CN103740962A - 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
- Publication number
- CN103740962A CN103740962A CN201310692695.XA CN201310692695A CN103740962A CN 103740962 A CN103740962 A CN 103740962A CN 201310692695 A CN201310692695 A CN 201310692695A CN 103740962 A CN103740962 A CN 103740962A
- Authority
- CN
- China
- Prior art keywords
- vacuum
- speed
- insulation
- sintering
- vacuum tightness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Powder Metallurgy (AREA)
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 treatment osseous tissue wound, bone formation necrosis and alternative dense bone tissue as important and special purposes such as dentales, and existing this common class material has porous metal stainless steel, porous metal titanium etc.As the porous embedded material of 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, to human body, implantation becomes more and more urgent by the demand of porous metal tantalum/niobium material to people, 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 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 metal powder sintered legal system to make the bibliographical information of porous tantalum/niobium little, particularly to obtain medical embedded material with almost not having as porous tantalum/niobium powder sintering process bibliographical information of 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 ".But its porous metal that obtain or for filtering material use, or for aerospace and other high-temperature field, share 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 carries out carbon skeleton that thermal destruction obtains as support take polyurethane precursor, this carbon skeleton is multiple dodecahedron, it in it, is mesh-like structure, entirety spreads all over micropore, porosity can be up to 98%, then commercially pure tantalum is attached on carbon skeleton to form porous metal microstructure, referred to as chemical deposition by the method for chemical vapour deposition, infiltration.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, amount of plastic deformation 15%.But using it as dense bone tissue as the porous tantalum of the medical embedded materials such as dentale, the mechanical property of its material has obvious weak point as ductility, ultimate compression strength, flexural strength etc., and can have influence on the follow-up processing to porous tantalum material itself, the cutting of such as profiled member etc.Also all there is such deficiency in the same product obtaining in aforesaid metal powder sintered method.
Summary of the invention
The object of the present invention is to provide a kind of dentale of good biocompatibility to substitute the preparation method of medical porous metallic substance.
The object of the invention is to realize by following technique means:
A preparation method for the medical porous metallic substance of alternative dentale, is characterized in that: with tantalum powder and pore-forming material, forming agent, be mixed into mixed powder, more repressed moulding, degreasing, sintering, cooling and thermal treatment make porous tantalum material; Described compression moulding is that described mixed powder is pressed in Organic Foam Material, 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 has creatively proposed the medical porous tantalum embedded material that adopts above-mentioned processing step to prepare, through its foreign matter content of test can be lower than 0.2%, its biocompatibility and biological safety good, density reachable 11.67～13.34g/cm
3, porosity can reach 20～30%, and pore diameter can reach 5～30 μ m; Young's modulus can reach that 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 substituting the medical embedded material of dentale 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, 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, 50 °～80 ° of hardness) polyurethane foam in.
In R&D process, contriver further studies discovery, if bad by system in above-mentioned preparation, though can make be suitable for as mentioned above substitute dentale medical embedded material conforming product rate is not high, production stability is bad: as powder pressing forming difficulty, 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, 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, in volumn concentration, (in volumn concentration, be the unit of directly calculating by the situation of final porous tantalum material, in above-mentioned mixed powder weighs or according to the densometer of respective substance, calculate its corresponding quality weighing), 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 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 to be progressively warming up to 400～800 ℃ with the speed of 2 ℃/min～3.5 ℃/min, with argon gas, passes into and forms protective atmosphere and be incubated 100min～240min; Further preferably with the speed of 3～3.5 ℃/min, be progressively warming up to 400～800 ℃, with argon gas, pass into and form protective atmosphere and be incubated 150min～200min.
Further preferably with the also rate of 3 ℃/min, be progressively warming up to 400～800 ℃, with argon gas, pass into and form protective atmosphere and be incubated 170min.
The present invention's further feature is on the other hand: in vacuum tightness, be not less than 10
-4～10
-3pa, 2000～2200 ℃ of temperature, the soaking time vacuum sintering processing of 1～5 hour makes porous sintered body.During sintering process insulation, can filling with inert gas protection replace vacuum protection; Finally carry out vacuum annealing processing, wherein vacuum annealing processing refers to and after vacuum sintering, continues to keep temperature in 1000～1250 ℃, soaking time 1～4 hour, and 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 ℃～1500 ℃ with the temperature rise rate of 10～20 ℃/min from room temperature, after insulation 1h～2h; To be warming up to 2000～2200 ℃ lower than the temperature rise rate of 20 ℃/min, be at least incubated 2h～4h again.
