ 80 0polyurethane foam in molding, defat, vacuum-sintering, cooling and heat treatment obtain porous tantalum material;
Described ungrease treatment condition is: be progressively warming up to 600 ~ 800 DEG C, specifically pass into formation protective atmosphere with 99.9999% pure argon gas, 400 DEG C are risen to from room temperature with the speed of 1 ~ 3 DEG C/min, insulation 60 ~ 120min, 600 ~ 800 DEG C are risen to from 400 DEG C, insulation 180 ~ 240min with the speed of 1.5 ~ 2.5 DEG C/min;
Described vacuum-sintering condition is: rise to 1200 ~ 1250 DEG C with the speed of 10 ~ 15 DEG C/min from room temperature, and insulation 30 ~ 60min, vacuum is 10 -4pa ~ 10 -3pa; Rise to 1500 DEG C with the speed of 10 ~ 20 DEG C/min, insulation 30 ~ 60min, vacuum is 10 -4pa ~ 10 -3pa, rises to 2000 ~ 2200 DEG C with the speed of 6 ~ 20 DEG C/min, and insulation 120 ~ 240min, vacuum is 10 -4pa ~ 10 -3pa;
Cooling condition after vacuum-sintering is: vacuum is 10 -4pa ~ 10 -3pa; 1500 ~ 1600 DEG C are cooled to, insulation 30 ~ 60min with the speed of 10 ~ 20 DEG C/min; 1200 ~ 1250 DEG C are cooled to, insulation 60 ~ 90min with the speed of 12 ~ 20 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 10 ~ 20 DEG C/min;
Described vacuum annealing condition is: rise to 1000 ~ 1250 DEG C with the speed of 15 ~ 30 DEG C/min, and insulation 240 ~ 480min, vacuum is 10 -4pa ~ 10 -3pa, then be cooled to 1000 DEG C with the speed of 5 ~ 10 DEG C/min, insulation 90 ~ 180min, vacuum is 10 -4pa ~ 10 -3pa; Be cooled to 800 DEG C with the speed of 10 ~ 20 DEG C/min, insulation 60 ~ 120min, vacuum is 10 -4pa; Be cooled to room temperature with the speed of 20 ~ 30 DEG C/min, vacuum is 10 -4pa ~ 10 -3pa.
2. the as claimed in claim 1 medical porous tantalum material substituting dentale, is characterized in that: in described mixed-powder, polyvinyl alcohol accounts for 7 ~ 9%, sodium bicarbonate accounts for 26 ~ 29%, surplus is tantalum powder, in volumn concentration; Pressure in described compressing process is 70 ~ 80Mpa.
3. the as claimed in claim 1 medical porous tantalum material substituting dentale, is characterized in that: the mean diameter of described Ta powder is less than 43 microns, oxygen content is less than 0.1%; Described mixed powder is that polyvinyl alcohol accounts for 7 ~ 9%, sodium bicarbonate accounts for 26 ~ 29%, surplus is tantalum powder, in volumn concentration.
4. the medical porous tantalum material of the alternative dentale as described in claim 1,2 or 3, is characterized in that: described mixed powder is that polyvinyl alcohol accounts for 8%, sodium bicarbonate accounts for 27%, surplus is tantalum powder, in volumn concentration.
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