CN102796904B - 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 PDFInfo
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- CN102796904B CN102796904B CN 201110301039 CN201110301039A CN102796904B CN 102796904 B CN102796904 B CN 102796904B CN 201110301039 CN201110301039 CN 201110301039 CN 201110301039 A CN201110301039 A CN 201110301039A CN 102796904 B CN102796904 B CN 102796904B
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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
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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
- A61L27/50—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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
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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
- 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
Technical field
The present invention relates to a kind of porous medical metal implanted material and preparation method thereof, particularly relate to medical embedded porous metal material of a kind of alternative weight bearing area osseous tissue and preparation method thereof.
Background technology
The porous medical metal implanted material has the important and special purposes such as treatment osseous tissue wound, bone formation necrosis, and existing this common class material has porous metals rustless steel, porous metals titanium etc.Porous embedded material as osseous tissue wound and the use of bone formation necrosis therapeutic, its porosity should reach 30～80%, and hole preferably all is communicated with and is uniformly distributed, or make it as required both consistent with the bone growth of human body, alleviate again the weight of material itself, to be applicable to human body, implanted use.
And refractory metals tantalum/niobium, because it has outstanding biocompatibility, its porous material is expected to the conventional medical metallic biomaterial such as aforementioned as an alternative.Due to metal tantalum/niobium to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, further the going deep into as the body implanting material cognition to tantalum/niobium, people implant and become more and more urgent by the demand of porous metals tantalum/niobium material human body, also more and more higher to its requirement.Wherein, as the medical embedded metal tantalum/niobium of porous, if can have the very high physical and mechanical properties that is uniformly distributed interconnected pore and adapts with human body, it is expected to as a kind of novel osseous tissue substitution material.
As medical embedded porous metal material just as porous metal material be to take powder sintering as main processing method like that basically, in particular for obtain porosity communication and equally distributed porous metal foam structure adopt after the dipping of metal dust slurry on Organic Foam Material in powder sintering drying to reburn to be called for short the foam impregnation method in the majority for knot.About powder sintered obtained porous metal material usually its Metal Mechanic Property be not fine, its main cause is the problem of subsiding how arranged on technique in the support of pore-forming medium and elimination relation, metal powder sintered process.And all there is no good solution in known bibliographical information and laissez-faire nature.
Adopt bibliographical information that metal powder sintered legal system makes porous tantalum/niobium seldom, particularly take and obtain medical embedded material and almost do not have with the porous tantalum/niobium powder sintering process bibliographical information that is purpose.Can reference be that publication number is CN200510032174, title " three-dimensional through hole or part hole are connected with each other porous metal foam and preparation method thereof " and CN200710152394, title " a kind of porous foam tungsten and preparation method thereof ".Yet porous metals that it obtains or for filtering material use, or share for Aero-Space and other high-temperature field but not use as medical metal implanted material, moreover also non-porous tantalum/niobium of the porous metals of processing.
About porous tantalum, US5282861 discloses a kind of perforate tantalum material and preparation thereof that is applied to spongy bone implant, cell and organizes sensor.This porous tantalum is made by pure business tantalum, it take the polyurethane precursor, and to carry out the carbon skeleton that thermal degradation obtains be support, this carbon skeleton is multiple dodecahedron, it in it, is the mesh-like structure, integral body spreads all over micropore, porosity can be up to 98%, then the method by chemical vapour deposition, infiltration is attached on carbon skeleton to form the porous metals micro structure, referred to as chemical deposition by the commercially pure tantalum.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtains is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight accounts for 1% left and right.Document is further put down in writing, the comprcssive strength 50～70MPa of this porous material, elastic modelling quantity 2.5～3.5GPa, tensile strength 63MPa.But the load-bearing bone tissue is as the porous tantalum of the medical embedded materials such as skull as an alternative by it, and the mechanical property of its material is obvious weak point as ductility has, can have influence on the follow-up processing to porous tantalum material itself, such as cutting of profiled member etc.Also all there is such deficiency in the same product obtained in aforesaid metal powder sintered method.Due to the limitation of its preparation method, the finished product purity of acquisition is inadequate, 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 medical porous metal material that is applicable to substitute the load-bearing bone tissue that a kind of product purity is high.
