CN103736147B - Medical porous metal material replacing bearing bone tissue and preparation method thereof - Google Patents
Medical porous metal material replacing bearing bone tissue and preparation method thereof Download PDFInfo
- Publication number
- CN103736147B CN103736147B CN201310700104.9A CN201310700104A CN103736147B CN 103736147 B CN103736147 B CN 103736147B CN 201310700104 A CN201310700104 A CN 201310700104A CN 103736147 B CN103736147 B CN 103736147B
- Authority
- CN
- China
- Prior art keywords
- vacuum
- speed
- insulation
- cooled
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a medical porous metal material replacing a bearing bone tissue and a preparation method thereof. The preparation method of the medical porous metal material comprises the following steps: mixing tantalum powder, a pore forming substance and a moulding agent; then, compacting mixed powder to an organic foam body to mould, degrease, sinter, cool and thermally treat, wherein the pressure of compression moulding is 50-100Mpa; the degreasing process comprises the following steps of: gradually heating to 400-800 DEG C at a speed of 0.3 DEG C/minute to 2 DEG C/minute, introducing argon to form a protective atmosphere, and preserving heat for 300-360 minutes; the pore forming substance is ammonium hydrogen carbonate or hydrogen peroxide, and the moulding agent is one or more of stearic acid, zinc stearate, paraffin and synthesized resin. The pore diameter of the formed medical porous tantalum material is 100-500 mu m, the porosity is ranged from 55% to 65%, the elasticity modulus is 3.8-4.2Gpa, and the ductility is 9.3-10.7%. According to the porous tantalum preparation method provided by the invention, the porous tantalum material is extremely low in impurity, and meanwhile effectively solves the contradiction that the medical porous tantalum material replacing the bearing bone tissue not only requires greater porosity, but also requires good mechanical property.
Description
The present patent application is application number 201110301039.3, the applying date on 09 29th, 2011, the divisional application of denomination of invention " medical porous metal material of a kind of alternative load-bearing bone tissue and preparation method thereof ".
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
Porous medical metal implanted material has the important and special purposes such as treatment osseous tissue wound, bone formation necrosis, and existing common this kind of material has porous metals rustless steel, porous metals titanium etc.As the porous embedded material that osseous tissue wound and bone formation necrosis therapeutic use, its porosity should reach 30 ~ 80%, and hole is preferably all communicated with and is uniformly distributed, or make it both consistent with the bone growth of human body as required, alleviate again the weight of material itself, implant with applicable human body and 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, to tantalum/niobium going deep into further as body implanting material cognition, the demand of people to human body implantation porous metals tantalum/niobium material becomes more and more urgent, 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 being uniformly distributed interconnected pore and adapting with human body, then it is expected to as a kind of novel osseous tissue substitution material.
Be main processing method with powder sintering substantially just as one porous metal material as medical embedded porous metal material, especially obtain porosity communication and equally distributed porous metal foam structure adopt the dipping of the metal dust slurry in powder sintering on Organic Foam Material after drying reburn and tie that to be called for short foam impregnation method in the majority.About powder sintered obtained porous metal material usually its Metal Mechanic Property be not very well, its main cause how technique arranges the problem of subsiding 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 let alone nature.
Adopt metal powder sintered legal system to make the bibliographical information of porous tantalum/niobium seldom, particularly almost do not have by the porous tantalum/niobium powder sintering process bibliographical information obtained for the purpose of medical embedded material use.Can reference be publication number be CN200510032174, title " three-dimensional through hole or some perforations 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 ".But its porous metals obtained or for filtering material use, or share for Aero-Space and other high-temperature field but not use as medical metal implanted material, moreover the porous metals processed also non-porous tantalum/niobium.
