CN103736151A - Preparation method of medical porous metal material capable of replacing weight bearing bone tissue - Google Patents
Preparation method of medical porous metal material capable of replacing weight bearing bone tissue Download PDFInfo
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Abstract
The invention provides a preparation method of a medical porous metal material capable of replacing weight bearing bone tissue, which comprises the following steps: mixing tantalum powder and ammonium bicarbonate or hydrogen peroxide, and a forming agent (one or more of stearic acid, zine stearate, paraffin and synthetic resin), compression moulding, degreasing, sintering, cooling and heat treating; wherein the compression moulding step is characterized in that a mixture is compacted in organic foams, the pressure is 50-100MPa, the degreasing step is characterized in that heating is gradually carried out at the rate of 0.3 DEG C/min-2 DEG C to the temperature of 400-800 DEG C, argon is protection atmosphere and is insulated for 300-360 minutes; the sintering step is characterized in that the degree of vacuum is 10<-4>Pa-10<-3>Pa, heating is carried out at the rate of 10-20 DEG C/min to the temperature of 1500-1800 DEG C, the insulation is carried out for 120-240 minutes, and then cooling is carried out to 200-300 DEG C, heating is carried out at the rate of 10-20 DEG C/min to 1500-1800 DEG C, insulation is carried out for 180-240 minutes, then heating is carried out at the rate of 5-10 DEG C/minutes to 2000-2200 DEG C, and then insulation is carried out for 120-360 minutes. The medical porous metal material is a medical implantation material which has the advantages of large porosity and good mechanical property, and is suitable for replacing the weight bearing bone tissue.
Description
The present patent application is application number 201110296535.4, the applying date on 09 29th, 2011, the divisional application of denomination of invention " a kind of preparation method of medical porous metal material of alternative load-bearing bone tissue ".
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 of medical porous metal implant material of alternative weight bearing area osseous tissue.
Background technology
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.As the porous embedded material of osseous tissue wound and the use of bone formation necrosis therapeutic, its porosity should reach 30～80%, and hole is preferably all 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 body implanting material cognition to tantalum/niobium, to human body, implantation becomes more and more urgent by the demand of porous metals tantalum/niobium material to people, 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 take powder sintering as main processing method like that substantially, in particular for obtain porosity communication and equally distributed porous metal foam structure adopt metal dust slurry in the powder sintering dipping on Organic Foam Material afterwards the dry knot that reburns to be called for short foam impregnation method in the majority.About powder sintered obtained porous metal material conventionally its Metal Mechanic Property be not fine, its main cause is the problem of subsiding how arranging in technique in the support of pore-forming medium and elimination relation, metal powder sintered process.And in known bibliographical information, all there is no good solution and laissez-faire nature.
Adopt metal powder sintered legal system to make the bibliographical information of porous tantalum/niobium little, particularly to obtain medical embedded material with almost not having as porous tantalum/niobium powder sintering process bibliographical information of object.Can reference be that publication number is CN200510032174, title " three-dimensional through hole or part hole porous metal foam connected with each other and preparation method thereof " and CN200710152394, title " a kind of porous foam tungsten and preparation method thereof ".But its porous metals that obtain or for filtering material use, or for Aero-Space and other high-temperature field, share 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 carries out carbon skeleton that thermal degradation obtains as support take polyurethane precursor, this carbon skeleton is multiple dodecahedron, it in it, is mesh-like structure, entirety spreads all over micropore, porosity can be up to 98%, then commercially pure tantalum is attached on carbon skeleton to form porous metals micro structure, referred to as chemical deposition by the method for chemical vapour deposition, infiltration.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 recorded, the comprcssive strength 50～70MPa of this porous material, elastic modelling quantity 2.5～3.5GPa, tensile strength 63MPa.But 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, the cutting of such as profiled member etc.Also all there is such deficiency in the same product obtaining in aforesaid metal powder sintered method.Due to the limitation of its preparation method, the finished product purity of acquisition is inadequate, has carbon skeleton residue again, causes biological safety to reduce.
Summary of the invention
The object of the present invention is to provide a kind of obdurability excellence, be applicable to substitute the preparation method of medical porous metal implant material of weight bearing area osseous tissue.
