CN103740961A - Preparation method of medical porous metal material capable of replacing weight-bearing bone tissue - Google Patents
Preparation method of medical porous metal material capable of replacing weight-bearing bone tissue Download PDFInfo
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Abstract
The invention 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, and denomination of invention " a kind of preparation method of medical porous metallic substance of alternative load bone tissue " divides an application.
Technical field
The present invention relates to a kind of preparation method of porous medical metal implanted material, particularly relate to a kind of preparation method of medical porous metal implant material of alternative weight bearing area osseous tissue.
Background technology
Porous medical metal implanted material has the important and special purposes such as treatment osseous tissue wound, bone formation necrosis, and existing this common class material has porous metal stainless steel, porous metal titanium etc.Porous embedded material as osseous tissue wound and the use of bone formation necrosis therapeutic, its porosity should reach 30～80%, and hole is preferably all communicated with and is uniformly distributed, or make it as required both consistent with the bone growth of human body, alleviate again the weight of material itself, to be applicable to human body, implanted use.
And refractory metals tantalum/niobium, because it has outstanding biocompatibility, its porous material is expected to the conventional medical metallic biomaterial such as aforementioned as an alternative.Due to metal tantalum/niobium to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, further the going deep into as body implanting material cognition to tantalum/niobium, people implant and become more and more urgent by the demand of porous metal tantalum/niobium material human body, also more and more higher to its requirement.Wherein, as the medical embedded metal tantalum/niobium of porous, if can have the very high physical and mechanical properties that is uniformly distributed open pore and adapts with human body, 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 to take powder sintering as main working method like that substantially, in particular for obtain porosity communication and equally distributed porous metal foam structure adopt metal-powder slurry in the powder sintering dipping on Organic Foam Material afterwards the dry knot that reburns to be called for short foam impregnation method in the majority.About powder sintered obtained porous metal material conventionally its Metal Mechanic Property be not fine, its major cause is the problem of subsiding how arranging in technique in the support of pore-forming medium and elimination relation, metal powder sintered process.And in known bibliographical information, all there is no good solution and laissez-faire nature.
Adopt bibliographical information that metal powder sintered legal system makes porous tantalum/niobium seldom, particularly take and obtain medical embedded material and almost do not have with the porous tantalum/niobium powder sintering process bibliographical information that is object.Can reference be that publication number is CN200510032174, title " three-dimensional through hole or part hole porous metal foam connected with each other and preparation method thereof " and CN200710152394, title " a kind of porous foam tungsten and preparation method thereof ".Yet porous metal that it obtains or for filtering material use, or share for aerospace and other high-temperature field but not use as medical metal implanted material, moreover also non-porous tantalum/niobium of the porous metal of processing.
About porous tantalum, US5282861 discloses a kind of perforate tantalum material and preparation thereof that is applied to spongy bone implant, cell and organizes susceptor.This porous tantalum is made by pure business tantalum, it take polyurethane precursor, and to carry out the carbon skeleton that thermal destruction obtains be support, this carbon skeleton is multiple dodecahedron, it in it, is mesh-like structure, integral body spreads all over micropore, porosity can be up to 98%, then the method by chemical vapour deposition, infiltration is attached on carbon skeleton to form porous metal microstructure, referred to as chemical deposition by commercially pure tantalum.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtains is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight accounts for 1% left and right.Document is further recorded, the ultimate compression strength 50～70MPa of this porous material, Young's modulus 2.5～3.5GPa, tensile strength 63MPa.But load bone tissue is as the porous tantalum of the medical embedded materials such as skull as an alternative by it, and the mechanical property of its material is obvious weak point as ductility has, can have influence on the follow-up processing to porous tantalum material itself, such as cutting of profiled member etc.Also all there is such deficiency in the same product obtaining in aforesaid metal powder sintered method.Due to the limitation of its preparation method, the finished product purity of acquisition is inadequate, has carbon skeleton residue again, causes biological safety to reduce.
Summary of the invention
The object of the present invention is to provide good being applicable to of a kind of mechanical strength to substitute the preparation method of the porous metal material of human bearing position osseous tissue.