About porous tantalum, US5282861 discloses and is a kind ofly applied to cancellous bone implants, the perforate tantalum material of biological cells and tissues sensor and preparation thereof.This porous tantalum is made up of pure business tantalum, it carries out carbon skeleton that thermal degradation obtains for support with polyurethane precursor, this carbon skeleton is multiple dodecahedron, it is mesh-like structure in it, entirety spreads all over micropore, porosity can up to 98%, then by commercially pure tantalum by the methods combining of chemical vapour deposition, infiltration to carbon skeleton to form porous metals micro structure, referred to as chemical deposition.The tantalum layer thickness on its surface of porous tantalum material that this method obtains is between 40 ~ 60 μm; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight then accounts for about 1%.Document is recorded further, the comprcssive strength 50 ~ 70MPa of this porous material, elastic modelling quantity 2.5 ~ 3.5GPa, tensile strength 63MPa.But by it, load-bearing bone tissue is as the porous tantalum of the medical embedded materials such as skull as an alternative, and the mechanical property of its material is obvious weak point as ductility has, and can have influence on the follow-up processing to porous tantalum material itself, the cutting etc. of such as profiled member.Also all there is such deficiency in the product obtained in aforesaid metal powder sintered method equally.Again due to the limitation of its preparation method, the finished product purity of acquisition is inadequate, has carbon skeleton residue, causes biological safety to reduce.
Summary of the invention
The object of the present invention is to provide the medical porous metal material being applicable to alternative load-bearing bone tissue that a kind of product purity is high.
Another object of the present invention is to the preparation method that above-mentioned medical porous metal material is provided.
The object of the invention is to be realized by following technological means:
A medical porous metal material for alternative load-bearing bone tissue, is characterized in that: mixed with pore creating material, forming agent by tantalum powder, more repressed molding, defat, sintering, cooling and heat treatment are obtained; Described compressing be that described mixed-powder is pressed in Organic Foam Material, its pressure is 50 ~ 100Mpa, described skimming processes is progressively warming up to 400 ~ 800 DEG C with the speed of 0.3 DEG C/min ~ 2 DEG C/min, passes into formed protective atmosphere and be incubated 300min ~ 360min with argon; 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 (be preferably butadiene-styrene rubber or isoprene rubber), the medical porous tantalum material pore diameter of formation is 100 ~ 500 μm, porosity between 55 ~ 65%, elastic modelling quantity is 3.8 ~ 4.2Gpa, percentage elongation is 9.3 ~ 10.7%.
In the R&D process of medical porous metal material, the material of medical porous metal material load-bearing bone tissue as an alternative, require its porosity comparatively large, like this tissue just easily grow into, good biocompatibility thus play its effect fully, but porosity is larger, aperture is larger, mechanical property such as intensity, toughness just can not be guaranteed; Otherwise mechanical property is got well and is easily made that porosity is too small, biocompatibility is bad, density is also excessive causes discomfort; The syntheti c route of medical porous tantalum is numerous, but inventor creatively proposes and adopts above-mentioned steps, technique to prepare medical porous tantalum embedded material, effectively prevent the plug-hole adopting cement-dipping method easily to occur, the problem such as soaking paste process difficulty controls, obtained product quality is uneven; Its obtained porous tantalum material through its impurity content of test can lower than 0.2%, its biocompatibility and biological safety good, density can reach 5.83 ~ 7.50g/cm
3, porosity can reach 55 ~ 65%, and pore diameter can reach 100 ~ 500 μm; 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, its biocompatibility, obdurability are all excellent, close to human bearing's osseous tissue, porous tantalum of the present invention is suitable for the medical embedded material of alternative load-bearing bone tissue very much.
The present invention adopt Ta powder mean diameter 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.Vacuum environment of the present invention preferably adopts vacuum to be 10
-4pa ~ 10
-3the vacuum condition of Pa.Above-mentioned Organic Foam Material optimization polyurethane foam, more preferably aperture 0.48 ~ 0.89mm, 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, hardness 50 ° ~ 80 °) polyurethane foam in.
In R&D process, inventor studies discovery further, if control bad in above-mentioned preparation, though the medical embedded material that is suitable for alternative load-bearing bone tissue as mentioned above can be obtained but constant product quality is undesirable, qualification rate is not high: as difficult in powder pressing forming, after pressing part easily there is layering, uneven, defat rear section there will be the technical problems such as crackle.
