CN102796892B - Preparation method for medical porous metal material for replacing dentale - Google Patents

Preparation method for medical porous metal material for replacing dentale Download PDF

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CN102796892B
CN102796892B CN2011102958416A CN201110295841A CN102796892B CN 102796892 B CN102796892 B CN 102796892B CN 2011102958416 A CN2011102958416 A CN 2011102958416A CN 201110295841 A CN201110295841 A CN 201110295841A CN 102796892 B CN102796892 B CN 102796892B
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CN102796892A (en
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叶雷
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Chongqing Runze Pharmaceutical Co Ltd
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Chongqing Runze Pharmaceutical Co Ltd
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    • 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
    • B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • 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)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a preparation method for a medical porous metal material for replacing dentale. The preparation method comprises the following steps of: mixing tantalum powder, a pore forming agent, and a forming agent to obtain mixed powder; pressing the powder into an organic foam and forming; degreasing; sintering; and cooling; and performing thermal treatment to obtain a porous tantalum material, wherein the pressure adopted in the pressing and forming step is 50 to 100 MPa, the pore forming agent is one or more of combination of urea, sodium chloride, ethyecellulose, and methylcellulose, and the forming agent is one or more of combination of stearic acid, zinc stearate, paraffins and synthetic rubber. By the preparation method, the test proves that the impurity content of the final porous tantalum material is less than 0.2 percent, the density can reach 11.67 to 13.34 g/cm<3>, the porosity can reach 20 to 30 percent, the pore diameter can reach 5 to 30 mu m, the elastic modulus can reach 4.5 to 6.0 GPa, the bending strength can reach 110 to 130 MPa, and the compressive strength can reach 100 to 130 MPa. The porous tantalum is suitable to be used for a metal implant material for replacing the dentale.

Description

A kind of dentale substitutes the preparation method of medical porous metal material
Technical field
The present invention relates to a kind of preparation method of medical porous metal implant material, particularly relate to a kind of preparation method of medical embedded porous metal material of alternative compact bone tissue.
Background technology
The porous medical metal implanted material has treatment osseous tissue wound, bone formation necrosis and alternative compact bone tissue as important and special purposes such as dentales, and existing this common class material has porous metals rustless steel, porous metals titanium etc.Porous embedded material as osseous tissue wound and the use of bone formation necrosis therapeutic, its porosity should reach 30～80%, and hole preferably all is communicated with and is uniformly distributed, or make it as required both consistent with the bone growth of human body, alleviate again the weight of material itself, to be applicable to human body, implanted use.
And refractory metals tantalum/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 the body implanting material cognition to tantalum/niobium, people implant and become more and more urgent by the demand of porous metals tantalum/niobium material human body, 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 to take powder sintering as main processing method like that basically, in particular for obtain porosity communication and equally distributed porous metal foam structure adopt after the dipping of metal dust slurry on Organic Foam Material in powder sintering drying to reburn to be called for short the foam impregnation method in the majority for knot.About powder sintered obtained porous metal material usually its Metal Mechanic Property be not fine, its main cause is the problem of subsiding how arranged on technique 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 laissez-faire nature.
Adopt bibliographical information that metal powder sintered legal system makes porous tantalum/niobium seldom, particularly take and obtain medical embedded material and almost do not have with the porous tantalum/niobium powder sintering process bibliographical information that is purpose.Can reference be that publication number is CN200510032174, title " three-dimensional through hole or part hole 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 ".Yet porous metals that it obtains or for filtering material use, or share for Aero-Space and other high-temperature field but not use as medical metal implanted material, moreover also non-porous tantalum/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 by pure business tantalum, it take the polyurethane precursor, and to carry out the carbon skeleton that thermal degradation obtains be support, this carbon skeleton is multiple dodecahedron, it in it, is the mesh-like structure, integral body spreads all over micropore, porosity can be up to 98%, then the method by chemical vapour deposition, infiltration is attached on carbon skeleton to form the porous metals micro structure, referred to as chemical deposition by the commercially pure tantalum.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtains is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight accounts for 1% left and right.Document is further put down in writing, 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 the compact bone tissue porous tantalum as medical embedded materials such as dentales, the mechanical property of its material has obvious weak point as ductility, comprcssive strength, bending strength etc., and can have influence on the follow-up processing to porous tantalum material itself, such as cutting of profiled member etc.Also all there is such deficiency in the same product obtained in aforesaid metal powder sintered method.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the alternative medical porous metal material of dentale of good biocompatibility.