The object of the invention is to realize by following technique means:
A preparation method for the medical porous metallic substance of alternative load bone tissue, is characterized in that: by tantalum powder, mixed with pore-forming material, forming agent, more repressed moulding, degreasing, sintering, cooling and thermal treatment makes; Described compression moulding is that described mixed powder is pressed into moulding in Organic Foam Material, its pressure is 50～100Mpa, described skimming processes is that the speed with 0.3 ℃/min～2 ℃/min is progressively warming up to 400～800 ℃, with argon gas, passes into and forms protective atmosphere and be incubated 300min～360min; 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 (being preferably styrene-butadiene rubber(SBR) or polyisoprene rubber); Described sintering step is that vacuum tightness is 10
-4pa～10
-3pa, with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 120～240min, with stove, be chilled to 200～300 ℃, with 10～20 ℃/min, be warming up to 1500～1800 ℃, insulation 180～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, insulation 120～360min.
In the R&D process of medical porous metallic substance, medical porous metallic substance is the material of load bone tissue as an alternative, require that its porosity is large, tissue is just easily grown into like this, thereby good biocompatibility brings into play its effect fully, but porosity is larger, aperture is larger, mechanical property just can not be guaranteed as intensity, toughness; Otherwise, mechanical property got well and easily make that porosity is too small, biocompatibility is bad, the also excessive discomfort that causes of density; The syntheti c route of medical porous tantalum is numerous, but contriver has creatively proposed employing above-mentioned steps, technique is prepared medical porous tantalum embedded material, the problems such as the difficult quality product of controlling, making of plug-hole, soaking paste process that adopts cement-dipping method to be prone to is inhomogeneous have effectively been prevented, the above-mentioned sintering process particularly adopting, make idiosome become heating element, more even, thorough thereby sintering obtains; Porous tantalum material that it makes through its foreign matter content of test can be lower than 0.2%, its biocompatibility and biological safety good, density reachable 5.00～6.67g/cm
3, porosity can reach 60～70%, and pore diameter can reach 200～400 μ m; Young's modulus can reach that 3.8～4.2Gpa, unit elongation reach 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 substituting the medical embedded material of load bone tissue very much.
The median size of the Ta powder that the present invention adopts 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.It is 10 that vacuum environment of the present invention preferably adopts vacuum tightness
-4pa～10
-3the vacuum condition of Pa.Above-mentioned Organic Foam Material optimization polyurethane foam, aperture 0.48～0.89mm more preferably, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °, and (most preferably aperture is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness) polyurethane foam in.
In R&D process, contriver further studies discovery, if control bad in above-mentioned preparation, though can make and be suitable for as mentioned above substituting the medical embedded material of load bone tissue 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, in compacting rear section, be prone to layering, inhomogeneous, degreasing rear section there will be the technical problems such as crackle.
In order to make in powder compaction process moulding easier, thereby 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, in volumn concentration, (in volumn concentration, be all the unit of directly calculating by the situation of final porous tantalum material, at above-mentioned pore-forming material, pressed powder or calculate its corresponding quality weighing according to the densometer of respective substance in the weighing of forming agent, if liquid substance 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 in skimming processes, idiosome is more stable, minimizing is prone to the distortion of part idiosome, aperture inhomogeneous, thereby further improve yield rate, quality stability, above-mentioned skimming processes is that the speed with 0.3 ℃/min～1 ℃/min is progressively warming up to 400～800 ℃, with argon gas, passes into and forms protective atmosphere and be incubated 330min～350min; Further preferably with the speed of 0.8 ℃/min, be progressively warming up to 400～800 ℃, with argon gas, pass into and form protective atmosphere and be incubated 340min.
For make idiosome sintering obtain more evenly, thorough, make the medical porous tantalum mechanics of materials intensity that makes higher, it is 10 that above-mentioned sintering step is preferably vacuum tightness
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, insulation 220～240min again, with 5～8 ℃/min, be warming up to 2000～2200 ℃, insulation 250～320min; Further being preferably vacuum tightness is 10
-4pa～10
-3pa, is warming up to 1800 ℃, is incubated 200min, with stove, is chilled to 200～300 ℃ with 13 ℃/min, then is warming up to 1800 ℃, insulation 230min with 17 ℃/min, with 7 ℃/min, is warming up to 2000～2200 ℃, insulation 300min.
Cooling conditions after vacuum sintering also includes: vacuum tightness is not less than 10
-3pa, with not higher than 25 ℃/min, is not less than 10 ℃/min and gradually falls rate of cooling mode, and to sintered porous bodies segmentation cooling down to 800 ℃, 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 ℃ with the speed higher than 30 ℃/min not, insulation 4h～6h; To be not less than 5 ℃/min but not to be cooled to room temperature higher than the rate of cooling segmentation of 30 ℃/min soon after first slow, the soaking time of each section tapers off and is no more than in 1.5h～3h and selects again.
