CN102796900A - Medical porous metal material and preparation method thereof - Google Patents

Medical porous metal material and preparation method thereof Download PDF

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Publication number
CN102796900A
CN102796900A CN2011102980000A CN201110298000A CN102796900A CN 102796900 A CN102796900 A CN 102796900A CN 2011102980000 A CN2011102980000 A CN 2011102980000A CN 201110298000 A CN201110298000 A CN 201110298000A CN 102796900 A CN102796900 A CN 102796900A
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insulation
powder
speed
warming
tantalum
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CN2011102980000A
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CN102796900B (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 CN201110298000.0A priority Critical patent/CN102796900B/en
Priority to PCT/CN2012/081864 priority patent/WO2013044778A1/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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/08—Methods for forming porous structures using a negative form which is filled and then removed by pyrolysis or dissolution
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process

Abstract

The invention discloses a medical porous metal material for replacing dentale and a preparation method of the medical porous metal material. The preparation method of the medical porous metal material comprises the following steps of: mixing tantalum powder with polyvinyl alcohol and sodium bicarbonate to form mixed powder, and then pressing the mixed powder in an organic foam under the pressure of 50-100 MPa; and carrying out the steps of forming, degreasing, sintering, cooling and heat processing to obtain the medical porous metal material; in the step of heat processing, the vacuum degree is 10 to the power of -4 Pa to 10 to the power of -3 Pa, the temperature is raised to 800-900 DEG C at a speed of 10-20 DEG C per minute and is preserved for 240-480 minutes, then the temperature is reduced to 400 DEG C at a speed of 2-5 DEG C per minute and is preserved for 120-300 minutes, and then furnace cooling is carried out till room temperature; and the formed porous tantalum material has the pore diameter of 10-25 microns, the porosity degree of 25-35%, the elastic modulus of 6.0-7.0 Gpa and the elongation percentage of 14-15%.

Description

A kind of medical porous metallic substance and preparation method thereof
Technical field
The present invention relates to a kind of medical porous metal implant material and preparation method thereof, particularly relate to medical porous metal implant material of a kind of alternative dense bone tissue and preparation method thereof.
Background technology
Porous medical metal embedded material has treatment osseous tissue wound, bone formation is downright bad and important and special purposes such as alternative dense bone tissue such as tooth, 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, amount of plastic deformation 15%.But with its porous tantalum as medical embedded materials such as dense bone tissue such as teeth, the mechanical property of its material such as ductility have obvious weak point, and can have influence on the follow-up processing to porous tantalum material itself, for example cutting of profiled member etc.Also all there is such deficiency at the product that aforesaid metal powder sintered method obtained equally.
Summary of the invention
The object of the present invention is to provide a kind of medical porous metallic substance that substitutes dentale that is applicable to of good toughness.
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; It is characterized in that: be mixed into mixed powder by tantalum powder and Z 150PH, sodium hydrogencarbonate, under 50～100Mpa, said mixed powder be pressed into again that moulding in the organic foam body, degreasing, sintering, cooling and heat treatment step make; Said heat treatment step 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; The medical porous tantalum material pore diameter that forms is 10～25 μ m, porosity between 25～35%, Young's modulus is 6.0～7.0Gpa, unit elongation 14～15%.
In the R&D process of medical porous tantalum material; The preparation route is numerous; But the contriver has creatively proposed to adopt above-mentioned process step to prepare fine and close medical porous tantalum embedded material; The above-mentioned thermal treatment process that particularly adopts has been eliminated internal stress fully, has been made the toughness of organizing more evenly, improved greatly prepared porous tantalum material of porous tantalum material; Through its foreign matter content of test can be lower than 0.2%, its biocompatibility and biological safety be good, density can reach 10.84～12.50g/cm 3, porosity can reach 25～35%, and pore diameter can reach 10～25 μ m; Young's modulus can reach that 6.0～7.0Gpa, unit elongation 14～15%, flexural strength can reach 120～130Mpa, ultimate compression strength can reach 100～140MPa, and porous tantalum of the present invention is suitable for substituting the medical embedded material of dentale very much.
The 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 Z 150PH, sodium hydrogencarbonate also are the commercially available prod.Above-mentioned Z 150PH mainly plays the moulding effect but it also possesses the pore-creating effect simultaneously, and above-mentioned sodium hydrogencarbonate plays the pore-creating effect.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 dentale as stated but product percent of pass is not high; Technology stable not ideal enough, influence its commercial scale prodn: difficult like powder pressing forming, be prone to layering, inhomogeneous in the compacting 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 Z 150PH is 5～10% in the above-mentioned mixed powder, the consumption of sodium hydrogencarbonate is 20～30%, surplus is the tantalum powder; (in volumn concentration is the unit of directly calculating through the situation of final porous tantalum material in volumn concentration; In above-mentioned mixed powder weighing, still calculate its corresponding quality weighing according to the densometer of respective substance), be preferably further that Z 150PH accounts for 7～9%, sodium hydrogencarbonate accounts for 26～29%, surplus is the tantalum powder; Pressure in the above-mentioned compression moulding process is preferably 70～80Mpa.
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 0.5 ℃/min～3 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 60min～240min; Further preferably progressively be warming up to 400～800 ℃, feed with argon gas and constitute protective atmosphere and be incubated 150min～240min with the speed of 2.5～3 ℃/min.
The preparation method of above-mentioned medical porous metallic substance; Adopt the compression molding sintering to form; Its characteristics are to be mixed into powder mix with tantalum powder and Z 150PH, sodium bicarbonate powder; Wherein the consumption of Z 150PH accounts for 5～10%, the consumption of sodium hydrogencarbonate accounts for 20～30%, surplus is the tantalum powder, in volumn concentration; Under 50～100Mpa, said mixed powder is pressed into moulding in the organic foam body, degreasing, vacuum sintering, cooling and thermal treatment again and makes the porous tantalum material; Said heat treatment step 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, is chilled to room temperature with stove then.
The median size of above-mentioned raw materials tantalum powder less than 43 microns, oxygen level less than 0.1%; Above-mentioned powder mix is preferably that Z 150PH accounts for 7～9%, sodium hydrogencarbonate accounts for 26～29%, surplus is the tantalum powder, is preferably further that Z 150PH accounts for 8%, sodium hydrogencarbonate accounts for 27%, 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, thus make final porous tantalum void distribution more evenly, quality is more stable, the pressure that adopts in the above-mentioned pressing process is preferably 70～80Mpa; The speed that is preferably in the above-mentioned skimming processes with 0.5 ℃/min～3 ℃/min progressively is warming up to 400～800 ℃; Feed the formation protective atmosphere and be incubated 60min～240min with argon gas; Further preferably progressively be warming up to 400～800 ℃ with the speed of 2.5～3 ℃/min; Feed to constitute protective atmosphere and be incubated 150min～240min with argon gas, further preferably progressively be warming up to 400～800 ℃, feed with argon gas and constitute protective atmosphere and be incubated 220min with the speed of 2.5 ℃/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: progressively be warming up to 600～800 ℃; Specifically be to feed with pure argon gas (99.9999%) to constitute protective atmosphere; Speed with 1～3 ℃/min rises to 400 ℃ from room temperature; Insulation 60～120min rises to 600～800 ℃, insulation 180～240min with the speed of 1.5～2.5 ℃/min 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; Effectively improved the mechanical property of porous tantalum, particularly its toughness is greatly enhanced, and density also is effectively controlled, makes its comfort as the dentale equivalent 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 93%.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 10.84～12.50g/cm 3, porosity can reach 25～35%, and pore diameter can reach 10～25 μ m; Young's modulus can reach that 6.0～7.0Gpa, unit elongation can reach 14%～15%, flexural strength can reach 120～130Mpa, ultimate compression strength can reach 100～140Mpa, and porous tantalum of the present invention is suitable for substituting the medical embedded material of dentale very much.