In order to make molding in powder compaction process easier, thus 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, (be all the unit directly calculated by the situation of final porous tantalum material in volumn concentration in volumn concentration, at above-mentioned pore creating material, in the weighing of forming agent, pressed powder still calculates the quality weighing of its correspondence according to the densimeter of respective substance, if liquid substance then 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, the part idiosome that is more stable, that reduce easily appearance of idiosome in skimming processes is out of shape, aperture is uneven, thus improve yield rate, quality stability further, above-mentioned skimming processes is progressively warming up to 400 ~ 800 DEG C with the speed of 0.3 DEG C/min ~ 1 DEG C/min, passes into formed protective atmosphere and be incubated 330min ~ 350min with argon; Preferably further progressively be warming up to 400 ~ 800 DEG C with the speed of 0.8 DEG C/min, pass into argon and formed protective atmosphere and be incubated 340min.
A kind of preparation method of medical porous metal material of alternative load-bearing bone tissue, die pressing sintering is adopted to form, its feature is: mixed with pore creating material, forming agent by tantalum powder, more described mixed-powder is pressed into the medical porous metal material that molding in Organic Foam Material, defat, sintering, cooling and heat treatment obtain alternative load-bearing bone tissue under 50 ~ 100Mpa; 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 (be 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 tantalum powder, all in volumn concentration; Described skimming processes is progressively warming up to 400 ~ 800 DEG C with the speed of 0.3 DEG C/min ~ 2 DEG C/min, passes into formed protective atmosphere and be incubated 300min ~ 360min with argon.
The mean diameter of above-mentioned raw materials tantalum powder is less than 43 microns, oxygen content 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 tantalum powder, in volumn concentration.Above-mentioned Organic Foam Material optimization polyurethane foam, more preferably aperture 0.48 ~ 0.89mm, 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, hardness 50 ° ~ 80 °) polyurethane foam in.
In order to make pressing pressure in compacting embryo process even, not stratified; thus make final porous tantalum distribution of pores evenly, quality is more stable; the pressure adopted in above-mentioned pressing process is preferably 75 ~ 87Mpa; be preferably in above-mentioned skimming processes and be progressively warming up to 400 ~ 800 DEG C with the speed of 0.3 DEG C/min ~ 1 DEG C/min; pass into argon and formed protective atmosphere and be incubated 330min ~ 350min; preferably further progressively be warming up to 400 ~ 800 DEG C with the speed of 0.8 DEG C/min, pass into argon and formed protective atmosphere and be incubated 340min.
The present invention's further feature is on the other hand: be not less than 10 in vacuum
-4~ 10
-3pa, temperature 2000 ~ 2200 DEG C, the temperature retention time vacuum-sintering process of 1 ~ 5 hour obtains porous sintered body.Filling with inert gas protection vacuum protection can be replaced during sintering process insulation; Finally carry out vacuum annealing process, wherein vacuum annealing process refers to that after vacuum-sintering, continue maintenance temperature is in 1000 ~ 1250 DEG C, and temperature retention time 1 ~ 4 hour, vacuum is not less than 10
-4~ 10
-3pa.
Vacuum-sintering condition also includes: vacuum is not less than 10
-3pa, rises to 1200 DEG C ~ 1500 DEG C with the heating rate of 10 ~ 20 DEG C/min from room temperature, after insulation 1h ~ 2h; Again to be warming up to 2000 ~ 2200 DEG C lower than the heating rate of 20 DEG C/min, be at least incubated 2h ~ 4h.
Cooling condition after vacuum-sintering also includes: vacuum is not less than 10
-3pa, with not higher than 25 DEG C/min, is not less than 10 DEG C/min and gradually falls cooldown rate mode, and to sintered porous bodies segmentation cooling down to 800 DEG C, each section of temperature retention time 30min ~ 90min, then cools to room temperature with the furnace.
Vacuum annealing condition also includes: vacuum is not less than 10
-4pa, rises to 1000 ~ 1250 DEG C with the speed not higher than 30 DEG C/min, insulation 4h ~ 6h; Again with after first slow fast be not less than 5 DEG C/min but not higher than the cooldown rate sub-sectional cooling of 30 DEG C/min to room temperature, the temperature retention time of each section tapers off and is no more than in 1.5h ~ 3h and selects.
