CN103846443A - Porous tantalum applicable to replacement of human dental bone tissue - Google Patents
Porous tantalum applicable to replacement of human dental bone tissue Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- 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
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
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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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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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
- 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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
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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
- A61L2430/02—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The invention discloses porous tantalum applicable to replacement of human dental bone tissue. The porous tantalum is prepared by mixing tantalum powder, a pore-forming agent and a forming agent into a powder mixture, granulating the powder mixture, injecting the powder mixture into a mold for forming, de-molding, degreasing and sintering the powder mixture, and performing heat treatment on the powder mixture, wherein the pore-forming agent is one or multiple of sodium bicarbonate, urea, sodium chloride, methyl cellulose and ethyl cellulose; the forming agent is one or multiple of polyvinyl alcohol, stearic acid, zinc stearate, paraffin and synthetic rubber. The degreasing process comprises the following steps: gradually increasing the temperature to 400-800 DEG C at the speed of 0.5-3 DEG C/min, introducing argon gas to form a protective atmosphere, and maintaining the temperature for 60-240 minutes. The sintering process comprises the following steps: under the condition of a vacuum degree of 10<-4>-10<-3>Pa, increasing the temperature to 1,500-1,800 DEG C at the speed of 10-20 DEG C/min, maintaining the temperature for 120-240 minutes, cooling together with a furnace to 200-300 DEG C, increasing the temperature to 1,500-1,800 DEG C at the speed of 10-20 DEG C/min, maintaining the temperature for 180-240 minutes, increasing the temperature to 2,000-2,200 DEG C at the speed of 5-10 DEG C/min, and maintaining the temperature for 120-360 minutes. The prepared porous tantalum is very suitable for serving as a medical implant material for the replacement of the human dental bone tissue.
Description
The present patent application is application number 201110295867.0, the applying date on 09 29th, 2011, the divisional application of denomination of invention " a kind of preparation method who is applicable to the porous tantalum that substitutes human body dentale tissue ".
Technical field
The present invention relates to a kind of preparation method of medical metal implanted material, especially relate to a kind of preparation method who is applicable to the medical porous metal implant material that substitutes human body dentale tissue.
Background technology
Porous medical metal implanted material has treatment bone 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 metals stainless steel, porous metals titanium etc.As the porous embedded material of bone 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, implanted use to be applicable to human body.
And refractory metals tantalum, 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 to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, tantalum is goed deep into as the further of body implanting material cognition, and to human body, implantation becomes more and more urgent by the demand of porous metals tantalum material to people, also more and more higher to its requirement.Wherein, as the medical embedded metal tantalum of porous, if can have the very high physical and mechanical properties that is uniformly distributed interconnected pore and adapts with human body, it is expected to as a kind of novel bone tissue substitution material.
Just as one porous metal material, be taking powder sintering as main processing method substantially as medical embedded porous metal material, in particular for obtain porosity communication and equally distributed porous metal foam structure adopt metal dust 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 main 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 little, particularly to obtain medical embedded material with almost not having as the porous tantalum powder sintering 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 metals that obtain or for filtering material use, or share for Aero-Space and other high-temperature field but not use as medical metal implanted material, moreover also non-porous tantalum of the porous metals of processing.
About porous tantalum, US5282861 discloses a kind of perforate tantalum material and preparation thereof that is applied to cancellous bone implant, cell and organizes receptor.This porous tantalum is made up of pure business tantalum, it carries out carbon skeleton that thermal degradation obtains as support taking 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 metals micro-structural, 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 compression strength 50～70MPa of this porous material, elastic modelling quantity 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, compression strength, bending 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 the medical porous tantalum that is applicable to substitute human body dentale tissue that a kind of biocompatibility, mechanical property are good.