The object of the invention is to realize by following technological means:
A preparation method for the medical porous metal material of alternative load-bearing bone tissue, is characterized in that: by tantalum powder, mixed with pore creating material, forming agent, 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 to be progressively warming up to 400～800 ℃ with the speed of 0.3 ℃/min～2 ℃/min, 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 sintering step is that vacuum is 10
-4pa～10
-3pa, with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 120～240min, with stove, be chilled to 200～300 ℃, with 10～20 ℃/min, be warming up to 1500～1800 ℃, insulation 180～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, insulation 120～360min; Described heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 240～480min with 10～20 ℃/min, then is chilled to 400 ℃, insulation 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 be guaranteed as intensity, toughness; Otherwise mechanical property has been got well and has easily been made 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 inventor has creatively proposed employing above-mentioned steps, technique is prepared medical porous tantalum embedded material, the problems such as the difficult product quality of controlling, make 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 adopting, inventor finds that in the process of studying for a long period of time this Technology for Heating Processing eliminated fully internal stress, made the toughness of organizing more evenly, greatly improved prepared porous tantalum material of porous tantalum material; Above-mentioned sintering processes technique, makes idiosome become heater, more even, thorough thereby sintering obtains; 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 300～500 μ m; Elastic modelling quantity can reach that 4.5～6.0Gpa, percentage elongation reach 10.5～11.7%, bending strength can reach 125～150Mpa, comprcssive strength can reach 72～90Mpa, 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 are also 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, more preferably aperture 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, hardness is greater than 50
0(most preferably aperture is 0.56～0.72mm, density 0.025g/cm
3, hardness 50
0～80
0) polyurethane foam in.
In R&D process, inventor further studies discovery, if control bad in above-mentioned preparation, though can make be suitable for as mentioned above substitute load-bearing bone tissue medical embedded material constant product quality is undesirable, qualification rate is not high: as powder pressing forming difficulty, suppress rear section be prone to layering, inhomogeneous, 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 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 volume to weigh certainly), more preferably pore creating material is that hydrogen peroxide accounts for 18%, forming agent is that zinc stearate accounts for 11%, surplus is 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 to be progressively warming up to 400～800 ℃ with the speed of 0.3 ℃/min～1 ℃/min, with argon, passes into and forms protective atmosphere and be incubated 330min～350min; Further preferably with the speed of 0.8 ℃/min, be progressively warming up to 400～800 ℃, with argon, pass into and form protective atmosphere and be incubated 340min.
More preferably, the condition of above-mentioned skimming processes is: the speed with 1～2 ℃/min rises to 400 ℃ from room temperature, and insulation 300～330min rises to 600～800 ℃, insulation 180～240min with the speed of 1.5～2.5 ℃/min from 400 ℃.
For make idiosome sintering obtain more evenly, thorough, make the medical porous tantalum strength of materials that makes higher, it is 10 that above-mentioned sintering step is preferably vacuum
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, insulation 220～240min again, with 5～8 ℃/min, be warming up to 2000～2200 ℃, insulation 250～320min; Further being preferably vacuum is 10
-4pa～10
-3pa, is warming up to 1800 ℃, is incubated 200min, with stove, is chilled to 200～300 ℃ with 13 ℃/min, then is warming up to 1800 ℃, insulation 230min with 17 ℃/min, with 7 ℃/min, is warming up to 2000～2200 ℃, insulation 300min.
Better in order to eliminate more fully internal stress, the toughness of material, above-mentioned heat treatment step is that vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 260～320min with 15 ℃/min, then is chilled to 400 ℃, insulation 120min with 3 ℃/min, then is cooled to room temperature with 18 ℃/min～23 ℃/min.
Cooling condition after above-mentioned vacuum-sintering also includes: vacuum is not less than 10
-3pa, with not higher than 25 ℃/min, is not less than 10 ℃/min and gradually falls cooldown rate mode, and to sintered porous bodies segmentation cooling down to 800 ℃, each section of temperature retention time 30min～90min, then cools to room temperature with the furnace.
Preferably, the cooling condition after above-mentioned vacuum-sintering is: vacuum is 10
-4pa～10
-3pa; With the speed of 10～20 ℃/min, be cooled to 1500～1600 ℃, insulation 30～60min; With the speed of 12～20 ℃/min, be cooled to 1200～1250 ℃, insulation 60～90min; With the speed of 10～20 ℃/min, be cooled to 800 ℃, then furnace cooling.
