CN102796904A - Medical porous metal material for replacing weight-bearing bone tissues and preparation method of medical porous metal material - Google Patents

Medical porous metal material for replacing weight-bearing bone tissues and preparation method of medical porous metal material Download PDF

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CN102796904A
CN102796904A CN2011103010393A CN201110301039A CN102796904A CN 102796904 A CN102796904 A CN 102796904A CN 2011103010393 A CN2011103010393 A CN 2011103010393A CN 201110301039 A CN201110301039 A CN 201110301039A CN 102796904 A CN102796904 A CN 102796904A
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speed
insulation
medical porous
tantalum
pore
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CN102796904B (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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Priority to PCT/CN2012/081866 priority patent/WO2013044780A1/en
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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
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • 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
    • 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
    • B22F3/1137—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers by coating porous removable preforms
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention discloses a medical porous metal material for replacing weight-bearing bone tissues 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 a pore creating material and a forming agent, and then pressing the mixed powder in an organic foam; performing forming, degreasing, sintering, cooling and heat processing to prepare the medical porous metal material; the pressure adopted in the process of press forming is 50-100 MPa, the temperature is gradually raised to 400-800 DEG C at a speed of 0.3-2 DEG C per minute in the degreasing process, argon is introduced in to form protective atmosphere, and the temperature is preserved for 300-360 minutes; the pore creating material is ammonium hydrogen carbonate or hydrogen peroxide, the forming agent is one or more of stearic acid, zinc stearate, wax and synthetic resin, and the formed medical porous tantalum material has the pore diameter of 100-500 microns, the porosity degree of 55-65%, the elastic modulus of 3.8-4.2 Gpa and the elongation percentage of 9.3-10.7%. Through the preparation method of porous tantalum disclosed by the invention, the final content of impurity in the porous tantalum material is very low, and simultaneously the contradiction that the medical porous tantalum material for replacing a weight-bearing site requires larger porosity and also requires good mechanical property is efficiently solved.

Description

Medical porous metallic substance of a kind of alternative load bone tissue and preparation method thereof
Technical field
The present invention relates to a kind of porous medical metal embedded material and preparation method thereof, particularly relate to medical embedded porous metal material of a kind of alternative weight bearing area osseous tissue and preparation method thereof.
Background technology
Porous medical metal embedded material has important and special purposes such as treatment osseous tissue wound, bone formation necrosis, and existing common this type material has porous metal stainless steel, porous metal 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 uniform distribution; Or make it as required that both the osseous tissue growth phase with human body was consistent, and alleviated the weight of material itself again, implant and use to be fit to human body.
And refractory metals tantalum/niobium, because it has outstanding biocompatibility, its porous material is expected to as substituting conventional medical metallic biomaterials such as aforementioned.Since metal tantalum/niobium to human body harmless, nontoxic, have no side effect; And along with the develop rapidly of domestic and international medical science; To tantalum/niobium further going deep into as the body implanting material cognition; The demand that people implant with porous metal tantalum/niobium material human body becomes more and more urgent, and is also increasingly high to its requirement.Wherein as the medical embedded metal tantalum/niobium of porous, if can have very high uniform distribution open pore and the physical and mechanical properties that adapts with human body, then it is expected to as a kind of novel osseous tissue equivalent material.
As medical embedded porous metal material just as the porous metal material that kind be to be main working method basically with powder sintering, in particular for obtain porosity communication and equally distributed porous metal foam structure adopt the dipping after drying of metal-powder slurry on the organic foam body in the powder sintering to reburn to be called for short the foam impregnation method in the majority for knot.About common its Metal Mechanic Property of the powder sintered porous metal material that obtains not is fine, and its major cause is how to arrange the support and the problem of eliminating in relation, the metal powder sintered process of subsiding of pore-forming medium on the technology.And all do not have good solution in the known bibliographical information and laissez-faire nature.
The bibliographical information that adopts metal powder sintered manufactured porous tantalum/niobium seldom particularly uses the porous tantalum/niobium powder sintering process bibliographical information as purpose almost not have to obtain medical embedded material.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 novel porous foam tungsten and preparation method thereof ".Yet porous metal that it obtained or for filtering material usefulness, or share for aerospace and other high-temperature field but not use as the medical metal embedded material, moreover the also non-porous tantalum/niobium of the porous metal of being processed.
