CN102796898A - Method for preparing medical porous metal implant material - Google Patents
Method for preparing medical porous metal implant material Download PDFInfo
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- CN102796898A CN102796898A CN2011102965759A CN201110296575A CN102796898A CN 102796898 A CN102796898 A CN 102796898A CN 2011102965759 A CN2011102965759 A CN 2011102965759A CN 201110296575 A CN201110296575 A CN 201110296575A CN 102796898 A CN102796898 A CN 102796898A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/08—Methods for forming porous structures using a negative form which is filled and then removed by pyrolysis or dissolution
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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Abstract
The invention discloses a method for preparing a medical porous metal implant material. The method comprises the following steps of: mixing tantalum powder, a pore forming agent and a forming agent to obtain mixed power, wherein the pore forming agent is one or more of sodium bicarbonate, urea, sodium chloride, methylcellulose and ethylcellulose, and the forming agent is one or more of polyvinyl alcohol, stearic acid, zinc stearate, paraffin wax and synthetic rubber; pelletizing; injecting into a mould and forming; demoulding; degreasing, namely gradually raising temperature to 400 to 800 DEG C at the speed of 0.5 to 3 DEG C/min, introducing argon to form protective atmosphere and preserving heat for 60 to 240 minutes; sintering; and performing thermal treatment, namely raising temperature to 800 to 900 DGE C at the speed of 10 to 20 DEG C/min under the vacuum degree of 10<-4> to 10<-3> Pa, preserving heat for 240 to 480 minutes, cooling to 400 DEG C at the speed of 2 to 5 DEG C/min, preserving heat for 120 to 300 minutes, and cooling to room temperature along with a furnace, and finally, the medical porous metal implant material for replacing dentale tissues can be obtained. Through tests, the prepared porous tantalum material is very suitable to be used as the medical implant material for replacing dentale tissues.
Description
Technical field
The present invention relates to a kind of preparation method of medical metal embedded material, especially relate to a kind of preparation method of medical porous metal implant material.
Background technology
Porous medical metal embedded material has treatment osseous tissue wound, bone formation is downright bad and important and special purposes such as alternative dense bone tissue such as dentale, and existing common this type material has porous metal stainless steel, porous metal titanium etc.Porous embedded material as osseous tissue wound and the use of bone formation necrosis therapeutic; Its porosity should reach 30～80%; And hole preferably all is communicated with and uniform distribution; Or make it as required that both the osseous tissue growth phase with human body was consistent, and alleviated the weight of material itself again, implant and use to be fit to human body.
And refractory metals tantalum, because it has outstanding biocompatibility, its porous material is expected to as substituting conventional medical metallic biomaterials such as aforementioned.Since metal tantalum to human body harmless, nontoxic, have no side effect; And along with the develop rapidly of domestic and international medical science; As cognitive further the going deep into of body implanting material, the demand that people implant with the porous metal tantalum material human body becomes more and more urgent, and is also increasingly high to its requirement to tantalum.Wherein as the medical embedded metal tantalum of porous, if can have very high uniform distribution open pore and the physical and mechanical properties that adapts 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 the porous metal material that kind be to be main working method basically with powder sintering, in particular for obtain porosity communication and equally distributed porous metal foam structure adopt the dipping after drying of metal-powder slurry on the organic foam body in the powder sintering to reburn to be called for short the foam impregnation method in the majority for knot.About common its Metal Mechanic Property of the powder sintered porous metal material that obtains not is fine, and its major cause is how to arrange the support and the problem of eliminating in relation, the metal powder sintered process of subsiding of pore-forming medium on the technology.And all do not have good solution in the known bibliographical information and laissez-faire nature.
The bibliographical information that adopts metal powder sintered manufactured porous tantalum seldom particularly uses the porous tantalum powder sintering bibliographical information as purpose almost not have to obtain medical embedded material.Can reference be that publication number is CN200510032174, title " three-dimensional through hole or part hole are connected with each other porous metal foam and preparation method thereof " and CN200710152394, title " a kind of novel porous foam tungsten and preparation method thereof ".Yet porous metal that it obtained or for filtering material usefulness, or share for aerospace and other high-temperature field but not use as the medical metal embedded material, moreover the also non-porous tantalum of the porous metal of being processed.
