CN103740961B - 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
- Publication number
- CN103740961B CN103740961B CN201310692180.XA CN201310692180A CN103740961B CN 103740961 B CN103740961 B CN 103740961B CN 201310692180 A CN201310692180 A CN 201310692180A CN 103740961 B CN103740961 B CN 103740961B
- Authority
- CN
- China
- Prior art keywords
- insulation
- speed
- vacuum
- reach
- warming
- 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 preparation method of a medical porous metal material capable of replacing a weight-bearing bone tissue. The method comprises the following steps: mixing tantalum powder with a pore-forming agent and a molding agent; pressing mixed powder into an organic foaming body; molding, degreasing, sintering and cooling; and performing heat treatment, wherein carrying out the degreasing under the conditions of gradually heating to 400 DEG C to 800 DEG C according to the speed rate of 0.3 DEG C/minute to 2 DEG C/minute, forming a protective atmosphere in an argon leading-in mode and carrying out the heat preservation for 300 to 360 minutes; and carrying out the sintering at 10<-4>Pa to 10<-3>Pa under the conditions of gradually heating to 1500 DEFG C to 1800 DEG C at the speed rate of 10 DEG C/minute to 20 DEG C/minute, carrying out the heat preservation for 120 to 240 minutes, cooling to 200 DEG C to 300 DEG C along with a furnace, then gradually heating to 1500 DEG C to 1800 DEG C at the speed rate of 10 DEG C/minute to 20 DEG C/minute, carrying out the heat preservation for 180 to 240 minutes, heating to 2000 DEG C to 2200 DEG C according to the speed rate of 5 DEG C/minute to 10 DEG C/minute and carrying out the heat preservation for 120 to 360 minutes. By testing, the content of impurities in the material is below 0.2%; the density of the material can reach 5.00g/cm<3> to 6.67g/cm<3>; the porosity of the material can reach 60% to 70%; the pore diameter of the material can reach 200 mu m to 400 mu m; the elasticity modulus of the material can reach 3.8Gpa to 4.2Gpa; the bending strength of the material can reach 125Mpa to 150Mpa; the compressive strength of the material can reach 72Mpa to 90Mpa. Thus, the contradiction that the medical porous metal material for replacing the weight-bearing bone tissue is required to have the large porosity and the good mechanical property is effectively solved.
Description
The present patent application is application number 201110295814.9, the applying date on 09 29th, 2011, the divisional application of denomination of invention " a kind of preparation method of medical porous metallic substance of alternative load 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 common this kind of material has porous metal stainless steel, porous metal 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 metal 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 open pore and adapting with human body, then it is expected to as a kind of novel osseous tissue equivalent material.
As medical embedded porous metal material just as porous metal material be main working method with powder sintering like that substantially, especially obtain porosity communication and equally distributed porous metal foam structure adopt the dipping of the metal-powder 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 major 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 metal obtained or for filtering material use, or share for aerospace and other high-temperature field but not use as medical metal implanted material, moreover the porous metal 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 susceptor and preparation thereof.This porous tantalum is made up of pure business tantalum, it carries out carbon skeleton that thermal destruction 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 metal microstructure, 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 ultimate compression strength 50 ~ 70MPa of this porous material, Young's modulus 2.5 ~ 3.5GPa, tensile strength 63MPa.But by it, load 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 preparation method being applicable to the porous metal material of alternative human bearing position osseous tissue that a kind of mechanical strength is good.
The object of the invention is to be realized by following technique means:
A preparation method for the medical porous metallic substance of alternative load bone tissue, is characterized in that: mixed with pore-forming material, forming agent by tantalum powder, more repressed shaping, degreasing, sintering, cooling and thermal treatment are obtained; Described compression moulding is pressed in Organic Foam Material shaping by described mixed powder, 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 gas; Described pore-forming material is bicarbonate of ammonia or hydrogen peroxide, and described forming agent is one or more in stearic acid, Zinic stearas, paraffin, synthetic resins (be preferably styrene-butadiene rubber(SBR) or polyisoprene rubber); Described sintering step is vacuum tightness is 10
-4pa ~ 10
-3pa, be warming up to 1500 ~ 1800 DEG C with 10 ~ 20 DEG C/min, be incubated 120 ~ 240min, be chilled to 200 ~ 300 DEG C with stove, be warming up to 1500 ~ 1800 DEG C, insulation 180 ~ 240min with 10 ~ 20 DEG C/min again, be warming up to 2000 ~ 2200 DEG C, insulation 120 ~ 360min with 5 ~ 10 DEG C/min.
