CN103740962B - Preparation method of medical porous metal material substituting for dental bone - Google Patents
Preparation method of medical porous metal material substituting for dental bone Download PDFInfo
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Abstract
The invention relates to a preparation method of a medical porous metal material substituting for a dental bone. The preparation method comprises the steps of mixing tantalum powder, a pore-forming agent and a forming agent to form mixed powder, and further pressing the powder into an organic foam body for forming, degreasing, sintering, cooling and performing heat treatment to prepare a porous tantalum material, wherein the press-forming pressure is 50-100Mpa, the pore-forming agent is one or more of urea, sodium chloride, ethyl cellulose and methyl cellulose, and the forming agent is one or more of stearic acid, zinc stearate, paraffin wax and synthetic rubber. According to the preparation method provided by the invention, tests prove that in the final porous tantalum material, the impurity content can be lower than 0.2%, the density can achieve 11.67-13.34g/cm<3>, the porosity can achieve 20-30%, and the pore diameter can achieve 5-30mu m; the elastic modulus can achieve 4.5-6.0Gpa, the bending strength can achieve 110-130Mpa, and the compressive strength can achieve 100-130Mpa. The porous tantalum material provided by the invention is very suitable for the medical implant material substituting for the dental bone.
Description
The present patent application is application number 201110295841.6, the applying date on 09 29th, 2011, the divisional application of denomination of invention " a kind of dentale substitutes the preparation method of medical porous metallic substance ".
Technical field
The present invention relates to a kind of preparation method of medical porous metal implant material, particularly relate to a kind of preparation method of medical embedded porous metal material of alternative dense bone tissue.
Background technology
Porous medical metal implanted material has the downright bad and alternative dense bone tissue for the treatment of osseous tissue wound, bone formation purposes as important and special in dentale etc., and showing 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, amount of plastic deformation 15%.But using it as dense bone tissue as the porous tantalum of the medical embedded materials such as dentale, mechanical property such as ductility, ultimate compression strength, the flexural strength etc. of its material have obvious weak point, and the follow-up processing to porous tantalum material itself can be had influence on, 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.
Summary of the invention
A kind of dentale of good biocompatibility is the object of the present invention is to provide to substitute the preparation method of medical porous metallic substance.
The object of the invention is to be realized by following technique means:
A preparation method for the medical porous metallic substance of alternative dentale, is characterized in that: be mixed into mixed powder with tantalum powder and pore-forming material, forming agent, more repressed shaping, degreasing, sintering, cooling and thermal treatment obtain porous tantalum material; Described compression moulding is pressed in Organic Foam Material by described mixed powder, its pressure is 50 ~ 100Mpa, described pore-forming material is one or more arbitrary combination in urea, sodium-chlor, ethyl cellulose, methylcellulose gum, and described forming agent is one or more arbitrary combination in stearic acid, Zinic stearas, paraffin, synthetic rubber.
In the R&D process of medical porous tantalum material, syntheti c route is numerous, but contriver creatively proposes the medical porous tantalum embedded material adopting above-mentioned processing step to prepare, through its foreign matter content of test can lower than 0.2%, its biocompatibility and biological safety good, density can reach 11.67 ~ 13.34g/cm
3, porosity can reach 20 ~ 30%, and pore diameter can reach 5 ~ 30 μm; Young's modulus can reach 4.5 ~ 6.0Gpa, flexural strength can reach 110 ~ 130Mpa, ultimate compression strength can reach 100 ~ 130Mpa, and porous tantalum of the present invention is suitable for the medical embedded material of alternative dentale 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 bad by system in above-mentioned preparation, though the medical embedded material that is suitable for alternative dentale as mentioned above can be obtained but conforming product rate is not high, production stability is bad: 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, in above-mentioned mixed powder, the consumption of forming agent is 5 ~ 10%, above-mentioned pore-forming material consumption is 20 ~ 30%, surplus is tantalum powder, (be the unit directly calculated by the situation of final porous tantalum material in volumn concentration in volumn concentration, the quality weighing of its correspondence is calculated) in above-mentioned mixed powder weighs or according to the densometer of respective substance, more preferably above-mentioned forming agent accounts for 5 ~ 6.5%, above-mentioned pore-forming material accounts for 21 ~ 24%, surplus is tantalum powder, pressure in above-mentioned compression moulding process is preferably 55 ~ 65Mpa, further be preferably that above-mentioned forming agent accounts for 6%, above-mentioned pore-forming material accounts for 23%, surplus is tantalum powder, in volumn concentration.