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 processed by pure commercial tantalum; It carries out the carbon skeleton that thermal destruction obtains with the polyurethane precursor is support, and this carbon skeleton is multiple dodecahedron, is the mesh-like structure in it; Integral body spreads all over micropore; Porosity can be up to 98%, the method for commercially pure tantalum through chemical vapour deposition, infiltration is attached on the carbon skeleton to form the porous metal microstructure again, abbreviates chemical deposition as.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtained is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight then accounts for about 1%.Document is further put down in writing, 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 with its porous tantalum as medical embedded materials such as dense bone tissue such as dentales; The mechanical property of its material such as ductility, ultimate compression strength, flexural strength etc. have obvious weak point; And can have influence on follow-up processing, for example cutting of profiled member etc. to porous tantalum material itself.Also all there is such deficiency at the product that aforesaid metal powder sintered method obtained equally.
Summary of the invention
The object of the present invention is to provide the preparation method of the good medical porous metal implant material of a kind of biocompatibility and mechanical property.
The objective of the invention is to realize through following technique means:
A kind of preparation method of medical porous metal implant material; Tantalum powder and pore-forming material, forming agent are mixed into mixed powder, again through granulation, be injected into mould molding, the demoulding, degreasing, sintering and thermal treatment and make the medical porous metal implant material that substitutes the dentale tissue; It is characterized in that: said pore-forming material is one or more in sodium hydrogencarbonate, urea, sodium-chlor, methylcellulose gum, the TKK 021, and said forming agent is one or more in Z 150PH, Triple Pressed Stearic Acid, Zinic stearas, paraffin, the viton; Said skimming processes is that the speed with 0.5 ℃/min～3 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 60min～240min, and said heat treatment step is that vacuum tightness is 10
-4Pa～10
-3Pa is warming up to 800～900 ℃, insulation 240～480min with 10～20 ℃/min, is chilled to 400 ℃, insulation 120～300min with 2～5 ℃/min again.
In the R&D process of medical porous tantalum material; The preparation route is numerous; But the contriver has creatively proposed to adopt above-mentioned process step to prepare fine and close medical porous tantalum embedded material; The above-mentioned thermal treatment process that particularly adopts has been eliminated internal stress fully, has been made the toughness of organizing more evenly, improved greatly prepared porous tantalum material of porous tantalum material.
For the porous tantalum material porosity that makes the alternative dentale tissue that makes suitable so that biocompatibility excellent; Improve the mechanical property of its material simultaneously; Above-mentioned granulation process is to be that 450～650 ℃, WP are under 12～15MPa said mixed powder to be a granulated into the circular granular that particle diameter is not higher than 20 μ m in working temperature, and the temperature that said circular granular is injected into mould is that 380～540 ℃, pressure are 72～90MPa.
The median size of the Ta powder that the present invention adopts less than 0.1%, is the commercially available prod less than 43 microns, oxygen level; Above-mentioned pore-forming material, forming agent also are the commercially available prod.It is 10 that vacuum environment of the present invention preferably adopts vacuum tightness
-4Pa～10
-3The vacuum condition of Pa.
The contriver further discovers in R&D process; If control is bad in the above-mentioned preparation; Though can make and be suitable for substituting the medical embedded material of dentale as stated but product percent of pass is not high: difficult like powder pressing forming, be prone to layering, inhomogeneous in the compacting rear section, technical problems such as crackle can appear in the degreasing rear section.
In order to make in the powder compaction process moulding easier; Thereby improve yield rate, finished product porous nickel property, make the preparation process more stable; The consumption of forming agent is 5～10% in the above-mentioned mixed powder, the consumption of pore-forming material is 20～30%, surplus is the tantalum powder; (in volumn concentration is the unit of directly calculating through the situation of final porous tantalum material in volumn concentration; Still be to calculate its corresponding quality weighing in above-mentioned mixed powder weighing) according to the densometer of respective substance; Further be preferably forming agent and be that paraffin accounts for 7～9%, pore-forming material is that TKK 021 accounts for 26～29%, surplus is the tantalum powder, is preferably further that paraffin accounts for 8%, TKK 021 accounts for 27%, surplus is the tantalum powder, all in volumn concentration; Above-mentioned demould time is preferably 6～9S, further is preferably 7S.