Another object of the present invention is to provide the preparation method of above-mentioned medical porous metal material.
The objective of the invention is to realize by following technological means:
A kind of medical porous metal material of alternative load-bearing bone tissue is characterized in that: by the tantalum powder, with pore creating material, forming agent, mixed, more repressed molding, defat, sintering, cooling and heat treatment makes; Described compressing be that described mixed-powder is pressed in Organic Foam Material, its pressure is 50～100Mpa, described skimming processes is that the speed with 0.3 ℃/min～2 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 300min～360min; Described pore creating material is ammonium bicarbonate or hydrogen peroxide, described forming agent is one or more in stearic acid, zinc stearate, paraffin, synthetic resin (being preferably butadiene-styrene rubber or isoprene rubber), and the medical porous tantalum material pore diameter of formation is 100～500 μ m, porosity between 55～65%, elastic modelling quantity is that 3.8～4.2Gpa, percentage elongation are 9.3～10.7%.
In the R&D process of medical porous metal material, medical porous metal material is the material of load-bearing bone tissue as an alternative, require that its porosity is large, tissue is just easily grown into like this, thereby good biocompatibility brings into play its effect fully, but porosity is larger, aperture is larger, mechanical property just can not get guaranteeing as intensity, toughness; Otherwise, mechanical property got well and easily make that porosity is too small, biocompatibility is bad, the also excessive discomfort that causes of density; The syntheti c route of medical porous tantalum is numerous, but the inventor has creatively proposed the employing above-mentioned steps, technique prepares the medical porous tantalum embedded material, the problems such as the difficult product quality of controlling, making of plug-hole, soaking paste process that adopts cement-dipping method to be prone to is inhomogeneous have effectively been prevented; Porous tantalum material that it makes through its impurity content of test can be lower than 0.2%, its biocompatibility and biological safety good, density reachable 5.83～7.50g/cm
3, porosity can reach 55～65%, and pore diameter can reach 100～500 μ m; Elastic modelling quantity can reach that 3.8～4.2Gpa, percentage elongation reach 9.3～10.7%, bending strength can reach 100～120Mpa, comprcssive strength can reach 60～70Mpa, its biocompatibility, obdurability are all excellent, approach human bearing's osseous tissue, porous tantalum of the present invention is suitable for substituting the medical embedded material of load-bearing bone tissue very much.
The mean diameter of the Ta powder that the present invention adopts is less than 43 microns, oxygen content is less than 0.1%, is commercially available prod; Above-mentioned pore creating material, forming agent also are commercially available prod.It is 10 that vacuum environment of the present invention preferably adopts vacuum
-4pa～10
-3the vacuum condition of Pa.Above-mentioned Organic Foam Material optimization polyurethane foam, aperture 0.48～0.89mm more preferably, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °, and (most preferably aperture is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness) polyurethane foam in.
In R&D process, the inventor further studies discovery, if control bad in above-mentioned preparation, though can make and be suitable for as mentioned above substituting the medical embedded material of load-bearing bone tissue but constant product quality is undesirable, qualification rate is not high: as difficult as powder pressing forming, be prone to layering, inhomogeneous suppressing rear section, the defat rear section there will be the technical problems such as crackle.
In order to make in powder compaction process molding easier, thereby raising yield rate, finished product hole uniformity, make preparation process more stable, the consumption of above-mentioned pore creating material is 15～25%, the consumption of forming agent is 7～12%, surplus is the tantalum powder, in volumn concentration, (in volumn concentration, be all the unit of directly calculating by the situation of final porous tantalum material, at above-mentioned pore creating material, pressed powder or calculate its corresponding quality weighing according to the densimeter of respective substance in the weighing of forming agent, if liquid substance directly adopts the volume weighing certainly), more preferably pore creating material is that hydrogen peroxide accounts for 18%, forming agent is that zinc stearate accounts for 11%, surplus is the tantalum powder, in volumn concentration, pressure in above-mentioned compressing process is preferably 75～87Mpa.
In order to make in skimming processes, idiosome is more stable, minimizing is prone to the distortion of part idiosome, aperture inhomogeneous, thereby further improve yield rate, quality stability, above-mentioned skimming processes is that the speed with 0.3 ℃/min～1 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 330min～350min; Further preferably with the speed of 0.8 ℃/min, progressively be warming up to 400～800 ℃, with argon, pass into and form protective atmosphere and be incubated 340min.
A kind of preparation method of medical porous metal material of alternative load-bearing bone tissue, adopt the die pressing sintering to form, its characteristics are: the tantalum powder is mixed with pore creating material, forming agent, then molding under 50～100Mpa, described mixed-powder being pressed into to Organic Foam Material, defat, sintering, cooling and heat treatment make the medical porous metal material that substitutes the load-bearing bone tissue; Described pore creating material is ammonium bicarbonate or hydrogen peroxide, described forming agent is one or more in stearic acid, zinc stearate, paraffin, synthetic resin (being preferably butadiene-styrene rubber or isoprene rubber), wherein the consumption of pore creating material is 15～25%, the consumption of forming agent is 7～12%, surplus is the tantalum powder, all in volumn concentration; Described skimming processes is that the speed with 0.3 ℃/min～2 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 300min～360min.
The mean diameter of above-mentioned raw materials tantalum powder is less than 43 microns, oxygen content and is less than 0.1%; More preferably hydrogen peroxide accounts for 18% to above-mentioned pore creating material, forming agent is that zinc stearate accounts for 11%, surplus is the tantalum powder, in volumn concentration.Above-mentioned Organic Foam Material optimization polyurethane foam, aperture 0.48～0.89mm more preferably, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °, and (most preferably aperture is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness) polyurethane foam in.
For make the compacting embryo process processed in pressing pressure even, not stratified; thereby make final porous tantalum distribution of pores more evenly, quality is more stable; the pressure adopted in above-mentioned pressing process is preferably 75～87Mpa; the speed be preferably in above-mentioned skimming processes with 0.3 ℃/min～1 ℃/min progressively is warming up to 400～800 ℃; pass into and form protective atmosphere and be incubated 330min～350min with argon; further preferably with the speed of 0.8 ℃/min, progressively be warming up to 400～800 ℃, with argon, pass into and form protective atmosphere and be incubated 340min.
The present invention's further characteristics on the other hand are: in vacuum, be not less than 10
-4～10
-3pa, 2000～2200 ℃ of temperature, the temperature retention time vacuum-sintering of 1～5 hour is processed and is made porous sintered body.Can the filling with inert gas protection replace vacuum protection during the sintering process insulation; Finally carry out the vacuum annealing processing, wherein vacuum annealing is processed and is referred to that continuation keeps temperature in 1000～1250 ℃ after vacuum-sintering, temperature retention time 1～4 hour, and vacuum is not less than 10
-4～10
-3pa.
The vacuum-sintering condition also includes: vacuum is not less than 10
-3pa, rise to 1200 ℃～1500 ℃ with the heating rate of 10～20 ℃/min from room temperature, after insulation 1h～2h; Be warming up to 2000～2200 ℃ with the heating rate lower than 20 ℃/min again, at least be incubated 2h～4h.
Cooling condition after vacuum-sintering also includes: vacuum is not less than 10
-3pa, with not higher than 25 ℃/min, be not less than 10 ℃/min and gradually fall the cooldown rate mode, and to sintered porous bodies segmentation cooling down to 800 ℃, each section temperature retention time 30min～90min, then cool to room temperature with the furnace.
The vacuum annealing condition also includes: vacuum is not less than 10
-4pa, rise to 1000～1250 ℃ with the speed higher than 30 ℃/min not, insulation 4h～6h; After first slow, to be not less than 5 ℃/min but higher than the cooldown rate segmentation of 30 ℃/min, not to be cooled to room temperature soon, the temperature retention time of each section tapers off and is no more than in 1.5h～3h and selects again.
Further characteristics are on this basis: described ungrease treatment condition also includes: the speed with 1～2 ℃/min rises to 400 ℃ from room temperature, insulation 300～330min, rise to 600～800 ℃ with the speed of 0.3～0.8 ℃/min from 400 ℃, be incubated 340～360min; Described vacuum-sintering condition also includes: the speed with 10～15 ℃/min rises to 1200～1250 ℃ from room temperature, is incubated 30～60min, and vacuum is 10
-4pa～10
-3pa, rise to 1500 ℃ with the speed of 10～20 ℃/min, is incubated 30～60min, and vacuum is 10
-4pa～10
-3pa, rise to 2000～2200 ℃ with the speed of 6～20 ℃/min, is incubated 120～240min, and vacuum is 10
-4pa～10
-3pa; Cooling condition after vacuum-sintering also includes: vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, is incubated 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, is incubated 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Described vacuum annealing condition also includes: the speed with 15～30 ℃/min rises to 1000～1250 ℃, is incubated 240～480min, and vacuum is 10
-4pa～10
-3pa, then be cooled to 1000 ℃ with the speed of 5～10 ℃/min, being incubated 90～180min, vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 800 ℃, is incubated 60～120min, and vacuum is 10
-4pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum is 10
-4pa～10
-3pa.
The character of metal tantalum and niobium is extremely similar, and said method equally also is applicable to the preparation of medical porous niobium material.
Porous tantalum preparation method of the present invention has adopted pure physics die pressing, makes the content of impurity in final porous tantalum material extremely low, has effectively improved biocompatibility and biological safety; The optimization of process conditions of, defat compressing to the present invention, sintering and annealing steps, make that yield rate is high, finished product aperture uniformity is better, make that preparation process is more stable, quality stability good, effectively eliminated thermal stress, made organizing of porous tantalum material more even, with the mechanical property that further improves porous tantalum, as intensity, toughness, all be improved simultaneously, preparation technology of the present invention make product qualified rate high, produce stablely, conforming product rate can be up to 92%.Porous tantalum finished product even pore distribution and connection that the present invention makes, good biocompatibility, through its impurity content of test can be lower than 0.2%, density reachable 5.83～7.50g/cm
3, porosity can reach 55～65%, and pore diameter can reach 100～500 μ m; Elastic modelling quantity can reach 3.8～4.2Gpa, percentage elongation reaches 9.3～10.7%, bending strength can reach 100～120Mpa, comprcssive strength can reach 60～70Mpa, efficiently solve the medical porous tantalum material of weight bearing area as an alternative and should ask its porosity to require more greatly, again the contradiction that mechanical property is good, porous tantalum of the present invention is suitable for the medical embedded material of load-bearing bone tissue as an alternative very much.
The specific embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples only are used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in art can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
It is pore creating material for forming agent, ammonium bicarbonate or hydrogen peroxide that a kind of medical porous tantalum material of alternative load-bearing bone tissue is specifically selected one or more in stearic acid, zinc stearate, paraffin, synthetic rubber, being less than 43 microns, oxygen content with mean diameter is less than 0.1% tantalum powder and mixes, molding under 50～100Mpa, described mixed-powder being pressed into to Organic Foam Material, then through defat, sintering, cooling and heat treatment and obtain; Described skimming processes is that the speed with 0.3 ℃/min～2 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 300min～360min.The medical porous tantalum material pore diameter formed is 100～500 μ m, porosity between 55～65%, elastic modelling quantity is that 3.8～4.2Gpa, percentage elongation are 9.3～10.7%.
More particularly, above-mentioned porous tantalum is that the tantalum powder of the above-mentioned pore creating material of the above-mentioned forming agent, 15～25% (in volumn concentration) of 7～12% (in volumn concentrations) and surplus is mixed, and puts it in injection moulding machine and is pressed into molding in polyurethane foam; Being placed in the tungsten device puts into the special atmosphere oven that pure argon gas (99.9999%) passes into formation and progressively is warming up to uniform temperature again, and insulation is carried out ungrease treatment to remove pore creating material, forming agent and polyurethane foam, wherein before heating up, first pass into argon to get rid of furnace air, the sample furnace cooling after defat; Be placed in the fine vacuum high temperature sintering furnace and progressively be warming up to 2000～2200 ℃ with the tungsten device for the sample after ungrease treatment; temperature retention time is carried out vacuum-sintering in 1～5 hour; before heating up, the vacuum of sintering furnace at least will reach proper level; sample furnace cooling after vacuum-sintering; keep certain vacuum or cooling to keep uniform temperature in reasonable time by certain cooldown rate segmentation in cooling procedure, in insulating process, can adopt filling with inert gas as protective atmosphere.Being placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with the corundum container progressively heats up, is incubated and carry out the stress relief annealing processing; the certain vacuum of maintenance before heating up in annealing furnace; sample furnace cooling after vacuum annealing is processed; also keep certain vacuum or cooling to keep uniform temperature in reasonable time by certain cooldown rate segmentation in cooling procedure; in insulating process, can adopt filling with inert gas as protective atmosphere, finally carry out conventional post processing and make porous tantalum.