The objective of the invention is to realize by following technological means:
A kind of preparation method of medical porous metal material of alternative dentale is characterized in that: be mixed into mixed-powder with tantalum powder and pore creating material, forming agent, more repressed molding, defat, sintering, cooling and heat treatment make the porous tantalum material; Described compressing be that described mixed-powder is pressed in Organic Foam Material, its pressure is 50～100Mpa, described pore creating material is one or more combination in any in carbamide, sodium chloride, ethyl cellulose, methylcellulose, and described forming agent is one or more combination in any in stearic acid, zinc stearate, paraffin, synthetic rubber.
In the R&D process of medical porous tantalum material, syntheti c route is numerous, but the inventor has creatively proposed the medical porous tantalum embedded material that adopts above-mentioned processing step to prepare, through its impurity content of test can be lower than 0.2%, its biocompatibility and biological safety good, density reachable 11.67～13.34g/cm 3, porosity can reach 20～30%, and pore diameter can reach 5～30 μ m; Elastic modelling quantity can reach that 4.5～6.0Gpa, bending strength can reach 110～130Mpa, comprcssive strength can reach 100～130Mpa, 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 pore creating material, forming agent also are commercially available prod.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, aperture 0.48～0.89mm more preferably, 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, the inventor further studies discovery, if control bad in above-mentioned preparation, though can make and be suitable for as mentioned above substituting the medical embedded material of dentale but conforming product rate is not high, production stability is bad: as difficult as powder pressing forming, in the compacting rear section, be prone to layering, inhomogeneous, the defat rear section there will be the technical problems such as crackle.
In order to make in powder compaction process molding easier, thereby raising yield rate, finished product hole uniformity, make preparation process more stable, in above-mentioned mixed-powder, the consumption of forming agent is 5～10%, above-mentioned pore creating material consumption is 20～30%, surplus is the tantalum powder, in volumn concentration, (in volumn concentration, be the unit of directly calculating by the situation of final porous tantalum material, calculate its corresponding quality weighing in the above-mentioned mixed-powder weighing or according to the densimeter of respective substance), more preferably above-mentioned forming agent accounts for 5～6.5%, above-mentioned pore creating material accounts for 21～24%, surplus is the tantalum powder, pressure in above-mentioned compressing process is preferably 55～65Mpa, further be preferably that above-mentioned forming agent accounts for 6%, above-mentioned pore creating material accounts for 23%, surplus is the tantalum powder, in volumn concentration.
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 that the speed with 2 ℃/min～3.5 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 100min～240min; Further preferably with the speed of 3～3.5 ℃/min, progressively be warming up to 400～800 ℃, with argon, pass into and form protective atmosphere and be incubated 150min～200min.
Further preferably with the speed of 3 ℃/min, progressively be warming up to 400～800 ℃, with argon, pass into and form protective atmosphere and be incubated 170min.
The present invention's further characteristics on the other hand are: in vacuum, be not less than 10 -4～10 -3pa, 2000～2200 ℃ of temperature, the temperature retention time vacuum-sintering of 1～5 hour is processed and is made porous sintered body.Can the filling with inert gas protection replace vacuum protection during the sintering process insulation; Finally carry out the vacuum annealing processing, wherein vacuum annealing is processed and is referred to that continuation keeps temperature in 1000～1250 ℃ after vacuum-sintering, temperature retention time 1～4 hour, and vacuum is not less than 10 -4～10 -3pa.
The vacuum-sintering condition also includes: vacuum is not less than 10 -3pa, rise to 1200 ℃～1500 ℃ with the heating rate of 10～20 ℃/min from room temperature, after insulation 1h～2h; Be warming up to 2000～2200 ℃ with the heating rate lower than 20 ℃/min again, at least be incubated 2h～4h.