The object of the invention is to realize by following technological means:
A kind ofly be applicable to substitute human body dentale and organize the preparation method of porous tantalum, tantalum powder and pore creating material, forming agent are mixed into mixed-powder, then through granulation, be injected into mould molding, the demoulding, degreasing, sintering and heat treatment and make and substitute the medical porous metal implant material of dentale tissue; It is characterized in that: described pore creating material is one or more in sodium acid carbonate, urea, sodium chloride, methylcellulose, ethyl cellulose, described forming agent is one or more in polyvinyl alcohol, stearic acid, zinc stearate, paraffin, synthetic rubber; Described skimming processes is to be progressively warming up to 400～800 DEG C with the speed of 0.5 DEG C/min～3 DEG C/min, passes into and forms protective atmosphere and be incubated 60min～240min with argon gas, and described sintering step is that vacuum is 10
-4pa～10
-3pa, be warming up to 1500～1800 DEG C, be incubated 120～240min, be chilled to 200～300 DEG C with stove with 10～20 DEG C/min, be warming up to 1500～1800 DEG C, insulation 180～240min with 10～20 DEG C/min again, be warming up to 2000～2200 DEG C, insulation 120～360min with 5～10 DEG C/min.
In the R&D process of medical porous tantalum material, syntheti c route is numerous, but inventor has creatively proposed to adopt above-mentioned processing step to prepare fine and close medical porous tantalum embedded material, the above-mentioned sintering process particularly adopting, make idiosome become heater, thereby sintering obtains more even, thorough, in ensureing excellent biocompatibility, has also effectively improved mechanical strength.
For the porous tantalum material porosity of the alternative dentale tissue that makes to make suitable so that biocompatibility excellence, improve the mechanical property of its material simultaneously, above-mentioned granulation process is to be that 450～650 DEG C, operating pressure are under 12～15MPa, described mixed-powder to be a granulated into particle diameter not higher than the circular granular of 20 μ m in operating temperature, and the temperature that described circular granular is injected into mould is that 380～540 DEG C, pressure are 72～90MPa.
The average grain diameter of the Ta powder that the present invention adopts is less than 43 microns, oxygen content is less than 0.1%, is commercially available prod; Above-mentioned pore creating material, forming agent are also commercially available prod.It is 10 that vacuum environment of the present invention preferably adopts vacuum
-4pa～10
-3the vacuum condition of Pa.
In R&D process, inventor further studies discovery, if control bad in above-mentioned preparation, though can make be suitable for as mentioned above substitute dentale medical embedded material product percent of pass is not high: 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 uniformity, make preparation process more stable, in above-mentioned mixed-powder, the consumption of forming agent is 5～10%, the consumption of pore creating material is 20～30%, surplus is tantalum powder, (be the unit of directly calculating by the situation of final porous tantalum material in volumn concentration in volumn concentration, in above-mentioned mixed-powder weighs or according to the densitometer of respective substance, calculate its corresponding quality weighing), more preferably forming agent is that paraffin accounts for 7～9%, pore creating material is that ethyl cellulose accounts for 26～29%, surplus is tantalum powder, further be preferably paraffin and account for 8%, ethyl cellulose accounts for 27%, surplus is tantalum powder, all in volumn concentration, above-mentioned demould time is preferably 6～9S, more preferably 7S.
In order to make in skimming processes idiosome more stable, reduce the part idiosome distortion being prone to, aperture is inhomogeneous, thereby further improve yield rate, quality of production stability, in the preparation of the porous tantalum material of above-mentioned alternative dentale tissue, skimming processes is preferably progressively warming up to 400～800 DEG C with the speed of 2.5～3 DEG C/min, pass into and form protective atmosphere and be incubated 150min～240min with argon gas, further preferably progressively be warming up to 400～800 DEG C with the speed of 2.5 DEG C/min, pass into and form protective atmosphere and be incubated 220min with argon gas, most preferably, above-mentioned degreasing is to rise to 400 DEG C with the speed of 1～3 DEG C/min from room temperature, insulation 60～120min, speed with 1.5～2.5 DEG C/min rises to 600～800 DEG C from 400 DEG C, insulation 180～240min, the preferred temperature of above-mentioned granulation process is that 510～535 DEG C, operating pressure are under 13MPa, described mixed-powder to be a granulated into particle diameter 10～20 μ m (more preferably 13 μ circular granular m) is that 465～490 DEG C, pressure are 83～85MPa by injection molding described circular granular temperature.