Further feature is on this basis: described ungrease treatment condition also includes: rise to 400 DEG C with the speed of 1 ~ 2 DEG C/min from room temperature, insulation 300 ~ 330min, 600 ~ 800 DEG C are risen to from 400 DEG C, insulation 340 ~ 360min with the speed of 0.3 ~ 0.8 DEG C/min; Described vacuum-sintering condition also includes: rise to 1200 ~ 1250 DEG C with the speed of 10 ~ 15 DEG C/min from room temperature, and insulation 30 ~ 60min, vacuum is 10
-4pa ~ 10
-3pa, rises to 1500 DEG C with the speed of 10 ~ 20 DEG C/min, and insulation 30 ~ 60min, vacuum is 10
-4pa ~ 10
-3pa, rises to 2000 ~ 2200 DEG C with the speed of 6 ~ 20 DEG C/min, and insulation 120 ~ 240min, vacuum is 10
-4pa ~ 10
-3pa; Cooling condition after vacuum-sintering also includes: vacuum is 10
-4pa ~ 10
-3pa; 1500 ~ 1600 DEG C are cooled to, insulation 30 ~ 60min with the speed of 10 ~ 20 DEG C/min; 1200 ~ 1250 DEG C are cooled to, insulation 60 ~ 90min with the speed of 12 ~ 20 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 10 ~ 20 DEG C/min; Described vacuum annealing condition also includes: rise to 1000 ~ 1250 DEG C with the speed of 15 ~ 30 DEG C/min, and insulation 240 ~ 480min, vacuum is 10
-4pa ~ 10
-3pa, then be cooled to 1000 DEG C with the speed of 5 ~ 10 DEG C/min, insulation 90 ~ 180min, vacuum is 10
-4pa ~ 10
-3pa; Be cooled to 800 DEG C with the speed of 10 ~ 20 DEG C/min, insulation 60 ~ 120min, vacuum is 10
-4pa; Be cooled to room temperature with the speed of 20 ~ 30 DEG C/min, vacuum is 10
-4pa ~ 10
-3pa.
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 have employed pure physical abrasion method, makes the content of impurity in final porous tantalum material extremely low, effectively improves 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 eliminate thermal stress, make porous tantalum materials microstructure evenly, all be improved with the mechanical property such as intensity, the toughness that improve porous tantalum further simultaneously, preparation technology of the present invention makes that product qualified rate is high, administration measure, and conforming product rate can up to 92%.The porous tantalum finished product even pore distribution that the present invention obtains and being communicated with, good biocompatibility, through test its impurity content can lower than 0.2%, density can reach 5.83 ~ 7.50g/cm
3, porosity can reach 55 ~ 65%, and pore diameter can reach 100 ~ 500 μm; 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, the medical porous tantalum material efficiently solving weight bearing area as an alternative should ask its porosity to require more greatly, again the contradiction that mechanical property is good, and porous tantalum of the present invention is suitable for the medical embedded material of load-bearing bone tissue as an alternative very much.
Detailed description of the invention
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that 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 according to the invention described above content to the present invention.
A kind of medical porous tantalum material of alternative load-bearing bone tissue specifically select in stearic acid, zinc stearate, paraffin, synthetic rubber one or more for forming agent, ammonium bicarbonate or hydrogen peroxide be pore creating material, be less than 43 microns with mean diameter, the oxygen content tantalum powder that is less than 0.1% mixes, under 50 ~ 100Mpa, described mixed-powder is pressed into molding in Organic Foam Material, then obtains through defat, sintering, cooling and heat treatment; Described skimming processes is progressively warming up to 400 ~ 800 DEG C with the speed of 0.3 DEG C/min ~ 2 DEG C/min, passes into formed protective atmosphere and be incubated 300min ~ 360min with argon.The medical porous tantalum material pore diameter formed is 100 ~ 500 μm, porosity between 55 ~ 65%, elastic modelling quantity is 3.8 ~ 4.2Gpa, percentage elongation is 9.3 ~ 10.7%.