Further feature is on this basis: described skimming treatment condition also includes: the speed with 1～2 ℃/min rises to 400 ℃ from room temperature, insulation 300～330min, speed with 0.3～0.8 ℃/min rises to 600～800 ℃, insulation 340～360min from 400 ℃; Described vacuum sintering condition: vacuum tightness is 10
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, insulation 220～240min again, with 5～8 ℃/min, be warming up to 2000～2200 ℃, insulation 250～320min; Cooling conditions after vacuum sintering also includes: vacuum tightness is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, insulation 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, insulation 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Described vacuum annealing condition includes: the speed with 15～30 ℃/min rises to 1000～1250 ℃, insulation 240～480min, and vacuum tightness is 10
-4pa～10
-3pa, then be cooled to 1000 ℃ with the speed of 5～10 ℃/min, insulation 90～180min, vacuum tightness is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 800 ℃, insulation 60～120min, and vacuum tightness is 10
-4pa; Speed with 20～30 ℃/min is cooled to room temperature, and 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 has adopted pure physics compression molding, makes the content of impurity in final porous tantalum material extremely low, has effectively improved biocompatibility and biological safety; Optimization of process conditions to 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 eliminated thermal stresses, made organizing of porous tantalum material more even, effectively improved the mechanical property of porous tantalum, particularly its intensity is greatly enhanced; Preparation technology of the present invention make product qualified rate high, produce stablely, conforming product rate can be up to 93%.Porous tantalum finished product even pore distribution and connection that the present invention makes, good biocompatibility, through its foreign matter content of test can be lower than 0.2%, density reachable 5.00～6.67g/cm
3, porosity can reach 60～70%, and pore diameter can reach 200～400 μ m; 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, efficiently solve the medical porous tantalum material of weight bearing area as an alternative and should ask its porosity to require more greatly, again the contradiction that mechanical property is good, porous tantalum of the present invention is suitable for the medical embedded material of load bone tissue as an alternative very much.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, person skilled in art can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
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, being less than 43 microns, oxygen level with median size is less than 0.1% tantalum powder and mixes, moulding in described mixed powder being pressed into Organic Foam Material under 50～100Mpa, then through degreasing, sintering, cooling and thermal treatment and obtain; Described skimming processes is that the speed with 0.3 ℃/min～2 ℃/min is progressively warming up to 400～800 ℃, with argon gas, passes into and forms protective atmosphere and be incubated 300min～360min; Described sintering step is that vacuum tightness is 10
-4pa～10
-3pa, with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 120～240min, with stove, be chilled to 200～300 ℃, with 10～20 ℃/min, be warming up to 1500～1800 ℃, insulation 180～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, insulation 120～360min.The medical porous tantalum material pore diameter forming is 200～400 μ m, porosity between 60～70%, Young's modulus is that 3.8～4.2Gpa, unit elongation are 9.3～10.7%.
More particularly, above-mentioned porous tantalum is that the above-mentioned pore-forming material of above-mentioned forming agent, 15～25% (in volumn concentration) of 7～12% (in volumn concentrations) and the tantalum powder of surplus are mixed, and puts it into and in injection moulding machine, is pressed into moulding in polyurethane foam; Being placed in tungsten device puts into the special atmosphere oven that pure argon gas (99.9999%) passes into formation and is progressively warming up to certain temperature again, and insulation is carried out skimming treatment to remove pore-forming material, forming agent and polyurethane foam, wherein before heating up, first pass into argon gas to get rid of furnace air, the sample furnace cooling after degreasing; For the sample after skimming treatment, with tungsten device, being placed in sintering vacuum tightness in high vacuum high temperature sintering furnace is 10
-4pa～10
-3pa; with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃; with 16～19 ℃/min, be warming up to 1500～1800 ℃, insulation 220～240min again; with 5～8 ℃/min, be warming up to 2000～2200 ℃, insulation 250～320min; sample furnace cooling after vacuum sintering; in process of cooling, keep certain vacuum tightness or cooling to keep certain temperature in reasonable time by certain rate of cooling segmentation, in insulating process, can adopt filling with inert gas as protective atmosphere.For the cooled sample of vacuum sintering, with corundum container, being placed in vacuum annealing furnace progressively heats up, is incubated and carry out stress relief annealing processing; the certain vacuum tightness of maintenance before heating up in annealing furnace; sample furnace cooling after vacuum annealing is processed; in process of cooling, also keep certain vacuum tightness or cooling to keep certain temperature in reasonable time by certain rate of cooling segmentation; in insulating process, can adopt filling with inert gas as protective atmosphere, finally carry out conventional aftertreatment and make porous tantalum.
For skimming treatment, skimming processes is that the speed with 0.3 ℃/min～1 ℃/min is progressively warming up to 400～800 ℃, with argon gas, passes into and forms protective atmosphere and be incubated 330min～350min; Further preferably with the speed of 0.8 ℃/min, be progressively warming up to 400～800 ℃, with argon gas, pass into and form protective atmosphere and be incubated 340min.Above-mentioned vacuum sintering is complete, keeps vacuum, with certain rate of temperature fall, is cooled to for example 1500 ℃～1600 ℃, insulation, then with certain rate of temperature fall, be cooled to for example 1200 ℃～1250 ℃, insulation, also with certain rate of temperature fall, be cooled to for example 800 ℃, then furnace cooling.For the cooled sample of vacuum sintering, carry out vacuum annealing processing, it to be placed in to vacuum annealing furnace with corundum container with certain temperature rise rate, be warming up to for example 1000 ℃～1250 ℃ and carry out stress relief annealing processing, maintenance vacuum tightness before heating up in annealing furnace, with certain temperature rise rate, from room temperature, rise to 1000 ℃～1250 ℃, insulation, keeps vacuum; With certain rate of temperature fall, be cooled to for example 1000 ℃ again, insulation; With certain rate of temperature fall, be cooled to for example 800 ℃ again, insulation; Also with the cooling room temperature of certain rate of temperature fall.Finally carry out conventional aftertreatment and make porous tantalum.
Contriver adopts metal powder sintered method mainly to take physics compression molding as main, has done a large amount of theoretical analysises and experimental verification, obtain porous tantalum product through its foreign matter content of test can be lower than 0.2%, density reachable 5.00～6.67g/cm
3, porosity can reach 60～70%, and pore diameter can reach 200～400 μ m; 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 and be less than 43 microns of oxygen levels and be less than 0.1% tantalum powder and hydrogen peroxide and 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 and be pressed into urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in injection moulding machine under 82Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle moulding.Skimming treatment: vacuum tightness 10
-4pa, is warming up to 400 ℃, insulation 320min with the temperature rise rate of 1.5 ℃/min from room temperature; Temperature rise rate with 0.6 ℃/min is warming up to 700 ℃, soaking time 350 minutes from 400 ℃ again.Vacuum sintering: vacuum tightness is 10
-4pa～10
-3pa, is warming up to 1800 ℃, is incubated 200min, with stove, is chilled to 200～300 ℃ with 13 ℃/min, then is warming up to 1800 ℃, insulation 230min with 17 ℃/min, with 7 ℃/min, is warming up to 2000～2200 ℃, insulation 300min; The protection of sintering process applying argon gas, removes surface dirt and dirt after taking-up product, and the sample making 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%, hole mean diameter 300 μ m, Young's modulus 4.0Gpa, unit elongation 10.02%, flexural strength 145MPa, ultimate compression strength 89MPa.
Embodiment 2: take stearic acid, median size and be less than 43 microns of oxygen levels and be less than 0.1% tantalum powder and bicarbonate of ammonia and 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 and be pressed into urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in injection moulding machine under 75Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle moulding.Skimming treatment: vacuum tightness 10
-4pa, is warming up to 500 ℃, insulation 360min with the temperature rise rate of 0.3 ℃/min from room temperature.Vacuum sintering: vacuum tightness is 10
-3pa, is warming up to 1500 ℃, is incubated 150min, with stove, is chilled to 200～300 ℃ with 10 ℃/min, then is warming up to 1600 ℃, insulation 240min with 20 ℃/min, with 10 ℃/min, is warming up to 2000～2200 ℃, insulation 120min; The protection of sintering process applying argon gas, removes surface dirt and dirt after taking-up product, and the sample making 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%, hole mean diameter 200 μ m, Young's modulus 3.8Gpa, unit elongation 9.3%, flexural strength 125MPa, ultimate compression strength 75MPa.
Embodiment 3: take paraffin, median size and be less than 43 microns of oxygen levels and be less than 0.1% tantalum powder and hydrogen peroxide and 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 and be pressed into urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in injection moulding machine under 52Mpa
3～0.035g/cm
3, hardness is greater than 500) and middle moulding.Skimming treatment: vacuum tightness 10
-4pa, is warming up to 400 ℃, insulation 300min with the temperature rise rate of 2 ℃/min from room temperature.Vacuum sintering: vacuum tightness is 10
-4pa, is warming up to 1600 ℃, is incubated 120min, with stove, is chilled to 200～300 ℃ with 20 ℃/min, then is warming up to 1500 ℃, insulation 180min with 10 ℃/min, with 5 ℃/min, is warming up to 2000～2200 ℃, insulation 360min; The protection of sintering process applying argon gas, cooling coming out of the stove, removes product surface dust and dirt, and the sample making 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%, hole mean diameter 400 μ m, Young's modulus 3.9Gpa, unit elongation 9.8%, flexural strength 133MPa, ultimate compression strength 85MPa.
Embodiment 4: take polyisoprene rubber, median size and be less than 43 microns of oxygen levels and be less than 0.1% niobium powder and bicarbonate of ammonia and 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 and be pressed into urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in injection moulding machine under 96Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle moulding.Skimming treatment: vacuum tightness 10
-4pa, is warming up to 400 ℃, insulation 340min with the temperature rise rate of 0.8 ℃/min from room temperature.Vacuum sintering: vacuum tightness is 10
-4pa, is warming up to 1700 ℃, is incubated 180min, with stove, is chilled to 200～300 ℃ with 15 ℃/min, then is warming up to 1700 ℃, insulation 220min with 19 ℃/min, with 8 ℃/min, is warming up to 2000～2200 ℃, insulation 320min; The protection of sintering process applying argon gas, cooling coming out of the stove, removes product surface dust and dirt, and the sample making 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%, hole mean diameter 238 μ m, Young's modulus 2.6Gpa, unit elongation 10.03%, flexural strength 92MPa, ultimate compression strength 81MPa.
Embodiment 5: a kind of porous tantalum, and it is less than with particle diameter the ta powder that 43 μ m, oxygen level are less than 0.1%, and stearic acid and hydrogen peroxide powder mix are raw material, more repressed moulding, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment make.
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 and be pressed into urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in injection moulding machine under 83Mpa
3～0.035g/cm
3, hardness is greater than 50 °) and middle moulding;
After compression moulding, mixed powder is put into nonoxidizing atmosphere stove and be warming up to 800 ℃ with certain temperature rise rate, protective atmosphere is that 99.999% argon gas carries out skimming treatment, its before heating up, first pass into pure argon gas at least 30min to get rid of furnace air, temperature control process: the speed with 1.3 ℃/min rises to 400 ℃ from room temperature, insulation 310min, argon gas intake 0.5L/min; Speed with 0.4 ℃/min rises to 800 ℃, insulation 358min, argon gas intake 1L/min from 400 ℃; Powered-down again, the sample furnace cooling after degreasing, argon gas intake 1L/min, until close argon gas while being cooled to room temperature;
For the sample after skimming treatment, with tungsten device, be placed in and in high vacuum high temperature sintering furnace, with certain temperature rise rate, be warming up to 2200 ℃ and carry out vacuum sintering, before heating up, the vacuum tightness of sintering oven at least will reach 10
-4pa, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, insulation 220～240min again, with 5～8 ℃/min, be warming up to 2000～2200 ℃, insulation 250～320min; Sintering is complete, and vacuum tightness is 10
-3pa, is cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; Speed with 12 ℃/min is cooled to 1200 ℃, insulation 60min; Speed with 10 ℃/min is cooled to 800 ℃, then furnace cooling;
For the cooled sample of vacuum sintering, with corundum container, be placed in vacuum annealing furnace and with certain temperature rise rate, be warming up to 1250 ℃ and carry out stress relief annealing processing, the vacuum tightness before heating up in annealing furnace at least will reach 10
-4pa, rises to 1250 ℃ with the speed of 15 ℃/min from room temperature, insulation 240min, and vacuum tightness is 10
-4pa～10
-3pa; Speed with 5 ℃/min is cooled to 1000 ℃ again, insulation 180min, and vacuum tightness is 10
-4pa～10
-3pa; Speed with 10 ℃/min is cooled to 800 ℃, insulation 120min, and vacuum tightness is 10
-4pa; Speed with 20 ℃/min is cooled to room temperature, and vacuum tightness is 10
-4pa.Finally carry out conventional aftertreatment and make 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%, hole mean diameter 200～340 μ m, 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 be up to 92% left and right as calculated.
In the method providing at above-described embodiment 5, we can also do other selections to wherein each kind of condition can obtain porous tantalum of the present invention or porous niobium equally.
Gained porous tantalum or porous niobium finished product are pressed preceding method and are detected:
| Embodiment | 6 | 7 | 8 |
| Density (g/cm 3) | 3.09 | 6.55 | 5.00 |
| Porosity (%) | 65 | 60 | 63 |
| Aperture (μ m) | 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: with particle diameter, be less than the ta powder that 42 μ m, oxygen level are less than 0.1% left and right, Zinic stearas and bicarbonate of ammonia powder mix are raw material, more repressed moulding, 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 greatly 65.5%, in volumn concentration;
Compression moulding: raw material mixed powder is added and be pressed into urethane foam (aperture 0.48～0.89mm, density 0.015 g/cm in injection moulding machine under 93Mpa
3～0.035g/cm
3, hardness is greater than 50
0) middle moulding;
After compression moulding, mixed powder is put into nonoxidizing atmosphere stove temperature to 800 ℃, protective atmosphere is that 99.999% argon gas carries out skimming treatment, its before heating up, first pass into pure argon gas at least 30min to get rid of furnace air, temperature control process: the speed with 2 ℃/min rises to 400 ℃ from room temperature, insulation 330min, argon gas intake 0.5L/min; Speed with 0.3 ℃/min rises to 680 ℃, insulation 348min, argon gas intake 1L/min from 400 ℃; Powered-down again, the sample furnace cooling after degreasing, argon gas intake 1L/min, until close argon gas while being cooled to room temperature;
For the sample after skimming treatment, with tungsten device, be placed in and in high vacuum high temperature sintering furnace, be warming up to 2200 ℃ and carry out vacuum sintering, before heating up, the vacuum tightness of sintering oven at least will reach 10
-4pa, is warming up to 1650 ℃, is incubated 150min, with stove, is chilled to 200～300 ℃ with 19 ℃/min, then is warming up to 1600 ℃, insulation 190min with 13 ℃/min, with 9 ℃/min, is warming up to 2000～2200 ℃, insulation 180min; Sintering is complete, and vacuum tightness is 10
-4pa～10
-3pa, is cooled to 1540 ℃ with the speed of 13 ℃/min, insulation 50min; Speed with 15 ℃/min is cooled to 1220 ℃, insulation 80min; Speed with 15 ℃/min is cooled to 800 ℃, then furnace cooling;
For the cooled sample of vacuum sintering, with corundum container, be placed in vacuum annealing furnace and be warming up to 1250 ℃ and carry out stress relief annealing processing, the vacuum tightness before heating up in annealing furnace at least will reach 10
-4pa, rises to 1100 ℃ with the speed of 20 ℃/min from room temperature, insulation 420min, and vacuum tightness is 10
-3pa; Speed with 7 ℃/min is cooled to 1000 ℃ again, insulation 130min, and vacuum tightness is 10
-3pa; Speed with 13 ℃/min is cooled to 800 ℃, insulation 96min, and vacuum tightness is 10
-3pa; Speed with 23 ℃/min is cooled to room temperature, and vacuum tightness is 10
-3pa, finally carries out conventional aftertreatment and makes porous tantalum.
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| CN107745126A (en) * | 2017-09-30 | 2018-03-02 | 中国振华（集团）新云电子元器件有限责任公司 | A kind of method for improving sintering tantalum block wood interior porosity |
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| US5282861A (en) * | 1992-03-11 | 1994-02-01 | Ultramet | Open cell tantalum structures for cancellous bone implants and cell and tissue receptors |
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| US5282861A (en) * | 1992-03-11 | 1994-02-01 | Ultramet | Open cell tantalum structures for cancellous bone implants and cell and tissue receptors |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
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| CN107745126A (en) * | 2017-09-30 | 2018-03-02 | 中国振华（集团）新云电子元器件有限责任公司 | A kind of method for improving sintering tantalum block wood interior porosity |
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