About porous tantalum, US5282861 discloses a kind of perforate tantalum material and preparation thereof that is applied to spongy bone implant, cell and organizes susceptor.This porous tantalum is processed by pure commercial tantalum; It carries out the carbon skeleton that thermal destruction obtains with the polyurethane precursor is support, and this carbon skeleton is multiple dodecahedron, is the mesh-like structure in it; Integral body spreads all over micropore; Porosity can be up to 98%, the method for commercially pure tantalum through chemical vapour deposition, infiltration is attached on the carbon skeleton to form the porous metal microstructure again, abbreviates chemical deposition as.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtained is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight then accounts for about 1%.Document is further put down in writing, the ultimate compression strength 50～70MPa of this porous material, Young's modulus 2.5～3.5GPa, tensile strength 63MPa.But as the porous tantalum that substitutes medical embedded materials such as load bone tissue such as skull, the mechanical property of its material such as ductility have obvious weak point, can have influence on the follow-up processing to porous tantalum material itself with it, for example the cutting of profiled member etc.Also all there is such deficiency at the product that aforesaid metal powder sintered method obtained equally.Owing to the limitation of its preparation method, the finished product purity of acquisition is not enough, and the carbon skeleton residue is arranged again, causes biological safety to reduce.
Summary of the invention
The object of the present invention is to provide the high medical porous metallic substance that is applicable to alternative load bone tissue of a kind of product purity.
Another object of the present invention is to provide the preparation method of above-mentioned medical porous metallic substance.
The objective of the invention is to realize through following technique means:
A kind of medical porous metallic substance of alternative load bone tissue is characterized in that: mixed with pore-forming material, forming agent by the tantalum powder, make through compression moulding, degreasing, sintering, cooling and thermal treatment; Said compression moulding is that described mixed powder is pressed in the organic foam body; Its pressure is 50～100Mpa; Said skimming processes is that the speed with 0.3 ℃/min～2 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 300min～360min; Said pore-forming material is bicarbonate of ammonia or ydrogen peroxide 50; Said forming agent is one or more in Triple Pressed Stearic Acid, Zinic stearas, paraffin, the synthetic resins (being preferably styrene-butadiene rubber(SBR) or polyisoprene rubber), and the medical porous tantalum material pore diameter of formation is 100～500 μ m, porosity between 55～65%, Young's modulus is that 3.8～4.2Gpa, unit elongation are 9.3～10.7%.
In the R&D process of medical porous metallic substance; Medical porous metallic substance is as the material that substitutes the load bone tissue; Require that its porosity is big, tissue just is prone to grow into like this, thereby good biocompatibility brings into play its effect fully; But porosity is bigger, the aperture is big more, and mechanical property such as intensity, toughness just can not get guaranteeing; Otherwise mechanical property has been got well and has been prone to make that porosity is too small, biocompatibility is bad, the also excessive discomfort that causes of density; The preparation route of medical porous tantalum is numerous; Problems such as but the contriver has creatively proposed employing above-mentioned steps, the medical porous tantalum embedded material of prepared, and the difficult control of plug-hole, soaking paste process that has effectively prevented to adopt cement-dipping method to be prone to, the quality product that makes are inhomogeneous; Porous tantalum material that it makes through its foreign matter content of test can be lower than 0.2%, its biocompatibility and biological safety be good, density can reach 5.83～7.50g/cm 3, porosity can reach 55～65%, and pore diameter can reach 100～500 μ m; Young's modulus can reach that 3.8～4.2Gpa, unit elongation reach 9.3～10.7%, flexural strength can reach 100～120Mpa, ultimate compression strength can reach 60～70Mpa; Its biocompatibility, obdurability are all excellent; Near human bearing's osseous tissue, porous tantalum of the present invention is suitable for substituting the medical embedded material of load bone tissue very much.
The median size of the Ta powder that the present invention adopts less than 0.1%, is the commercially available prod less than 43 microns, oxygen level; Above-mentioned pore-forming material, forming agent also are the commercially available prod.It is 10 that vacuum environment of the present invention preferably adopts vacuum tightness -4Pa～10 -3The vacuum condition of Pa.Above-mentioned organic foam body optimization polyurethane foam further is preferably aperture 0.48～0.89mm, density 0.015g/cm 3～0.035g/cm 3, (most preferably the aperture is 0.56～0.72mm to hardness, density 0.025g/cm greater than 50 ° 3, 50 °～80 ° of hardness) polyurethane foam in.
The contriver further discovers in R&D process; If control is bad in the above-mentioned preparation; Though can make and be suitable for substituting the medical embedded material of load bone tissue as stated but constant product quality property is undesirable, qualification rate is not high: difficult like powder pressing forming, be prone to layering, inhomogeneous suppressing the rear section, technical problems such as crackle can appear in the degreasing rear section.