Cooling condition after vacuum-sintering also includes: vacuum is not less than 10 -3pa, with not higher than 25 ℃/min, be not less than 10 ℃/min and gradually fall the cooldown rate mode, and to sintered porous bodies segmentation cooling down to 800 ℃, each section temperature retention time 30min～90min, then cool to room temperature with the furnace.
The vacuum annealing condition also includes: vacuum is not less than 10 -4pa, rise to 1000～1250 ℃ with the speed higher than 30 ℃/min not, insulation 4h～6h; After first slow, to be not less than 5 ℃/min but higher than the cooldown rate segmentation of 30 ℃/min, not to be cooled to room temperature soon, the temperature retention time of each section tapers off and is no more than in 1.5h～3h and selects again.
Further characteristics are on this basis: described ungrease treatment condition also includes: progressively be warming up to 600～800 ℃, specifically with pure argon gas (99.9999%), pass into the formation protective atmosphere, speed with 1～2 ℃/min rises to 400 ℃ from room temperature, insulation 100～120min, rise to 600～800 ℃ with the speed of 2～3 ℃/min from 400 ℃, be incubated 200～240min; Described vacuum-sintering condition also includes: the speed with 10～15 ℃/min rises to 1200～1250 ℃ from room temperature, is incubated 30～60min, and vacuum is 10 -4pa～10 -3pa; Speed with 10～20 ℃/min rises to 1500 ℃, is incubated 30～60min, and vacuum is 10 -4pa～10 -3pa, rise to 2000～2200 ℃ with the speed of 6～20 ℃/min, is incubated 120～240min, and vacuum is 10 -4pa～10 -3pa; Cooling condition after vacuum-sintering also includes: vacuum is 10 -4pa～10 -3pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, is incubated 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, is incubated 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Described vacuum annealing condition also includes: the speed with 15～30 ℃/min rises to 1000～1250 ℃, is incubated 240～480min, and vacuum is 10 -4pa～10 -3pa, then be cooled to 1000 ℃ with the speed of 5～10 ℃/min, being incubated 90～180min, vacuum is 10 -4pa～10 -3pa; Speed with 10～20 ℃/min is cooled to 800 ℃, is incubated 60～120min, and vacuum is 10 -4pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum is 10 -4pa～10 -3pa.
The character of metal tantalum and niobium is extremely similar, and said method equally also is 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 eliminated thermal stress, made organizing of porous tantalum material more even, with the mechanical property that further improves porous tantalum, as intensity, toughness, all be improved 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 11.67～13.34g/cm 3, porosity can reach 20～30%, and pore diameter can reach 5～30 μ m; Elastic modelling quantity can reach that 4.5～6.0Gpa, bending strength can reach 110～130Mpa, comprcssive strength can reach 100～130Mpa, 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 only are used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in art can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
A kind of preparation method of medical porous metal material of alternative dentale, to select forming agent, (described forming agent is stearic acid to pore creating material, zinc stearate, paraffin, one or more combination in any in synthetic rubber, described pore creating material is carbamide, sodium chloride, ethyl cellulose, one or more combination in any in methylcellulose) be less than 43 microns with mean diameter, oxygen content is less than 0.1% tantalum powder and is mixed into mixed powder, molding under 50～100Mpa, mixed-powder being pressed into to Organic Foam Material, again through defat, sintering, the cooling porous tantalum material that obtains with heat treatment.The porous tantalum formed after testing porosity between 20～30%, pore diameter 5～30 μ m.