In the R&D process of medical porous metallic substance, the material of medical porous metallic substance load 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 contriver creatively proposes and adopts above-mentioned steps, technique prepares 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 quality product is uneven, the above-mentioned sintering process particularly adopted, make idiosome become heating element, thus sinter evenly, thorough; Its obtained porous tantalum material through its foreign matter content of test can lower than 0.2%, its biocompatibility and biological safety good, density can reach 5.00 ~ 6.67g/cm
3, porosity can reach 60 ~ 70%, and pore diameter can reach 200 ~ 400 μm; Young's modulus can reach 3.8 ~ 4.2Gpa, unit elongation reaches 9.3 ~ 10.7%, flexural strength can reach 125 ~ 150Mpa, ultimate compression strength can reach 72 ~ 90Mpa, its biocompatibility, obdurability are close to the characteristic of human bearing's osseous tissue, and porous tantalum of the present invention is suitable for the medical embedded material of alternative load bone tissue very much.
The present invention adopt Ta powder median size is less than 43 microns, oxygen level is less than 0.1%, is commercially available prod; Above-mentioned pore-forming material, forming agent are also commercially available prod.Vacuum environment of the present invention preferably adopts vacuum tightness 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, contriver studies discovery further, if control bad in above-mentioned preparation, though the medical embedded material that is suitable for alternative load bone tissue as mentioned above can be obtained but conforming product rate is not high, the stability of technique is not ideal enough, affect its commercial scale production: as difficult in powder pressing forming, after pressing part easily there is layering, uneven, degreasing rear section there will be the technical problems such as crackle.
Shaping easier in order to make in powder compaction process, thus raising yield rate, finished product hole homogeneity, make preparation process more stable, the consumption of above-mentioned pore-forming 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-forming material, in the weighing of forming agent, pressed powder still calculates the quality weighing of its correspondence according to the densometer of respective substance, if liquid substance then directly adopts volume to weigh certainly), more preferably pore-forming material is that hydrogen peroxide accounts for 18%, forming agent is that Zinic stearas accounts for 11%, surplus is tantalum powder, in volumn concentration, pressure in above-mentioned compression moulding 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 gas; Preferably further progressively be warming up to 400 ~ 800 DEG C with the speed of 0.8 DEG C/min, pass into argon gas and formed protective atmosphere and be incubated 340min.
Sinter to make idiosome evenly, thorough, make the medical porous tantalum mechanics of materials intensity that obtains higher, it is 10 that above-mentioned sintering step is preferably vacuum tightness
-4pa ~ 10
-3pa, be warming up to 1500 ~ 1800 DEG C with 12 ~ 15 DEG C/min, be incubated 180 ~ 200min, be chilled to 200 ~ 300 DEG C with stove, be warming up to 1500 ~ 1800 DEG C, insulation 220 ~ 240min with 16 ~ 19 DEG C/min again, be warming up to 2000 ~ 2200 DEG C, insulation 250 ~ 320min with 5 ~ 8 DEG C/min; Further being preferably vacuum tightness is 10
-4pa ~ 10
-3pa, is warming up to 1800 DEG C with 13 DEG C/min, is incubated 200min, is chilled to 200 ~ 300 DEG C with stove, then is warming up to 1800 DEG C, insulation 230min with 17 DEG C/min, is warming up to 2000 ~ 2200 DEG C, insulation 300min with 7 DEG C/min.
Cooling conditions after vacuum sintering also includes: vacuum tightness 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 rate of cooling mode, and to sintered porous bodies segmentation cooling down to 800 DEG C, each section of soaking time 30min ~ 90min, then cools to normal temperature with the furnace.
Vacuum annealing condition also includes: vacuum tightness 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 rate of cooling sub-sectional cooling of 30 DEG C/min to room temperature, the soaking time of each section tapers off and is no more than in 1.5h ~ 3h and selects.