In order to make in the powder compaction process moulding easier; Thereby improve yield rate, finished product porous nickel property, make the preparation process more stable; The consumption of above-mentioned pore-forming material is 15～25%, the consumption of forming agent is 7～12%, surplus is the tantalum powder; All (in volumn concentration is the unit of directly calculating through the situation of final porous tantalum material in volumn concentration; In the weighing of above-mentioned pore-forming material, forming agent pressed powder still according to the densometer of respective substance calculate its corresponding quality weighing, if liquid substance then directly adopts the volume weighing certainly), further be preferably pore-forming material and be that ydrogen peroxide 50 accounts for 18%, forming agent is that Zinic stearas accounts for 11%, surplus is the tantalum powder, in volumn concentration; Pressure in the above-mentioned compression moulding process is preferably 75～87Mpa.
In order to make idiosome is more stable in the skimming processes, 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 0.3 ℃/min～1 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 330min～350min; Further preferably progressively be warming up to 400～800 ℃, feed with argon gas and constitute protective atmosphere and be incubated 340min with the speed of 0.8 ℃/min.
A kind of preparation method of medical porous metallic substance of alternative load bone tissue; Adopt the compression molding sintering to form; Its characteristics are: the tantalum powder is mixed with pore-forming material, forming agent, under 50～100Mpa, said mixed powder is pressed into moulding in the organic foam body, degreasing, sintering, cooling and thermal treatment again and makes the medical porous metallic substance that substitutes the load bone tissue; Said pore-forming material is bicarbonate of ammonia or ydrogen peroxide 50; Said forming agent is one or more in Triple Pressed Stearic Acid, Zinic stearas, paraffin, the synthetic resins (being preferably styrene-butadiene rubber(SBR) or polyisoprene rubber); Wherein the consumption of pore-forming material is 15～25%, the consumption of forming agent is 7～12%, surplus is the tantalum powder, all in volumn concentration; Said skimming processes is that the speed with 0.3 ℃/min～2 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 300min～360min.
The median size of above-mentioned raw materials tantalum powder less than 43 microns, oxygen level less than 0.1%; Above-mentioned pore-forming material is preferably further that ydrogen peroxide 50 accounts for 18%, forming agent is that Zinic stearas accounts for 11%, surplus is the tantalum powder, in volumn concentration.Above-mentioned organic foam body optimization polyurethane foam further is preferably aperture 0.48～0.89mm, density 0.015g/cm 3～0.035g/cm 3, (most preferably the aperture is 0.56～0.72mm to hardness, density 0.025g/cm greater than 50 ° 3, 50 °～80 ° of hardness) polyurethane foam in.
In order to make in the compacting system embryo process pressing pressure even, not stratified; Final porous tantalum void distribution is more even, quality is more stable thereby make; The pressure that adopts in the above-mentioned pressing process is preferably 75～87Mpa; The speed that is preferably in the above-mentioned skimming processes with 0.3 ℃/min～1 ℃/min progressively is warming up to 400～800 ℃; Feed to constitute protective atmosphere and be incubated 330min～350min with argon gas, further preferably progressively be warming up to 400～800 ℃, feed with argon gas and constitute protective atmosphere and be incubated 340min with the speed of 0.8 ℃/min.
The present invention's further characteristics on the other hand are: be not less than 10 in vacuum tightness -4～10 -3Pa, 2000～2200 ℃ of temperature, 1～5 hour vacuum sintering of soaking time is handled and is made porous sintered body.Can the filling with inert gas protection replace vacuum protection during the sintering process insulation; Carry out vacuum annealing at last and handle, wherein vacuum annealing is handled and is meant that process vacuum sintering continued keeps temperature to be in 1000～1250 ℃, soaking time 1～4 hour, and vacuum tightness is not less than 10 -4～10 -3Pa.
The vacuum sintering condition also includes: vacuum tightness is not less than 10 -3Pa rises to 1200 ℃～1500 ℃ with the temperature rise rate of 10～20 ℃/min from room temperature, behind insulation 1h～2h; Be warming up to 2000～2200 ℃ with the temperature rise rate that is lower than 20 ℃/min again, be incubated 2h～4h at least.
Cooling conditions after the vacuum sintering also includes: vacuum tightness is not less than 10 -3Pa not to be higher than 25 ℃/min, to be not less than 10 ℃/min and gradually to fall the rate of cooling mode, and sintered porous bodies segmentation cooling is cooled to 800 ℃, and each section soaking time 30min～90min cools to normal temperature then with the furnace.
