CN102796903A - Method for preparing medical porous metal material capable of replacing bearing bone tissue - Google Patents

Method for preparing medical porous metal material capable of replacing bearing bone tissue Download PDF

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Publication number
CN102796903A
CN102796903A CN2011103003864A CN201110300386A CN102796903A CN 102796903 A CN102796903 A CN 102796903A CN 2011103003864 A CN2011103003864 A CN 2011103003864A CN 201110300386 A CN201110300386 A CN 201110300386A CN 102796903 A CN102796903 A CN 102796903A
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insulation
speed
warming
vacuum tightness
cooled
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CN102796903B (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/CN2012/082084 priority patent/WO2013044809A1/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1121Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1125Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02Alloys based on vanadium, niobium, or tantalum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps

Abstract

A method for preparing a medical porous metal material for replacing a bearing bone tissue comprises the steps of mixing titanium powder, a pore forming agent and a molding agent, then pressing the mixed powder into an organic foaming body, and then molding, degreasing, sintering, cooling and conducting heat treatment. The compression molding pressure is 50-100Mpa, and the degreasing process is as follows: the temperature is increased to be 400-800 DEG C according to the rate of 0.3 DEG C/min-2 DEG C/min, and argon is introduced to form protective atmosphere, and the temperature is kept for 300-360min; the pore forming agent adopts ammonium bicarbonate or hydrogen peroxide, and the molding agent is one or multiple of stearic acid, zinc stearate, paraffins and synthetic resin; the temperature is increased to be 800-900 DEG C according to the rate of 10-20 DEG C/min under 10<-4>Pa-10<-3>Pa and is kept for 240-480min, then the temperature is cooled to be 400 DEG C according to the rate of 2-5 DEG C/min and is kept for 120-300min, and then the temperature is cooled to be room temperature along with the furnace. According to the test, the impurity content is lower than 0.2%, the density reaches 6.67-8.34g/cm<3>, the porosity is 50-60%, and the diameter of each pore is 150-450mu m; and modulus of elasticity reaches 4.5-6.0Gpa, and the bending strength reaches 100-120Mpa.

Description

A kind of method for preparing the medical porous metallic substance that substitutes the load bone tissue
Technical field
The present invention relates to a kind of preparation method of porous medical metal embedded material, particularly relate to a kind of preparation method who is applicable to the medical embedded metallic substance of porous that substitutes the weight bearing area osseous tissue.
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 a kind of preparation method who is applicable to the porous metal material that substitutes the weight bearing area osseous tissue of good toughness.
The objective of the invention is to realize through following technique means:
A kind of preparation method who prepares the medical porous metallic substance that substitutes the load bone tissue is characterized in that: mixed with pore-forming material, forming agent by the tantalum powder, make this porous metal material through compression moulding, degreasing, sintering, cooling and thermal treatment again; Said compression moulding is that 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, and 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); Said thermal treatment is that vacuum tightness is 10 -4Pa~10 -3Pa is warming up to 800~900 ℃, insulation 240~480min with 10~20 ℃/min, is chilled to 400 ℃, insulation 120~300min with 2~5 ℃/min again, cools to room temperature then with the furnace.
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; The above-mentioned thermal treatment process that particularly adopts has been eliminated internal stress fully, has been made the toughness and the technology of organizing more evenly, improved greatly prepared porous tantalum material of porous tantalum material quick and easy; 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 6.67~8.34g/cm 3, porosity can reach 50~60%, and pore diameter can reach 150~450 μ m; Young's modulus can reach that 4.5~6.0Gpa, unit elongation reach 10.5~11.7%, 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.
Better for internal stress, the toughness of eliminating material more fully, above-mentioned heat treatment step is that vacuum tightness is 10 -4Pa~10 -3Pa is warming up to 800~900 ℃, insulation 260~320min with 15 ℃/min, is chilled to 400 ℃, insulation 120min with 3 ℃/min again, is cooled to room temperature with 18 ℃/min~23 ℃/min again.
Vacuum sintering condition of the present invention includes: vacuum tightness 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.
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; Speed with 10~20 ℃/min rises to 1500 ℃, 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 is: vacuum tightness is 10 -4Pa~10 -3Pa is warming up to 800~900 ℃, insulation 260~320min with 15 ℃/min, is chilled to 400 ℃, insulation 120min with 3 ℃/min again, is cooled to room temperature with 18 ℃/min~23 ℃/min again.
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, particularly its toughness is greatly enhanced, and density also is effectively controlled, makes its comfort as the human loaded bone tissue substitute material good simultaneously; 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 94%.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 6.67~8.34g/cm 3Porosity can reach 50~60%; Pore diameter can reach 150~450 μ m, and Young's modulus can reach 4.5~6.0Gpa, unit elongation reaches 10.5~11.7%, and 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.
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 80Mpa 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 324min with the temperature rise rate of 1.3 ℃/min from room temperature; Temperature rise rate with 0.7 ℃/min is warming up to 650 ℃, soaking time 340 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, carries out conventional processing under cooling again.Thermal treatment: be that vacuum tightness is 10 -4Pa~10 -3Pa is warming up to 800~900 ℃, insulation 260~320min with 15 ℃/min, is chilled to 400 ℃, insulation 120min with 3 ℃/min again, is cooled to room temperature with 18~23 ℃/min.
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 6.69g/cm 3, porosity 57%, hole mean diameter 330 μ m, Young's modulus 6.0Gpa, unit elongation 11.33%, flexural strength 20MPa, ultimate compression strength 67MPa.
Embodiment 2: take by weighing styrene-butadiene rubber(SBR), median size and be mixed into mixed powder less than 43 microns oxygen levels less than 0.1% tantalum powder and bicarbonate of ammonia; Wherein styrene-butadiene rubber(SBR) accounts for 11.5%, bicarbonate of ammonia accounts for 17%, the tantalum powder accounts for 71.5%, all in volumn concentration.Extrusion forming: with arriving urethane foam (aperture 0.48~0.89mm, density 0.015g/cm in the 64Mpa 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 700 ℃, insulation 332min with the temperature rise rate of 1.2 ℃/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, carries out conventional processing under cooling again.Thermal treatment: be that vacuum tightness is 10 -3Pa is warming up to 800~900 ℃, insulation 400min with 14 ℃/min, is chilled to 400 ℃, insulation 200min with 4 ℃/min again, is cooled to room temperature with 21 ℃/min.
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 7.3g/cm 3, porosity 53%, hole mean diameter 209 μ m, Young's modulus 5.3Gpa, unit elongation 11.54%, flexural strength 110MPa, ultimate compression strength 66MPa.
Embodiment 3: take by weighing paraffin, median size and mix less than 0.1% tantalum powder and ydrogen peroxide 50 less than 43 microns oxygen levels, wherein paraffin accounts for 7%, ydrogen peroxide 50 accounts for 15%, the tantalum powder accounts for 78%, 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 -3Pa is warming up to 800 ℃, insulation 300min with the temperature rise rate of 2 ℃/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, carries out conventional processing under cooling again.Thermal treatment: be that vacuum tightness is 10 -4Pa is warming up to 800~900 ℃, insulation 240min with 20 ℃/min, is chilled to 400 ℃, insulation 300min with 5 ℃/min again, is cooled to room temperature with 23 ℃/min.
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 6.67g/cm 3, porosity 51%, hole mean diameter 430 μ m, Young's modulus 4.7Gpa, unit elongation 10.6%, flexural strength 102MPa, ultimate compression strength 60MPa.
Embodiment 4: take by weighing Triple Pressed Stearic Acid, median size and mix less than 0.1% niobium powder and bicarbonate of ammonia less than 43 microns oxygen levels, wherein Triple Pressed Stearic Acid accounts for 12%, bicarbonate of ammonia accounts for 25%, the niobium powder accounts for 63%, 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 740 ℃, 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, carries out conventional processing under cooling again.Thermal treatment: be that vacuum tightness is 10 -3Pa is warming up to 800~900 ℃, insulation 480min with 10 ℃/min, is chilled to 400 ℃, insulation 120min with 2 ℃/min again, is cooled to room temperature with 18 ℃/min.
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 3.86g/cm 3, porosity 55%, hole mean diameter 450 μ m, Young's modulus 3.0Gpa, unit elongation 11.6%, flexural strength 78MPa, ultimate compression strength 52MPa.
Embodiment 5: a kind of porous tantalum, it with particle diameter less than 43 μ m, oxygen level less than 0.1% ta powder, Zinic stearas and bicarbonate of ammonia powder mix are raw material, make through compression moulding, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment again.
Wherein, Zinic stearas accounts for 9%, bicarbonate of ammonia accounts for 20%, ta powder accounts for 71%, in volumn concentration;
Compression moulding: with arriving urethane foam (aperture 0.48~0.89mm, density 0.015g/cm in the 69Mpa 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 1L/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 handle with certain temperature rise rate intensification stress relief annealing with the corundum container, and the vacuum tightness before heating up in the lehre will reach 10 at least -4Pa is that vacuum tightness is 10 -4Pa~10 -3Pa is warming up to 800~900 ℃, insulation 300min with 17 ℃/min, is chilled to 400 ℃, insulation 220min with 4.5 ℃/min again, is cooled to room temperature with 19~21 ℃/min.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 7.5g/cm 3, porosity 67%, hole mean diameter 300 μ m, Young's modulus 5.25Gpa, unit elongation 11.32%, flexural strength 110MPa, ultimate compression strength 65MPa.Through calculating this preparation technology's product qualification rate reaching 92.4%.
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 BDA0000096236210000071
Figure BDA0000096236210000072
Figure BDA0000096236210000081
Gained porous tantalum or porous niobium finished product are pressed preceding method and are detected:
Embodiment 6 7 8
Density (g/cm 3) 6.91 3.94 8.34
Porosity (%) 60 54 57
Aperture (μ m) 169 360 436
Young's modulus (GPa) 4.9 3.6 6.0
Unit elongation (%) 11.39 10.52 11.52
Flexural strength (MPa) 104 95 111
Ultimate compression strength (MPa) 65 71 70

Claims (9)

1. a preparation method who prepares the medical porous metallic substance that substitutes the load bone tissue is characterized in that: mixed with pore-forming material, forming agent by the tantalum powder, make this porous metal material through compression moulding, degreasing, sintering, cooling and thermal treatment again; Said compression moulding is that 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, and said forming agent is one or more in Triple Pressed Stearic Acid, Zinic stearas, paraffin, the synthetic resins; Said thermal treatment is that vacuum tightness is 10 -4Pa~10 -3Pa is warming up to 800~900 ℃, insulation 240~480min with 10~20 ℃/min, is chilled to 400 ℃, insulation 120~300min with 2~5 ℃/min again, cools to room temperature then with the furnace.
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 preparation method 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. preparation method as claimed in claim 3 is characterized in that: 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.
5. according to claim 1 or claim 2 preparation method 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.
6. preparation method as claimed in claim 3 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.
7. preparation method as claimed in claim 4 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.
8. like each described preparation method of claim 1~7, it is characterized in that: said heat treatment step is that vacuum tightness is 10 -4Pa~10 -3Pa is warming up to 800~900 ℃, insulation 260~320min with 15 ℃/min, is chilled to 400 ℃, insulation 120min with 3 ℃/min again, is cooled to room temperature with 18 ℃/min~23 ℃/min again.
9. like each described preparation method of claim 1~4; 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; Speed with 10~20 ℃/min rises to 1500 ℃, 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 is: vacuum tightness is 10 -4Pa~10 -3Pa is warming up to 800~900 ℃, insulation 260~320min with 15 ℃/min, is chilled to 400 ℃, insulation 120min with 3 ℃/min again, is cooled to room temperature with 18 ℃/min~23 ℃/min again.
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