More particularly, above-mentioned porous tantalum is that the above-mentioned pore creating material of the above-mentioned forming agent, 20～30% (in volumn concentration) of 5～10% (in volumn concentrations) and the tantalum powder of surplus are mixed into to mixed powder, puts it in injection moulding machine and is pressed into molding in polyurethane foam; Being placed in the tungsten device puts into the special atmosphere oven that pure argon gas (99.9999%) passes into formation and progressively is warming up to uniform temperature again, and insulation is carried out ungrease treatment to remove pore creating material, forming agent and polyurethane foam, wherein before heating up, first pass into argon to get rid of furnace air, the sample furnace cooling after defat; Be placed in the fine vacuum high temperature sintering furnace and progressively be warming up to 2000～2200 ℃ with the tungsten device for the sample after ungrease treatment; temperature retention time is carried 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 or cooling to keep uniform temperature in reasonable time by certain cooldown rate segmentation in cooling procedure, in insulating process, can adopt filling with inert gas as protective atmosphere.Being placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with the corundum container progressively heats up, is incubated and carry out the stress relief annealing processing; the certain vacuum of maintenance before heating up in annealing furnace; sample furnace cooling after vacuum annealing is processed; also keep certain vacuum or cooling to keep uniform temperature in reasonable time by certain cooldown rate segmentation in cooling procedure; in insulating process, can adopt filling with inert gas as protective atmosphere, finally carry out conventional post processing and make porous tantalum.
For ungrease treatment, be to be placed in the tungsten device 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 heating up, and the temperature control process is to rise to certain temperature with suitable heating rate from room temperature, insulation, then heat up, be incubated.Carry out the vacuum-sintering processing for the sample after ungrease treatment, it to be placed in the fine vacuum high temperature sintering furnace to the highest sintering temperature that is warming up to tantalum with certain heating rate with the tungsten device carry out vacuum-sintering, before heating up, sintering furnace keeps certain vacuum, be warming up to for example 1200 ℃～1250 ℃ with certain heating rate, insulation, keep vacuum; Be warming up to again for example 1250 ℃～1500 ℃ with certain heating rate, insulation, then be warming up to for example the highest sintering temperature of tantalum with certain heating rate, insulation, maintenance vacuum; Sintering is complete, keeps vacuum, with certain rate of temperature fall, is cooled to for example 1500 ℃～1600 ℃, insulation, then be cooled to for example 1200 ℃～1250 ℃ with certain rate of temperature fall, insulation, also with certain rate of temperature fall, be cooled to for example 800 ℃, then furnace cooling.Carry out the vacuum annealing processing for the cooled sample of vacuum-sintering, it to be placed in to vacuum annealing furnace with the corundum container be warming up to for example 1000 ℃～1250 ℃ with certain heating rate and carry out the stress relief annealing processing, maintenance vacuum before heating up in annealing furnace, rise to 1000 ℃～1250 ℃ with certain heating rate from room temperature, insulation, keep vacuum; Be cooled to for example 1000 ℃ with certain rate of temperature fall again, insulation; Be cooled to for example 800 ℃ with certain rate of temperature fall again, insulation; Also with the cooling room temperature of certain rate of temperature fall.Finally carry out conventional post processing and make porous tantalum.
The inventor adopts metal powder sintered method mainly to take the physics die pressing as main, has done a large amount of theory analysises and experimental verification, obtain the porous tantalum product through its impurity content of test can be lower than 0.2%, density reachable 11.67～13.34g/cm 3, porosity can reach 20～30%, and pore diameter can reach 5～30 μ m; Elastic modelling quantity can reach that 4.5～6.0Gpa, bending strength can reach 110～130Mpa, comprcssive strength can reach 100～130Mpa.
Embodiment 1: take zinc stearate, mean diameter and be less than 43 microns oxygen contents and be less than 0.1% tantalum powder and methylcellulose and be mixed into mixed-powder, wherein zinc stearate accounts for 6%, methylcellulose accounts for 23%, the tantalum powder accounts for 71%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm under 62Mpa 3～0.035g/cm 3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10 -4pa, be warming up to 400 ℃, insulation 110min with the heating rate of 1.5 ℃/min from room temperature; Heating rate with 2.5 ℃/min is warming up to 700 ℃, temperature retention time 210 minutes from 400 ℃ again.Vacuum-sintering: sintering in vacuum drying oven, 2000 ℃ of sintering temperatures, be incubated 2 hours, vacuum 10 -4pa, the protection of sintering process applying argon gas, remove surface dirt and dirt after the taking-up product, and the sample made carries out conventional post processing again and obtains the porous tantalum finished product.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous tantalum finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 12.67g/cm 3, porosity 24%, hole average diameter 16 μ m, elastic modelling quantity 6.0GPa, bending strength 130MPa, comprcssive strength 130MPa.