For make idiosome sintering obtain more evenly, thorough, make the medical porous tantalum strength of materials that makes higher, it is 10 that above-mentioned sintering step is preferably vacuum
-4pa～10
-3pa, be warming up to 1500～1800 DEG C, be incubated 180～200min, be chilled to 200～300 DEG C with stove with 12～15 DEG C/min, be warming up to 1500～1800 DEG C, insulation 220～240min with 16～19 DEG C/min again, be warming up to 2000～2200 DEG C, insulation 250～320min with 5～10 DEG C/min.
Further feature is on this basis: described ungrease 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%), speed with 1～3 DEG C/min rises to 400 DEG C from room temperature, insulation 60～120min, speed with 1.5～2.5 DEG C/min rises to 600～800 DEG C, insulation 180～240min from 400 DEG C; Described vacuum-sintering condition also includes: vacuum is 10
-4pa～10
-3pa, is warming up to 1800 DEG C, is incubated 200min, is chilled to 200～300 DEG C with stove with 13 DEG C/min, then is warming up to 1800 DEG C, insulation 230min with 17 DEG C/min, is warming up to 2000～2200 DEG C, insulation 300min with 7 DEG C/min; Cooling condition after vacuum-sintering also includes: vacuum is 10
-4pa～10
-3pa; Be cooled to 1500～1600 DEG C with the speed of 10～20 DEG C/min, insulation 30～60min; Be cooled to 1200～1250 DEG C with the speed of 12～20 DEG C/min, insulation 60～90min; Be cooled to 800 DEG C with the speed of 10～20 DEG C/min, then cooling with stove; Described heat-treat condition also includes: rise to 1000～1250 DEG C with the speed of 15～30 DEG C/min, and insulation 240～480min, vacuum 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 is 10
-4pa～10
-3pa; Be cooled to 800 DEG C with the speed of 10～20 DEG C/min, insulation 60～120min, vacuum is 10
-4pa; Speed with 20～30 DEG C/min is cooled to room temperature, and vacuum is 10
-4pa～10
-3pa.
The character of metal tantalum and niobium is extremely similar, and said method is equally also applicable to the preparation of medical porous niobium material.
Preparation methods for porous metal materials of the present invention has adopted injection moulding, 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 granulation of the present invention, injection moulding, degreasing, sintering and annealing steps, make that yield rate is high, finished product aperture uniformity is better, make that preparation process is more stable, quality stability good, effectively eliminate thermal stress, made organizing of porous tantalum material more even, all be improved as intensity, toughness with the mechanical property that further improves porous tantalum simultaneously, the above-mentioned sintering process particularly adopting, make idiosome become heater, thereby sintering obtains more even, thorough, and mechanical strength significantly improves.As everyone knows, the qualification rate of product, production stability are determined by manual operation factor and process route itself determines, manual operation can be tending towards normal level in high standardization after all, therefore quality of production stability is mainly determined by technique 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 92.5%～95.0%.Porous tantalum finished product even pore distribution and connection that the present invention makes, good biocompatibility.Through its impurity 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 12～25 μ m, elastic modelling quantity can reach that 4.5～6.0Gpa, percentage elongation reach 12.0～13.8%, bending strength can reach 160～180Mpa, compression strength can reach 115～130Mpa; It is suitable for substituting the medical embedded material of human body dentale tissue very much.
Detailed description of the invention
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.
Embodiment 1: take paraffin, average grain diameter and be less than 43 microns of oxygen contents and be less than 0.1% tantalum powder and ethyl cellulose and be mixed into mixed-powder, wherein paraffin accounts for 8%, ethyl cellulose accounts for 27%, tantalum powder accounts for 65%, all in volumn concentration.Granulation: be that 510～520 DEG C, operating pressure are the circular granular that under 12～13MPa, described mixed-powder is a granulated into particle diameter 10～13 μ m in operating temperature.Injection moulding: the temperature that described circular granular is injected into mould is that 465～490 DEG C, pressure are 83～85MPa.Demould time: 6～7S.Ungrease treatment: vacuum 10
-4pa, rises to 400 DEG C with the speed of 1～3 DEG C/min from room temperature, and insulation 60～120min rises to 600～800 DEG C, insulation 180～240min with the speed of 1.5～2.5 DEG C/min from 400 DEG C.Vacuum-sintering: vacuum is 10
-4pa～10
-3pa; be warming up to 1800 DEG C, be incubated 200min, be chilled to 200～300 DEG C with stove with 13 DEG C/min; be warming up to 1800 DEG C, insulation 230min with 17 DEG C/min again; be warming up to 2000～2200 DEG C, insulation 300min with 7 DEG C/min; the protection of sintering process applying argon gas; after taking out product, remove surface dirt and dirt, make porous tantalum finished product.