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, not rise to 1000～1250 ℃ higher than the speed of 30 ℃/min, insulation 4h～6h; Again with after first slow soon to be not less than 5 ℃/min but be not cooled to room temperature higher than the rate of cooling segmentation of 30 ℃/min, 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 ℃, specifically with pure argon gas (99.9999%), pass into formation protective atmosphere, speed with 1～2 ℃/min rises to 400 ℃ from room temperature, insulation 100～120min, speed with 2～3 ℃/min rises to 600～800 ℃, insulation 200～240min from 400 ℃; Described vacuum sintering condition also includes: the speed with 10～15 ℃/min rises to 1200～1250 ℃ from room temperature, insulation 30～60min, and vacuum tightness is 10
-4pa～10
-3pa; With the speed of 10～20 ℃/min, rise to 1500 ℃, insulation 30～60min, vacuum tightness is 10
-4pa～10
-3pa, rises to 2000～2200 ℃ with the speed of 6～20 ℃/min, insulation 120～240min, and vacuum tightness is 10
-4pa～10
-3pa; Cooling conditions after vacuum sintering also includes: vacuum tightness is 10
-4pa～10
-3pa; With 1500～1600 ℃ of the cooling little molehills of speed of 10～20 ℃/min, insulation 30～60min; With the speed of 12～20 ℃/min, be cooled to 1200～1250 ℃, insulation 60～90min; With the speed of 10～20 ℃/min, be cooled to 800 ℃, then furnace cooling; Described vacuum annealing condition also includes: with the speed of 15～30 ℃/min, rise to 1000～1250 ℃, and insulation 240～480min, 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; With the speed of 10～20 ℃/min, be cooled to 800 ℃, insulation 60～120min, 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; 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 eliminated thermal stresses, made organizing of porous tantalum material more even, with the mechanical property that further improves porous tantalum, be all improved as intensity, toughness simultaneously, 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 in 0.2%, density reachable 11.67～13.34g/cm
3, porosity can reach 20～30%, and pore diameter can reach 5～30 μ m; Young's modulus can reach that 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 substituting the medical embedded material of dentale 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 preparation method of medical porous metallic substance of alternative dentale, to 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, oxygen level is less than 0.1% tantalum powder and is mixed into powder mix, moulding in mixed powder being pressed into Organic Foam Material under 50～100Mpa, again through degreasing, sintering, the cooling porous tantalum material that obtains with thermal treatment, form porous tantalum after testing porosity between 20～30%, pore diameter 5～30 μ m.
More particularly, above-mentioned porous tantalum is that the above-mentioned pore-forming material of above-mentioned forming agent, 20～30% (in volumn concentration) of 5～10% (in volumn concentrations) and the tantalum powder of surplus are mixed into powder mix, 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, be placed in high vacuum high temperature sintering furnace and be progressively warming up to 2000～2200 ℃; soaking time is carried out vacuum sintering for 1～5 hour; before heating up, the vacuum tightness of sintering oven at least will reach proper level; 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; vacuum annealing sample furnace cooling after treatment; 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, be to 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 heating up, and temperature control process is from room temperature, to rise to certain temperature with suitable temperature rise rate, insulation, then heat up, be incubated.For the sample after skimming treatment, carry out vacuum sintering processing, it to be placed in high vacuum high temperature sintering furnace to the highest sintering temperature that is warming up to tantalum with certain temperature rise rate with tungsten device carry out vacuum sintering, before heating up, sintering oven keeps certain vacuum tightness, with certain temperature rise rate, be warming up to for example 1200 ℃～1250 ℃, insulation, keeps vacuum; With certain temperature rise rate, be warming up to again for example 1250 ℃～1500 ℃, be incubated, then with certain temperature rise rate, be warming up to the highest sintering temperature of for example tantalum, insulation, maintenance 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 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 11.67～13.34g/cm
3, porosity can reach 20～30%, and pore diameter can reach 5～30 μ m; Young's modulus can reach that 4.5～6.0Gpa, flexural strength can reach 110～130Mpa, ultimate compression strength can reach 100～130Mpa.
Embodiment 1: take Zinic stearas, median size and be less than 43 microns of oxygen levels and be less than 0.1% tantalum powder and methylcellulose gum and 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 and be pressed into urethane foam (aperture 0.48～0.89mm, density 0.015g/cm in injection moulding machine under 62Mpa
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 110min with the temperature rise rate of 1.5 ℃/min from room temperature; With the temperature rise rate of 2.5 ℃/min, from 400 ℃, be warming up to 700 ℃, 210 points of bracelets of soaking time again.Vacuum sintering: sintering in vacuum oven, 2000 ℃ of sintering temperatures, are incubated 2 hours, vacuum tightness 10
-4pa, 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 by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product 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%, hole mean diameter 16 μ m, Young's modulus 6.0GPa, flexural strength 130MPa, ultimate compression strength 130MPa.