The vacuum annealing condition also includes: vacuum tightness is not less than 10 -4Pa rises to 1000～1250 ℃ with the speed that is not higher than 30 ℃/min, insulation 4h～6h; Again with after earlier slow soon to be not less than 5 ℃/min but the rate of cooling segmentation that is not higher than 30 ℃/min is cooled to room temperature, the soaking time of each section tapers off and is no more than in 1.5h～3h and selects.
Further characteristics are on this basis: said skimming treatment condition also includes: the speed with 1～2 ℃/min rises to 400 ℃ from room temperature; Insulation 300～330min; Speed with 0.3～0.8 ℃/min rises to 600～800 ℃, insulation 340～360min from 400 ℃; Said vacuum sintering condition also includes: the speed with 10～15 ℃/min rises to 1200～1250 ℃ from room temperature, insulation 30～60min, and vacuum tightness is 10 -4Pa～10 -3Pa rises to 1500 ℃ with the speed of 10～20 ℃/min, insulation 30～60min, and vacuum tightness is 10 -4Pa～10 -3Pa rises to 2000～2200 ℃ with the speed of 6～20 ℃/min, insulation 120～240min, and vacuum tightness is 10 -4Pa～10 -3Pa; Cooling conditions after the vacuum sintering also includes: vacuum tightness is 10 -4Pa～10 -3Pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, insulation 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, insulation 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Said vacuum annealing condition also includes: the speed with 15～30 ℃/min rises to 1000～1250 ℃, insulation 240～480min, and vacuum tightness is 10 -4Pa～10 -3Pa, the speed with 5～10 ℃/min is cooled to 1000 ℃ again, insulation 90～180min, vacuum tightness is 10 -4Pa～10 -3Pa; Speed with 10～20 ℃/min is cooled to 800 ℃, insulation 60～120min, and vacuum tightness is 10 -4Pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum tightness is 10 -4Pa～10 -3Pa.
The character of metal tantalum and niobium is extremely similar, and aforesaid method equally also is fit to the preparation of medical porous niobium material.
Porous tantalum preparation method of the present invention has adopted pure physics compression molding, makes that the content of impurity is extremely low in the final porous tantalum material, has improved biocompatibility and biological safety effectively; Optimization of process conditions to compression moulding of the present invention, degreasing, sintering and annealing steps; Make that yield rate is high, finished product aperture homogeneity better, make that the preparation process is more stable, quality stability is good; Eliminated thermal stresses effectively, made organizing of porous tantalum material more even; All be improved simultaneously with the mechanical property of further raising porous tantalum such as intensity, toughness, preparation technology of the present invention makes that product qualified rate is high, it is stable to produce, and product percent of pass can be up to 92%.Porous tantalum finished product even pore distribution and connection that the present invention makes, good biocompatibility, through its foreign matter content of test can be lower than 0.2%, density can reach 5.83～7.50g/cm 3, porosity can reach 55～65%, and pore diameter can reach 100～500 μ m; Young's modulus can reach 3.8～4.2Gpa, unit elongation reaches 9.3～10.7%; Flexural strength can reach 100～120Mpa, ultimate compression strength can reach 60～70Mpa; Efficiently solve as the medical porous tantalum material that substitutes weight bearing area not only required its porosity more greatly, but also require the good contradiction of mechanical property, porous tantalum of the present invention to be suitable for very much as the medical embedded material that substitutes the load bone tissue.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
A kind of medical porous tantalum material of alternative load bone tissue specifically is that to select in Triple Pressed Stearic Acid, Zinic stearas, paraffin, the viton one or more for use be pore-forming material for forming agent, bicarbonate of ammonia or ydrogen peroxide 50; Mix less than 0.1% tantalum powder less than 43 microns, oxygen level with median size; Under 50～100Mpa, said mixed powder is pressed into moulding in the organic foam body, gets through degreasing, sintering, cooling and thermal treatment again; Said skimming processes is that the speed with 0.3 ℃/min～2 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 300min～360min.The medical porous tantalum material pore diameter that forms is 100～500 μ m, porosity between 55～65%, Young's modulus is that 3.8～4.2Gpa, unit elongation are 9.3～10.7%.