Further feature is on this basis: described skimming 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: vacuum tightness is 10
-4pa ~ 10
-3pa, be warming up to 1500 ~ 1800 DEG C with 12 ~ 15 DEG C/min, be incubated 180 ~ 200min, be chilled to 200 ~ 300 DEG C with stove, be warming up to 1500 ~ 1800 DEG C, insulation 220 ~ 240min with 16 ~ 19 DEG C/min again, be warming up to 2000 ~ 2200 DEG C, insulation 250 ~ 320min with 5 ~ 8 DEG C/min; Cooling conditions after vacuum sintering also includes: vacuum tightness 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 includes: rise to 1000 ~ 1250 DEG C with the speed of 15 ~ 30 DEG C/min, and insulation 240 ~ 480min, vacuum tightness 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 tightness is 10
-4pa ~ 10
-3pa; Be cooled to 800 DEG C with the speed of 10 ~ 20 DEG C/min, insulation 60 ~ 120min, vacuum tightness is 10
-4pa; Be cooled to room temperature with the speed of 20 ~ 30 DEG C/min, vacuum tightness is 10
-4pa ~ 10
-3pa.
The character of metal tantalum and niobium is extremely similar, and aforesaid 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; To the optimization of process conditions of compression moulding of the present invention, degreasing, sintering and annealing steps, make that yield rate is high, finished product aperture homogeneity is better, make that preparation process is more stable, quality stability good, effectively eliminate thermal stresses, make porous tantalum materials microstructure evenly, effectively improve the mechanical property of porous tantalum, particularly its intensity is greatly enhanced; Preparation technology of the present invention makes that product qualified rate is high, administration measure, and conforming product rate can up to 93%.The porous tantalum finished product even pore distribution that the present invention obtains and being communicated with, good biocompatibility, through test its foreign matter content can lower than 0.2%, density can reach 5.00 ~ 6.67g/cm
3, porosity can reach 60 ~ 70%, and pore diameter can reach 200 ~ 400 μm; Young's modulus can reach 3.8 ~ 4.2Gpa, unit elongation reaches 9.3 ~ 10.7%, flexural strength can reach 125 ~ 150Mpa, ultimate compression strength can reach 72 ~ 90Mpa, 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 bone tissue as an alternative very much.
Embodiment
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 bone tissue specifically select in stearic acid, Zinic stearas, paraffin, synthetic rubber one or more for forming agent, bicarbonate of ammonia or hydrogen peroxide be pore-forming material, be less than 43 microns with median size, the oxygen level tantalum powder that is less than 0.1% mixes, under 50 ~ 100Mpa, described mixed powder is pressed in Organic Foam Material shaping, then obtains through degreasing, sintering, cooling and thermal 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 gas; Described sintering step is vacuum tightness is 10
-4pa ~ 10
-3pa, be warming up to 1500 ~ 1800 DEG C with 10 ~ 20 DEG C/min, be incubated 120 ~ 240min, be chilled to 200 ~ 300 DEG C with stove, be warming up to 1500 ~ 1800 DEG C, insulation 180 ~ 240min with 10 ~ 20 DEG C/min again, be warming up to 2000 ~ 2200 DEG C, insulation 120 ~ 360min with 5 ~ 10 DEG C/min.The medical porous tantalum material pore diameter formed is 200 ~ 400 μm, porosity between 60 ~ 70%, Young's modulus is 3.8 ~ 4.2Gpa, unit elongation is 9.3 ~ 10.7%.
More particularly, above-mentioned porous tantalum is by the mixing of the tantalum powder of the above-mentioned pore-forming material of the above-mentioned forming agent of 7 ~ 12% (in volumn concentrations), 15 ~ 25% (in volumn concentrations) and surplus, put it into be pressed in polyurethane foam in injection moulding machine shaping; 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 certain temperature, and insulation carries out skimming treatment to remove pore-forming material, forming agent and polyurethane foam, wherein before intensification, first pass into argon gas to get rid of furnace air, the sample furnace cooling after degreasing; Sample after skimming treatment is placed in high vacuum high temperature sintering furnace with tungsten device to sinter vacuum tightness be 10
-4pa ~ 10
-3pa; be warming up to 1500 ~ 1800 DEG C with 12 ~ 15 DEG C/min, be incubated 180 ~ 200min, be chilled to 200 ~ 300 DEG C with stove; 1500 ~ 1800 DEG C, insulation 220 ~ 240min is warming up to again with 16 ~ 19 DEG C/min; 2000 ~ 2200 DEG C, insulation 250 ~ 320min is warming up to 5 ~ 8 DEG C/min; sample furnace cooling after vacuum sintering; keep certain vacuum tightness in process of cooling or by certain rate of cooling sub-sectional cooling to keep certain 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 tightness that maintenance before heating up in annealing furnace is certain; sample furnace cooling after vacuum annealing process; also keep certain vacuum tightness in process of cooling or by certain rate of cooling sub-sectional cooling to keep certain temperature in reasonable time; filling with inert gas can be adopted in insulating process as protective atmosphere, finally carry out conventional aftertreatment and obtain porous tantalum.