For ungrease treatment, skimming processes is that the speed with 0.3 ℃/min～1 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 330min～350min; Further preferably with the speed of 0.8 ℃/min, progressively be warming up to 400～800 ℃, with argon, pass into and form protective atmosphere and be incubated 340min.Carry out the vacuum-sintering processing for the sample after ungrease treatment, it to be placed in the fine vacuum high temperature sintering furnace to the highest sintering temperature that is warming up to tantalum with certain heating rate with the tungsten device carry out vacuum-sintering, before heating up, sintering furnace keeps certain vacuum, be warming up to for example 1200 ℃～1250 ℃ with certain heating rate, insulation, keep vacuum; Be warming up to again for example 1250 ℃～1500 ℃ with certain heating rate, insulation, then be warming up to for example the highest sintering temperature of tantalum with certain heating rate, insulation, maintenance vacuum; Sintering is complete, keeps vacuum, with certain rate of temperature fall, is cooled to for example 1500 ℃～1600 ℃, insulation, then be cooled to for example 1200 ℃～1250 ℃ with certain rate of temperature fall, insulation, also with certain rate of temperature fall, be cooled to for example 800 ℃, then furnace cooling.Carry out the vacuum annealing processing for the cooled sample of vacuum-sintering, it to be placed in to vacuum annealing furnace with the corundum container be warming up to for example 1000 ℃～1250 ℃ with certain heating rate and carry out the stress relief annealing processing, maintenance vacuum before heating up in annealing furnace, rise to 1000 ℃～1250 ℃ with certain heating rate from room temperature, insulation, keep vacuum; Be cooled to for example 1000 ℃ with certain rate of temperature fall again, insulation; Be cooled to for example 800 ℃ with certain rate of temperature fall again, insulation; Also with the cooling room temperature of certain rate of temperature fall.Finally carry out conventional post processing and make porous tantalum.
The inventor adopts metal powder sintered method mainly to take the physics die pressing as main, has done a large amount of theory analysises and experimental verification, obtain the porous tantalum product through its impurity content of test can be lower than 0.2%, density reachable 5.83～7.50g/cm
3, porosity can reach 55～65%, and pore diameter can reach 100～500 μ m; Elastic modelling quantity can reach 3.8～4.2Gpa, percentage elongation reaches 9.3～10.7%, and bending strength can reach 100～120Mpa, comprcssive strength can reach 60～70Mpa.
Embodiment 1: weighing zinc stearate, mean diameter are less than tantalum powder and the hydrogen peroxide mix homogeneously that 43 microns oxygen contents are less than 0.1%, and wherein zinc stearate accounts for 11%, and hydrogen peroxide accounts for 18%, the tantalum powder accounts for 71%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm under 82Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10
-4pa, be warming up to 400 ℃, insulation 320min with the heating rate of 2.0 ℃/min from room temperature; Heating rate with 0.5 ℃/min is warming up to 700 ℃, temperature retention time 350 minutes from 400 ℃ again.Vacuum-sintering: sintering in vacuum drying oven, 2000 ℃ of sintering temperatures, be incubated 2 hours, vacuum 10
-4pa, the protection of sintering process applying argon gas, remove surface dirt and dirt after the taking-up product, and the sample made carries out conventional post processing again and obtains the porous tantalum finished product.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous tantalum finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 6.24g/cm
3, porosity 60%, hole average diameter 200 μ m, elastic modelling quantity 4.0Gpa, percentage elongation 10.02%, bending strength 115MPa, comprcssive strength 66MPa.
Embodiment 2: take stearic acid, mean diameter is less than tantalum powder and the ammonium bicarbonate mix homogeneously that 43 microns oxygen contents are less than 0.1%, wherein stearic acid accounts for 7%, ammonium bicarbonate accounts for 25%, the tantalum powder accounts for 68%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm under 87Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10
-4pa, be warming up to 400 ℃, insulation 300min with the heating rate of 2 ℃/min from room temperature.Vacuum-sintering: sintering in vacuum drying oven, 2100 ℃ of sintering temperatures, be incubated 4 hours, vacuum 10
-4pa, the protection of sintering process applying argon gas, remove surface dirt and dirt after the taking-up product, and the sample made carries out conventional post processing again and obtains the porous tantalum finished product.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous tantalum finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 6.05g/cm
3, porosity 65%, hole average diameter 400 μ m, elastic modelling quantity 3.8Gpa, percentage elongation 9.5%, bending strength 100MPa, comprcssive strength 60MPa.
Embodiment 3: take butadiene-styrene rubber, mean diameter is less than tantalum powder and the hydrogen peroxide mix homogeneously that 43 microns oxygen contents are less than 0.1%, wherein butadiene-styrene rubber accounts for 12%, hydrogen peroxide accounts for 15%, the tantalum powder accounts for 73%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm under 52Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10
-4pa, be warming up to 400 ℃, insulation 360min with the heating rate of 0.3 ℃/min from room temperature.Vacuum-sintering: sintering in vacuum drying oven, 2200 ℃ of sintering temperatures, be incubated 2.5 hours, vacuum 10
-3pa, the protection of sintering process applying argon gas, cooling coming out of the stove, remove product surface dust and dirt, and the sample made carries out conventional post processing again and obtains the porous tantalum finished product.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous tantalum finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 6.31g/cm
3, porosity 55%, hole average diameter 100 μ m, elastic modelling quantity 3.9Gpa, percentage elongation 9.3%, bending strength 105MPa, comprcssive strength 63MPa.
Embodiment 4: take paraffin, mean diameter is less than niobium powder and the ammonium bicarbonate mix homogeneously that 43 microns oxygen contents are less than 0.1%, wherein paraffin accounts for 10%, ammonium bicarbonate accounts for 20%, the niobium powder accounts for 70%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added in injection moulding machine and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm under 96Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10
-4pa, be warming up to 400 ℃, insulation 340min with the heating rate of 0.8 ℃/min from room temperature.Vacuum-sintering: sintering in vacuum drying oven, 2150 ℃ of sintering temperatures, be incubated 2 hours, vacuum 10
-4pa, the protection of sintering process applying argon gas, cooling coming out of the stove, remove product surface dust and dirt, and the sample made carries out conventional post processing again and obtains the porous niobium finished product.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous niobium finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 3.77g/cm
3, porosity 56%, hole average diameter 108 μ m, elastic modelling quantity 3.0Gpa, percentage elongation 9.8%, bending strength 67MPa, comprcssive strength 54MPa.
Embodiment 5: a kind of porous tantalum, and it is less than with particle diameter the ta powder that 43 μ m, oxygen content are less than 0.1%, and stearic acid and hydrogen peroxide mixed powder are raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, stearic acid accounts for 11%, hydrogen peroxide accounts for 22%, ta powder accounts for 67%, in volumn concentration;
Compressing: that the raw material mixed-powder is added in injection moulding machine and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015g/cm under 78Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding;
After compressing, mixed-powder is put into to the nonoxidizing atmosphere stove and be warming up to 800 ℃ with certain heating rate, protective atmosphere is that 99.999% argon carries out ungrease treatment, its before heating up, first pass into pure argon gas at least 30min to get rid of furnace air, the temperature control process: the speed with 1.5 ℃/min rises to 400 ℃ from room temperature, insulation 300min, argon intake 0.5L/min; Speed with 0.6 ℃/min rises to 800 ℃, insulation 340min, argon intake 1/L/min from 400 ℃; Powered-down again, the sample furnace cooling after defat, argon intake 1L/min, until close argon while being cooled to room temperature;
Be placed in and be warming up to 2200 ℃ with certain heating rate in the fine vacuum high temperature sintering furnace and carry out vacuum-sintering with the tungsten device for the sample after ungrease treatment, before heating up, the vacuum of sintering furnace at least will reach 10
-4pa, rise to 1200 ℃ with the speed of 10～15 ℃/min from room temperature, insulation 30min, and vacuum is 10
-4pa; Speed with 10 ℃/min rises to 1500 ℃, insulation 30min, and vacuum is 10
-4pa～10
-3pa; Speed with 6 ℃/min rises to 2200 ℃, insulation 120min, and vacuum is 10
-3pa; Sintering is complete, and vacuum is 10
-3pa, be cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; Speed with 12 ℃/min is cooled to 1200 ℃, insulation 60min; Speed with 10 ℃/min is cooled to 800 ℃, then furnace cooling;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with the corundum container and be warming up to 1250 ℃ with certain heating rate and carry out the stress relief annealing processing, the vacuum before heating up in annealing furnace at least will reach 10
-4pa, rise to 1250 ℃ with the speed of 15 ℃/min from room temperature, insulation 240min, and vacuum is 10
-4pa～10
-3pa; Speed with 5 ℃/min is cooled to 1000 ℃ again, insulation 180min, and vacuum is 10
-4pa～10
-3pa; Speed with 10 ℃/min is cooled to 800 ℃, insulation 120min, and vacuum is 10
-4pa; Speed with 20 ℃/min is cooled to room temperature, and vacuum is 10
-4pa.Finally carry out conventional post processing and make porous tantalum.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous tantalum finished product detected the inventor: its impurity content is lower than 0.2%, its even pore distribution, density 6.8g/cm
3, porosity 62%, hole average diameter 250 μ m, elastic modelling quantity 4.15Gpa, percentage elongation 10.32%, bending strength 118MPa, comprcssive strength 65MPa.This preparation technology's product qualification rate reaching 90.3% as calculated.
In the method provided at above-described embodiment 5, we can also do other selections to wherein each kind of condition can obtain porous tantalum of the present invention or porous niobium equally.
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 |
| Elastic modelling quantity (GPa) | 3.9 | 2.1 | 4.2 |
| Percentage elongation (%) | 9.8 | 10.03 | 9.4 |
| Bending strength (MPa) | 120 | 79 | 109 |
| Comprcssive strength (MPa) | 63 | 55 | 68 |
Claims (10)
1. the medical porous metal material of an alternative load-bearing bone tissue is characterized in that: by the tantalum powder, with pore creating material, forming agent, mixed, more repressed molding, defat, sintering, cooling and heat treatment makes; Described compressing be that described mixed-powder is pressed into to molding in Organic Foam Material, compressing pressure is 50～100MPa, described skimming processes is that the speed with 0.3 ℃/min～2 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 300min～360min; Described pore creating material is ammonium bicarbonate or hydrogen peroxide, described forming agent is one or more in stearic acid, zinc stearate, paraffin, synthetic resin, and the medical porous tantalum material pore diameter of formation is 100～500 μ m, porosity between 55～65%, elastic modelling quantity is that 3.8～4.2GPa, percentage elongation are 9.3～10.7%.
2. medical porous metal material as claimed in claim 1 is characterized in that: the mean diameter of Ta powder is less than 43 microns, oxygen content and is less than 0.1%; Described synthetic resin is butadiene-styrene rubber or isoprene rubber; Described Organic Foam Material is aperture 0.56～0.72mm, density 0.025g/cm
3, hardness 50
0～80
0polyurethane foam.
3. medical porous metal material as claimed in claim 1 or 2 is characterized in that: the consumption of described pore creating material is 15～25%, the consumption of described forming agent is 7～12%, surplus is the tantalum powder, all in volumn concentration; Pressure in described compressing process is 75～87MPa.
4. medical porous metal material as claimed in claim 3 is characterized in that: described pore creating material is that hydrogen peroxide accounts for 18%, described forming agent is that zinc stearate accounts for 11%, surplus is the tantalum powder, in volumn concentration.
5. medical porous metal material as claimed in claim 1 is characterized in that: described skimming processes is that the speed with 0.3 ℃/min～1 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 330min～350min.
6. the preparation method of the medical porous metal material of an alternative load-bearing bone tissue as claimed in claim 1, adopt the die pressing sintering to form, its characteristics are: the tantalum powder is mixed with pore creating material, forming agent, then to be pressed into aperture under 50～100MPa be 0.56～0.72mm density 0.025g/cm
3, hardness 50
0～80
0polyurethane foam in molding, defat, sintering, cooling and heat treatment make the medical porous metal material that substitutes the load-bearing bone tissue; Described pore creating material is ammonium bicarbonate or hydrogen peroxide, described forming agent is one or more in stearic acid, zinc stearate, paraffin, synthetic resin, the consumption of described pore creating material is 15～25%, the consumption of described forming agent is 7～12%, surplus is the tantalum powder, all in volumn concentration; Described skimming processes is that the speed with 0.3 ℃/min～2 ℃/min progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 300min～360min.
7. preparation method as claimed in claim 6 is characterized in that: the mean diameter of Ta powder is less than 43 microns, oxygen content and is less than 0.1%; Described pore creating material is that hydrogen peroxide accounts for 18%, described forming agent is that zinc stearate accounts for 11%, surplus is the tantalum powder, in volumn concentration; The pressure adopted in described pressing process is 75～87MPa.
8. preparation method as claimed in claim 7 is characterized in that: the speed with 0.3 ℃/min～1 ℃/min in described skimming processes progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 330min～350min.
9. preparation method as claimed in claim 8, it is characterized in that: the speed with 0.8 ℃/min in described skimming processes progressively is warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 340min.
10. preparation method as described as claim 6 or 7, it is characterized in that: described vacuum-sintering condition is: the speed with 10～15 ℃/min rises to 1200～1250 ℃ from room temperature, is incubated 30～60min, and vacuum is 10
-4pa～10
-3pa, rise to 1500 ℃ with the speed of 10～20 ℃/min, is incubated 30～60min, and vacuum is 10
-4pa～10
-3pa, rise to 2000～2200 ℃ with the speed of 6～20 ℃/min, is incubated 120～240min, and vacuum is 10
-4pa～10
-3pa; Cooling condition after vacuum-sintering is: vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, is incubated 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, is incubated 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; The vacuum annealing heat-treat condition is: the speed with 15～30 ℃/min rises to 1000～1250 ℃, is incubated 240～480min, and vacuum is 10
-4pa～10
-3pa, then be cooled to 1000 ℃ with the speed of 5～10 ℃/min, being incubated 90～180min, vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 800 ℃, is incubated 60～120min, and vacuum is 10
-4pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum is 10
-4pa～10
-3pa.
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| PCT/CN2012/081866 WO2013044780A1 (en) | 2011-09-29 | 2012-09-24 | Medical porous metal material for weight-bearing bone tissue replacement and preparation method therefor |
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| CN104593659B (en) * | 2014-12-17 | 2017-01-18 | 北京科技大学 | Method for preparing porous metallic iron |
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| CN113263179B (en) * | 2021-05-25 | 2022-10-25 | 矿冶科技集团有限公司 | Tantalum powder for medical porous framework and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5282861A (en) * | 1992-03-11 | 1994-02-01 | Ultramet | Open cell tantalum structures for cancellous bone implants and cell and tissue receptors |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
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| US7635447B2 (en) * | 2006-02-17 | 2009-12-22 | Biomet Manufacturing Corp. | Method and apparatus for forming porous metal implants |
| EP2149414A1 (en) * | 2008-07-30 | 2010-02-03 | Nederlandse Centrale Organisatie Voor Toegepast Natuurwetenschappelijk Onderzoek TNO | Method of manufacturing a porous magnesium, or magnesium alloy, biomedical implant or medical appliance. |
| CN101660076A (en) * | 2009-10-14 | 2010-03-03 | 北京师范大学 | Macro mesh structural porous tantalum prepared by dipping and sintering organic foams |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5282861A (en) * | 1992-03-11 | 1994-02-01 | Ultramet | Open cell tantalum structures for cancellous bone implants and cell and tissue receptors |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
Non-Patent Citations (2)
| Title |
|---|
| 烧结温度对泡沫铌力学性能及微观组织的影响;节云峰等;《中国有色金属学报》;20101031;第20卷(第10期);第2014-2018页 * |
| 节云峰等.烧结温度对泡沫铌力学性能及微观组织的影响.《中国有色金属学报》.2010,第20卷(第10期),第2014-2018页. |
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