The character of metal tantalum and niobium is extremely similar, and said method is equally also 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, be all improved as intensity, toughness simultaneously, preparation technology of the present invention make product qualified rate high, produce stablely, conforming product rate can be up to 95.5%.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 300～500 μ m; Elastic modelling quantity can reach 4.5～6.0Gpa, percentage elongation reaches 10.5～11.7%, bending strength can reach 125～150Mpa, comprcssive strength can reach 72～90Mpa, 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 are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, person skilled in art can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1: weigh zinc stearate, mean diameter and be less than tantalum powder and the hydrogen peroxide mix homogeneously that 43 microns of oxygen contents are less than 0.1%, wherein zinc stearate accounts for 11%, hydrogen peroxide accounts for 18%, tantalum powder accounts for 71%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015 g/cm in injection moulding machine under 87Mpa
3～0.035g/cm
3, hardness is greater than 50
0) middle molding.Ungrease treatment: vacuum 10
-3pa, is warming up to 400 ℃, insulation 311min with the heating rate of 1.4 ℃/min from room temperature; With the heating rate of 0.4 ℃/min, from 400 ℃, be warming up to 750 ℃, temperature retention time 350 minutes again.Vacuum-sintering: vacuum is 10
-3pa, is warming up to 1800 ℃, is incubated 200min, with stove, is chilled to 200～300 ℃ with 13 ℃/min, then is warming up to 1800 ℃, insulation 230min with 17 ℃/min, with 7 ℃/min, is warming up to 2000～2200 ℃, insulation 300min.Cooling processing after vacuum-sintering: vacuum is 10
-4pa, is cooled to 1500～1600 ℃ with the speed of 10～20 ℃/min, and insulation 30～60min, is cooled to 1200～1250 ℃ with the speed of 12～20 ℃/min, and insulation 60～90min, is cooled to 800 ℃ with the speed of 10～20 ℃/min, then furnace cooling.Heat treatment: vacuum is 10
-4pa～10
-3pa, is warming up to 800～900 ℃, insulation 260～320min with 15 ℃/min, then is chilled to 400 ℃, insulation 120min with 3 ℃/min, then is cooled to room temperature with 18 ℃/min～23 ℃/min, more often regulation obtains medical porous tantalum embedded material.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 6.55g/cm
3, porosity 60%, hole average diameter 350 μ m, elastic modelling quantity 6.0Gpa, percentage elongation 11.02%, bending strength 145MPa, comprcssive strength 83Pa.
Embodiment 2: take stearic acid and paraffin, mean diameter is less than tantalum powder and the hydrogen peroxide mix homogeneously that 43 microns of oxygen contents are less than 0.1%, wherein stearic acid accounts for 9%, paraffin accounts for 3%, hydrogen peroxide accounts for 25%, tantalum powder accounts for 63%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015 g/cm in injection moulding machine under 75Mpa
3～0.035g/cm
3, hardness is greater than 50
0) middle molding.Ungrease treatment: vacuum 10
-4pa, is warming up to 600 ℃, insulation 360min with the heating rate of 0.3 ℃/min from room temperature.Vacuum-sintering: vacuum is 10
-4pa, is warming up to 1500 ℃, is incubated 240min, with stove, is chilled to 200～300 ℃ with 10 ℃/min, then is warming up to 1500 ℃, insulation 180min with 20 ℃/min, with 10 ℃/min, is warming up to 2000～2200 ℃, insulation 120min, cooling processing.Heat treatment: vacuum is 10
-3pa, is warming up to 800～900 ℃, insulation 240min with 20 ℃/min, then is chilled to 400 ℃, insulation 300min with 5 ℃/min, cool to room temperature with the furnace, more often regulation obtains medical porous tantalum embedded material.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 6.67g/cm
3, porosity 55%, hole average diameter 300 μ m, elastic modelling quantity 4.5Gpa, percentage elongation 10.7%, bending strength 143MPa, comprcssive strength 74MPa.
Embodiment 3: take isoprene rubber, mean diameter is less than tantalum powder and the ammonium bicarbonate mix homogeneously that 43 microns of oxygen contents are less than 0.1%, wherein isoprene rubber accounts for 7%, ammonium bicarbonate accounts for 15%, tantalum powder accounts for 78%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015 g/cm in injection moulding machine under 96Mpa
3～0.035g/cm
3, hardness is greater than 50
0) middle molding.Ungrease treatment: vacuum 10
-4pa, is warming up to 400 ℃, insulation 300min with the heating rate of 2 ℃/min from room temperature.Vacuum-sintering: vacuum is 10
-3pa, is warming up to 1700 ℃, is incubated 120min, with stove, is chilled to 200～300 ℃ with 20 ℃/min, then is warming up to 1670 ℃, insulation 240min with 10 ℃/min, with 5 ℃/min, is warming up to 2000～2200 ℃, insulation 360min, cooling processing.Heat treatment: vacuum is 10
-4pa, is warming up to 800～900 ℃, insulation 480min with 10 ℃/min, then is chilled to 400 ℃, insulation 120min with 2 ℃/min, cool to room temperature with the furnace, more often regulation obtains medical porous tantalum embedded material.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 6.13g/cm
3, porosity 65%, hole average diameter 456 μ m, elastic modelling quantity 5.2Gpa, percentage elongation 11.0%, bending strength 126MPa, comprcssive strength 88MPa.
Embodiment 4: take stearic acid, mean diameter is less than niobium powder and the hydrogen peroxide mix homogeneously that 43 microns of oxygen contents are less than 0.1%, wherein stearic acid accounts for 8%, hydrogen peroxide accounts for 21%, niobium powder accounts for 71%, all in volumn concentration.Extrusion forming: above-mentioned mixed-powder is added and be pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015 g/cm in injection moulding machine under 76Mpa
3～0.035g/cm
3, hardness is greater than 50
0) middle molding.Ungrease treatment: vacuum 10
-4pa, is warming up to 400 ℃, insulation 340min with the heating rate of 0.8 ℃/min from room temperature.Vacuum-sintering: vacuum is 10
-4pa, is warming up to 1650 ℃, is incubated 180min, with stove, is chilled to 200～300 ℃ with 12 ℃/min, then is warming up to 1700 ℃, insulation 220min with 16 ℃/min, with 8 ℃/min, is warming up to 2000～2200 ℃, insulation 320min, cooling processing.Heat treatment: vacuum is 10
-4pa, is warming up to 800～900 ℃, insulation 275min with 13 ℃/min, then is chilled to 400 ℃, insulation 220min with 4 ℃/min, cool to room temperature with the furnace, more often regulation obtains medical porous tantalum embedded material.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous niobium finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 3.51g/cm
3, porosity 59%, hole average diameter 344 μ m, elastic modelling quantity 2.8Gpa, percentage elongation 10.8%, bending strength 100MPa, comprcssive strength 65MPa.
Embodiment 5: a kind of porous tantalum, it is less than with particle diameter the ta powder that 43 μ m, oxygen content are less than 0.1%, and paraffin and ammonium bicarbonate are mixed into raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, paraffin accounts for 10%, ammonium bicarbonate accounts for 23%, ta powder accounts for 67%, in volumn concentration;
Compressing: raw material mixed-powder is added and in injection moulding machine, under 60Mpa, is pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, hardness is greater than 50
0) middle molding;
After compressing, mixed-powder is put into 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 heat up before first pass into pure argon gas at least 30min with get rid of furnace air, temperature control process: the speed with 1.8 ℃/min rises to 400 ℃ from room temperature, insulation 323min, argon intake 0.5L/min; Speed with 0.5 ℃/min rises to 800 ℃, insulation 350min, 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;
For the sample after ungrease treatment, with tungsten device, be placed in fine vacuum high temperature sintering furnace and heat up and carry out vacuum-sintering with certain heating rate, before heating up, the vacuum of sintering furnace at least will reach 10
-4pa, rises to 1500 ℃ with the speed of 12～15 ℃/min from room temperature, is incubated 200min, with stove, is chilled to 200～300 ℃, and vacuum is 10
-4pa; With the speed of 17 ℃/min, rise to 1500 ℃ again, insulation 180min, vacuum is 10
-4pa～10
-3pa; With the speed of 8 ℃/min, rise to 2200 ℃, insulation 320min, vacuum is 10
-3pa; Sintering is complete, and vacuum is 10
-3pa, is cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; With the speed of 12 ℃/min, be cooled to 1200 ℃, insulation 60min; With the speed of 10 ℃/min, be cooled to 800 ℃, then furnace cooling;
For the cooled sample of vacuum-sintering, with corundum container, be placed in vacuum annealing furnace and with certain heating rate, be warming up to 1250 ℃ and carry out stress relief annealing processing, the vacuum before heating up in annealing furnace at least will reach 10
-4pa, rises to 880 ℃ with the speed of 15 ℃/min from room temperature, insulation 340min, and vacuum is 10
-4pa～10
-3pa; With the speed of 3 ℃/min, be cooled to 400 ℃ again, insulation 180min, vacuum is 10
-4pa～10
-3pa; Speed with 22 ℃/min is cooled to room temperature.Finally carry out conventional post processing and make porous tantalum.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 6.2g/cm
3, porosity 64%, hole average diameter 350 μ m, elastic modelling quantity 4.8Gpa, percentage elongation 11.32%, bending strength 138MPa, comprcssive strength 85MPa.As calculated this preparation technology make product qualified rate high, produce stable, product qualification rate reaching 94.6% left and right.