Embodiment 2: take paraffin, median size and be less than 43 microns of oxygen levels and be less than 0.1% niobium powder and urea and 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, to be pressed into aperture under 65Mpa be 0.56～0.72mm, density 0.025g/cm
3, moulding in the polyurethane foam that hardness is 50 °～80 °.Skimming treatment: vacuum tightness 10
-4pa, is warming up to 400 ℃, insulation 100min with the temperature rise rate of 2 ℃/min from room temperature; With the temperature rise rate of 3 ℃/min, from 400 ℃, be warming up to 800 ℃, soaking time 200 minutes again.Vacuum sintering: sintering in vacuum oven, 2100 ℃ of sintering temperatures, are incubated 4 hours, vacuum tightness 10
-4pa, 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 niobium finished product.
Contriver detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous niobium finished product 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%, hole mean diameter 28 μ m, Young's modulus 2.0GPa, flexural strength 73MPa, ultimate compression strength 82MPa.
Embodiment 3: 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 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, to be pressed into aperture under 97Mpa be 0.56～0.72mm, density 0.025g/cm
3, moulding in the polyurethane foam that hardness is 50 °～80 °.Skimming treatment: vacuum tightness 10
-4pa, is warming up to 400 ℃, insulation 120min with the temperature rise rate of 1 ℃/min from room temperature; With the temperature rise rate of 2 ℃/min, from 400 ℃, be warming up to 750 ℃, 240 points of bracelets of soaking time again.Vacuum sintering: sintering in vacuum oven, 2200 ℃ of sintering temperatures, are incubated 2.5 hours, vacuum tightness 10
-3pa, 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 by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product 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%, hole mean diameter 27 μ m, Young's modulus 4.8GPa, flexural strength 128MPa, ultimate compression strength 120MPa.
Embodiment 4: take paraffin and Zinic stearas, median size and be less than 43 microns of oxygen levels and be less than 0.1% tantalum powder and sodium-chlor and 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 to be pressed into aperture in injection moulding machine under 57Mpa be 0.56～0.72mm, density 0.025g/cm
3, moulding in the polyurethane foam that hardness is 50 °～80 °.Skimming treatment: vacuum tightness 10
-4pa, is warming up to 400 ℃, insulation 105min with the temperature rise rate of 1.5 ℃/min from room temperature; With the temperature rise rate of 2.2 ℃/min, from 400 ℃, be warming up to 800 ℃, soaking time 225 minutes again.Vacuum sintering: sintering in vacuum oven, 2150 ℃ of sintering temperatures, are incubated 2 hours, vacuum tightness 10
-4pa, 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 by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product 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%, hole mean diameter 26 μ m, Young's modulus 5.0GPa, flexural strength 120MPa, ultimate compression strength 125MPa.
Embodiment 5: a kind of porous tantalum, 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 ethyl cellulose powder mix are raw material, more repressed moulding, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment make.
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 to be pressed into aperture in injection moulding machine under 55Mpa be 0.56～0.72mm, density 0.025g/cm
3, moulding 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 ℃～800 ℃ with 1～2/min, take argon gas as protective atmosphere, soaking time 100～120 minutes to be to remove stearic acid and ethyl cellulose wherein;
Vacuum sintering: low vacuum is in 10
-4pa～10
-3pa, 2000～2200 ℃ of temperature, soaking time 1～5 hour, applying argon gas or other protection of inert gas during sintering process insulation, to obtain porous material;
Vacuum annealing: after vacuum sintering, continue to keep temperature in 1000～1250 ℃, soaking time 1～4 hour, vacuum tightness is 10
-4～10
-3pa, to carry out stress relief annealing processing; The sample making carries out conventional aftertreatment again and obtains porous tantalum finished product.
Contriver detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product 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%, hole mean diameter 19 μ m, Young's modulus 5.5GPa, flexural strength 122MPa, ultimate compression strength 124MPa.
Embodiment 6: a kind of porous tantalum, 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 sodium-chlor powder mix are raw material, more repressed moulding, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment make.