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 2 DEG C/min ~ 3.5 DEG C/min, passes into formed protective atmosphere and be incubated 100min ~ 240min with argon gas; Preferably further progressively be warming up to 400 ~ 800 DEG C with the speed of 3 ~ 3.5 DEG C/min, pass into argon gas and formed protective atmosphere and be incubated 150min ~ 200min.
Further the preferred also rate with 3 DEG C/min is progressively warming up to 400 ~ 800 DEG C, passes into formed protective atmosphere and be incubated 170min with argon gas.
The present invention's further feature is on the other hand: be not less than 10 in vacuum tightness
-4~ 10
-3pa, temperature 2000 ~ 2200 DEG C, the soaking time vacuum sintering process of 1 ~ 5 hour obtains porous sintered body.Filling with inert gas protection vacuum protection can be replaced during sintering process insulation; Finally carry out vacuum annealing process, wherein vacuum annealing process refers to that after vacuum sintering, continue maintenance temperature is in 1000 ~ 1250 DEG C, and soaking time 1 ~ 4 hour, vacuum tightness is not less than 10
-4~ 10
-3pa.
Vacuum sintering condition also includes: vacuum tightness is not less than 10
-3pa, rises to 1200 DEG C ~ 1500 DEG C with the temperature rise rate of 10 ~ 20 DEG C/min from room temperature, after insulation 1h ~ 2h; Again to be warming up to 2000 ~ 2200 DEG C lower than the temperature rise rate of 20 DEG C/min, be at least incubated 2h ~ 4h.
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: be progressively warming up to 600 ~ 800 DEG C, specifically pass into formation protective atmosphere with pure argon gas (99.9999%), 400 DEG C are risen to from room temperature with the speed of 1 ~ 2 DEG C/min, insulation 100 ~ 120min, 600 ~ 800 DEG C are risen to from 400 DEG C, insulation 200 ~ 240min with the speed of 2 ~ 3 DEG C/min; Described vacuum sintering condition also includes: rise to 1200 ~ 1250 DEG C with the speed of 10 ~ 15 DEG C/min from room temperature, and insulation 30 ~ 60min, vacuum tightness is 10
-4pa ~ 10
-3pa; Rise to 1500 DEG C with the speed of 10 ~ 20 DEG C/min, insulation 30 ~ 60min, vacuum tightness is 10
-4pa ~ 10
-3pa, rises to 2000 ~ 2200 DEG C with the speed of 6 ~ 20 DEG C/min, and insulation 120 ~ 240min, vacuum tightness is 10
-4pa ~ 10
-3pa; Cooling conditions after vacuum sintering also includes: vacuum tightness is 10
-4pa ~ 10
-3pa; With the speed of 10 ~ 20 DEG C/min cooling little molehill 1500 ~ 1600 DEG C, insulation 30 ~ 60min; 1200 ~ 1250 DEG C are cooled to, insulation 60 ~ 90min with the speed of 12 ~ 20 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 10 ~ 20 DEG C/min; Described vacuum annealing condition also includes: rise to 1000 ~ 1250 DEG C with the speed of 15 ~ 30 DEG C/min, and insulation 240 ~ 480min, vacuum 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, all be improved with the mechanical property such as intensity, the toughness that improve porous tantalum further simultaneously, preparation technology of the present invention makes that product qualified rate is high, administration measure, and conforming product rate can up to 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 in 0.2%, density can reach 11.67 ~ 13.34g/cm
3, porosity can reach 20 ~ 30%, and pore diameter can reach 5 ~ 30 μm; Young's modulus can reach 4.5 ~ 6.0Gpa, flexural strength can reach 110 ~ 130Mpa, ultimate compression strength can reach 100 ~ 130Mpa, and porous tantalum of the present invention is suitable for the medical embedded material of alternative dentale 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 preparation method of medical porous metallic substance of alternative dentale, select forming agent, (described forming agent is stearic acid to pore-forming material, Zinic stearas, paraffin, one or more arbitrary combination in synthetic rubber, described pore-forming material is urea, sodium-chlor, ethyl cellulose, one or more arbitrary combination in methylcellulose gum) be less than 43 microns with median size, the tantalum powder that oxygen level is less than 0.1% is mixed into powder mix, mixed powder is pressed in Organic Foam Material shaping under 50 ~ 100Mpa, again through degreasing, sintering, cooling and thermal treatment and must porous tantalum material, formed porous tantalum after testing porosity between 20 ~ 30%, pore diameter 5 ~ 30 μm.
More particularly, above-mentioned porous tantalum is that the above-mentioned forming agent of 5 ~ 10% (in volumn concentrations), the above-mentioned pore-forming material of 20 ~ 30% (in volumn concentrations) and the tantalum powder of surplus are mixed into powder mix, 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 and is progressively warming up to 2000 ~ 2200 DEG C; soaking time carries out vacuum sintering in 1 ~ 5 hour; before heating up, the vacuum tightness of sintering oven at least will reach proper level; 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, be be placed in tungsten device to put into atmosphere furnace and heat up with certain temperature rise rate, it first passed into argon gas or other rare gas elementes to get rid of furnace air before intensification, and temperature control process rises to certain temperature with suitable temperature rise rate from room temperature, insulation, then heat up, be incubated.Vacuum sintering process is carried out for the sample after skimming treatment, it is placed in tungsten device the most high sintering temperature being warming up to tantalum with certain temperature rise rate in high vacuum high temperature sintering furnace carry out vacuum sintering, before intensification, sintering oven keeps certain vacuum tightness, such as 1200 DEG C ~ 1250 DEG C are warming up to certain temperature rise rate, insulation, keeps vacuum; Be warming up to such as 1250 DEG C ~ 1500 DEG C again with certain temperature rise rate, insulation, then be warming up to the most high sintering temperature of such as tantalum with certain temperature rise rate, insulation, keep vacuum; Sinter complete, keep vacuum, be cooled to such as 1500 DEG C ~ 1600 DEG C with certain rate of temperature fall, insulation, then be cooled to such as 1200 DEG C ~ 1250 DEG C with certain rate of temperature fall, insulation, also be cooled to such as 800 DEG C with certain rate of temperature fall, then furnace cooling.Vacuum annealing process is carried out for the cooled sample of vacuum sintering, it is placed in vacuum annealing furnace with corundum container be warming up to such as 1000 DEG C ~ 1250 DEG C with certain 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 11.67 ~ 13.34g/cm
3, porosity can reach 20 ~ 30%, and pore diameter can reach 5 ~ 30 μm; Young's modulus can reach 4.5 ~ 6.0Gpa, flexural strength can reach 110 ~ 130Mpa, ultimate compression strength can reach 100 ~ 130Mpa.
Embodiment 1: take Zinic stearas, median size be less than 43 microns of oxygen levels be less than 0.1% tantalum powder and methylcellulose gum be mixed into mixed powder, wherein Zinic stearas accounts for 6%, methylcellulose gum accounts for 23%, 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 62Mpa
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 110min; 700 DEG C are warming up to from 400 DEG C again, soaking time 210 points of bracelets with the temperature rise rate of 2.5 DEG C/min.Vacuum sintering: sinter in a vacuum furnace, sintering temperature 2000 DEG C, is incubated 2 hours, vacuum tightness 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.
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 12.67g/cm
3, porosity 24%, pore mean diameters 16 μm, Young's modulus 6.0GPa, flexural strength 130MPa, ultimate compression strength 130MPa.
Embodiment 2: take paraffin, median size be less than 43 microns of oxygen levels be less than 0.1% niobium powder and urea be mixed into mixed powder, wherein paraffin accounts for 5%, ethyl cellulose accounts for 30%, niobium powder accounts for 65%, all in volumn concentration.Extrusion forming; Above-mentioned mixed powder is added in injection moulding machine that under 65Mpa, be pressed into aperture be 0.56 ~ 0.72mm, density 0.025g/cm
3, shaping in the polyurethane foam that hardness is 50 ° ~ 80 °.Skimming treatment: vacuum tightness 10
-4pa, with the temperature rise rate of 2 DEG C/min from room temperature to 400 DEG C, insulation 100min; 800 DEG C are warming up to from 400 DEG C again, soaking time 200 minutes with the temperature rise rate of 3 DEG C/min.Vacuum sintering: sinter in a vacuum furnace, sintering temperature 2100 DEG C, is incubated 4 hours, vacuum tightness 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 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 6.00g/cm
3, porosity 30%, pore mean diameters 28 μm, Young's modulus 2.0GPa, flexural strength 73MPa, ultimate compression strength 82MPa.
Embodiment 3: 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 10%, sodium-chlor accounts for 20%, tantalum powder accounts for 70%, all in volumn concentration.Extrusion forming; Above-mentioned mixed powder is added in injection moulding machine that under 97Mpa, be pressed into aperture be 0.56 ~ 0.72mm, density 0.025g/cm
3, shaping in the polyurethane foam that hardness is 50 ° ~ 80 °.Skimming treatment: vacuum tightness 10
-4pa, with the temperature rise rate of 1 DEG C/min from room temperature to 400 DEG C, insulation 120min; 750 DEG C are warming up to from 400 DEG C again, soaking time 240 points of bracelets with the temperature rise rate of 2 DEG C/min.Vacuum sintering: sinter in a vacuum furnace, sintering temperature 2200 DEG C, is incubated 2.5 hours, vacuum tightness 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.
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 13.37g/cm
3, porosity 20%, pore mean diameters 27 μm, Young's modulus 4.8GPa, flexural strength 128MPa, ultimate compression strength 120MPa.
Embodiment 4: take paraffin and Zinic stearas, median size be less than 43 microns of oxygen levels be less than 0.1% tantalum powder and sodium-chlor be mixed into mixed powder, wherein paraffin and Zinic stearas (wherein paraffin and Zinic stearas mass ratio are 1:2.5) account for 5%, sodium-chlor accounts for 28%, tantalum powder accounts for 67%, all in volumn concentration.Extrusion forming: above-mentioned mixed powder is added in injection moulding machine that to be pressed into aperture under 57Mpa be 0.56 ~ 0.72mm, density 0.025g/cm
3, shaping in the polyurethane foam that hardness is 50 ° ~ 80 °.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 105min; 800 DEG C are warming up to from 400 DEG C again, soaking time 225 minutes with the temperature rise rate of 2.2 DEG C/min.Vacuum sintering: sinter in a vacuum furnace, sintering temperature 2150 DEG C, is incubated 2 hours, vacuum tightness 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.
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 12.84g/cm
3, porosity 23%, pore mean diameters 26 μm, Young's modulus 5.0GPa, flexural strength 120MPa, ultimate compression strength 125MPa.
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 ethyl cellulose powder mix are raw material, more repressed shaping, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment obtain.
Wherein, stearic acid accounts for 7%, ethyl cellulose accounts for 20%, ta powder accounts for 73%, in volumn concentration; Compression moulding: raw material mixed powder is added in injection moulding machine that to be pressed into aperture under 55Mpa be 0.56 ~ 0.72mm, density 0.025g/cm
3, shaping in the polyurethane foam that hardness is 50 ° ~ 80 °;
Skimming treatment: under protection of inert gas atmosphere or vacuum tightness 10
-4~ 10
-3pa, is warming up to 400 DEG C ~ 800 DEG C with 1 ~ 2/min, is that protective atmosphere, soaking time 100 ~ 120 minutes are with removing stearic acid wherein and ethyl cellulose with argon gas;
Vacuum sintering: low vacuum is in 10
-4pa ~ 10
-3pa, temperature 2000 ~ 2200 DEG C, soaking time 1 ~ 5 hour, 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 ~ 4 hour after vacuum sintering, vacuum tightness is 10
-4~ 10
-3pa, to carry out stress relief annealing process; 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 12.00g/cm
3, porosity 28%, pore mean diameters 19 μm, Young's modulus 5.5GPa, flexural strength 122MPa, ultimate compression strength 124MPa.
Embodiment 6: 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 sodium-chlor powder mix are raw material, more repressed shaping, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment obtain.
Wherein, stearic acid accounts for 10%, urea accounts for 30%, ta powder accounts for 60%, in volumn concentration;
Compression moulding: raw material mixed powder is added in injection moulding machine that to be pressed into aperture under 53Mpa be 0.56 ~ 0.72mm, density 0.025g/cm
3, shaping in the polyurethane foam that hardness is 50 ° ~ 80 °;
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 1.5 DEG C/min, insulation 108min, argon gas intake 0.5L/min; 800 DEG C are risen to from 400 DEG C, insulation 215min, argon gas intake 1L/min with the speed of 2.0 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, rises to 1200 DEG C with the speed of 10 ~ 15 DEG C/min from room temperature, and insulation 30min, vacuum tightness is 10
-4pa; Rise to 1500 DEG C with the speed of 10 DEG C/min, insulation 30min, vacuum tightness is 10
-4pa ~ 10
-3pa; Rise to 2200 DEG C with the speed of 6 DEG C/min, insulation 120min, vacuum tightness is 10
-3pa; 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 12.34g/cm
3, porosity 26%, pore mean diameters 10 μm, Young's modulus 4.8GPa, flexural strength 117MPa, ultimate compression strength 125MPa.This preparation technology makes that product qualified rate is high, administration measure, product qualification rate reaching 90.3%.
In the method that above-described embodiment 6 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 | 7 | 8 | 9 | 10 | 11 | 12 | 13 |
| Density (g/cm 3) | 12.00 | 11.67 | 6.86 | 13.00 | 6.43 | 12.67 | 12.17 |
| Porosity (%) | 28 | 30 | 20 | 22 | 25 | 24 | 27 |
| Aperture (μm) | 19 | 15 | 8 | 11 | 27 | 23 | 25 |
| Young's modulus (GPa) | 4.5 | 5.0 | 2.6 | 4.8 | 1.5 | 5.0 | 5.7 |
| Flexural strength (MPa) | 120 | 115 | 76 | 130 | 82 | 122 | 117 |
| Ultimate compression strength (MPa) | 118 | 100 | 55 | 127 | 67 | 123 | 107 |
Claims (1)
1. the preparation method of the medical porous metallic substance of an alternative dentale, it is characterized in that: be less than 42 μm, the oxygen level ta powder that is less than 0.1% with particle diameter, stearic acid, paraffin and urea, sodium-chlor powder mix are raw material, more repressed shaping, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment;
Wherein, stearic acid and paraffin accounts for 7.5%, wherein paraffin and stearic acid mass ratio be 1:1.7, urea and sodium-chlor accounts for 30%, wherein urea and sodium-chlor mass ratio be 1:1, ta powder accounts for 62.5%, in volumn concentration;
Compression moulding: raw material mixed powder is added in injection moulding machine that to be pressed into aperture under 55Mpa be 0.56 ~ 0.72mm, density 0.025g/cm
3, hardness 50
0~ 80
0polyurethane foam in shaping;
After compression moulding, mixed powder is put into nonoxidizing atmosphere stove and be warming up to 600 DEG C, 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 1.6 DEG C/min, insulation 104min, argon gas intake 0.5L/min; 600 DEG C are risen to from 400 DEG C, insulation 215min, argon gas intake 1L/min with the speed of 2.6 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 2170 DEG C and to carry out vacuum sintering, before heating up, the vacuum tightness of sintering oven at least will reach 10
-4pa, rises to 1250 DEG C with the speed of 15 DEG C/min from room temperature, and insulation 30min, vacuum tightness is 10
-4pa; Rise to 1450 DEG C with the speed of 16 DEG C/min, insulation 35min, vacuum tightness is 10
-4pa ~ 10
-3pa; Rise to 2170 DEG C with the speed of 16 DEG C/min, insulation 140min, vacuum tightness is 10
-3pa; Sinter complete, vacuum tightness is 10
-4pa ~ 10
-3pa, is cooled to 1570 DEG C with the speed of 16 DEG C/min, insulation 35min; 1245 DEG C are cooled to, insulation 65min with the speed of 18 DEG C/min; 800 DEG C are cooled to, then furnace cooling with the speed of 18 DEG C/min;
Be placed in vacuum annealing furnace for the cooled sample of vacuum sintering with corundum container to be warming up to 1230 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 1230 DEG C with the speed of 27 DEG C/min from room temperature, and insulation 270min, vacuum tightness is 10
-4pa; Be cooled to 1000 DEG C with the speed of 10 DEG C/min again, insulation 90min, vacuum tightness is 10
-4pa; Be cooled to 800 DEG C with the speed of 16 DEG C/min, insulation 78min, vacuum tightness is 10
-4pa; Be cooled to room temperature with the speed of 27 DEG C/min, vacuum tightness is 10
-4pa; Finally carry out conventional aftertreatment and obtain porous tantalum.
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| CN107354335B (en) * | 2017-07-14 | 2018-11-20 | 东北大学 | A kind of method and apparatus being used to prepare bio-medical open celled foam Zinc material |
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