More particularly; Above-mentioned porous tantalum is with the tantalum powder mixing of the above-mentioned pore-forming material of the above-mentioned forming agent, 15～25% (in volumn concentration) of 7～12% (in volumn concentrations) and surplus, puts it into and is pressed into moulding in the urethane foam in the injection moulding machine; The special atmosphere oven that places the tungsten device to put into pure argon gas (99.9999%) feeding formation more progressively is warming up to certain temperature; And insulation is carried out skimming treatment to remove pore-forming material, forming agent and polyurethane foam; Wherein before heating up, feed argon gas earlier to get rid of furnace air, the sample furnace cooling after the degreasing; Place with the tungsten device for the sample after the skimming treatment and progressively to be warming up to 2000～2200 ℃ in the high vacuum high temperature sintering furnace; Soaking time was carried out vacuum sintering in 1～5 hour; The vacuum tightness of sintering oven will reach proper level at least before heating up; Sample furnace cooling after the vacuum sintering keeps certain vacuum tightness or presses certain rate of cooling segmentation cooling to keep certain temperature in reasonable time in the process of cooling, in insulating process, can adopt filling with inert gas as protective atmosphere.The cooled sample of against vacuum sintering places vacuum annealing furnace progressively to heat up, be incubated to carry out stress relief annealing to handle with the corundum container; The certain vacuum tightness of maintenance before heating up in the lehre; Sample furnace cooling after vacuum annealing is handled; Also keep certain vacuum tightness in the process of cooling or by certain rate of cooling segmentation cooling to keep certain temperature in reasonable time; In insulating process, can adopt filling with inert gas as protective atmosphere, carry out conventional aftertreatment at last and make porous tantalum.
For skimming treatment, skimming processes is that the speed with 0.3 ℃/min～1 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 330min～350min; Further preferably progressively be warming up to 400～800 ℃, feed with argon gas and constitute protective atmosphere and be incubated 340min with the speed of 0.8 ℃/min.Carrying out vacuum sintering for the sample after the skimming treatment handles; Be to place in the high vacuum high temperature sintering furnace the highest sintering temperature that is warming up to tantalum with certain temperature rise rate to carry out vacuum sintering with the tungsten device it; Sintering oven keeps certain vacuum tightness before heating up; Be warming up to for example 1200 ℃～1250 ℃ with certain temperature rise rate, insulation keeps vacuum; Be warming up to for example 1250 ℃～1500 ℃ again with certain temperature rise rate, insulation is warming up to the for example the highest sintering temperature of tantalum with certain temperature rise rate again, insulation, maintenance vacuum; Sintering finishes, and keeps vacuum, is cooled to for example 1500 ℃～1600 ℃ with certain rate of temperature fall; Insulation is cooled to for example 1200 ℃～1250 ℃ with certain rate of temperature fall again, insulation; Also be cooled to for example 800 ℃, then furnace cooling with certain rate of temperature fall.The cooled sample of against vacuum sintering carries out vacuum annealing to be handled; Be to place vacuum annealing furnace to be warming up to for example 1000 ℃～1250 ℃ with the corundum container it to carry out the stress relief annealing processing with certain temperature rise rate; Maintenance vacuum tightness before heating up in the lehre; Rise to 1000 ℃～1250 ℃ with certain temperature rise rate from room temperature, insulation keeps 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 certain rate of temperature fall cooling room temperature.Carry out conventional aftertreatment at last and make porous tantalum.
It is main with the physics compression molding mainly that the contriver adopts metal powder sintered method, has done a large amount of theoretical analysises and experimental verification, obtain the porous tantalum product through its foreign matter content of test can be lower than 0.2%, density can reach 5.83～7.50g/cm 3, porosity can reach 55～65%, and pore diameter can reach 100～500 μ m; Young's modulus can reach 3.8～4.2Gpa, unit elongation reaches 9.3～10.7%, and flexural strength can reach 100～120Mpa, ultimate compression strength can reach 60～70Mpa.
Embodiment 1: weighing Zinic stearas, median size mix less than 0.1% tantalum powder and ydrogen peroxide 50 less than 43 microns oxygen levels, and wherein Zinic stearas accounts for 11%, and ydrogen peroxide 50 accounts for 18%, the tantalum powder accounts for 71%, all in volumn concentration.Extrusion forming: with arriving urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in the 82Mpa pressed in the above-mentioned mixed powder adding injection moulding machine 3～0.035g/cm 3, hardness is greater than 50 °) and middle moulding.Skimming treatment: vacuum tightness 10 -4Pa is warming up to 400 ℃, insulation 320min with the temperature rise rate of 2.0 ℃/min from room temperature; Temperature rise rate with 0.5 ℃/min is warming up to 700 ℃, soaking time 350 minutes from 400 ℃ again.Vacuum sintering: sintering in vacuum oven, 2000 ℃ of sintering temperatures are incubated 2 hours, vacuum tightness 10 -4Pa, the protection of sintering process applying argon gas is removed surface dirt and dirt behind the taking-up product, and the sample that makes carries out conventional aftertreatment again and gets the porous tantalum finished product.