Embodiment 2: take paraffin, mean diameter and be less than 43 microns oxygen contents and be less than 0.1% niobium powder and carbamide and be mixed into mixed-powder, wherein paraffin accounts for 5%, ethyl cellulose accounts for 30%, the niobium powder accounts for 65%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine to be pressed into aperture under 65Mpa 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, be warming up to 400 ℃, insulation 100min with the heating rate of 2 ℃/min from room temperature; Heating rate with 3 ℃/min is warming up to 800 ℃, temperature retention time 200 minutes from 400 ℃ again.Vacuum-sintering: sintering in vacuum drying oven, 2100 ℃ of sintering temperatures, be incubated 4 hours, vacuum 10 -4pa, the protection of sintering process applying argon gas, remove surface dirt and dirt after the taking-up product, and the sample made carries out conventional post processing again and obtains the porous niobium finished product.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous niobium finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 6.00g/cm 3, porosity 30%, hole average diameter 28 μ m, elastic modelling quantity 2.0GPa, bending strength 73MPa, comprcssive strength 82MPa.
Embodiment 3: take stearic acid, mean diameter and be less than 43 microns oxygen contents and be less than 0.1% tantalum powder and ammonium bicarbonate and be mixed into mixed-powder, wherein stearic acid accounts for 10%, sodium chloride accounts for 20%, the tantalum powder accounts for 70%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine to be pressed into aperture under 97Mpa 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, be warming up to 400 ℃, insulation 120min with the heating rate of 1 ℃/min from room temperature; Heating rate with 2 ℃/min is warming up to 750 ℃, temperature retention time 240 minutes from 400 ℃ again.Vacuum-sintering: sintering in vacuum drying oven, 2200 ℃ of sintering temperatures, be incubated 2.5 hours, vacuum 10 -3pa, the protection of sintering process applying argon gas, cooling coming out of the stove, remove product surface dust and dirt, and the sample made carries out conventional post processing again and obtains the porous tantalum finished product.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous tantalum finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 13.37g/cm 3, porosity 20%, hole average diameter 27 μ m, elastic modelling quantity 4.8GPa, bending strength 128MPa, comprcssive strength 120MPa.
Embodiment 4: take paraffin and zinc stearate, mean diameter and be less than 43 microns oxygen contents and be less than 0.1% tantalum powder and sodium chloride and be mixed into mixed-powder, wherein paraffin and zinc stearate (wherein paraffin and zinc stearate mass ratio are 1: 2.5) account for 5%, sodium chloride accounts for 28%, the tantalum powder accounts for 67%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine to be pressed into aperture under 57Mpa 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, be warming up to 400 ℃, insulation 105min with the heating rate of 1.5 ℃/min from room temperature; Heating rate with 2.2 ℃/min is warming up to 800 ℃, temperature retention time 225 minutes from 400 ℃ again.Vacuum-sintering: sintering in vacuum drying oven, 2150 ℃ of sintering temperatures, be incubated 2 hours, vacuum 10 -4pa, the protection of sintering process applying argon gas, cooling coming out of the stove, remove product surface dust and dirt, and the sample made carries out conventional post processing again and obtains the porous tantalum finished product.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous tantalum finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 12.84g/cm 3, porosity 23%, hole average diameter 26 μ m, elastic modelling quantity 5.0GPa, bending strength 120MPa, comprcssive strength 125MPa.