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 to be pressed into aperture in injection moulding machine under 53Mpa be 0.56～0.72mm, density 0.025g/cm
3, moulding 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 ℃ with certain temperature rise rate, protective atmosphere is that 99.999% argon gas carries out skimming treatment, its heat up before first pass into pure argon gas at least 30min with get rid of furnace air, temperature control process: the speed with 1.5 ℃/min rises to 400 ℃ from room temperature, insulation 108min, argon gas intake 0.5L/min; Speed with 2.0 ℃/min rises to 800 ℃, insulation 215min, 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, rises to 1200 ℃ with the speed of 10～15 ℃/min from room temperature, insulation 30min, and vacuum tightness is 10
-4pa; With the speed of 10 ℃/min, rise to 1500 ℃, insulation 30min, vacuum tightness is 10
-4pa～10
-3pa; With the speed of 6 ℃/min, rise to 2200 ℃, insulation 120min, vacuum tightness is 10
-3pa; Sintering is complete, and vacuum tightness is 10
-3pa, is cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; With the speed of 12 ℃/min, be cooled to 1200 ℃, insulation 60min; With the speed of 10 ℃/min, be 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; With the speed of 5 ℃/min, be cooled to 1000 ℃ again, insulation 180min, vacuum tightness is 10
-4pa～10
-3pa; With the speed of 10 ℃/min, be cooled to 800 ℃, insulation 120min, 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 by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product 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%, hole mean diameter 10 μ m, Young's modulus 4.8GPa, flexural strength 117MPa, ultimate compression strength 125MPa.This preparation technology make product qualified rate high, produce stable, product qualification rate reaching 90.3%.
In the method providing at above-described embodiment 6, we can also do other to wherein each kind of condition and select can obtain equally porous tantalum of the present invention or porous niobium.
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 |
| (μ m) in aperture | 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: with particle diameter, be less than the ta powder that 42 μ m, oxygen level are less than 0.1%, stearic acid, paraffin and urea, sodium-chlor powder mix are raw material, more repressed moulding, 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 are 1:1.7, and urea and sodium-chlor accounts for 30%, wherein urea and sodium-chlor mass ratio are 1:1, and ta powder accounts for 62.5%, in volumn concentration;
Compression moulding: raw material mixed powder is added to be pressed into aperture in injection moulding machine under 55Mpa be 0.56～0.72mm, density 0.025g/cm
3, hardness 50
0～80
0polyurethane foam in moulding;
After compression moulding, mixed powder is put into nonoxidizing atmosphere stove and be warming up to 800 ℃, protective atmosphere is that 99.999% argon gas carries out skimming treatment, its heat up before first pass into pure argon gas at least 30min with get rid of furnace air, temperature control process: the speed with 1.6 ℃/min rises to 400 ℃ from room temperature, insulation 104min, argon gas intake 0.5L/min; Speed with 2.6 ℃/min rises to 600 ℃, insulation 215min, 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, rises to 1250 ℃ with the speed of 15 ℃/min from room temperature, insulation 30min, and vacuum tightness is 10
-4pa; With the speed of 16 ℃/min, rise to 1450 ℃, insulation 35min, vacuum tightness is 10
-4pa～10
-3pa; With the speed of 16 ℃/min, rise to 2170 ℃, insulation 140min, vacuum tightness is 10
-3pa; Sintering is complete, and vacuum tightness is 10
-4pa～10
-3pa, is cooled to 1570 ℃ with the speed of 16 ℃/min, insulation 35min; With the speed of 18 ℃/min, be cooled to 1245 ℃, insulation 65min; With the speed of 18 ℃/min, be 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 1230 ℃ with the speed of 27 ℃/min from room temperature, insulation 270min, and vacuum tightness is 10
-4pa; With the speed of 10 ℃/min, be cooled to 1000 ℃ again, insulation 90min, vacuum tightness is 10
-4pa; With the speed of 16 ℃/min, be cooled to 800 ℃, insulation 78min, vacuum tightness is 10
-4pa; Speed with 27 ℃/min is cooled to room temperature, and vacuum tightness is 10
-4pa; Finally carry out conventional aftertreatment and make porous tantalum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310692695.XA CN103740962B (en) | 2011-09-29 | 2011-09-29 | Preparation method of medical porous metal material substituting for dental bone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310692695.XA CN103740962B (en) | 2011-09-29 | 2011-09-29 | Preparation method of medical porous metal material substituting for dental bone |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102958416A Division CN102796892B (en) | 2011-09-29 | 2011-09-29 | Preparation method for medical porous metal material for replacing dentale |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103740962A true CN103740962A (en) | 2014-04-23 |
| CN103740962B CN103740962B (en) | 2015-04-08 |
Family
ID=50498026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310692695.XA Active CN103740962B (en) | 2011-09-29 | 2011-09-29 | Preparation method of medical porous metal material substituting for dental bone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103740962B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105855553A (en) * | 2016-03-30 | 2016-08-17 | 山东省立医院 | Preparation method of porous tantalum material for mouth cavity implantation |
| CN107354335A (en) * | 2017-07-14 | 2017-11-17 | 东北大学 | A kind of method and apparatus for preparing bio-medical open celled foam Zinc material |
| CN110814331A (en) * | 2018-08-13 | 2020-02-21 | 株式会社韩亚科技 | Titanium filter for injection and infusion solution for infusion bottle and manufacturing method thereof |
| CN115229189A (en) * | 2022-06-27 | 2022-10-25 | 北京科技大学 | Preparation method of uniform porous tungsten product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5282861A (en) * | 1992-03-11 | 1994-02-01 | Ultramet | Open cell tantalum structures for cancellous bone implants and cell and tissue receptors |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
-
2011
- 2011-09-29 CN CN201310692695.XA patent/CN103740962B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5282861A (en) * | 1992-03-11 | 1994-02-01 | Ultramet | Open cell tantalum structures for cancellous bone implants and cell and tissue receptors |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105855553A (en) * | 2016-03-30 | 2016-08-17 | 山东省立医院 | Preparation method of porous tantalum material for mouth cavity implantation |
| CN105855553B (en) * | 2016-03-30 | 2018-01-23 | 山东省立医院 | A kind of preparation method of porous tantalum material for oral cavity implantation |
| CN107354335A (en) * | 2017-07-14 | 2017-11-17 | 东北大学 | A kind of method and apparatus for preparing bio-medical open celled foam Zinc material |
| 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 |
| CN110814331A (en) * | 2018-08-13 | 2020-02-21 | 株式会社韩亚科技 | Titanium filter for injection and infusion solution for infusion bottle and manufacturing method thereof |
| CN110814331B (en) * | 2018-08-13 | 2021-07-27 | 株式会社韩亚科技 | Titanium filter for injection and infusion solution for infusion bottle and manufacturing method thereof |
| CN115229189A (en) * | 2022-06-27 | 2022-10-25 | 北京科技大学 | Preparation method of uniform porous tungsten product |
| CN115229189B (en) * | 2022-06-27 | 2024-04-05 | 北京科技大学 | Preparation method of uniform porous tungsten product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103740962B (en) | 2015-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102796892B (en) | Preparation method for medical porous metal material for replacing dentale | |
| CN103849792B (en) | A kind of porous tantalum being applicable to alternative human dentale tissue | |
| CN103740964B (en) | Preparation method of medical porous metal implant material | |
| CN102796904B (en) | Medical porous metal material for replacing weight-bearing bone tissues and preparation method of medical porous metal material | |
| CN103740962B (en) | Preparation method of medical porous metal material substituting for dental bone | |
| CN102796901B (en) | Method for preparing medical porous metal implant material | |
| CN102796899B (en) | Preparation method of medical porous metal implanting material | |
| CN102793945B (en) | Medical porous tantalum material of a kind of alternative dentale and preparation method thereof | |
| CN102796898A (en) | Method for preparing medical porous metal implant material | |
| CN102796900B (en) | Medical porous metal material and preparation method thereof | |
| CN103691004B (en) | Method for preparing medical porous metal implant material | |
| CN103740967B (en) | Method for preparing medical porous tantalum implantation material | |
| CN103736147B (en) | Medical porous metal material replacing bearing bone tissue and preparation method thereof | |
| CN103740961B (en) | Preparation method of medical porous metal material capable of replacing weight-bearing bone tissue | |
| CN102796891A (en) | Method for preparing medical porous metal material | |
| CN103740966B (en) | Method for preparing medical porous metal material substituting for load-bearing bone tissue | |
| CN102796903B (en) | Method for preparing medical porous metal material capable of replacing bearing bone tissue | |
| CN102793946B (en) | Medical porous metal material for replacing dentale and preparation method thereof | |
| CN103667763B (en) | Method for preparing medical porous metal implant material | |
| CN104225673B (en) | Medical porous metal material of a kind of alternative dentale and preparation method thereof | |
| CN102796890A (en) | Preparation method for medical porous metal material capable of replacing loading bone tissue | |
| CN102796889B (en) | Preparation method of medical porous tantalum material for replacing weight-bearing bone tissues of human body | |
| CN103740960A (en) | Preparation method of medical porous tantalum implantation material | |
| CN102796895A (en) | Preparation method for medical porous metal material capable of replacing bearing bone tissue | |
| CN103736151A (en) | Preparation method of medical porous metal material capable of replacing weight bearing bone tissue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |