CN102796903B - 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 PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- 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
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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- 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
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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
Technical field
The present invention relates to a kind of preparation method of porous medical metal implanted material, particularly relate to a kind of preparation method that is applicable to the medical embedded metal material of porous of alternative weight bearing area osseous tissue.
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 a kind of preparation method of the porous metal material that is applicable to alternative weight bearing area osseous tissue of good toughness.
The objective of the invention is to realize by following technological means:
A kind of preparation method for preparing the medical porous metal material that substitutes the 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 make this porous metal material; Described compressing be that 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, and described forming agent is one or more in stearic acid, zinc stearate, paraffin, synthetic resin (being preferably butadiene-styrene rubber or isoprene rubber); Described heat treatment is that vacuum is 10
-4pa～10
-3pa, be warming up to 800～900 ℃, be incubated 240～480min with 10～20 ℃/min, then be chilled to 400 ℃, be incubated 120～300min with 2～5 ℃/min, then cools to room temperature with the furnace.
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; The above-mentioned Technology for Heating Processing particularly adopted, eliminated fully internal stress, made toughness and the technique of organizing more evenly, greatly improved prepared porous tantalum material of porous tantalum material quick and easy; 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 6.67～8.34g/cm
3, porosity can reach 50～60%, and pore diameter can reach 150～450 μ m; Elastic modelling quantity can reach that 4.5～6.0Gpa, percentage elongation reach 10.5～11.7%, 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.
Better for internal stress, the toughness of eliminating more fully material, above-mentioned heat treatment step is that vacuum is 10
-4pa～10
-3pa, be warming up to 800～900 ℃, be incubated 260～320min with 15 ℃/min, then be chilled to 400 ℃, insulation 120min with 3 ℃/min, then be cooled to room temperature with 18 ℃/min～23 ℃/min.
Vacuum-sintering condition of the present invention includes: vacuum 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.
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; Speed with 10～20 ℃/min rises to 1500 ℃, is incubated 30～60min, and vacuum is 10
-4pa～10
-3pa, rise to 2000～2200 ℃ with the speed of 6～20 ℃/min, is incubated 120～240min, and vacuum is 10
-4pa～10
-3pa; Cooling condition after vacuum-sintering also includes: vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, is incubated 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, is incubated 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Described vacuum annealing condition is: vacuum is 10
-4pa～10
-3pa, be warming up to 800～900 ℃, be incubated 260～320min with 15 ℃/min, then be chilled to 400 ℃, insulation 120min with 3 ℃/min, then be cooled to room temperature with 18 ℃/min～23 ℃/min.
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, compressing to the present invention, defat, the optimization of process conditions of sintering and annealing steps, make yield rate high, finished product aperture uniformity is better, make preparation process more stable, quality stability is good, effectively eliminated thermal stress, make organizing of porous tantalum material more even, with the mechanical property that further improves porous tantalum as intensity, toughness all is improved simultaneously, particularly its toughness is greatly enhanced, density also is effectively controlled simultaneously, make its comfort as the human loaded bone tissue substitute material good, preparation technology of the present invention makes product qualified rate high, produce stable, conforming product rate can be up to 94%.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 6.67～8.34g/cm
3porosity can reach 50～60%, pore diameter can reach 150～450 μ m, elastic modelling quantity can reach 4.5～6.0Gpa, percentage elongation reaches 10.5～11.7%, 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.
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 80Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10
-4pa, be warming up to 400 ℃, insulation 324min with the heating rate of 1.3 ℃/min from room temperature; Heating rate with 0.7 ℃/min is warming up to 650 ℃, temperature retention time 340 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, then carry out conventional cooling processing.Heat treatment: be that vacuum is 10
-4pa～10
-3pa, be warming up to 800～900 ℃, be incubated 260～320min with 15 ℃/min, then be chilled to 400 ℃, insulation 120min with 3 ℃/min, with 18～23 ℃/min, is cooled to room temperature.
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 6.69g/cm
3, porosity 57%, hole average diameter 330 μ m, elastic modelling quantity 6.0Gpa, percentage elongation 11.33%, bending strength 20MPa, comprcssive strength 67MPa.
Embodiment 2: take butadiene-styrene rubber, mean diameter and be less than 43 microns oxygen contents and be less than 0.1% tantalum powder and ammonium bicarbonate and be mixed into mixed-powder, wherein butadiene-styrene rubber accounts for 11.5%, ammonium bicarbonate accounts for 17%, the tantalum powder accounts for 71.5%, 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 64Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle molding.Ungrease treatment: vacuum 10
-4pa, be warming up to 700 ℃, insulation 332min with the heating rate of 1.2 ℃/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, then carry out conventional cooling processing.Heat treatment: be that vacuum is 10
-3pa, be warming up to 800～900 ℃, insulation 400min with 14 ℃/min, then be chilled to 400 ℃, insulation 200min with 4 ℃/min, with 21 ℃/min, is cooled to room temperature.
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 7.3g/cm
3, porosity 53%, hole average diameter 209 μ m, elastic modelling quantity 5.3Gpa, percentage elongation 11.54%, bending strength 110MPa, comprcssive strength 66MPa.
Embodiment 3: take paraffin, mean diameter is less than tantalum powder and the hydrogen peroxide mix homogeneously that 43 microns oxygen contents are less than 0.1%, wherein paraffin accounts for 7%, hydrogen peroxide accounts for 15%, the tantalum powder accounts for 78%, 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
-3pa, be warming up to 800 ℃, insulation 300min with the heating rate of 2 ℃/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, then carry out conventional cooling processing.Heat treatment: be that vacuum is 10
-4pa, be warming up to 800～900 ℃, insulation 240min with 20 ℃/min, then be chilled to 400 ℃, insulation 300min with 5 ℃/min, with 23 ℃/min, is cooled to room temperature.
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 6.67g/cm
3, porosity 51%, hole average diameter 430 μ m, elastic modelling quantity 4.7Gpa, percentage elongation 10.6%, bending strength 102MPa, comprcssive strength 60MPa.
Embodiment 4: take stearic acid, mean diameter is less than niobium powder and the ammonium bicarbonate mix homogeneously that 43 microns oxygen contents are less than 0.1%, wherein stearic acid accounts for 12%, ammonium bicarbonate accounts for 25%, the niobium powder accounts for 63%, 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 740 ℃, 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, then carry out conventional cooling processing.Heat treatment: be that vacuum is 10
-3pa, be warming up to 800～900 ℃, insulation 480min with 10 ℃/min, then be chilled to 400 ℃, insulation 120min with 2 ℃/min, with 18 ℃/min, is cooled to room temperature.
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 3.86g/cm
3, porosity 55%, hole average diameter 450 μ m, elastic modelling quantity 3.0Gpa, percentage elongation 11.6%, bending strength 78MPa, comprcssive strength 52MPa.
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 zinc stearate and ammonium bicarbonate mixed powder are raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, zinc stearate accounts for 9%, ammonium bicarbonate accounts for 20%, ta powder accounts for 71%, 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 69Mpa
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 1L/min from 400 ℃; Powered-down again, the sample furnace cooling after defat, argon intake 1L/min, until close argon while being cooled to room temperature;
Be placed in and be warming up to 2200 ℃ with certain heating rate in the fine vacuum high temperature sintering furnace and carry out vacuum-sintering with the tungsten device for the sample after ungrease treatment, before heating up, the vacuum of sintering furnace at least will reach 10
-4pa, rise to 1200 ℃ with the speed of 10～15 ℃/min from room temperature, insulation 30min, and vacuum is 10
-4pa; Speed with 10 ℃/min rises to 1500 ℃, insulation 30min, and vacuum is 10
-4pa～10
-3pa; Speed with 6 ℃/min rises to 2200 ℃, insulation 120min, and vacuum is 10
-3pa; Sintering is complete, and vacuum is 10
-3pa, be cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; Speed with 12 ℃/min is cooled to 1200 ℃, insulation 60min; Speed with 10 ℃/min is cooled to 800 ℃, then furnace cooling;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with the corundum container and process with certain heating rate intensification stress relief annealing, the vacuum before heating up in annealing furnace at least will reach 10
-4pa is that vacuum is 10
-4pa～10
-3pa, be warming up to 800～900 ℃, insulation 300min with 17 ℃/min, then be chilled to 400 ℃, insulation 220min with 4.5 ℃/min, with 19～21 ℃/min, is cooled to room temperature.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 7.5g/cm
3, porosity 67%, hole average diameter 300 μ m, elastic modelling quantity 5.25Gpa, percentage elongation 11.32%, bending strength 110MPa, comprcssive strength 65MPa.This preparation technology's product qualification rate reaching 92.4% 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) | 6.91 | 3.94 | 8.34 |
| Porosity (%) | 60 | 54 | 57 |
| Aperture (μ m) | 169 | 360 | 436 |
| Elastic modelling quantity (GPa) | 4.9 | 3.6 | 6.0 |
| Percentage elongation (%) | 11.39 | 10.52 | 11.52 |
| Bending strength (MPa) | 104 | 95 | 111 |
| Comprcssive strength (MPa) | 65 | 71 | 70 |
Claims (8)
1. a preparation method for preparing the medical porous metal material that substitutes the 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 make this porous metal material; Described compressing be that 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, and described forming agent is one or more in stearic acid, zinc stearate, paraffin, synthetic resin; Described heat treatment is that vacuum is 10
-4pa～10
-3pa, be warming up to 800～900 ℃, be incubated 240～480min with 10～20 ℃/min, then be chilled to 400 ℃, be incubated 120～300min with 2～5 ℃/min, then cools to room temperature with the furnace.
2. the preparation method of 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. preparation method 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. preparation method 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. preparation method as claimed in claim 1 or 2 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. preparation method as claimed in claim 3 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.
7. preparation method as claimed in claim 4 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.
8. preparation method as claimed in claim 1 or 2, it is characterized in that: the vacuum-sintering condition is: the speed with 10～15 ℃/min rises to 1200～1250 ℃ from room temperature, is incubated 30～60min, and vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min rises to 1500 ℃, is incubated 30～60min, and vacuum is 10
-4pa～10
-3pa, rise to 2000～2200 ℃ with the speed of 6～20 ℃/min, is incubated 120～240min, and vacuum is 10
-4pa～10
-3pa; Cooling condition after vacuum-sintering is: vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, is incubated 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, is incubated 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling.
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| CN201110300386.4A CN102796903B (en) | 2011-09-29 | 2011-09-29 | Method for preparing medical porous metal material capable of replacing bearing bone tissue |
| PCT/CN2012/082084 WO2013044809A1 (en) | 2011-09-29 | 2012-09-26 | Preparation method for medical porous metal material for weight-bearing bone tissue replacement |
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|---|---|---|---|
| CN201110300386.4A CN102796903B (en) | 2011-09-29 | 2011-09-29 | Method for preparing medical porous metal material capable of replacing bearing bone tissue |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7674426B2 (en) * | 2004-07-02 | 2010-03-09 | Praxis Powder Technology, Inc. | Porous metal articles having a predetermined pore character |
| 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. |
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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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| WO2013044809A1 (en) | 2013-04-04 |
| CN102796903A (en) | 2012-11-28 |
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