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 polyvinyl alcohol, median size are mixed into mixed powder less than 43 microns oxygen levels less than 0.1% tantalum powder and sodium hydrogencarbonate, and wherein Z 150PH accounts for 8%, sodium hydrogencarbonate accounts for 27%, the tantalum powder accounts for 65%, all in volumn concentration.Compression moulding: with arriving urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in the 70Mpa 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 protective atmosphere with the argon gas, is warming up to 400 ℃, insulation 110min with the temperature rise rate of 0.6 ℃/min from room temperature; Temperature rise rate with 1.5 ℃/min is warming up to 700 ℃, soaking time 190 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 12.50g/cm 3, porosity 25%, hole mean diameter 22 μ m, Young's modulus 6.5Gpa, unit elongation be 14.5%, flexural strength 130MPa, ultimate compression strength 135MPa.
Embodiment 2: weighing polyvinyl alcohol, median size are mixed into mixed powder less than 43 microns oxygen levels less than 0.1% tantalum powder and sodium hydrogencarbonate, and wherein Z 150PH accounts for 9%, sodium hydrogencarbonate accounts for 23%, the tantalum powder accounts for 68%, all in volumn concentration.Compression moulding: 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 protective atmosphere with the argon gas, is warming up to 400 ℃, insulation 100min with the temperature rise rate of 1.5 ℃/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 -4Pa～10 -3Pa is warming up to 800～900 ℃, insulation 240min with 10 ℃/min, is chilled to 400 ℃, insulation 300min with 5 ℃/min again, cools to room temperature with the furnace.
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 10.83g/cm 3, porosity 35%, unit elongation is 14%, hole mean diameter 10 μ m, Young's modulus 6.2GPa, flexural strength 122MPa, ultimate compression strength 113MPa.
Embodiment 3: weighing polyvinyl alcohol, median size are mixed into mixed powder less than 43 microns oxygen levels less than 0.1% tantalum powder and sodium hydrogencarbonate, and wherein Z 150PH accounts for 6%, sodium hydrogencarbonate accounts for 28%, the tantalum powder accounts for 66%, all in volumn concentration.Compression moulding: with arriving urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in the 66Mpa 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 protective atmosphere with the argon gas, is warming up to 700 ℃, insulation 200min with the temperature rise rate of 3 ℃/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 deepfreeze.Thermal treatment: be that vacuum tightness is 10 -4Pa is warming up to 800～900 ℃, insulation 480min with 20 ℃/min, is chilled to 400 ℃, insulation 120min with 2 ℃/min again, cools to room temperature with the furnace.
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 11.17g/cm 3, porosity 33%, hole mean diameter 20 μ m, Young's modulus 7.0GPa, unit elongation are 15%, flexural strength 120MPa, ultimate compression strength 130MPa.
Embodiment 4: weighing polyvinyl alcohol, median size are mixed into mixed powder less than 43 microns oxygen levels less than 0.1% niobium powder and sodium hydrogencarbonate, and wherein Z 150PH accounts for 5%, sodium hydrogencarbonate accounts for 20%, the niobium powder accounts for 75%, 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 protective atmosphere with the argon gas, is warming up to 550 ℃, insulation 240min with the temperature rise rate of 2.5 ℃/min from room temperature.Vacuum sintering: vacuum tightness is lower than 10 -4Pa～10 -3Pa, 2000～2200 ℃ of temperature, soaking time 1～5 hour, applying argon gas or other protection of inert gas during the sintering process insulation are to obtain porous material; Conventional processing under cooling.Thermal treatment: be that vacuum tightness is 10 -3Pa is warming up to 800～900 ℃, insulation 300min with 13 ℃/min, is chilled to 400 ℃, insulation 150min with 4 ℃/min again, cools to room temperature with the furnace.
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 6.02g/cm 3, porosity 30%, hole mean diameter 24 μ m, Young's modulus 2.8GPa, unit elongation are 14.8%, flexural strength 88MPa, ultimate compression strength 78MPa.
Embodiment 5: a kind of porous tantalum, it with particle diameter less than 43 μ m, oxygen level less than 0.1% ta powder, Z 150PH and sodium hydrogencarbonate powder mix are raw material, make through compression moulding, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment again.
Wherein, Z 150PH accounts for 10%, sodium hydrogencarbonate accounts for 30%, ta powder accounts for 60%, in volumn concentration;
Compression moulding: with arriving urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in the 56Mpa 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 1.8 ℃/min rises to 400 ℃ from room temperature, insulation 76min, argon gas feeding amount 0.5L/min; Speed with 2.5 ℃/min rises to 800 ℃, insulation 215min, 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 be warming up to 800 ℃ 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 is that vacuum tightness is 10 -3Pa is warming up to 800 ℃, insulation 270min with 18 ℃/min, is chilled to 400 ℃, insulation 130min with 3 ℃/min again, cools to room temperature with the furnace.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 12.34g/cm 3, porosity 26%, hole mean diameter 17 μ m, Young's modulus 6.8GPa, unit elongation are 15%, flexural strength 122MPa, ultimate compression strength 135MPa.This preparation technology's product qualification rate reaching 92.55%.
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 BDA0000096078110000071
Figure BDA0000096078110000072
Figure BDA0000096078110000081
Figure BDA0000096078110000091
Gained porous tantalum or porous niobium finished product are pressed preceding method and are detected:
Embodiment 6 7 8
Density (g/cm 3) 12.00 11.34 5.57
Porosity (%) 28 32 35
Aperture (μ m) 20 25 18
Young's modulus (GPa) 6.5 6.9 3.2
Flexural strength (MPa) 122 130 78
Ultimate compression strength (MPa) 115 130 73
Unit elongation (%) 14.86 14.21 14.55