For skimming 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 gas; Preferably further progressively be warming up to 400 ~ 800 DEG C with the speed of 0.8 DEG C/min, pass into argon gas and formed protective atmosphere and be incubated 340min.Above-mentioned vacuum sintering is complete, keeps vacuum, is 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 temperature rise rate and carry out stress relief annealing process, maintenance vacuum tightness before heating up in annealing furnace, 1000 DEG C ~ 1250 DEG C are risen to from room temperature with certain temperature rise 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 aftertreatment and obtain porous tantalum.
Contriver adopts metal powder sintered method mainly based on physical abrasion method, has done a large amount of theoretical analysises and experimental verification, obtain porous tantalum product through its foreign matter content of test can lower than 0.2%, density can reach 5.00 ~ 6.67g/cm
3, porosity can reach 60 ~ 70%, and pore diameter can reach 200 ~ 400 μm; Young's modulus can reach 3.8 ~ 4.2Gpa, unit elongation reaches 9.3 ~ 10.7%, and flexural strength can reach 125 ~ 150Mpa, ultimate compression strength can reach 72 ~ 90Mpa.
Embodiment 1: weigh Zinic stearas, median size be less than 43 microns of oxygen levels be less than 0.1% tantalum powder and hydrogen peroxide mix, wherein Zinic stearas accounts for 11%, and 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 urethane foam (aperture 0.48 ~ 0.89mm, density 0.015g/cm under 82Mpa
3~ 0.035g/cm
3, hardness is greater than 50 °) in shaping.Skimming treatment: vacuum tightness 10
-4pa, with the temperature rise rate of 1.5 DEG C/min from room temperature to 400 DEG C, insulation 320min; 700 DEG C are warming up to from 400 DEG C again, soaking time 350 minutes with the temperature rise rate of 0.6 DEG C/min.Vacuum sintering: vacuum tightness is 10
-4pa ~ 10
-3pa, is warming up to 1800 DEG C with 13 DEG C/min, is incubated 200min, is chilled to 200 ~ 300 DEG C with stove, then is warming up to 1800 DEG C, insulation 230min with 17 DEG C/min, is warming up to 2000 ~ 2200 DEG C, insulation 300min with 7 DEG C/min; Sintering process applying argon gas is protected, and removes surface dirt and dirt after taking out product, and obtained sample carries out conventional aftertreatment again and obtains porous tantalum finished product.
Contriver 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 foreign matter content is lower than 0.2%, its even pore distribution, density 6.56g/cm
3, porosity 65%, pore mean diameters 300 μm, Young's modulus 4.0Gpa, unit elongation 10.02%, flexural strength 145MPa, ultimate compression strength 89MPa.
Embodiment 2: take stearic acid, median size be less than 43 microns of oxygen levels be less than 0.1% tantalum powder and bicarbonate of ammonia be mixed into mixed powder, wherein stearic acid accounts for 12%, bicarbonate of ammonia accounts for 23%, tantalum powder accounts for 65%, all in volumn concentration.Extrusion forming: above-mentioned mixed powder is added in injection moulding machine and be pressed into urethane foam (aperture 0.48 ~ 0.89mm, density 0.015g/cm under 75Mpa
3~ 0.035g/cm
3, hardness is greater than 50 °) in shaping.Skimming treatment: vacuum tightness 10
-4pa, with the temperature rise rate of 0.3 DEG C/min from room temperature to 500 DEG C, insulation 360min.Vacuum sintering: vacuum tightness is 10
-3pa, is warming up to 1500 DEG C with 10 DEG C/min, is incubated 150min, is chilled to 200 ~ 300 DEG C with stove, then is warming up to 1600 DEG C, insulation 240min with 20 DEG C/min, is warming up to 2000 ~ 2200 DEG C, insulation 120min with 10 DEG C/min; Sintering process applying argon gas is protected, and removes surface dirt and dirt after taking out product, and obtained sample carries out conventional aftertreatment again and obtains porous tantalum finished product.