Claims (1)
1. the preparation method of the medical porous metal material of an alternative load-bearing bone tissue, it is characterized in that: with particle diameter, be less than the ta powder that 43 μ m, oxygen content are less than 0.1%, paraffin and ammonium bicarbonate are mixed into raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing;
Wherein, paraffin accounts for that 10% left and right, ammonium bicarbonate account for greatly 23%, ta powder accounts for 67% left and right, in volumn concentration;
Compressing: raw material mixed-powder is added and in injection moulding machine, under 60Mpa, is pressed into polyurethane foam (aperture 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, hardness is greater than 50
0) middle molding;
After compressing, mixed-powder is put into nonoxidizing atmosphere stove and be warming up to 800 ℃, protective atmosphere is that 99.999% argon carries out ungrease treatment, its heat up before first pass into pure argon gas at least 30min with get rid of furnace air, temperature control process: the speed with 1.8 ℃/min rises to 400 ℃ from room temperature, insulation 323min, argon intake 0.5L/min; Speed with 0.5 ℃/min rises to 800 ℃, insulation 350min, 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;
For the sample after ungrease treatment, with tungsten device, be placed in fine vacuum high temperature sintering furnace and heat up and carry out vacuum-sintering, before heating up, the vacuum of sintering furnace at least will reach 10
-4pa, rises to 1500 ℃ with the speed of 12～15 ℃/min from room temperature, is incubated 200min, with stove, is chilled to 200～300 ℃, and vacuum is 10
-4pa; With the speed of 17 ℃/min, rise to 1500 ℃ again, insulation 180min, vacuum is 10
-4pa～10
-3pa; With the speed of 8 ℃/min, rise to 2200 ℃, insulation 320min, vacuum is 10
-3pa; Sintering is complete, and vacuum is 10
-3pa, is cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; With the speed of 12 ℃/min, be cooled to 1200 ℃, insulation 60min; With the speed of 10 ℃/min, be cooled to 800 ℃, then furnace cooling;
For the cooled sample of vacuum-sintering, with corundum container, be placed in vacuum annealing furnace and be warming up to 1250 ℃ and carry out stress relief annealing processing, the vacuum before heating up in annealing furnace at least will reach 10
-4pa, rises to 880 ℃ with the speed of 15 ℃/min from room temperature, insulation 340min, and vacuum is 10
-4pa～10
-3pa; With the speed of 3 ℃/min, be cooled to 400 ℃ again, insulation 180min, vacuum is 10
-4pa～10
-3pa; Speed with 22 ℃/min is cooled to room temperature.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0560279B1 (en) * | 1992-03-11 | 2000-06-14 | Ultramet | Open cell tantalum structures for cancellous bone implants and cell and tissue receptors |
| CN101121982A (en) * | 2007-09-30 | 2008-02-13 | 北京师范大学 | Porous foam tungsten and preparation method thereof |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
| 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 |
| CN101709419A (en) * | 2009-12-18 | 2010-05-19 | 北京有色金属研究总院 | Tantalum foam and preparation method thereof |
-
2011
- 2011-09-29 CN CN201310688627.6A patent/CN103736151B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0560279B1 (en) * | 1992-03-11 | 2000-06-14 | Ultramet | Open cell tantalum structures for cancellous bone implants and cell and tissue receptors |
| CN101121982A (en) * | 2007-09-30 | 2008-02-13 | 北京师范大学 | Porous foam tungsten and preparation method thereof |
| 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. |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
| 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 |
| CN101709419A (en) * | 2009-12-18 | 2010-05-19 | 北京有色金属研究总院 | Tantalum foam and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 夏凤金等: "多孔钽的制备方法", 《科技创新导报》 * |
| 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》 * |
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