Claims (10)

1. medical porous metallic substance; It is characterized in that: be mixed into mixed powder by tantalum powder and Z 150PH, sodium hydrogencarbonate, under 50～100Mpa, said mixed powder be pressed into again that moulding in the organic foam body, degreasing, sintering, cooling and heat treatment step make; Said heat treatment step 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; The medical porous tantalum material pore diameter that forms is 10～25 μ m, porosity between 25～35%, Young's modulus is 6.0～7.0Gpa, unit elongation 14～15%.
2. medical porous metallic substance as claimed in claim 1 is characterized in that: the consumption of Z 150PH is 5～10% in the said mixed powder, the consumption of sodium hydrogencarbonate is 20～30%, surplus is the tantalum powder, in volumn concentration; Said organic foam body is aperture 0.56～0.72mm, density 0.025g/cm 3, hardness 50 0～80 0Polyurethane foam.
3. medical porous metallic substance as claimed in claim 2 is characterized in that: Z 150PH accounts for 7～9% in the said mixed powder, sodium hydrogencarbonate accounts for 26～29%, surplus is the tantalum powder; Pressure in the said compression moulding process is preferably 70～80Mpa.
4. like claim 1,2 or 3 described medical porous metallic substance, it is characterized in that: said skimming processes is that the speed with 0.5 ℃/min～3 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 60min～240min; Further preferably progressively be warming up to 400～800 ℃, feed with argon gas and constitute protective atmosphere and be incubated 150min～240min with the speed of 2.5～3 ℃/min.
5. the preparation method of a medical porous metallic substance; Adopt the compression molding sintering to form; Its characteristics are: be mixed into powder mix with tantalum powder and Z 150PH, sodium bicarbonate powder; Wherein the consumption of Z 150PH accounts for 5～10%, the consumption of sodium hydrogencarbonate accounts for 20～30%, surplus is the tantalum powder, in volumn concentration; To the aperture 0.56～0.72mm in 50～100Mpa pressed again, density 0.025g/cm 3, hardness 50 0～80 0Polyurethane foam in moulding, degreasing, vacuum sintering, cooling and thermal treatment make the porous tantalum material; Said heat treatment step 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, is chilled to room temperature with stove then.
6. preparation method as claimed in claim 5 is characterized in that: the median size of said Ta powder less than 43 microns, oxygen level less than 0.1%; Said powder mix is preferably that Z 150PH accounts for 7～9%, sodium hydrogencarbonate accounts for 26～29%, surplus is the tantalum powder, in volumn concentration.
7. preparation method as claimed in claim 6 is characterized in that: said powder mix is preferably that Z 150PH accounts for 8%, sodium hydrogencarbonate accounts for 27%, surplus is the tantalum powder, in volumn concentration.
8. like claim 5,6 or 7 described preparing methods, it is characterized in that: the pressure that adopts in the said pressing process is preferably 70～80Mpa; 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 claim 5,6,7 or 8 described preparing methods, it is characterized in that: the speed that is preferably in the said skimming processes with 0.5 ℃/min～3 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 60min～240min;
Said vacuum sintering condition 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 said 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.
10. preparation method as claimed in claim 5; It is characterized in that: said skimming treatment is: progressively be warming up to 600～800 ℃; Specifically be feed to constitute protective atmosphere, rise to 400 ℃ from room temperature, insulation 60～120min with the speed of 1～3 ℃/min with pure argon gas (99.9999%); Speed with 1.5～2.5 ℃/min rises to 600～800 ℃, insulation 180～240min from 400 ℃; Said vacuum sintering is: 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; Being cooled to after the vacuum sintering: 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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