More particularly, above-mentioned porous tantalum is the tantalum powder mixing by the above-mentioned pore creating material of the above-mentioned forming agent of 7 ~ 12% (in volumn concentrations), 15 ~ 25% (in volumn concentrations) and surplus, puts it in injection moulding machine and is pressed into molding in polyurethane foam; Be placed in tungsten device again to put into the special atmosphere oven that pure argon gas (99.9999%) passes into formation and be progressively warming up to uniform temperature, and insulation carries out ungrease treatment to remove pore creating material, forming agent and polyurethane foam, wherein before intensification, first pass into argon to get rid of furnace air, the sample furnace cooling after defat; Sample after ungrease treatment is placed in fine vacuum high temperature sintering furnace with tungsten device and is progressively warming up to 2000 ~ 2200 DEG C; temperature retention time carries 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 in cooling procedure or by certain cooldown rate sub-sectional cooling to keep uniform temperature in reasonable time, filling with inert gas can be adopted in insulating process as protective atmosphere.With corundum container, vacuum annealing furnace is placed in for the cooled sample of vacuum-sintering progressively heat up, be incubated and carry out stress relief annealing process; the vacuum that maintenance before heating up in annealing furnace is certain; sample furnace cooling after vacuum annealing process; also keep certain vacuum in cooling procedure or by certain cooldown rate sub-sectional cooling to keep uniform temperature in reasonable time; filling with inert gas can be adopted in insulating process as protective atmosphere, finally carry out conventional post processing and obtain porous tantalum.
For ungrease treatment, skimming processes is progressively warming up to 400 ~ 800 DEG C with the speed of 0.3 DEG C/min ~ 1 DEG C/min, passes into formed protective atmosphere and be incubated 330min ~ 350min with argon; Preferably further progressively be warming up to 400 ~ 800 DEG C with the speed of 0.8 DEG C/min, pass into argon and formed protective atmosphere and be incubated 340min.Vacuum-sintering process is carried out for the sample after ungrease treatment, it is placed in tungsten device the most high sintering temperature being warming up to tantalum with certain heating rate in fine vacuum high temperature sintering furnace carry out vacuum-sintering, before intensification, sintering furnace keeps certain vacuum, such as 1200 DEG C ~ 1250 DEG C are warming up to certain heating rate, insulation, keeps vacuum; Be warming up to such as 1250 DEG C ~ 1500 DEG C again with certain heating rate, insulation, then be warming up to the most high sintering temperature of such as tantalum with certain heating rate, insulation, keep vacuum; Sinter complete, keep vacuum, be cooled to such as 1500 DEG C ~ 1600 DEG C with certain rate of temperature fall, insulation, then be cooled to such as 1200 DEG C ~ 1250 DEG C with certain rate of temperature fall, insulation, also be cooled to such as 800 DEG C with certain rate of temperature fall, then furnace cooling.Vacuum annealing process is carried out for the cooled sample of vacuum-sintering, it is placed in vacuum annealing furnace with corundum container be warming up to such as 1000 DEG C ~ 1250 DEG C with certain heating rate and carry out stress relief annealing process, maintenance vacuum before heating up in annealing furnace, 1000 DEG C ~ 1250 DEG C are risen to from room temperature with certain heating rate, insulation, keeps vacuum; Such as 1000 DEG C are cooled to again, insulation with certain rate of temperature fall; Such as 800 DEG C are cooled to again, insulation with certain rate of temperature fall; Also with certain rate of temperature fall cooling room temperature.Finally carry out conventional post processing and obtain porous tantalum.
Inventor adopts metal powder sintered method mainly based on physical abrasion method, has done a large amount of theory analysises and experimental verification, obtain porous tantalum product through its impurity content of test can lower than 0.2%, density can reach 5.83 ~ 7.50g/cm
3, porosity can reach 55 ~ 65%, and pore diameter can reach 100 ~ 500 μm; 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: 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 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, with the heating rate of 2.0 DEG C/min from room temperature to 400 DEG C, insulation 320min; 700 DEG C are warming up to from 400 DEG C again, temperature retention time 350 minutes with the heating rate of 0.5 DEG C/min.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 2000 DEG C, is incubated 2 hours, vacuum 10
-4pa, sintering process applying argon gas is protected, and removes surface dirt and dirt after taking out product, and obtained sample carries out conventional post processing again and obtains porous tantalum finished product.
Inventor detects the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 6.24g/cm
3, porosity 60%, pore mean diameters 200 μm, 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 of oxygen contents are less than 0.1%, wherein stearic acid accounts for 7%, ammonium bicarbonate accounts for 25%, 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, with the heating rate of 2 DEG C/min from room temperature to 400 DEG C, insulation 300min.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 2100 DEG C, is incubated 4 hours, vacuum 10
-4pa, sintering process applying argon gas is protected, and removes surface dirt and dirt after taking out product, and obtained sample carries out conventional post processing again and obtains porous tantalum finished product.
Inventor detects the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 6.05g/cm
3, porosity 65%, pore mean diameters 400 μm, 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 of oxygen contents are less than 0.1%, wherein butadiene-styrene rubber accounts for 12%, hydrogen peroxide accounts for 15%, 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, with the heating rate of 0.3 DEG C/min from room temperature to 400 DEG C, insulation 360min.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 2200 DEG C, is incubated 2.5 hours, vacuum 10
-3pa, sintering process applying argon gas is protected, and cooling is come out of the stove, and removes product surface dust and dirt, and obtained sample carries out conventional post processing again and obtains porous tantalum finished product.
Inventor detects the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 6.31g/cm
3, porosity 55%, pore mean diameters 100 μm, 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 of oxygen contents are less than 0.1%, wherein paraffin accounts for 10%, ammonium bicarbonate accounts for 20%, 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, with the heating rate of 0.8 DEG C/min from room temperature to 400 DEG C, insulation 340min.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 2150 DEG C, is incubated 2 hours, vacuum 10
-4pa, sintering process applying argon gas is protected, and cooling is come out of the stove, and removes product surface dust and dirt, and obtained sample carries out conventional post processing again and obtains porous niobium finished product.
Inventor detects the porous material density of above-mentioned porous niobium finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 3.77g/cm
3, porosity 56%, pore mean diameters 108 μm, elastic modelling quantity 3.0Gpa, percentage elongation 9.8%, bending strength 67MPa, comprcssive strength 54MPa.
Embodiment 5: a kind of porous tantalum, it is less than 43 μm, the oxygen content ta powder that is less than 0.1% with particle diameter, and stearic acid and hydrogen peroxide mixed powder are raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing are obtained.
Wherein, stearic acid accounts for 11%, hydrogen peroxide accounts for 22%, ta powder accounts for 67%, in volumn concentration;
Compressing: raw material mixed-powder to be added in injection moulding machine under 78Mpa, be pressed into polyurethane foam (aperture 0.48 ~ 0.89mm, density 0.015g/cm
3~ 0.035g/cm
3, hardness is greater than 50 °) and middle molding;
After compressing, mixed-powder is put into nonoxidizing atmosphere stove and be warming up to 800 DEG C with certain heating rate, protective atmosphere is that 99.999% argon carries out ungrease treatment, its intensification before first pass into pure argon gas at least 30min to get rid of furnace air, temperature control process: rise to 400 DEG C from room temperature with the speed of 1.5 DEG C/min, insulation 300min, argon intake 0.5L/min; 800 DEG C are risen to from 400 DEG C, insulation 340min, argon intake 1L/min with the speed of 0.6 DEG C/min; Powered-down again, the sample furnace cooling after defat, argon intake 1L/min, until close argon when being cooled to room temperature;
To be placed in tungsten device for the sample after ungrease treatment and to be warming up to 2200 DEG C with certain heating rate in fine vacuum high temperature sintering furnace and to carry out vacuum-sintering, before heating up, the vacuum of sintering furnace at least will reach 10
-4pa, rises to 1200 DEG C with the speed of 10 ~ 15 DEG C/min from room temperature, and insulation 30min, vacuum is 10
-4pa; Rise to 1500 DEG C with the speed of 10 DEG C/min, insulation 30min, vacuum is 10
-4pa ~ 10
-3pa; Rise to 2200 DEG C with the speed of 6 DEG C/min, insulation 120min, vacuum is 10
-3pa; Sinter complete, vacuum is 10
-3pa, is cooled to 1600 DEG C with the speed of 10 ~ 15 DEG C/min, insulation 30min; 1200 DEG C are cooled to, insulation 60min with the speed of 12 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 10 DEG C/min;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with corundum container to be warming up to 1250 DEG C with certain heating rate and to carry out stress relief annealing process, the vacuum before heating up in annealing furnace at least will reach 10
-4pa, rises to 1250 DEG C with the speed of 15 DEG C/min from room temperature, and insulation 240min, vacuum is 10
-4pa ~ 10
-3pa; Be cooled to 1000 DEG C with the speed of 5 DEG C/min again, insulation 180min, vacuum is 10
-4pa ~ 10
-3pa; Be cooled to 800 DEG C with the speed of 10 DEG C/min, insulation 120min, vacuum is 10
-4pa; Be cooled to room temperature with the speed of 20 DEG C/min, vacuum is 10
-4pa.Finally carry out conventional post processing system
Obtain porous tantalum.
Inventor detects the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 6.8g/cm
3, porosity 62%, pore mean diameters 250 μm, 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 that above-described embodiment 5 provides, 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 (μm) | 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 (1)
1. the medical porous metal material of an alternative load-bearing bone tissue, it is characterized in that: it is less than 43 μm, the oxygen content ta powder that is less than 0.1% with particle diameter, stearic acid and hydrogen peroxide mixture are raw material, more repressed molding, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing are obtained; The impurity content of described medical porous metal material lower than 0.2%, its even pore distribution, density 6.8g/cm
3, porosity 62%, pore mean diameters 250 μm, elastic modelling quantity 4.15GPa, percentage elongation 10.32%, bending strength 118MPa, comprcssive strength 65MPa;
Wherein, stearic acid accounts for 11%, hydrogen peroxide accounts for 22%, ta powder accounts for 67%, in volumn concentration;
Compressing: raw mixture to be added in injection moulding machine and be pressed into molding in polyurethane foam under 78MPa, the aperture 0.48 ~ 0.89mm of described polyurethane foam, density 0.015 g/cm
3~ 0.035g/cm
3, hardness is greater than 50
0;
Put into nonoxidizing atmosphere stove after mixture is compressing and be warming up to 800 DEG C, protective atmosphere is that 99.999% argon carries out ungrease treatment, its intensification before first pass into pure argon gas at least 30min to get rid of furnace air, temperature control process: rise to 400 DEG C from room temperature with the speed of 1.5 DEG C/min, insulation 300min, argon intake 0.5L/min; 800 DEG C are risen to from 400 DEG C, insulation 340min, argon intake 1L/min with the speed of 0.6 DEG C/min; Powered-down again, the sample furnace cooling after defat, argon intake 1L/min, until close argon when being cooled to room temperature;
To be placed in fine vacuum high temperature sintering furnace with tungsten device for the sample after ungrease treatment and to be warming up to 2200 DEG C and to carry out vacuum-sintering, before heating up, the vacuum of sintering furnace at least will reach 10
-4pa, rises to 1200 DEG C with the speed of 10 ~ 15 DEG C/min from room temperature, and insulation 30min, vacuum is 10
-4pa; Rise to 1500 DEG C with the speed of 10 DEG C/min, insulation 30min, vacuum is 10
-4pa ~ 10
-3pa; Rise to 2200 DEG C with the speed of 6 DEG C/min, insulation 120min, vacuum is 10
-3pa; Sinter complete, vacuum is 10
-3pa, is cooled to 1600 DEG C with the speed of 10 ~ 15 DEG C/min, insulation 30min; 1200 DEG C are cooled to, insulation 60min with the speed of 12 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 10 DEG C/min;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with corundum container to be warming up to 1250 DEG C and to carry out stress relief annealing process, the vacuum before heating up in annealing furnace at least will reach 10
-4pa, rises to 1250 DEG C with the speed of 15 DEG C/min from room temperature, and insulation 240min, vacuum is 10
-4pa ~ 10
-3pa; Be cooled to 1000 DEG C with the speed of 5 DEG C/min again, insulation 180min, vacuum is 10
-4pa ~ 10
-3pa; Be cooled to 800 DEG C with the speed of 10 DEG C/min, insulation 120min, vacuum is 10
-4pa; Be cooled to room temperature with the speed of 20 DEG C/min, vacuum is 10
-4pa; Finally carry out conventional post processing and obtain porous tantalum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310700104.9A CN103736147B (en) | 2011-09-29 | 2011-09-29 | Medical porous metal material replacing bearing bone tissue and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310700104.9A CN103736147B (en) | 2011-09-29 | 2011-09-29 | Medical porous metal material replacing bearing bone tissue and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110301039 Division CN102796904B (en) | 2011-09-29 | 2011-09-29 | Medical porous metal material for replacing weight-bearing bone tissues and preparation method of medical porous metal material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103736147A CN103736147A (en) | 2014-04-23 |
| CN103736147B true CN103736147B (en) | 2015-04-08 |
Family
ID=50493259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310700104.9A Active CN103736147B (en) | 2011-09-29 | 2011-09-29 | Medical porous metal material replacing bearing bone tissue and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103736147B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112170845B (en) * | 2020-09-28 | 2022-09-20 | 西部宝德科技股份有限公司 | Degreasing method for powder porous metal film |
Citations (6)
| 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 |
| 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 CN201310700104.9A patent/CN103736147B/en active Active
Patent Citations (6)
| 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 |
| 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 |
|---|
| 多孔钽的制备方法;夏凤金等;《科技创新导报》;20080131;2014-2018 * |
| 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2014-2018页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103736147A (en) | 2014-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102796904B (en) | Medical porous metal material for replacing weight-bearing bone tissues and preparation method of medical porous metal material | |
| CN102796892B (en) | Preparation method for medical porous metal material for replacing dentale | |
| CN103846443B (en) | A kind of porous tantalum being applicable to alternative human dentale tissue | |
| CN102796901B (en) | Method for preparing medical porous metal implant material | |
| CN102793945B (en) | Medical porous tantalum material of a kind of alternative dentale and preparation method thereof | |
| CN103740962B (en) | Preparation method of medical porous metal material substituting for dental bone | |
| CN102796899B (en) | Preparation method of medical porous metal implanting material | |
| CN103740964B (en) | Preparation method of medical porous metal implant material | |
| CN102796898B (en) | Method for preparing medical porous metal implant material | |
| CN103736147B (en) | Medical porous metal material replacing bearing bone tissue and preparation method thereof | |
| CN102796900B (en) | Medical porous metal material and preparation method thereof | |
| CN103691004B (en) | Method for preparing medical porous metal implant material | |
| CN103740966B (en) | Method for preparing medical porous metal material substituting for load-bearing bone tissue | |
| CN102796903B (en) | Method for preparing medical porous metal material capable of replacing bearing bone tissue | |
| CN102796891B (en) | Method for preparing medical porous metal material | |
| CN103740961B (en) | Preparation method of medical porous metal material capable of replacing weight-bearing bone tissue | |
| CN102796890B (en) | Preparation method for medical porous metal material capable of replacing loading bone tissue | |
| CN103736151B (en) | Preparation method of medical porous metal material capable of replacing weight bearing bone tissue | |
| CN102793946B (en) | Medical porous metal material for replacing dentale and preparation method thereof | |
| CN102796895B (en) | Preparation method for medical porous metal material capable of replacing bearing bone tissue | |
| CN104225673B (en) | Medical porous metal material of a kind of alternative dentale and preparation method thereof | |
| CN103667763B (en) | Method for preparing medical porous metal implant material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |