CN103740965B - Preparation method of medical metal implant material porous tantalum - Google Patents
Preparation method of medical metal implant material porous tantalum Download PDFInfo
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Abstract
The invention relates to a preparation method of medical implant material porous tantalum. The preparation method comprises the following steps: preparing tantalum powder slurry from a solution prepared from ethyl cellulose and anhydrous ethanol and tantalum powder, pouring into an organic foam body, soaking till pores of the organic foam body are filled with the tantalum powder slurry, then drying to remove a dispersant in the organic foam body poured with the tantalum powder slurry, performing degreasing treatment under a protective atmosphere of inert gas to remove an organic binder and the organic foam body, sintering in a vacuum state to prepare a porous sintered body, further annealing in the vacuum state, and performing conventional post-treatment to prepare the porous tantalum, wherein the average particle size of the tantalum powder is less than 10mu m, and the oxygen content is less than 0.1%. The porous tantalum medical implant material prepared by the preparation method provided by the invention has great biocompatibility and relatively good mechanical properties, and is particularly suitable for being used as the medical implant material for coupling members at wounds or defects of shoulder bone, skull and facial bone tissues. Simultaneously, the preparation method has the advantages of simple process and easiness in control; and the whole preparation process has no harm, no pollution, no toxic and harmful dust and no side effects against a human body.
Description
The present patent application is application number 201010547076.8, November 17 2010 applying date, the divisional application of denomination of invention " a kind of preparation method of medical metal implantation material porous tantalum ".
Technical field
The present invention relates to a kind of porous medical metal implanted material, particularly relate to a kind of preparation method of the porous tantalum as medical embedded material, particularly relate to and be a kind ofly applicable to the light position of human bearing and the preparation method of the porous tantalum embedded material of good biocompatibility.
Background technology
Porous medical metal implanted material has the important and special purposes such as treatment osseous tissue wound and 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 aperture sections is communicated with and is uniformly distributed as required, make it both consistent with the bone growth of human body, alleviate again the weight of material itself, implant with applicable human body and use.
And refractory metals tantalum, because it has outstanding biocompatibility and mechanical property, its porous material is expected to the conventional medical metallic biomaterial such as aforementioned as an alternative, becomes the biomaterial mainly as bone necrosis's treatment.Due to metal tantalum to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, to tantalum going deep into further as body implanting material cognition, the demand of people to human body implantation porous metal tantalum material becomes more and more urgent, also more and more higher to its requirement.Wherein as the medical embedded metal tantalum of porous, if the very high physical and mechanical properties being uniformly distributed open pore and adapting with human body can be had, then it is the heavy connection constituent material ensureing freshman bone tissue's normal growth.
Be main working 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-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 porosity communication and equally distributed 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 seldom, particularly almost do not have by the porous tantalum powder sintering 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.
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, amount of plastic deformation 15%.Such as, but using its porous tantalum as medical embedded material, 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 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 of a kind of biocompatibility and the good medical implant material multi-hole tantalum of biological safety, the porous tantalum material that the inventive method obtains is specially adapted to the medical embedded material of the coupling member as shoulder bone, skull and facial bone tissue injury or defect place.
In the research process to porous tantalum embedded material, contriver finds, have exquisite to the selection of organic adhesive, dispersion agent and use-pattern in the preparation of medical porous tantalum embedded material, if choice and operation is improper, poor biocompatibility on the one hand, the bonding force that there will be in obtained porous tantalum between tantalum powder is on the other hand little, porous tantalum surface is uneven as overstocked or too lax in local, the problem of series that the porosity of porous tantalum is excessive or too small etc., thus make its biocompatibility and mechanical property thereof not reach medical requirement.
The present invention seeks to be realized by following measure:
A kind of preparation method of medical implant material multi-hole tantalum, it is characterized in that: the solution be mixed with organic binder bond and dispersion agent and tantalum powder make tantalum powder slurry, and be cast in Organic Foam Material, dipping is until Organic Foam Material hole fills tantalum powder slurry, then drying removes the dispersion agent be cast with in the Organic Foam Material of tantalum powder slurry, under protection of inert gas atmosphere, skimming treatment is to remove organic binder bond and Organic Foam Material, the obtained porous sintered body of sintering under vacuum, then under vacuum, annealing and conventional aftertreatment obtain porous tantalum; Described organic adhesive is ethyl cellulose, and described dispersion agent is dehydrated alcohol, and the median size of described tantalum powder is less than 10 μm, oxygen level is less than 0.1%.
Sintering neck of the present invention refers to that at high temperature, powder is heated, and bonds between particle, is exactly the sintering phenomenon that we often say.Sintering refers to that the process of metallurgical property combination at high temperature occurs between powder particle particle, usually carries out under the fusing point of main component constituent element, and is realized by atomic migration.By microstructure observing, can find that the sintering neck (or claiming contact neck) of particle contacts is grown up, and therefore cause performance variation.Along with the raising of sintering temperature, or the prolongation of sintering time or the conservative control to sintering temperature and sintering time, sintering neck just can increase gradually, and the ratio of sintering neck just can increase, and the intensity of sintered compact increases.Also namely the present invention forms sintering neck structure also can realize the object of the invention between tantalum powder particles partly.
The present invention is that the porous tantalum of medical metal implantation purposes finds a kind of practicable preparation method, and the present invention adopts ethyl cellulose as organic binder bond, and ethyl cellulose is widely used in pharmaceutical industry, and it has better Biosafety performance; Adopt dehydrated alcohol as dispersion agent, dehydrated alcohol is volatile, effectively can save time of drying, can detect after having flooded whether sample interior has hollow, thus the even of dipping sizing agent quality can be ensured, also can reduce hydrogen, the oxygen level in the rear porous tantalum of sintering, thus reduce foreign matter content; Meanwhile, the porous tantalum shape after dipping can be fixed up soon, not easily occurs distortion, ensures the stable of the sample shape after sintering, size; The concentration of ethyl cellulose ethanolic soln of the present invention is low, viscosity is also little, and the quality therefore immersing slurry is few, can improve the porosity of obtained porous tantalum material, thus makes the porous tantalum Biocompatibility that obtains good.But meanwhile, contriver finds in research process, easily there is deferred reaction in ethanol and polymer organic foam at normal temperatures, and the internal structure of destructible sample affects the mechanical property of material; Heating when the ethanol in porous tantalum is put into inside stove without complete drying, due to ethanol rapid spatial expansion when heating, affecting purity and the mechanical property of material; When also having porosity excessive, mechanical property can be made to can not be guaranteed, based on above problem, easily make the porous tantalum as medical embedded material purposes not possess practical value.The present invention is reasonably coordinated by the technique means described in adopting, make the present invention with ethyl cellulose for caking agent, the ethanol slurry that is dispersion agent adopt described in the porous tantalum that obtains of pickling process when not affecting the usual mechanical property that existing porous tantalum has, still can obtain the porous tantalum with sintering neck structure, improve the mechanical properties such as porous tantalum ductility, for the convenience of porous tantalum in medical metal is implanted and the application of actual effect provide good method.Meanwhile, described preparation method's technique simply, is easily controlled; Whole preparation process is harmless, pollution-free, toxicological harmless dust, has no side effect to human body.
Above-mentioned Organic Foam Material optimization polyurethane foam, its aperture is 0.48 ~ 0.89mm, density 0.015g/cm
3~ 0.035g/cm
3, hardness is greater than 50 °; Described polyurethane foam is aperture 0.56 ~ 0.72mm more preferably, density 0.025g/cm
3, hardness 50 ° ~ 80 °.
In order to improve the mechanical property of the porous tantalum material that the inventive method obtains, be beneficial to the formation of sintering neck structure, more be conducive to formation and the processing of product structure simultaneously, described slurry is heated to by ethyl cellulose dehydrated alcohol dissolve, tantalum powder slurry is made with described ta powder, wherein the mass percentage concentration of ethyl cellulose ethanolic soln is 1 ~ 5% (preferably 3%), and the weight part ratio of described ethyl cellulose ethanolic soln and described ta powder is 1: 3 ~ 5 parts (preferably 1: 4 parts).
By the cast of above-mentioned slurry, impregnated in above-mentioned Organic Foam Material, then dryly remove the dispersion agent be cast with in the Organic Foam Material of tantalum powder slurry, the porosity of the porous tantalum dry body of formation between 50 ~ 85%, pore mean diameters 300 ~ 600 μm.Sintering neck structure is formed between described obtained medical porous tantalum embedded material finished product at least 50% tantalum powder particles.
Above-mentioned selection median size is less than 10 μm, the oxygen level ta powder that is less than 0.1% contributes to reducing the content of impurity, ensures that material has good mechanical property; Prioritizing selection aperture is 0.48 ~ 0.89mm, density 0.015g/cm
3~ 0.035g/cm
3, the polyurethane foam that hardness is greater than 50 ° contributes to the porosity and the pore diameter that ensure porous tantalum.The such technical finesse of the present invention optimizes processing condition, will ensure bio-compatibility and the biological safety of implanting porous tantalum material, is also conducive to the formation sintering neck structure simultaneously.
The present invention on the other hand feature is: dry vacuum tightness keeps 10
-2~ 1Pa vacuum tightness, then under protective atmosphere, as vacuum tightness 10
-4~ 10
-3pa, carries out the skimming treatment removing organic binder bond and Organic Foam Material under temperature 400 DEG C ~ 800 DEG C conditions; Again in vacuum tightness 10
-4~ 10
-3pa, temperature 2100 ~ 2350 DEG C, the soaking time vacuum sintering process of 2 ~ 8 hours obtains porous sintered body, filling with inert gas protection can replace vacuum protection 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 soaking time 1 ~ 8 hour, vacuum tightness is not higher than 10
-4~ 10
-3pa.
Above-mentioned skimming treatment condition also includes: be progressively warming up to 400 ~ 800 DEG C with the speed of 0.5 DEG C/min ~ 5 DEG C/min, pass into formed protective atmosphere and be incubated 30min ~ 180min with argon gas;
Vacuum sintering condition also includes: vacuum tightness is 10
-4~ 10
-3pa, rises to 1200 DEG C ~ 1500 DEG C with the temperature rise rate not higher than 10 ~ 20 DEG C/min from room temperature, after insulation 1.5h ~ 3h; 2100 ~ 2350 DEG C are warming up to again, insulation 3h ~ 5h with the temperature rise rate not higher than 20 DEG C/min;
Cooling conditions after vacuum sintering also includes: vacuum tightness is not higher than 10
-4~ 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 10
-4~ 10
-3pa, rises to 1000 ~ 1250 DEG C with the speed not higher than 30 DEG C/min, insulation 1h ~ 3h; 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.
Its further feature be: described vacuum drying drying temperature 70 ~ 90 DEG C, 4 ~ 5 hours time of drying; Described skimming treatment condition also includes: pass into formation protective atmosphere with pure argon gas (99.9999%); 400 DEG C are risen to from room temperature with the speed of 2 ~ 4 DEG C/min; insulation 50 ~ 60min; 600 ~ 800 DEG C are risen to from 400 DEG C with the speed of 1.0 ~ 1.5 DEG C/min; insulation 100 ~ 120min; 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 60 ~ 90min, vacuum tightness is 10
-4pa ~ 10
-3pa; Rise to 1500 DEG C with the speed of 10 ~ 20 DEG C/min, insulation 60 ~ 90min, vacuum tightness is 10
-4pa ~ 10
-3pa, rises to 2100 ~ 2350 DEG C with the speed of 6 ~ 20 DEG C/min, and insulation 180 ~ 300min, vacuum tightness is 10
-4pa ~ 10
-3pa; 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 ~ 15 DEG C/min; 1200 ~ 1250 DEG C are cooled to, insulation 60 ~ 90min with the speed of 12 ~ 16 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 10 ~ 13 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 tightness is 10
-4pa ~ 10
-3pa, then be cooled to 800 ~ 950 DEG C with the speed of 5 ~ 10 DEG C/min, insulation 90 ~ 180min, vacuum tightness is 10
-4pa ~ 10
-3pa; Be cooled to 600 ~ 700 DEG C with the speed of 10 ~ 20 DEG C/min, insulation 60 ~ 120min, vacuum tightness is 10
-4pa ~ 10
-3pa; Be cooled to room temperature with the speed of 20 ~ 30 DEG C/min, vacuum tightness is 10
-4pa ~ 10
-3pa.
More particularly, a kind of preparation method of medical implant material multi-hole tantalum, carries out as follows:
A. the preparation of tantalum powder slurry: ethyl cellulose is dissolved in dehydrated alcohol and is mixed with the ethyl cellulose ethanolic soln that mass percent concentration is 3%; Then joined in above-mentioned tantalum powder by described ethyl cellulose ethanolic soln and be made into slurry, the weight ratio of described tantalum powder and ethyl cellulose ethanolic soln is 4: 1;
B. the preparation of porous tantalum: it is 0.56 ~ 0.72mm, density 0.025g/cm that above-mentioned tantalum powder slurry is cast in aperture
3in the urethane Organic Foam Material that hardness is 50 ° ~ 80 °, dipping is until urethane Organic Foam Material hole fills tantalum powder slurry, then drying removes the dispersion agent be cast with in the Organic Foam Material of tantalum powder slurry, under protection of inert gas atmosphere, skimming treatment is to remove organic binder bond and Organic Foam Material, the obtained porous sintered body of sintering under vacuum, pure tantalum powder through sintering is piled up on the foam framework of formation, tantalum powder particles has sintering neck structure each other, then under vacuum, annealing and conventional aftertreatment obtain porous tantalum; Described vacuum drying vacuum tightness is 10
-2pa, drying temperature 78 DEG C, 4 hours time of drying; Described skimming treatment condition is: pass into formation protective atmosphere with pure argon gas (99.9999%); 400 DEG C are risen to from room temperature with the speed of 3 DEG C/min; insulation 50min; 700 DEG C are risen to from 400 DEG C with the speed of 1.5 DEG C/min; insulation 100min; described vacuum sintering condition is: rise to 1200 ~ 1250 DEG C with the speed of 12 DEG C/min from room temperature, and insulation 70min, vacuum tightness is 10
-4pa; Rise to 1500 DEG C with the speed of 15 DEG C/min, insulation 90min, vacuum tightness is 10
-4pa, rises to 2350 DEG C with the speed of 10 DEG C/min, and insulation 280min, vacuum tightness is 10
-3pa; Cooling conditions after vacuum sintering is: vacuum tightness is 10
-4pa, is cooled to 1500 ~ 1600 DEG C with the speed of 11 DEG C/min, insulation 40min; 1200 ~ 1250 DEG C are cooled to, insulation 70min with the speed of 13 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 10 DEG C/min; Described vacuum annealing condition is: rise to 1200 DEG C with the speed of 18 DEG C/min, and insulation 400min, vacuum tightness is 10
-3pa, then be cooled to 800 DEG C with the speed of 9 DEG C/min, insulation 150min, vacuum tightness is 10
-3pa; 600 DEG C are cooled to, insulation 100min, vacuum tightness 10 with the speed of 12 DEG C/min
-3pa; Be cooled to room temperature with the speed of 20 DEG C/min, vacuum tightness is 10
-3pa.
The medical implant material multi-hole tantalum with said structure feature can meet the requirement of bio-compatibility and biological safety completely, particularly its foam framework is piled up by the pure tantalum powder sintered to form, the sintering neck structure that tantalum powder particles has each other drastically increases the mechanical property of this material as ductility, anti-folding anti-bending strength, simultaneously through testing its foreign matter content lower than 0.5%; This porous tantalum finished product even pore distribution and be communicated with, density 3.32 ~ 9g/cm
3, porosity 46 ~ 80%, pore diameter 200 ~ 600 μm; Young's modulus 2.0 ~ 4.2GPa, yield strength 35 ~ 90MPa, ultimate compression strength 40 ~ 100MPa, hardness 150 ~ 300MPa, amount of plastic deformation 7.4% ~ 14.3%, tensile strength 60 ~ 72MPa, elongation 7.3% ~ 14.7% of having no progeny; Not only do not affect the Young's modulus, yield strength etc. of porous material, and be improve these performance perameters that porous material emphasizes.And when carrying out anti-bending test, the fracture rate of the sintering neck formed between each tantalum powder particles is less than 45%, the fracture rate of tantalum powder particles inside is greater than 55%, further illustrates product innovation reliability of structure of the present invention.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction analysis collection of illustrative plates (XRD figure) of porous tantalum prepared by preparation method of the present invention;
Fig. 2 is the vertical microscope analysis chart of the macrostructure of porous tantalum prepared by preparation method of the present invention;
Fig. 3 is the scanning electron microscope analysis figure (SEM figure) of the microtexture of porous tantalum prepared by preparation method of the present invention.
Can be observed from accompanying drawing: porous tantalum height hole of the present invention, even pore distribution and be communicated with; Porous tantalum of the present invention has three-dimensional communication hole, and this three-dimensional pore space is conducive to scleroblast to be adhered to, break up and growth, promotes growing into of bone, can strengthen the connection between implant and bone, be beneficial to and realize biological fixation; The sintering microtexture uniform particles of porous tantalum of the present invention, sintering neck is obvious, ensure that good mechanical property, and has good ductility.
Embodiment
Embodiment 1: take ethyl cellulose 8g, puts into the container that 240ml dehydrated alcohol is housed; Placing it in, electric furnace heats and stir makes it to become ethyl cellulose ethanolic soln.Weigh median size with 200g balance and be less than 10 microns, the oxygen level tantalum powder 60g that is less than 0.1%, add the ethyl cellulose ethanolic soln of 8ml cooling, be uniformly mixed, make it to become tantalum powder slurry.(mean pore size is 0.48mm, density 0.025g/cm to select 10 × 10 × 30mm cellular polyurethane foam
3, hardness 50 °) put into and wherein pour into a mould, until polyurethane foam hole fills tantalum powder slurry, the polyurethane foam going out to be filled tantalum powder slurry by clip puts into porcelain dish.Dry in vacuum drying oven, drying temperature 70 DEG C, time of drying 5h, vacuum tightness keeps 1Pa.Skimming treatment: vacuum tightness 1 × 10
-3pa ~ 1 × 10
-4pa, temperature 600 DEG C, soaking time 2h.Vacuum sintering: sinter in a vacuum furnace, sintering temperature 2100 DEG C, insulation 2h, vacuum tightness 1 × 10
-3pa ~ 1 × 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 aftertreatment again and obtains porous tantalum finished product.
Adopt the porous tantalum finished product that aforesaid method is obtained, have the foamy structure of hole three-dimensional communication distribution, on the foam framework that the pure tantalum powder accumulation through sintering is formed, tantalum powder particles has sintering neck structure each other.And the sintering neck structure formed between tantalum powder particles in this porous tantalum finished product microtexture is more than 50%.
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: this porous tantalum is the pore texture with three-dimensional communication distribution, its foreign matter content lower than 0.5% finished product, its even pore distribution and be communicated with, density 5.5g/cm
3, porosity 66.9%, pore mean diameters 300 μm, Young's modulus 4.0GPa, yield strength 65MPa, ultimate compression strength 80MPa, hardness 210MPa, amount of plastic deformation 10.3%, tensile strength 65MPa, elongation 10.7% of having no progeny; When the method measured by metal flexural strength carries out anti-bending test, the fracture rate sintering neck in this porous tantalum microtexture is less than 45%, and the fracture rate of granule interior is greater than 55%.
Embodiment 2: take ethyl cellulose 5g, puts into the container that 200ml dehydrated alcohol is housed; Placing it in, electric furnace heats and stir makes it to become ethyl cellulose ethanolic soln.Weigh median size with 200g balance and be less than 10 μm, the oxygen level tantalum powder 40g that is less than 0.1%, add 6ml ethyl cellulose ethanolic soln, be uniformly mixed, make it to become tantalum powder slurry.(mean pore size is 0.56mm, density 0.030g/cm to select 10 × 10 × 25mm cellular polyurethane foam
3, hardness 60 °) put into and wherein pour into a mould, until polyurethane foam hole fills tantalum powder slurry, the polyurethane foam going out to be filled tantalum powder slurry by clip puts into porcelain dish.Dry in vacuum drying oven, drying temperature 80 DEG C, time of drying 4h, vacuum tightness keeps 1 × 10
-2pa.Skimming treatment: vacuum tightness 1 × 10
-3pa, temperature 800 DEG C, soaking time 2h.Vacuum sintering: sinter in a vacuum furnace, sintering temperature 2100 DEG C, is incubated 4 hours, vacuum tightness 1 × 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 aftertreatment again and obtains porous tantalum finished product.
Adopt the porous tantalum finished product that aforesaid method is obtained, have the foamy structure of hole three-dimensional communication distribution, on the foam framework that the pure tantalum powder accumulation through sintering is formed, tantalum powder particles has sintering neck structure each other.And the sintering neck structure formed between tantalum powder particles in this porous tantalum finished product microtexture is more than 60%.
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: this porous tantalum is the pore texture with three-dimensional communication distribution, its foreign matter content lower than 0.5% finished product, its even pore distribution and be communicated with, density 5.8g/cm
3, porosity 65%, pore mean diameters 200 μm, Young's modulus 3.5GPa, yield strength 60MPa, ultimate compression strength 75MPa, hardness 150MPa, amount of plastic deformation 11%, tensile strength 68MPa, elongation 11% of having no progeny; When the method measured by metal flexural strength carries out anti-bending test, the fracture rate sintering neck in this porous tantalum microtexture is less than 40%, and the fracture rate of granule interior is greater than 60%.
Embodiment 3: take ethyl cellulose 6g, puts into the container that 220ml dehydrated alcohol is housed; Placing it in, electric furnace heats and stir makes it to become ethyl cellulose ethanolic soln.Weigh median size with 200g balance and be less than 10 μm, the oxygen level tantalum powder 45g that is less than 0.1%, add 8ml ethyl cellulose ethanolic soln, be uniformly mixed, make it to become tantalum powder slurry.(mean pore size is 0.70mm, density 0.035g/cm to select 8 × 8 × 25mm cellular polyurethane foam
3, hardness 70 °) put into and wherein pour into a mould, until polyurethane foam hole fills tantalum powder slurry, the polyurethane foam going out to be filled tantalum powder slurry by clip puts into porcelain dish.Dry in vacuum drying oven, drying temperature 90 DEG C, time of drying 4.5h, vacuum tightness keeps 1 × 10
-1pa.Skimming treatment: low vacuum is in 1 × 10
-3pa, temperature 700 DEG C, soaking time 1.5h.Vacuum sintering: sinter in a vacuum furnace, sintering temperature 2350 DEG C, is incubated 2.5 hours, vacuum tightness 1 × 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 aftertreatment again and obtains porous tantalum finished product.
Adopt the porous tantalum finished product that aforesaid method is obtained, have the foamy structure of hole three-dimensional communication distribution, on the foam framework that the pure tantalum powder accumulation through sintering is formed, tantalum powder particles has sintering neck structure each other.And the sintering neck structure formed between tantalum powder particles in this porous tantalum finished product microtexture is more than 55%.
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: this porous tantalum is the pore texture with three-dimensional communication distribution, its foreign matter content lower than 0.5% finished product, its even pore distribution and be communicated with, density 4.2g/cm
3, porosity 75%, pore mean diameters 400 μm, Young's modulus 3.0GPa, yield strength 50MPa, ultimate compression strength 60MPa, hardness 150MPa, amount of plastic deformation 9.2%, tensile strength 65MPa, elongation 9.5% of having no progeny; When the method measured by metal flexural strength carries out anti-bending test, the fracture rate sintering neck in this porous tantalum microtexture is less than 35%, and the fracture rate of granule interior is greater than 65%.
Embodiment 4: take ethyl cellulose 7g, puts into the container that 230ml dehydrated alcohol is housed; Placing it in, electric furnace heats and stir makes it to become ethyl cellulose ethanolic soln.Weigh median size with 200g balance and be less than 10 μm, the oxygen level tantalum powder 50g that is less than 0.1%, add 9ml ethyl cellulose ethanolic soln, be uniformly mixed, make it to become tantalum powder slurry.(aperture is 0.60mm, density 0.027g/cm to select 12 × 12 × 30mm cellular polyurethane foam
3, hardness 80 °) put into and wherein pour into a mould, until polyurethane foam hole fills tantalum powder slurry, the polyurethane foam going out to be filled tantalum powder slurry by clip puts into porcelain dish.Dry in vacuum drying oven, drying temperature 70 DEG C, time of drying 5h, vacuum tightness keeps 1Pa.Skimming treatment: vacuum tightness 1 × 10
-4pa ~ 1 × 10
-3pa, temperature 500 DEG C, soaking time 2h.Vacuum sintering: sinter in a vacuum furnace, sintering temperature 2150 DEG C, is incubated 2 hours, vacuum tightness 1 × 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 aftertreatment again and obtains porous tantalum finished product.
Adopt the porous tantalum finished product that aforesaid method is obtained, have the foamy structure of hole three-dimensional communication distribution, on the foam framework that the pure tantalum powder accumulation through sintering is formed, tantalum powder particles has sintering neck structure each other.And the sintering neck structure formed between tantalum powder particles in this porous tantalum finished product microtexture is more than 70%.
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: this porous tantalum is the pore texture with three-dimensional communication distribution, its foreign matter content lower than 0.5% finished product, its even pore distribution and be communicated with, density 6g/cm
3, porosity 60%, pore mean diameters 200 μm, Young's modulus 3.5GPa, yield strength 50MPa, ultimate compression strength 65MPa, hardness 200MPa, amount of plastic deformation 11.3%, tensile strength 70MPa, elongation 11.6% of having no progeny; When the method measured by metal flexural strength carries out anti-bending test, the fracture rate sintering neck in this porous tantalum microtexture is less than 10%, and the fracture rate of granule interior is greater than 57%.
Embodiment 5: a kind of porous tantalum, it is less than 10 μm with particle diameter, oxygen level is less than the ta powder of 0.1% for raw material, adopts mass percentage concentration to be that 1 ~ 5% ethyl cellulose ethanolic soln makes tantalum powder slurry, and is cast in polyurethane foam carrier; Then vacuum-drying, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment are obtained.
Wherein, the polyurethane foam selected, its aperture is 0.48 ~ 0.89mm, density 0.015g/cm
3~ 0.035g/cm
3, hardness is greater than 50 °;
Vacuum-drying: vacuum tightness keeps 10
-2~ 1Pa, to remove the ethanol in the polyurethane foam filling tantalum powder slurry;
Skimming treatment: under protection of inert gas atmosphere or vacuum tightness 1 × 10
-4pa ~ 1 × 10
-3pa, temperature 400 DEG C ~ 800 DEG C, and soaking time 0.5 ~ 3 hour is with removing ethyl cellulose wherein and polyurethane foam;
Vacuum sintering: vacuum tightness 1 × 10
-4pa ~ 1 × 10
-3pa, temperature 2100 ~ 2350 DEG C, soaking time 2 ~ 8 hours, applying argon gas or other protection of inert gas during sintering process insulation, to obtain porous material;
Vacuum annealing: continue to keep temperature to be in 1000 ~ 1250 DEG C, soaking time 1 ~ 8 hour, vacuum tightness 1 × 10 after vacuum sintering
-4pa ~ 1 × 10
-3pa, to carry out stress relief annealing process; Obtained sample carries out conventional aftertreatment again and obtains porous tantalum finished product.
In conjunction with each accompanying drawing, we can find out the porous tantalum finished product adopting aforesaid method obtained, have the foamy structure of hole three-dimensional communication distribution, and on the foam framework that the pure tantalum powder accumulation through sintering is formed, tantalum powder particles has sintering neck structure each other.And the sintering neck structure formed between tantalum powder particles in this porous tantalum finished product microtexture is more than 80%.
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: this porous tantalum is the pore texture with three-dimensional communication distribution, its foreign matter content lower than 0.5% finished product, its even pore distribution and be communicated with, density 3.32 ~ 9g/cm
3, porosity 46 ~ 80%, pore diameter 200 ~ 600 μm; Young's modulus 2.0 ~ 4.2GPa, yield strength 35 ~ 90MPa, ultimate compression strength 40 ~ 100MPa, hardness 150 ~ 300MPa, amount of plastic deformation 7.4% ~ 14.3%, tensile strength 60 ~ 72MPa, elongation 7.3% ~ 14.7% of having no progeny; When the method measured by metal flexural strength carries out anti-bending test, the fracture rate sintering neck in this porous tantalum microtexture is less than 45%, and the fracture rate of granule interior is greater than 55%.
Embodiment 6: a kind of porous tantalum, it is less than 10 μm with particle diameter, oxygen level is less than the ta powder of 0.1% for raw material, with ethyl cellulose ethanolic soln for binder solution makes tantalum powder slurry, and to be cast in its aperture be 0.56 ~ 0.72mm, density 0.025 ~ 0.035g/cm
3, in the polyurethane foam carrier that hardness is 50 ° ~ 80 °; Then vacuum-drying, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment are obtained.
Wherein, ethyl cellulose dehydrated alcohol is heated to dissolve the ethyl cellulose ethanolic soln being mixed with mass percentage concentration 3%; Then be that to add cooled weight be in the described ethyl cellulose ethanolic soln of 1 part for the ta powder of 3 ~ 5 parts by weight, stir and make starchiness; Above-mentioned polyurethane foam being put into floods until polyurethane foam hole fills in starchy tantalum powder slurry repeatedly again;
Vacuum-drying is to remove the ethanol that fills in the polyurethane foam of tantalum powder slurry, and vacuum tightness keeps 1Pa, drying temperature 70 ~ 90 DEG C, time of drying 4 ~ 5h;
Tungsten device is placed in for the polyurethane foam after vacuum-drying 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 argon gas at least 0.5h to get rid of furnace air, temperature control process: rise to 400 DEG C from room temperature with the speed of 3 DEG C/min, insulation 50min, argon gas passes into speed 0.5L/min; Rise to 800 DEG C with the speed of 1.5 DEG C/min from 400 DEG C, insulation 100min, argon gas passes into speed 1L/min; Powered-down again, the sample furnace cooling after degreasing, argon gas passes into speed 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 2100 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 1 × 10
-3pa, rises to 1200 DEG C with the speed of 10 ~ 15 DEG C/min from room temperature, and insulation 1.0h, vacuum tightness is 1 × 10
-4pa; Rise to 1500 DEG C with the speed of 10 DEG C/min, insulation 1.0h, vacuum tightness is 1 × 10
-4pa ~ 1 × 10
-3pa; Rise to 2100 DEG C with the speed of 6 DEG C/min, insulation 3h, vacuum tightness is 1 × 10
-3pa; Sinter complete, vacuum tightness is 1 × 10
-4pa ~ 1 × 10
-3pa; 1250 DEG C are cooled to, insulation 1h with the speed of 15 DEG C/min; 800 DEG C are cooled to, insulation 1.5h, then furnace cooling with the speed of 13 DEG C/min;
Be placed in vacuum annealing furnace for the cooled sample of vacuum sintering with corundum container to be warming up to 1000 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 1 × 10
-3pa, rises to 1000 DEG C with the speed of 15 DEG C/min from room temperature, and insulation 4h, vacuum tightness is 1 × 10
-4pa ~ 1 × 10
-3pa; Be cooled to 800 DEG C with the speed of 5 DEG C/min again, insulation 3h, vacuum tightness is 1 × 10
-4pa ~ 1 × 10
-3pa; Be cooled to 600 DEG C with the speed of 10 DEG C/min, insulation 2h, vacuum tightness is 1 × 10
-4pa; Be cooled to room temperature with the speed of 20 DEG C/min, vacuum tightness is 1 × 10
-3pa.Finally carry out conventional aftertreatment and obtain porous tantalum.
The porous tantalum finished product adopting aforesaid method to obtain has the foamy structure of hole three-dimensional communication distribution, and the pure tantalum powder through sintering is piled up on the foam framework of formation, and tantalum powder particles has sintering neck structure each other.And the sintering neck structure formed between tantalum powder particles in this porous tantalum finished product microtexture reaches 80%.
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: this porous tantalum is the pore texture with three-dimensional communication distribution, its foreign matter content lower than 0.5% finished product, its even pore distribution and be communicated with, density 7.45g/cm
3, porosity 63%, pore mean diameters 300 μm, Young's modulus 3.5GPa, yield strength 55MPa, ultimate compression strength 70MPa, hardness 230MPa, amount of plastic deformation 11.4%, tensile strength 70MPa, elongation 10.7% of having no progeny; When the method measured by metal flexural strength carries out anti-bending test, the fracture rate sintering neck in this porous tantalum microtexture is less than 40%, and the fracture rate of granule interior is greater than 60%.
In the method that above-described embodiment 6 provides, we can also do other selection to wherein each kind of condition can obtain porous tantalum of the present invention equally.In the following embodiments, if not otherwise specified, in table, parameters condition is all identical with previous embodiment 6.
Gained porous tantalum finished product is pressed preceding method and is detected:
Claims (1)
1. the preparation method of a medical implant material multi-hole tantalum, it is characterized in that: be less than 9 μm with particle diameter, oxygen level is less than the ta powder of 0.1% for raw material, with ethyl cellulose ethanolic soln for binder solution makes tantalum powder slurry, and to be cast in its aperture be 0.70mm, density 0.025g/cm
3, in the polyurethane foam carrier that hardness is 75 °; Then vacuum-drying, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment are obtained;
Wherein, ethyl cellulose dehydrated alcohol is heated to dissolve the ethyl cellulose ethanolic soln being mixed with mass percentage concentration 3%; Then be that to add cooled weight be in the described ethyl cellulose ethanolic soln of 1 part for the ta powder of 4 parts by weight, stir and make starchiness; Above-mentioned polyurethane foam being put into floods until polyurethane foam hole fills in starchy tantalum powder slurry repeatedly again;
Vacuum-drying is to remove the ethanol that fills in the polyurethane foam of tantalum powder slurry, and vacuum tightness keeps 0.01Pa, drying temperature 78 DEG C, time of drying 4.0h;
Be placed in tungsten device for the polyurethane foam after vacuum-drying to put into nonoxidizing atmosphere stove and be warming up to 700 DEG C, protective atmosphere is that 99.999% argon gas carries out skimming treatment, its first passed into before intensification argon gas at least 0.5h to get rid of furnace air, degreasing atmosphere 1 × 10
-4pa ~ 1 × 10
-3pa, temperature control process: rise to 400 DEG C from room temperature with the speed of 3 DEG C/min, insulation 50min, argon gas passes into speed 0.5L/min; Rise to 700 DEG C with the speed of 1.5 DEG C/min from 400 DEG C, insulation 100min, argon gas passes into speed 1L/min; Powered-down again, the sample furnace cooling after degreasing, argon gas passes into speed 1L/min, until close argon gas when being cooled to room temperature;
Sample after skimming treatment is placed in high vacuum high temperature sintering furnace with tungsten device and is warming up to 2350 DEG C and carries out vacuum sintering, sintering atmosphere 1 × 10
-4pa ~ 1 × 10
-3pa; Rise to 1200 DEG C with the speed of 12 DEG C/min from room temperature, insulation 70min, vacuum tightness is 1 × 10
-4pa; Rise to 1500 DEG C with the speed of 15 DEG C/min, insulation 90min, vacuum tightness is 1 × 10
-4pa ~ 1 × 10
-3pa; Rise to 2350 DEG C with the speed of 10 DEG C/min, insulation 280min, vacuum tightness is 1 × 10
-4pa; Sinter complete, vacuum tightness is 1 × 10
-4pa ~ 1 × 10
-3pa; 1600 DEG C are cooled to, insulation 40min with the speed of 11 DEG C/min; Be cooled to 1250 DEG C with the speed of 13 DEG C/min, insulation 70min, is cooled to 800 DEG C with the speed of 10 DEG C/min, then furnace cooling;
Be placed in vacuum annealing furnace for the cooled sample of vacuum sintering with corundum container to be warming up to 1200 DEG C and to carry out stress relief annealing process, the vacuum tightness before heating up in annealing furnace at least will reach 1 × 10
-3pa, rises to 1200 DEG C with the speed of 18 DEG C/min from room temperature, and insulation 400min, vacuum tightness is 1 × 10
-3pa; Be cooled to 800 DEG C with the speed of 9 DEG C/min again, insulation 150min, vacuum tightness is 1 × 10
-4pa ~ 1 × 10
-3pa; Be cooled to 600 DEG C with the speed of 12 DEG C/min, insulation 100min, vacuum tightness is 1 × 10
-4pa; Be cooled to room temperature with the speed of 20 DEG C/min, vacuum tightness is 1 × 10
-3pa.
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