In order to make idiosome is more stable in the skimming processes, minimizing is prone to the distortion of part idiosome, aperture inhomogeneous; Thereby further improve yield rate, quality of production stability; Skimming processes preferably progressively is warming up to 400～800 ℃, feeds with argon gas and constitute protective atmosphere and be incubated 150min～240min with the speed of 2.5～3 ℃/min in the preparation of the porous tantalum material of above-mentioned alternative dentale tissue; Further preferably progressively be warming up to 400～800 ℃, feed with argon gas and constitute protective atmosphere and be incubated 220min with the speed of 2.5 ℃/min; Most preferably, above-mentioned degreasing is that the speed with 1～3 ℃/min rises to 400 ℃ from room temperature, insulation 60～120min; Speed with 1.5～2.5 ℃/min rises to 600～800 ℃, insulation 180～240min from 400 ℃; The preferred temperature of above-mentioned granulation process is that 510～535 ℃, WP are the circular granular that under the 13MPa said mixed powder is a granulated into particle diameter 10～20 μ m (13 μ m more preferably), is that 465～490 ℃, pressure are 83～85MPa with the injection molding temperature of said circular granular.
The present invention's further characteristics on the other hand are: the 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, behind insulation 1h～2h; Be warming up to 2000～2200 ℃ with the temperature rise rate that is lower than 20 ℃/min again, be incubated 2h～4h at least.
Cooling conditions after the vacuum sintering also includes: vacuum tightness is not less than 10
-3Pa not to be higher than 25 ℃/min, to be not less than 10 ℃/min and gradually to fall the rate of cooling mode, and sintered porous bodies segmentation cooling is cooled to 800 ℃, and each section soaking time 30min～90min cools to normal temperature then with the furnace.
Further characteristics are on this basis: said skimming treatment condition also includes: progressively be warming up to 600～800 ℃; Specifically be to feed with pure argon gas (99.9999%) to constitute protective atmosphere; Speed with 1～3 ℃/min rises to 400 ℃ from room temperature; Insulation 60～120min rises to 600～800 ℃, insulation 180～240min with the speed of 1.5～2.5 ℃/min from 400 ℃; Said 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; Speed with 10～20 ℃/min rises to 1500 ℃, insulation 30～60min, and 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 the vacuum sintering also includes: vacuum tightness is 10
-4Pa～10
-3Pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, insulation 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, insulation 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Said heat-treat condition is: vacuum tightness is 10
-4Pa～10
-3Pa is warming up to 800～900 ℃, insulation 260～320min with 15 ℃/min, is chilled to 400 ℃, insulation 120min with 3 ℃/min again, is cooled to room temperature with 18 ℃/min～23 ℃/min again.
The character of metal tantalum and niobium is extremely similar, and aforesaid method equally also is fit to the preparation of medical porous niobium material.
Preparation methods for porous metal materials of the present invention has adopted injection moulding, makes that the content of impurity is extremely low in the final porous tantalum material, has improved biocompatibility and biological safety effectively; Optimization of process conditions to granulation of the present invention, injection molding, degreasing, sintering and annealing steps; Make that yield rate is high, finished product aperture homogeneity better, make that the preparation process is more stable, quality stability is good; Eliminated thermal stresses effectively, made organizing of porous tantalum material more even; All be improved simultaneously with the mechanical property of further raising porous tantalum such as intensity, toughness; The above-mentioned thermal treatment process that particularly adopts has been eliminated internal stress fully, has been made the toughness of organizing more evenly, improved greatly prepared porous tantalum material of porous tantalum material.As everyone knows; The qualification rate of product, production stability can be in high standardization after all and be tending towards normal level by the decision of manual operation factor and operational path decision itself, manual operation; Therefore quality of production stability is mainly by technology decision own; Its product qualified rate of preparation technology of the present invention is high, production is stable, and product percent of pass is up to 93.0%～95.0%.Porous tantalum finished product even pore distribution and connection that the present invention makes, good biocompatibility.The porous tantalum material that makes, through its foreign matter content of test can be lower than 0.2%, density can reach 11.67～13.34g/cm
3, porosity can reach 20～30%, and pore diameter can reach 12～25 μ m, Young's modulus can reach that 6.0～7.0Gpa, unit elongation reach 14.0～15.0%, flexural strength can reach 120～150Mpa, ultimate compression strength can reach 90～110Mpa.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1: take by weighing paraffin, median size and be mixed into mixed powder less than 43 microns oxygen levels less than 0.1% tantalum powder and TKK 021, wherein paraffin accounts for 8%, TKK 021 accounts for 27%, the tantalum powder accounts for 65%, all in volumn concentration.Granulation: in working temperature is that 510～520 ℃, WP are the circular granular that under 12～13MPa said mixed powder is a granulated into particle diameter 10～13 μ m.Injection molding: the temperature that said circular granular is injected into mould is that 465～490 ℃, pressure are 83～85MPa.Demould time: 6～7S.Skimming treatment: vacuum tightness 10
-4Pa rises to 400 ℃ with the speed of 1～3 ℃/min from room temperature, and insulation 60～120min rises to 600～800 ℃, insulation 180～240min with the speed of 1.5～2.5 ℃/min from 400 ℃.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 is removed surface dirt and dirt behind the taking-up product, and thermal treatment: reciprocal of duty cycle is 10
-4Pa～10
-3Pa is warming up to 800～900 ℃, insulation 260～320min with 15 ℃/min, is chilled to 400 ℃, insulation 120min with 3 ℃/min again, is cooled to room temperature with 18 ℃/min～23 ℃/min again, the porous tantalum finished product.
The contriver detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: its foreign matter content is lower than 0.2%; Its even pore distribution, density 12.54g/cm
3, porosity 25%, hole mean diameter 23 μ m, Young's modulus 6.6GPa, unit elongation 14.5%, flexural strength 132MPa, ultimate compression strength 100MPa.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
Embodiment 2: weighing polyvinyl alcohol, median size are mixed into mixed powder less than 43 microns oxygen levels less than 0.1% tantalum powder and sodium hydrogencarbonate, and wherein Z 150PH accounts for 6%, sodium hydrogencarbonate accounts for 29%, the tantalum powder accounts for 65%, all in volumn concentration.Granulation: in working temperature is that 450 ℃, WP are the circular granular that under the 15MPa said mixed powder is a granulated into particle diameter 20 μ m.Injection molding: the temperature that said circular granular is injected into mould is that 540 ℃, pressure are 90MPa.Demould time: 9S.Skimming treatment: vacuum tightness 10
-4Pa is warming up to 400 ℃, insulation 60min with the temperature rise rate of 1 ℃/min from room temperature; Temperature rise rate with 2.5 ℃/min is warming up to 800 ℃, soaking time 180 minutes from 400 ℃ 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 is removed surface dirt and dirt behind the taking-up product, and heat treatment step: vacuum tightness is 10
-3Pa is warming up to 800～900 ℃, insulation 480min with 10 ℃/min, is chilled to 400 ℃, insulation 120min with 5 ℃/min again, makes the porous tantalum finished product.