Contriver 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 foreign matter content is lower than 0.2%, its even pore distribution, density 6.25g/cm
3, porosity 61%, pore mean diameters 200 μm, Young's modulus 3.8Gpa, unit elongation 9.3%, flexural strength 125MPa, ultimate compression strength 75MPa.
Embodiment 3: take paraffin, median size be less than 43 microns of oxygen levels be less than 0.1% tantalum powder and hydrogen peroxide mix, wherein paraffin accounts for 7%, hydrogen peroxide 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 urethane foam (aperture 0.48 ~ 0.89mm, density 0.015g/cm under 52Mpa
3~ 0.035g/cm
3, hardness is greater than 500) in shaping.Skimming treatment: vacuum tightness 10
-4pa, with the temperature rise rate of 2 DEG C/min from room temperature to 400 DEG C, insulation 300min.Vacuum sintering: vacuum tightness is 10
-4pa, is warming up to 1600 DEG C with 20 DEG C/min, is incubated 120min, is chilled to 200 ~ 300 DEG C with stove, then is warming up to 1500 DEG C, insulation 180min with 10 DEG C/min, is warming up to 2000 ~ 2200 DEG C, insulation 360min with 5 DEG C/min; 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 aftertreatment again and obtains porous tantalum finished product.
Contriver 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 foreign matter content is lower than 0.2%, its even pore distribution, density 6.55g/cm
3, porosity 70%, pore mean diameters 400 μm, Young's modulus 3.9Gpa, unit elongation 9.8%, flexural strength 133MPa, ultimate compression strength 85MPa.
Embodiment 4: take polyisoprene rubber, median size be less than 43 microns of oxygen levels be less than 0.1% niobium powder and bicarbonate of ammonia mix, wherein polyisoprene rubber accounts for 9%, bicarbonate of ammonia accounts for 15%, niobium powder accounts for 76%, all in volumn concentration.Extrusion forming: above-mentioned mixed powder is added in injection moulding machine and be pressed into urethane foam (aperture 0.48 ~ 0.89mm, density 0.015g/cm under 96Mpa
3~ 0.035g/cm
3, hardness is greater than 50 °) in shaping.Skimming treatment: vacuum tightness 10
-4pa, with the temperature rise rate of 0.8 DEG C/min from room temperature to 400 DEG C, insulation 340min.Vacuum sintering: vacuum tightness is 10
-4pa, is warming up to 1700 DEG C with 15 DEG C/min, is incubated 180min, is chilled to 200 ~ 300 DEG C with stove, then is warming up to 1700 DEG C, insulation 220min with 19 DEG C/min, is warming up to 2000 ~ 2200 DEG C, insulation 320min with 8 DEG C/min; 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 aftertreatment again and obtains porous niobium finished product.
Contriver 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 foreign matter content is lower than 0.2%, its even pore distribution, density 2.74g/cm
3, porosity 68%, pore mean diameters 238 μm, Young's modulus 2.6Gpa, unit elongation 10.03%, flexural strength 92MPa, ultimate compression strength 81MPa.
Embodiment 5: a kind of porous tantalum, it is less than 43 μm, the oxygen level ta powder that is less than 0.1% with particle diameter, and stearic acid and hydrogen peroxide powder mix are raw material, more repressed shaping, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment obtain.