Inventor 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 impurity content is lower than 0.2%, its even pore distribution, density 12.54g/cm3, porosity 25%, hole average diameter 23 μ m, elastic modelling quantity 5.0GPa, percentage elongation 12.3%, bending strength 172MPa, compression strength 120MPa.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
Embodiment 2: weighing polyvinyl alcohol, average grain diameter are less than 43 microns of oxygen contents and are less than 0.1% tantalum powder and sodium acid carbonate and are mixed into mixed-powder, wherein polyvinyl alcohol accounts for 6%, sodium acid carbonate accounts for 29%, tantalum powder accounts for 65%, all in volumn concentration.Granulation: be that 450 DEG C, operating pressure are the circular granular that under 15MPa, described mixed-powder is a granulated into particle diameter 20 μ m in operating temperature.Injection moulding: the temperature that described circular granular is injected into mould is that 540 DEG C, pressure are 90MPa.Demould time: 9S.Ungrease treatment: vacuum 10
-4pa, is warming up to 400 DEG C, insulation 60min with the heating rate of 1 DEG C/min from room temperature; Be warming up to 800 DEG C, temperature retention time 180 minutes with the heating rate of 2.5 DEG C/min from 400 DEG C again.Vacuum-sintering: vacuum is 10
-4pa; be warming up to 1500 DEG C, be incubated 200min, be chilled to 200～300 DEG C with stove with 12 DEG C/min; be warming up to 1800 DEG C, insulation 220min with 16 DEG C/min again; be warming up to 2000～2200 DEG C, insulation 320min with 5 DEG C/min; the protection of sintering process applying argon gas; after taking out product, remove surface dirt and dirt, the sample making carries out conventional post processing again and obtains porous tantalum finished product.
Inventor 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 impurity content is lower than 0.2%, its even pore distribution, density 11.74g/cm
3, porosity 30%, hole average diameter 24 μ m, elastic modelling quantity 4.5GPa, percentage elongation 12.8%, bending strength 160MPa, compression strength 117MPa.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
Embodiment 3: take zinc stearate, average grain diameter and be less than 43 microns of oxygen contents and be less than 0.1% tantalum powder and methylcellulose and be mixed into mixed-powder, wherein zinc stearate accounts for 10%, methylcellulose accounts for 23%, tantalum powder accounts for 67%, all in volumn concentration.Granulation: be that 650 DEG C, operating pressure are the circular granular that under 12MPa, described mixed-powder is a granulated into particle diameter 10 μ m in operating temperature.Injection moulding: the temperature that described circular granular is injected into mould is that 380 DEG C, pressure are 72MPa.Demould time: 6S.Ungrease treatment: vacuum 10
-4pa, is warming up to 400 DEG C, insulation 120min with the heating rate of 3 DEG C/min from room temperature; Be warming up to 750 DEG C, temperature retention time 240 minutes with the heating rate of 1.5 DEG C/min from 400 DEG C again.Vacuum-sintering: vacuum is 10
-3pa; be warming up to 1800 DEG C, be incubated 200min, be chilled to 200～300 DEG C with stove with 15 DEG C/min; be warming up to 1600 DEG C, insulation 240min with 19 DEG C/min again; be warming up to 2000～2200 DEG C, insulation 320min with 10 DEG C/min; 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 post processing again and obtains porous tantalum finished product.
Inventor 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 impurity content is lower than 0.2%, its even pore distribution, density 13.30g/cm
3, porosity 20%, hole average diameter 20 μ m, elastic modelling quantity 5.0GPa, percentage elongation 12.05%, bending strength 178MPa, compression strength 125MPa.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 is less than with particle diameter the ta powder that 43 μ m, oxygen content are less than 0.1%, polyvinyl alcohol and sodium acid carbonate mixed powder are raw material, then make through granulation, injection moulding, the demoulding, ungrease treatment, vacuum-sintering, vacuum annealing processing.
Wherein, polyvinyl alcohol accounts for 7%, sodium acid carbonate accounts for 20%, ta powder accounts for 73%, in volumn concentration;
Granulation: be that 520 DEG C, operating pressure are the circular granular that under 14MPa, described mixed-powder is a granulated into particle diameter 16 μ m in operating temperature;
Injection moulding and the demoulding: the temperature that described circular granular is injected into mould is that 468 DEG C, pressure are 76MPa.Demould time: 8S;
Subsequently mixed-powder is put into nonoxidizing atmosphere stove and be warming up to 800 DEG C with certain heating rate, protective atmosphere is that 99.999% argon gas carries out ungrease 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 DEG C/min rises to 400 DEG C from room temperature, insulation 88min, argon gas intake 0.5L/min; Speed with 2.0 DEG C/min rises to 800 DEG C, insulation 195min, argon gas intake 1L/min from 400 DEG C; Powered-down again, the sample after degreasing is cooling with stove, and argon gas intake 1L/min, until close argon gas while being cooled to room temperature;
Being placed in vacuum in high vacuum high temperature sintering furnace for the sample after ungrease treatment with tungsten device is 10
-4pa～10
-3pa, is warming up to 1680 DEG C, is incubated 190min, is chilled to 200～300 DEG C with stove with 13 DEG C/min, then is warming up to 1600 DEG C, insulation 230min with 17 DEG C/min, is warming up to 2000～2200 DEG C, insulation 270min with 8 DEG C/min; Sintering is complete, and vacuum is 10
-3pa, is cooled to 1600 DEG C with the speed of 10～15 DEG C/min, insulation 30min; Be cooled to 1200 DEG C with the speed of 12 DEG C/min, insulation 60min; Be cooled to 800 DEG C with the speed of 10 DEG C/min, then cooling with stove;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with corundum container and be warming up to 1250 DEG C with certain heating rate and carry out stress relief annealing processing, the vacuum 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, insulation 240min, and vacuum is 10
-4pa～10
-3pa; Be cooled to 1000 DEG C with the speed of 5 DEG C/min again, insulation 180min, vacuum is 10
-4pa～10
-3pa; Be cooled to 800 DEG C with the speed of 10 DEG C/min, insulation 120min, vacuum is 10
-4pa; Speed with 20 DEG C/min is cooled to room temperature, and vacuum is 10
-4pa.Finally carry out conventional post processing and make porous tantalum.
Inventor 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 impurity content is lower than 0.2%, its even pore distribution, density 12.87g/cm
3, porosity 23%, hole average diameter 20 μ m, elastic modelling quantity 5.8GPa, bending strength 167MPa, compression strength 123MPa.Through long-term test, this preparation technology's product percent of pass is up to 95.4%.This porous tantalum is suitable for substituting the medical embedded material of human body dentale tissue very much.
In the method providing at above-described embodiment 4, we can also do other to wherein each kind of condition and select can obtain equally porous tantalum of the present invention.
Gained porous tantalum finished product is pressed preceding method and is detected:
| Embodiment | 5 | 6 | 7 | 8 |
| Density (g/cm 3) | 12.26 | 13.34 | 11.72 | 12.10 |
| Porosity (%) | 24 | 20 | 29 | 26 |
| (μ m) in aperture | 20 | 14 | 24 | 18 |
| Elastic modelling quantity (GPa) | 5.4 | 6.0 | 4.6 | 4.9 |
| Bending strength (MPa) | 173 | 176 | 162 | 168 |
| Compression strength (MPa) | 122 | 127 | 116 | 120 |
More than make porous tantalum and be highly suitable for the medical embedded material of human body dentale tissue as an alternative.
Claims (1)
1. one kind is applicable to substitute the porous tantalum of human body dentale tissue, it is characterized in that: it is less than with particle diameter the ta powder that 35 μ m, oxygen content are less than 0.1%, zinc stearate and urea, sodium acid carbonate mixed powder are raw material, then make through granulation, injection moulding, the demoulding, ungrease treatment, vacuum-sintering, vacuum annealing processing; Wherein, zinc stearate accounts for Shang Xia 7%, urea and sodium acid carbonate account for 26%, ta powder accounts for 67%, in volumn concentration;
Granulation: being approximately 650 DEG C, operating pressure in operating temperature is the circular granular that under 13MPa, described mixed-powder is a granulated into particle diameter 15 μ m;
Injection moulding and the demoulding: the temperature that described circular granular is injected into mould is that 380 DEG C, pressure are 72MPa, and demould time is about 5.8S;
Subsequently mixed-powder is put into nonoxidizing atmosphere stove and be warming up to 800 DEG C, protective atmosphere is that 99.999% argon gas carries out ungrease 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 1.2 DEG C/min rises to 400 DEG C from room temperature, insulation 60min, argon gas intake 0.5L/min; Speed with 1.5 DEG C/min rises to 600 DEG C, insulation 230min, argon gas intake 1L/min from 400 DEG C; Powered-down again, the sample after degreasing is cooling with stove, and argon gas intake 1L/min, until close argon gas while being cooled to room temperature;
Being placed in vacuum in high vacuum high temperature sintering furnace for the sample after ungrease treatment with tungsten device is 10
-3pa, is warming up to 1580 DEG C, is incubated 200min, is chilled to 200～300 DEG C with stove with 11 DEG C/min, then is warming up to 1700 DEG C, insulation 220min with 16 DEG C/min, is warming up to 2000～2200 DEG C, insulation 320min with 5 DEG C/min; Sintering is complete, and vacuum is 10
-4pa～10
-3pa, is cooled to 1520 DEG C with the speed of 11 DEG C/min, insulation 60min; Be cooled to 1200 DEG C with the speed of 13 DEG C/min, insulation 90min; Be cooled to 800 DEG C with the speed of 13 DEG C/min, then cooling with stove;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with corundum container and be warming up to 1250 DEG C and carry out stress relief annealing processing, the vacuum before heating up in annealing furnace reaches 10
-4pa, rises to 1030 DEG C with the speed of 15 DEG C/min from room temperature, insulation 480min; Be cooled to 1000 DEG C with the speed of 5 DEG C/min again, insulation 180min; Be cooled to 800 DEG C with the speed of 11 DEG C/min, insulation 108min; Speed with 21 DEG C/min is cooled to room temperature; Finally carry out conventional post processing and make porous tantalum.
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| CN103768655B (en) * | 2014-02-17 | 2015-12-09 | 苏州大学 | A kind of preparation method of porous tantalum skeleton |
| CN106474554B (en) * | 2015-08-31 | 2020-09-15 | 重庆润泽医药有限公司 | Porous metal material and preparation method thereof |
| 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 |
| CN106267331A (en) * | 2016-09-28 | 2017-01-04 | 广州凯耀资产管理有限公司 | A kind of oral implant and preparation technology thereof |
| CN110756810A (en) * | 2019-06-05 | 2020-02-07 | 湖南普林特医疗器械有限公司 | Method for reducing oxygen content through 3D printing metal tantalum post-treatment and high-temperature vacuum sintering |
| CN113618064A (en) * | 2020-05-09 | 2021-11-09 | 韩坤原 | Method for manufacturing implant prosthesis with biological fixed porous structure |
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| Publication number | Publication date |
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| WO2013044857A1 (en) | 2013-04-04 |
| CN102796893B (en) | 2014-03-05 |
| CN103849792B (en) | 2015-11-25 |
| CN103849792A (en) | 2014-06-11 |
| CN103846443B (en) | 2015-10-07 |
| CN102796893A (en) | 2012-11-28 |
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