The contriver detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: its foreign matter content is lower than 0.2%; Its even pore distribution, density 6.24g/cm 3, porosity 60%, hole mean diameter 200 μ m, Young's modulus 4.0Gpa, unit elongation 10.02%, flexural strength 115MPa, ultimate compression strength 66MPa.
Embodiment 2: take by weighing Triple Pressed Stearic Acid, median size and mix less than 0.1% tantalum powder and bicarbonate of ammonia less than 43 microns oxygen levels, wherein Triple Pressed Stearic Acid accounts for 7%, bicarbonate of ammonia accounts for 25%, the tantalum powder accounts for 68%, all in volumn concentration.Extrusion forming: with arriving urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in the 87Mpa pressed in the above-mentioned mixed powder adding injection moulding machine 3～0.035g/cm 3, hardness is greater than 50 °) and middle moulding.Skimming treatment: vacuum tightness 10 -4Pa is warming up to 400 ℃, insulation 300min with the temperature rise rate of 2 ℃/min from room temperature.Vacuum sintering: sintering in vacuum oven, 2100 ℃ of sintering temperatures are incubated 4 hours, vacuum tightness 10 -4Pa, the protection of sintering process applying argon gas is removed surface dirt and dirt behind the taking-up product, and the sample that makes carries out conventional aftertreatment again and gets the porous tantalum finished product.
The contriver detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: its foreign matter content is lower than 0.2%; Its even pore distribution, density 6.05g/cm 3, porosity 65%, hole mean diameter 400 μ m, Young's modulus 3.8Gpa, unit elongation 9.5%, flexural strength 100MPa, ultimate compression strength 60MPa.
Embodiment 3: take by weighing styrene-butadiene rubber(SBR), median size and mix less than 0.1% tantalum powder and ydrogen peroxide 50 less than 43 microns oxygen levels, wherein styrene-butadiene rubber(SBR) accounts for 12%, ydrogen peroxide 50 accounts for 15%, the tantalum powder accounts for 73%, all in volumn concentration.Extrusion forming: with arriving urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in the 52Mpa pressed in the above-mentioned mixed powder adding injection moulding machine 3～0.035g/cm 3, hardness is greater than 50 °) and middle moulding.Skimming treatment: vacuum tightness 10 -4Pa is warming up to 400 ℃, insulation 360min with the temperature rise rate of 0.3 ℃/min from room temperature.Vacuum sintering: sintering in vacuum oven, 2200 ℃ of sintering temperatures are incubated 2.5 hours, vacuum tightness 10 -3Pa, the protection of sintering process applying argon gas, cooling is come out of the stove, and removes product surface dust and dirt, and the sample that makes carries out conventional aftertreatment again and gets the porous tantalum finished product.
The contriver detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: its foreign matter content is lower than 0.2%; Its even pore distribution, density 6.31g/cm 3, porosity 55%, hole mean diameter 100 μ m, Young's modulus 3.9Gpa, unit elongation 9.3%, flexural strength 105MPa, ultimate compression strength 63MPa.
Embodiment 4: take by weighing paraffin, median size and mix less than 0.1% niobium powder and bicarbonate of ammonia less than 43 microns oxygen levels, wherein paraffin accounts for 10%, bicarbonate of ammonia accounts for 20%, the niobium powder accounts for 70%, all in volumn concentration.Extrusion forming: with arriving urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in the 96Mpa pressed in the above-mentioned mixed powder adding injection moulding machine 3～0.035g/cm 3, hardness is greater than 50 °) and middle moulding.Skimming treatment: vacuum tightness 10 -4Pa is warming up to 400 ℃, insulation 340min with the temperature rise rate of 0.8 ℃/min from room temperature.Vacuum sintering: sintering in vacuum oven, 2150 ℃ of sintering temperatures are incubated 2 hours, vacuum tightness 10 -4Pa, the protection of sintering process applying argon gas, cooling is come out of the stove, and removes product surface dust and dirt, and the sample that makes carries out conventional aftertreatment again and gets porous niobium finished product.
The contriver detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous niobium finished product: its foreign matter content is lower than 0.2%; Its even pore distribution, density 3.77g/cm 3, porosity 56%, hole mean diameter 108 μ m, Young's modulus 3.0Gpa, unit elongation 9.8%, flexural strength 67MPa, ultimate compression strength 54MPa.
Embodiment 5: a kind of porous tantalum, it with particle diameter less than 43 μ m, oxygen level less than 0.1% ta powder, Triple Pressed Stearic Acid and ydrogen peroxide 50 powder mix are raw material, make through compression moulding, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment again.
Wherein, Triple Pressed Stearic Acid accounts for 11%, ydrogen peroxide 50 accounts for 22%, ta powder accounts for 67%, in volumn concentration;
Compression moulding: with arriving urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in the 78Mpa pressed in the raw materials mix powder adding injection moulding machine 3～0.035g/cm 3, hardness is greater than 50 °) and middle moulding;
After the compression moulding mixed powder is put into the nonoxidizing atmosphere stove and be warming up to 800 ℃ with certain temperature rise rate; Protective atmosphere is that 99.999% argon gas carries out skimming treatment; Its before heating up, feed earlier 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 300min, argon gas feeding amount 0.5L/min; Speed with 0.6 ℃/min rises to 800 ℃, insulation 340min, argon gas feeding amount 1/L/min from 400 ℃; Powered-down again, the sample furnace cooling after the degreasing, argon gas feeding amount 1L/min closes argon gas when being cooled to room temperature;
Place with the tungsten device for the sample after the skimming treatment to be warming up to 2200 ℃ with certain temperature rise rate in the high vacuum high temperature sintering furnace and to carry out vacuum sintering, the vacuum tightness of sintering oven will reach 10 at least before heating up -4Pa rises to 1200 ℃ with the speed of 10～15 ℃/min from room temperature, insulation 30min, and vacuum tightness is 10 -4Pa; Speed with 10 ℃/min rises to 1500 ℃, insulation 30min, and vacuum tightness is 10 -4Pa～10 -3Pa; Speed with 6 ℃/min rises to 2200 ℃, insulation 120min, and vacuum tightness is 10 -3Pa; Sintering finishes, and vacuum tightness is 10 -3Pa is cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; Speed with 12 ℃/min is cooled to 1200 ℃, insulation 60min; Speed with 10 ℃/min is cooled to 800 ℃, then furnace cooling;
The cooled sample of against vacuum sintering places vacuum annealing furnace to be warming up to 1250 ℃ with certain temperature rise rate with the corundum container to carry out stress relief annealing and handle, and the vacuum tightness before heating up in the lehre will reach 10 at least -4Pa rises to 1250 ℃ with the speed of 15 ℃/min from room temperature, insulation 240min, and vacuum tightness is 10 -4Pa～10 -3Pa; Speed with 5 ℃/min is cooled to 1000 ℃ again, insulation 180min, and vacuum tightness is 10 -4Pa～10 -3Pa; Speed with 10 ℃/min is cooled to 800 ℃, insulation 120min, and vacuum tightness is 10 -4Pa; Speed with 20 ℃/min is cooled to room temperature, and vacuum tightness is 10 -4Pa.Carry out conventional aftertreatment at last and make porous tantalum.
The contriver detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: its foreign matter content is lower than 0.2%; Its even pore distribution, density 6.8g/cm 3, porosity 62%, hole mean diameter 250 μ m, Young's modulus 4.15Gpa, unit elongation 10.32%, flexural strength 118MPa, ultimate compression strength 65MPa.Through calculating this preparation technology's product qualification rate reaching 90.3%.
In the method that the foregoing description 5 provides, 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.
Figure BDA0000096342330000091
Figure BDA0000096342330000092
Figure BDA0000096342330000101
Gained porous tantalum or porous niobium finished product are pressed preceding method and are detected:
Embodiment 6 7 8
Density (g/cm 3) 6.3 3.3 7.0
Porosity (%) 56 63 60
Aperture (μ m) 150 260 390
Young's modulus (GPa) 3.9 2.1 4.2
Unit elongation (%) 9.8 10.03 9.4
Flexural strength (MPa) 120 79 109
Ultimate compression strength (MPa) 63 55 68

Claims (10)

1. the medical porous metallic substance of an alternative load bone tissue is characterized in that: mixed with pore-forming material, forming agent by the tantalum powder, make through compression moulding, degreasing, sintering, cooling and thermal treatment; Said compression moulding is that described mixed powder is pressed into moulding in the organic foam body; Its pressure is 50～100Mpa; Said skimming processes is that the speed with 0.3 ℃/min～2 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 300min～360min; Said pore-forming material is bicarbonate of ammonia or ydrogen peroxide 50; Said forming agent is one or more in Triple Pressed Stearic Acid, Zinic stearas, paraffin, the synthetic resins, and the medical porous tantalum material pore diameter of formation is 100～500 μ m, porosity between 55～65%, Young's modulus is that 3.8～4.2Gpa, unit elongation are 9.3～10.7%.
2. medical porous metallic substance as claimed in claim 1 is characterized in that: the median size of said Ta powder less than 43 microns, oxygen level less than 0.1%; Said forming agent synthetic resins is styrene-butadiene rubber(SBR) or polyisoprene rubber; Said organic foam body is aperture 0.56～0.72mm, density 0.025g/cm 3, hardness 50 0～80 0Polyurethane foam.
3. according to claim 1 or claim 2 medical porous metallic substance is characterized in that: the consumption of said pore-forming material is 15～25%, the consumption of forming agent is 7～12%, surplus is the tantalum powder, all in volumn concentration; Pressure in the said compression moulding process is preferably 75～87Mpa.
4. medical porous metallic substance as claimed in claim 3 is characterized in that: said for ydrogen peroxide 50 accounts for 18%, forming agent is that Zinic stearas accounts for 11%, surplus is the tantalum powder, in volumn concentration.
5. like each described medical porous metallic substance of claim 1～4; It is characterized in that: said skimming processes is that the speed with 0.3 ℃/min～1 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 330min～350min; Further preferably progressively be warming up to 400～800 ℃, feed with argon gas and constitute protective atmosphere and be incubated 340min with the speed of 0.8 ℃/min.
6. the preparation method of the medical porous metallic substance of an alternative load bone tissue; Adopt the compression molding sintering to form; Its characteristics are: the tantalum powder is mixed with pore-forming material, forming agent, is 0.56～0.72mm to the aperture in 50～100Mpa pressed again, density 0.025g/cm 3, hardness 50 0～80 0Polyurethane foam in moulding, degreasing, sintering, cooling and thermal treatment make the medical porous metallic substance that substitutes the load bone tissue; Said pore-forming material is bicarbonate of ammonia or ydrogen peroxide 50; Said forming agent is one or more in Triple Pressed Stearic Acid, Zinic stearas, paraffin, the synthetic resins; Wherein the consumption of pore-forming material is 15～25%, the consumption of forming agent is 7～12%, surplus is the tantalum powder, all in volumn concentration; Said skimming processes is that the speed with 0.3 ℃/min～2 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 300min～360min.
7. preparation method as claimed in claim 6 is characterized in that: the median size of said Ta powder less than 43 microns, oxygen level less than 0.1%; Said pore-forming material is that ydrogen peroxide 50 accounts for 18%, forming agent is that Zinic stearas accounts for 11%, surplus is the tantalum powder, in volumn concentration; The pressure that adopts in the said pressing process is preferably 75～87Mpa.
8. preparation method as claimed in claim 7 is characterized in that: the speed with 0.3 ℃/min～1 ℃/min in the said skimming processes progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 330min～350min.
9. preparation method as claimed in claim 8 is characterized in that: the speed with 0.8 ℃/min in the said skimming processes progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 340min.
10. like claim 6 or 7 described preparing methods; It is characterized in that: said skimming treatment condition also includes: the speed with 1～2 ℃/min rises to 400 ℃ from room temperature; Insulation 300～330min; Speed with 0.3～0.8 ℃/min rises to 600～800 ℃, insulation 340～360min from 400 ℃; Said vacuum sintering condition also includes: the speed with 10～15 ℃/min rises to 1200～1250 ℃ from room temperature, insulation 30～60min, and vacuum tightness is 10 -4Pa～10 -3Pa rises to 1500 ℃ with the speed of 10～20 ℃/min, insulation 30～60min, and vacuum tightness is 10 -4Pa～10 -3Pa rises to 2000～2200 ℃ with the speed of 6～20 ℃/min, insulation 120～240min, and vacuum tightness is 10 -4Pa～10 -3Pa; Cooling conditions after the vacuum sintering also includes: vacuum tightness is 10 -4Pa～10 -3Pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, insulation 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, insulation 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Said vacuum annealing condition also includes: the speed with 15～30 ℃/min rises to 1000～1250 ℃, insulation 240～480min, and vacuum tightness is 10 -4Pa～10 -3Pa, the speed with 5～10 ℃/min is cooled to 1000 ℃ again, insulation 90～180min, vacuum tightness is 10 -4Pa～10 -3Pa; Speed with 10～20 ℃/min is cooled to 800 ℃, insulation 60～120min, and vacuum tightness is 10 -4Pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum tightness is 10 -4Pa～10 -3Pa.
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