Embodiment 5: a kind of porous tantalum, and it is less than with particle diameter the ta powder that 43 μ m, oxygen content are less than 0.1%, and stearic acid and ethyl cellulose mixed powder are raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, stearic acid accounts for 7%, ethyl cellulose accounts for 20%, ta powder accounts for 73%, in volumn concentration;
Compressing: as the raw material mixed-powder to be added in injection moulding machine to be pressed into aperture under 55Mpa 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, be warming up to 400 ℃～800 ℃ with 1～2/min, take argon as protective atmosphere, temperature retention time 100～120 minutes to remove stearic acid and ethyl cellulose wherein;
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 during the sintering process insulation, to obtain porous material;
Vacuum annealing: after vacuum-sintering, continue to keep temperature in 1000～1250 ℃, temperature retention time 1～4 hour, vacuum is 10 -4～10 -3pa, to carry out the stress relief annealing processing; The sample made carries out conventional post processing again and obtains the porous tantalum finished product.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous tantalum finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 12.00g/cm 3, porosity 28%, hole average diameter 19 μ m, elastic modelling quantity 5.56Pa, bending strength 122MPa, comprcssive strength 124MPa.
Embodiment 6: a kind of porous tantalum, and it is less than with particle diameter the ta powder that 43 μ m, oxygen content are less than 0.1%, and stearic acid and sodium chloride mixed powder are raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, stearic acid accounts for 10%, carbamide accounts for 30%, ta powder accounts for 60%, in volumn concentration;
Compressing: as the raw material mixed-powder to be added in injection moulding machine to be pressed into aperture under 53Mpa 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 to the nonoxidizing atmosphere stove and be warming up to 800 ℃ with certain heating rate, protective atmosphere is that 99.999% argon carries out ungrease treatment, its before heating up, first pass into pure argon gas at least 30min to get rid of furnace air, the temperature control process: the speed with 1.5 ℃/min rises to 400 ℃ from room temperature, insulation 108min, argon intake 0.5L/min; Speed with 2.0 ℃/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 be warming up to 2200 ℃ with certain heating rate in the fine vacuum high temperature sintering furnace and carry out vacuum-sintering with the tungsten device for the sample after ungrease treatment, before heating up, the vacuum of sintering furnace at least will reach 10 -4pa, rise to 1200 ℃ with the speed of 10～15 ℃/min from room temperature, insulation 30min, and vacuum is 10 -4pa; Speed with 10 ℃/min rises to 1500 ℃, insulation 30min, and vacuum is 10 -4pa～10 -3pa; Speed with 6 ℃/min rises to 2200 ℃, insulation 120min, and vacuum is 10 -3pa; Sintering is complete, and vacuum is 10 -3pa, be cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; Speed with 12 ℃/min is cooled to 1200 ℃, insulation 60min; Speed with 10 ℃/min is cooled to 800 ℃, then furnace cooling;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with the corundum container and be warming up to 1250 ℃ with certain heating rate and carry out the stress relief annealing processing, the vacuum before heating up in annealing furnace at least will reach 10 -4pa, rise to 1250 ℃ with the speed of 15 ℃/min from room temperature, insulation 240min, and vacuum is 10 -4pa～10 -3pa; Speed with 5 ℃/min is cooled to 1000 ℃ again, insulation 180min, and vacuum is 10 -4pa～10 -3pa; Speed with 10 ℃/min is cooled to 800 ℃, insulation 120min, and vacuum is 10 -4pa; Speed with 20 ℃/min is cooled to room temperature, and vacuum is 10 -4pa.Finally carry out conventional post processing and make porous tantalum.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous tantalum finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 12.34g/cm 3, porosity 26%, hole average diameter 10 μ m, elastic modelling quantity 4.8GPa, bending strength 117MPa, comprcssive strength 125MPa.This preparation technology make product qualified rate high, produce stable, product qualification rate reaching 90.3%.
In the method provided at above-described embodiment 6, we can also do other selections to wherein each kind of condition can obtain porous tantalum of the present invention or porous niobium equally.
Figure BDA0000094794230000081
Figure BDA0000094794230000092
Figure BDA0000094794230000101
Figure BDA0000094794230000111
Figure BDA0000094794230000121
Gained porous tantalum or porous niobium finished product are pressed preceding method and are detected:
Embodiment 7 8 9 10 11 12 13
Density (g/cm 3) 12.00 11.67 6.86 13.00 6.43 12.67 12.17
Porosity (%) 28 30 20 22 25 24 27
Aperture (μ m) 19 15 8 11 27 23 25
Elastic modelling quantity (GPa) 4.5 5.0 2.6 4.8 1.5 5.0 5.7
Bending strength (MPa) 120 115 76 130 82 122 117
Comprcssive strength (MPa) 118 100 55 127 67 123 107

Claims (10)

1. the preparation method of the medical porous metal material of an alternative dentale, it is characterized in that: be mixed into mixed-powder with tantalum powder and pore creating material, forming agent, then by described mixed-powder be pressed into molding in Organic Foam Material, defat, sintering, cooling and heat treatment makes the porous tantalum material; The pressure of compressing employing is 50～100MPa, described pore creating material is one or more combination in any in carbamide, sodium chloride, ethyl cellulose, methylcellulose, and described forming agent is one or more combination in any in stearic acid, zinc stearate, paraffin, synthetic rubber; The heat treated condition of vacuum annealing is: vacuum is not less than 10 -4pa, rise to 1000～1250 ℃ with the speed higher than 30 ℃/min not, insulation 4h～6h; After first slow, to be not less than 5 ℃/min but higher than the cooldown rate segmentation of 30 ℃/min, not to be cooled to room temperature soon, the temperature retention time of each section tapers off and is no more than 3h again.
2. preparation method as claimed in claim 1 is characterized in that: in described mixed-powder, the consumption of forming agent is 5～10%, described pore creating material consumption is 20～30%, surplus is the 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. preparation method as claimed in claim 1 or 2 is characterized in that: described forming agent accounts for 5～6.5%, described pore creating material accounts for 21～24%, surplus is the tantalum powder, in volumn concentration; Pressure in compressing process is 55～65MPa.
4. preparation method as claimed in claim 3 is characterized in that: described forming agent accounts for 6%, described pore creating material accounts for 23%, surplus is the tantalum powder, in volumn concentration.
5. preparation method as claimed in claim 1 or 2 is characterized in that: described skimming processes is that the speed with 2 ℃/min～3.5 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 100min～240min.
6. preparation method as claimed in claim 3 is characterized in that: described skimming processes is that the speed with 2 ℃/min～3.5 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 100min～240min.
7. preparation method as claimed in claim 6 is characterized in that: described skimming processes is that the speed with 3～3.5 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 150min～200min.
8. preparation method as claimed in claim 6, it is characterized in that: described sintering is to be not less than 10 in vacuum -4pa, 2000～2200 ℃ of temperature, temperature retention time 1～5 hour; Finally carry out the vacuum annealing processing.
9. preparation method as claimed in claim 1, it is characterized in that: described vacuum-sintering condition is: vacuum is not less than 10 -3pa, rise to 1200 ℃～1500 ℃ with the heating rate of 10～20 ℃/min from room temperature, after insulation 1h～2h; Be warming up to 2000～2200 ℃ with the heating rate lower than 20 ℃/min again, insulation 2h～4h;
Cooling condition after described vacuum-sintering is: vacuum is not less than 10 -3pa, with not higher than 25 ℃/min, be not less than 10 ℃/min and gradually fall the cooldown rate mode, and to sintered porous bodies segmentation cooling down to 800 ℃, each section temperature retention time 30min～90min, then cool to room temperature with the furnace.
10. preparation method as claimed in claim 1, it is characterized in that: described ungrease treatment condition is: the pure argon gas with 99.9999% passes into the formation protective atmosphere, speed with 1～2 ℃/min rises to 400 ℃ from room temperature, insulation 100～120min, rise to 600～800 ℃ with the speed of 2～3 ℃/min from 400 ℃, be incubated 200～240min; Described vacuum-sintering condition is: the speed with 10～15 ℃/min rises to 1200～1250 ℃ from room temperature, is incubated 30～60min, and vacuum is 10 -4pa～10 -3pa; Speed with 10～20 ℃/min rises to 1500 ℃, is incubated 30～60min, and vacuum is 10 -4pa～10 -3pa, rise to 2000～2200 ℃ with the speed of 6～20 ℃/min, is incubated 120～240min, and vacuum is 10 -4pa～10 -3pa; Cooling condition after vacuum-sintering is: vacuum is 10 -4pa～10 -3pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, is incubated 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, is incubated 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling.
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