Wherein, stearic acid accounts for 10%, hydrogen peroxide accounts for 19%, ta powder accounts for 71%, in volumn concentration;
Compression moulding: raw material mixed powder is added in injection moulding machine and be pressed into urethane foam (aperture 0.48 ~ 0.89mm, density 0.015g/cm under 83Mpa
3~ 0.035g/cm
3, hardness is greater than 50 °) in shaping;
After compression moulding, mixed powder is put into nonoxidizing atmosphere stove and be warming up to 800 DEG C with certain temperature rise rate, protective atmosphere is that 99.999% argon gas carries out skimming 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 1.3 DEG C/min, insulation 310min, argon gas intake 0.5L/min; 800 DEG C are risen to from 400 DEG C, insulation 358min, argon gas intake 1L/min with the speed of 0.4 DEG C/min; Powered-down again, the sample furnace cooling after degreasing, argon gas intake 1L/min, until close argon gas when being cooled to room temperature;
To be placed in tungsten device for the sample after skimming treatment and to be warming up to 2200 DEG C with certain temperature rise rate in high vacuum high temperature sintering furnace and to carry out vacuum sintering, before heating up, the vacuum tightness of sintering oven at least will reach 10
-4pa, be warming up to 1500 ~ 1800 DEG C with 12 ~ 15 DEG C/min, be incubated 180 ~ 200min, be chilled to 200 ~ 300 DEG C with stove, be warming up to 1500 ~ 1800 DEG C, insulation 220 ~ 240min with 16 ~ 19 DEG C/min again, be warming up to 2000 ~ 2200 DEG C, insulation 250 ~ 320min with 5 ~ 8 DEG C/min; Sinter complete, vacuum tightness 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 temperature rise rate and to carry out stress relief annealing process, the vacuum tightness 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 tightness is 10
-4pa ~ 10
-3pa; Be cooled to 1000 DEG C with the speed of 5 DEG C/min again, insulation 180min, vacuum tightness is 10
-4pa ~ 10
-3pa; Be cooled to 800 DEG C with the speed of 10 DEG C/min, insulation 120min, vacuum tightness is 10
-4pa; Be cooled to room temperature with the speed of 20 DEG C/min, vacuum tightness is 10
-4pa.Finally carry out conventional aftertreatment and obtain porous tantalum.
Contriver 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 foreign matter content is lower than 0.2%, its even pore distribution, density 6.00 ~ 6.67g/cm
3, porosity 62 ~ 67%, pore mean diameters 200 ~ 340 μm, Young's modulus 3.8 ~ 4.0Gpa, unit elongation 9.3 ~ 9.9%, flexural strength 128 ~ 136MPa, ultimate compression strength 75 ~ 86MPa.Preparation technology's conforming product rate of the present invention can up to about 92% 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) | 3.09 | 6.55 | 5.00 |
| Porosity (%) | 65 | 60 | 63 |
| Aperture (μm) | 215 | 365 | 278 |
| Young's modulus (GPa) | 2.9 | 4.1 | 4.2 |
| Unit elongation (%) | 9.4 | 10.02 | 10.05 |
| Flexural strength (MPa) | 98 | 136 | 145 |
| Ultimate compression strength (MPa) | 67 | 88 | 77.5 |
Claims (1)
1. the preparation method of the medical porous metallic substance of an alternative load bone tissue, it is characterized in that: be less than 42 μm, the oxygen level ta powder that is less than 0.1% with particle diameter, Zinic stearas and bicarbonate of ammonia powder mix are raw material, more repressed shaping, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment;
Wherein, Zinic stearas accounts for greatly 11.5%, bicarbonate of ammonia accounts for greatly 23.0%, ta powder accounts for 65.5% greatly, in volumn concentration;
Compression moulding: raw material mixed powder is added in injection moulding machine and be pressed into aperture 0.48 ~ 0.89mm, density 0.015 g/cm under 93Mpa
3~ 0.035g/cm
3, hardness is greater than 50
0urethane foam in shaping;
Mixed powder is put into nonoxidizing atmosphere stove temperature to 800 DEG C after compression moulding, protective atmosphere is that 99.999% argon gas carries out skimming 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 2 DEG C/min, insulation 330min, argon gas intake 0.5L/min; 680 DEG C are risen to from 400 DEG C, insulation 348min, argon gas intake 1L/min with the speed of 0.3 DEG C/min; Powered-down again, the sample furnace cooling after degreasing, argon gas intake 1L/min, until close argon gas when being cooled to room temperature;
To be placed in high vacuum high temperature sintering furnace with tungsten device for the sample after skimming treatment and to be warming up to 2200 DEG C and to carry out vacuum sintering, before heating up, the vacuum tightness of sintering oven at least will reach 10
-4pa, is warming up to 1650 DEG C with 19 DEG C/min, is incubated 150min, is chilled to 200 ~ 300 DEG C with stove, then is warming up to 1600 DEG C, insulation 190min with 13 DEG C/min, is warming up to 2000 ~ 2200 DEG C, insulation 180min with 9 DEG C/min; Sinter complete, vacuum tightness is 10
-4pa ~ 10
-3pa, is cooled to 1540 DEG C with the speed of 13 DEG C/min, insulation 50min; 1220 DEG C are cooled to, insulation 80min with the speed of 15 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 15 DEG C/min;
Be placed in vacuum annealing furnace for the cooled sample of vacuum sintering with corundum container to be warming up to 1100 DEG C and to carry out stress relief annealing process, the vacuum tightness before heating up in annealing furnace at least will reach 10
-4pa, rises to 1100 DEG C with the speed of 20 DEG C/min from room temperature, and insulation 420min, vacuum tightness is 10
-3pa; Be cooled to 1000 DEG C with the speed of 7 DEG C/min again, insulation 130min, vacuum tightness is 10
-3pa; Be cooled to 800 DEG C with the speed of 13 DEG C/min, insulation 96min, vacuum tightness is 10
-3pa; Be cooled to room temperature with the speed of 23 DEG C/min, vacuum tightness is 10
-3pa, finally carries out conventional aftertreatment and obtains porous tantalum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310692180.XA CN103740961B (en) | 2011-09-29 | 2011-09-29 | Preparation method of medical porous metal material capable of replacing weight-bearing bone tissue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310692180.XA CN103740961B (en) | 2011-09-29 | 2011-09-29 | Preparation method of medical porous metal material capable of replacing weight-bearing bone tissue |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110295814 Division CN102796890B (en) | 2011-09-29 | 2011-09-29 | Preparation method for medical porous metal material capable of replacing loading bone tissue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103740961A CN103740961A (en) | 2014-04-23 |
| CN103740961B true CN103740961B (en) | 2015-04-08 |
Family
ID=50498025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310692180.XA Active CN103740961B (en) | 2011-09-29 | 2011-09-29 | Preparation method of medical porous metal material capable of replacing weight-bearing bone tissue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103740961B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107745126B (en) * | 2017-09-30 | 2020-01-31 | 中国振华（集团）新云电子元器件有限责任公司 | method for improving internal porosity of sintered tantalum block |
Citations (3)
| 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 |
| 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 |
-
2011
- 2011-09-29 CN CN201310692180.XA patent/CN103740961B/en active Active
Patent Citations (3)
| 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 |
| 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 |
Non-Patent Citations (1)
| 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);2014-2018 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103740961A (en) | 2014-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103849792B (en) | A kind of porous tantalum being applicable to alternative human dentale tissue | |
| CN102796892B (en) | Preparation method for medical porous metal material for replacing dentale | |
| CN102796904B (en) | Medical porous metal material for replacing weight-bearing bone tissues and preparation method of medical porous metal material | |
| 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 | |
| CN103740964B (en) | Preparation method of medical porous metal implant material | |
| CN102796899B (en) | Preparation method of medical porous metal implanting material | |
| CN102796898B (en) | Method for preparing medical porous metal implant material | |
| CN103740961B (en) | Preparation method of medical porous metal material capable of replacing weight-bearing bone tissue | |
| CN102796900B (en) | Medical porous metal material and preparation method thereof | |
| CN103691004B (en) | Method for preparing medical porous metal implant material | |
| CN102796890B (en) | Preparation method for medical porous metal material capable of replacing loading bone tissue | |
| CN103740966B (en) | Method for preparing medical porous metal material substituting for load-bearing bone tissue | |
| CN103736147B (en) | Medical porous metal material replacing bearing bone tissue and preparation method thereof | |
| CN102796903B (en) | Method for preparing medical porous metal material capable of replacing bearing bone tissue | |
| CN102796891A (en) | Method for preparing medical porous metal material | |
| CN103736151B (en) | Preparation method of medical porous metal material capable of replacing weight bearing bone tissue | |
| CN104225673B (en) | Medical porous metal material of a kind of alternative dentale and preparation method thereof | |
| CN102796895B (en) | Preparation method for medical porous metal material capable of replacing bearing bone tissue | |
| CN102793946B (en) | Medical porous metal material for replacing 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 |