The contriver detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: its foreign matter content is lower than 0.2%; Its even pore distribution, density 11.74g/cm
3, porosity 30%, hole mean diameter 24 μ m, Young's modulus 6.2GPa, unit elongation 14.0%, flexural strength 133MPa, ultimate compression strength 92MPa.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
Embodiment 3: take by weighing Zinic stearas, median size and be mixed into mixed powder less than 43 microns oxygen levels less than 0.1% tantalum powder and methylcellulose gum; Wherein Zinic stearas accounts for 10%, methylcellulose gum accounts for 23%, the tantalum powder accounts for 67%, all in volumn concentration.Granulation: in working temperature is that 650 ℃, WP are the circular granular that under the 12MPa said mixed powder is a granulated into particle diameter 10 μ m.Injection molding: the temperature that said circular granular is injected into mould is that 380 ℃, pressure are 72MPa.Demould time: 6S.Skimming treatment: vacuum tightness 10
-4Pa is warming up to 400 ℃, insulation 120min with the temperature rise rate of 3 ℃/min from room temperature; Temperature rise rate with 1.5 ℃/min is warming up to 750 ℃, soaking time 240 minutes from 400 ℃ 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 is come out of the stove, and removes product surface dust and dirt, thermal treatment: be that vacuum tightness is 10
-4Pa～10
-3Pa is warming up to 800～900 ℃, insulation 480min with 10 ℃/min, is chilled to 400 ℃, insulation 300min with 2 ℃/min again, makes the porous tantalum material.
The contriver detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: its foreign matter content is lower than 0.2%; Its even pore distribution, density 13.30g/cm
3, porosity 20%, hole mean diameter 20 μ m, Young's modulus 7.0GPa, unit elongation 14.82%, flexural strength 138MPa, ultimate compression strength 95MPa.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
Embodiment 4: a kind of porous tantalum; It with particle diameter less than 43 μ m, oxygen level less than 0.1% ta powder; Z 150PH and sodium hydrogencarbonate powder mix are raw material, handle and make through granulation, injection molding, the demoulding, skimming treatment, vacuum sintering, vacuum annealing again.
Wherein, Z 150PH accounts for 7%, sodium hydrogencarbonate accounts for 20%, ta powder accounts for 73%, in volumn concentration;
Granulation: in working temperature is that 520 ℃, WP are the circular granular that under the 14MPa said mixed powder is a granulated into particle diameter 16 μ m;
The injection molding and the demoulding: the temperature that said circular granular is injected into mould is that 468 ℃, pressure are 76MPa.Demould time: 8S;
Subsequently mixed powder is put into the nonoxidizing atmosphere stove and be warming up to 800 ℃ with certain temperature rise rate; Protective atmosphere is that 99.999% argon gas carries out skimming treatment; Its before heating up, feed earlier pure argon gas at least 30min to get rid of furnace air; The temperature control process: the speed with 1.5 ℃/min rises to 400 ℃ from room temperature, insulation 88min, argon gas feeding amount 0.5L/min; Speed with 2.0 ℃/min rises to 800 ℃, insulation 195min, argon gas feeding amount 1L/min from 400 ℃; Powered-down again, the sample furnace cooling after the degreasing, argon gas feeding amount 1L/min closes argon gas when being cooled to room temperature;
Place with the tungsten device for the sample after the skimming treatment to be warming up to 2200 ℃ with certain temperature rise rate in the high vacuum high temperature sintering furnace and to carry out vacuum sintering, the vacuum tightness of sintering oven will reach 10 at least before heating up
-4Pa rises to 1200 ℃ with the speed of 10～15 ℃/min from room temperature, insulation 30min, and vacuum tightness is 10
-4Pa; Speed with 10 ℃/min rises to 1500 ℃, insulation 30min, and vacuum tightness is 10
-4Pa～10
-3Pa; Speed with 6 ℃/min rises to 2200 ℃, insulation 120min, and vacuum tightness is 10
-3Pa; Sintering finishes, and vacuum tightness is 10
-3Pa is cooled to 1600 ℃ with the speed of 10～15 ℃/min, insulation 30min; Speed with 12 ℃/min is cooled to 1200 ℃, insulation 60min; Speed with 10 ℃/min is cooled to 800 ℃, then furnace cooling;
The cooled sample of against vacuum sintering places vacuum annealing furnace to carry out stress relief annealing with certain temperature rise rate intensification with the corundum container and handles, and the vacuum tightness before heating up in the lehre will reach 10 at least
-4Pa, said heat treatment step are that vacuum tightness is 10
-4Pa～10
-3Pa is warming up to 800～900 ℃, insulation 330min with 15 ℃/min, is chilled to 400 ℃, insulation 230min with 2.5 ℃/min again, makes porous tantalum.
The contriver detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: its foreign matter content is lower than 0.2%; Its even pore distribution, density 12.87g/cm
3, porosity 23%, hole mean diameter 20 μ m, Young's modulus 6.6GPa, flexural strength 137MPa, ultimate compression strength 103MPa.Through long-term test, this preparation technology's product percent of pass is up to 94.3%.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
In the method that the foregoing description 4 provides, we can also do other selections to wherein each kind of condition can obtain porous tantalum of the present invention equally, and all the other steps are with embodiment 4.
Gained porous tantalum finished product through its foreign matter content of test can be lower than 0.2%, density can reach 11.67～13.34g/cm
3Porosity can reach 20～30%; Pore diameter can reach 12～25 μ m, Young's modulus can reach that 6.0～7.0Gpa, unit elongation reach 14.0～15.0%, flexural strength can reach 120～150Mpa, ultimate compression strength can reach 90～110Mpa, is applicable to as the medical embedded material that substitutes human body dentale tissue.
Claims (10)
1. the preparation method of a medical porous metal implant material; Tantalum powder and pore-forming material, forming agent are mixed into mixed powder, again through granulation, be injected into mould molding, the demoulding, degreasing, sintering and thermal treatment and make the medical porous metal implant material that substitutes the dentale tissue; It is characterized in that: said pore-forming material is one or more in sodium hydrogencarbonate, urea, sodium-chlor, methylcellulose gum, the TKK 021, and said forming agent is one or more in Z 150PH, Triple Pressed Stearic Acid, Zinic stearas, paraffin, the viton; Said skimming processes is that the speed with 0.5 ℃/min～3 ℃/min progressively is warming up to 400～800 ℃, feeds with argon gas to constitute protective atmosphere and be incubated 60min～240min; Said heat treatment step is that vacuum tightness is 10
-4Pa～10
-3Pa is warming up to 800～900 ℃, insulation 240～480min with 10～20 ℃/min, is chilled to 400 ℃, insulation 120～300min with 2～5 ℃/min again, cools to room temperature then with the furnace.
2. preparation method as claimed in claim 1; It is characterized in that: said granulation process is to be that 450～650 ℃, WP are under 12～15MPa said mixed powder to be a granulated into the circular granular that particle diameter is not higher than 20 μ m in working temperature, and the temperature that said circular granular is injected into mould is that 380～540 ℃, pressure are 72～90MPa.
3. according to claim 1 or claim 2 preparation method is characterized in that: the consumption of forming agent is 5～10% in the said mixed powder, the consumption of pore-forming material is 20～30%, surplus is the tantalum powder, in volumn concentration; Said demould time is 6～9S.
4. preparation method as claimed in claim 3 is characterized in that: said forming agent is that paraffin accounts for 7～9%, pore-forming material is that TKK 021 accounts for 26～29%, surplus is the tantalum powder, all in volumn concentration.
5. preparation method as claimed in claim 4 is characterized in that: said paraffin accounts for 8%, TKK 021 accounts for 27%, surplus is the tantalum powder, all in volumn concentration; Said demould time is 7S.
6. according to claim 1 or claim 2 preparation method; It is characterized in that: skimming processes is that speed with 1～3 ℃/min rises to 400 ℃ from room temperature in the preparation of the porous tantalum material of said alternative dentale tissue; Insulation 60～120min; Speed with 1.5～2.5 ℃/min rises to 600～800 ℃, insulation 180～240min from 400 ℃; The temperature of said granulation process is that 510～535 ℃, WP are the circular granular that under the 13MPa said mixed powder is a granulated into particle diameter 10～20 μ m, is that 465～490 ℃, pressure are 83～85MPa with the injection molding temperature of said circular granular.
7. preparation method as claimed in claim 4; It is characterized in that: skimming processes is that speed with 1～3 ℃/min rises to 400 ℃ from room temperature in the preparation of the porous tantalum material of said alternative dentale tissue; Insulation 60～120min; Speed with 1.5～2.5 ℃/min rises to 600～800 ℃, insulation 180～240min from 400 ℃; The temperature of said granulation process is that 510～535 ℃, WP are the circular granular that under the 13MPa said mixed powder is a granulated into particle diameter 10～20 μ m (further being preferably 13 μ m), is that 465～490 ℃, pressure are 83～85MPa with the injection molding temperature of said circular granular.
8. preparation method as claimed in claim 7 is characterized in that: said 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, behind insulation 1h～2h; Be warming up to 2000～2200 ℃ with the temperature rise rate that is lower than 20 ℃/min again, be incubated 2h～4h at least;
Cooling conditions after the vacuum sintering also includes: vacuum tightness is not less than 10
-3Pa not to be higher than 25 ℃/min, to be not less than 10 ℃/min and gradually to fall the rate of cooling mode, and sintered porous bodies segmentation cooling is cooled to 800 ℃, and each section soaking time 30min～90min cools to normal temperature then with the furnace.
9. like claim 1,2,3 or 7 described preparing methods, it is characterized in that: said heat-treat condition is that vacuum tightness is 10
-4Pa～10
-3Pa is warming up to 800～900 ℃, insulation 260～320min with 15 ℃/min, is chilled to 400 ℃, insulation 120min with 3 ℃/min again, is cooled to room temperature with 18 ℃/min～23 ℃/min again.
10. preparation method as claimed in claim 6 is characterized in that: said 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; Speed with 10～20 ℃/min rises to 1500 ℃, insulation 30～60min, and 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 the vacuum sintering also includes: vacuum tightness is 10
-4Pa～10
-3Pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, insulation 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, insulation 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Said vacuum annealing condition is: vacuum tightness is 10
-4Pa～10
-3Pa is warming up to 800～900 ℃, insulation 260～320min with 15 ℃/min, is chilled to 400 ℃, insulation 120min with 3 ℃/min again, is cooled to room temperature with 18 ℃/min～23 ℃/min again.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103768655A (en) * | 2014-02-17 | 2014-05-07 | 苏州大学 | Preparation method of porous tantalum skeleton |
| CN114871433A (en) * | 2022-04-21 | 2022-08-09 | 湖北黄石科创模具技术研究院有限公司 | Preparation method of porous breathable steel based on sodium bicarbonate particles |
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| CN114905042A (en) * | 2022-04-08 | 2022-08-16 | 深圳市泛海统联精密制造股份有限公司 | Method for preparing porous wear-resistant product by metal injection molding process |
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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1936045A (en) * | 2005-09-22 | 2007-03-28 | 中南大学 | Three-dimensional through-hole or part-hole interconnecting porous metal foam and its preparing method |
| EP2149414A1 (en) * | 2008-07-30 | 2010-02-03 | Nederlandse Centrale Organisatie Voor Toegepast Natuurwetenschappelijk Onderzoek TNO | Method of manufacturing a porous magnesium, or magnesium alloy, biomedical implant or medical appliance. |
| CN101518467A (en) * | 2009-03-06 | 2009-09-02 | 中南大学 | Medicinal porous titanium implant and method for preparing same |
-
2011
- 2011-09-29 CN CN201110296575.9A patent/CN102796898B/en active Active
-
2012
- 2012-09-28 WO PCT/CN2012/082357 patent/WO2013044858A1/en active Application Filing
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 |
Non-Patent Citations (1)
| Title |
|---|
| 节云峰等: "烧结温度对泡沫铌力学性能及微观组织的影响", 《中国有色金属学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103768655A (en) * | 2014-02-17 | 2014-05-07 | 苏州大学 | Preparation method of porous tantalum skeleton |
| CN103768655B (en) * | 2014-02-17 | 2015-12-09 | 苏州大学 | A kind of preparation method of porous tantalum skeleton |
| CN114871433A (en) * | 2022-04-21 | 2022-08-09 | 湖北黄石科创模具技术研究院有限公司 | Preparation method of porous breathable steel based on sodium bicarbonate particles |
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