CN102796893B - Preparation method of porous tantalum applicable to replacing human dentale tissue - Google Patents
Preparation method of porous tantalum applicable to replacing human dentale 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 provides a preparation method of porous tantalum applicable to replacing human dentale tissue. The preparation method comprises the following steps of: mixing tantalum powder, pore-forming agent and forming agent to form into mixed powder, pelleting, injecting into a mould to be formed, demoulding, degreasing, sintering and carrying out thermal treatment, wherein the pore-forming agent is one kind or several kinds of sodium bicarbonate, urea, sodium chloride, methylcellulose and ethocel; the forming agent is one kind or several kinds of poval, stearic acid, zinc stearate, paraffins and synthetic rubber; the degreasing process comprises the following steps of: gradually heating up to 400-800 DEG C at the speed of the 0.5-3DEG C/min, forming the protective atmosphere by charging argon, and keeping the temperature for 60-240min; and the sintering step comprises the following steps of: heating up to 1500-1800 DEG C at the speed of 10-20 DEG C/min under the vacuum degree of 10<-4>-10<-3>Pa, keeping the temperature for 120-240min, cooling to 200-300DEG C along with a furnace, heating up to 1500-1800 DEG C at the speed of 10-20 DEG C/min, keeping the temperature for 180-240min, heating up to 2000-2200 DEG C at the speed of 5-10 DEG C/min, and keeping the temperature for 120-360min. The prepared porous tantalum is very applicable to the medical implant material capable of replacing the human dentale tissue.
Description
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 that is applicable to the medical porous metal implant material of alternative human body dentale tissue.
Background technology
Porous medical metal implanted material has treatment osseous tissue wound, bone formation necrosis and alternative compact bone tissue as important and special purposes such as dentales, and existing this common class material has porous metals rustless steel, porous metals 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 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, 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 people implant and become more and more urgent by the demand of porous metals tantalum material human body, 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 osseous tissue substitution material.
As medical embedded porous metal material just as porous metal material be to take powder sintering as main processing method like that substantially, 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 bibliographical information that metal powder sintered legal system makes porous tantalum seldom, particularly take and obtain medical embedded material and almost do not have with the porous tantalum powder sintering bibliographical information that is 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 ".Yet porous metals that it obtains 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 spongy bone implant, cell and organizes sensor.This porous tantalum is made by pure business tantalum, it take polyurethane precursor, and to carry out the carbon skeleton that thermal degradation obtains be support, this carbon skeleton is multiple dodecahedron, it in it, is mesh-like structure, integral body spreads all over micropore, porosity can be up to 98%, then the method by chemical vapour deposition, infiltration is attached on carbon skeleton to form porous metals micro structure, referred to as chemical deposition by commercially pure tantalum.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 comprcssive 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 compact 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, comprcssive strength, bending strength etc., and can have influence on the follow-up processing to porous tantalum material itself, such as cutting of 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 biocompatibility, good being applicable to of mechanical property to substitute the preparation method of the medical porous tantalum of human body dentale tissue.
The object of the invention is to realize by following technological means:
A kind ofly be applicable to substitute the preparation method that human body dentale is organized porous tantalum, tantalum powder and pore creating material, forming agent are mixed into mixed-powder, then through pelletize, be injected into mould molding, the demoulding, defat, sintering and heat treatment and make the medical porous metal implant material that substitutes dentale tissue; It is characterized in that: described pore creating material is one or more in sodium bicarbonate, carbamide, 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 that the speed with 0.5 ℃/min～3 ℃/min is progressively warming up to 400～800 ℃; with argon, pass into and form protective atmosphere and be incubated 60min～240min; described sintering step is that vacuum is 10-4Pa～10-3Pa; with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 120～240min, with stove, be chilled to 200～300 ℃; with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 120～360min.
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, when guaranteeing 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 excellent, improve the mechanical property of its material simultaneously, above-mentioned granulation process is to be that 450～650 ℃, 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 ℃, pressure are 72～90MPa.
The mean 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 and be suitable for as mentioned above substituting the medical embedded material of dentale but conforming product rate is not high: as difficult in powder pressing forming, be prone to layering, inhomogeneous in compacting rear section, defat rear section there will be the technical problems such as crackle.
In order to make in powder compaction process molding 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, 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 densimeter 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 ℃ with the speed of 2.5～3 ℃/min, with argon, pass into and form protective atmosphere and be incubated 150min～240min, further preferably with the speed of 2.5 ℃/min, be progressively warming up to 400～800 ℃, with argon, pass into and form protective atmosphere and be incubated 220min, most preferably, above-mentioned defat 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 ℃ from 400 ℃, insulation 180～240min, the preferred temperature of above-mentioned granulation process is that 510～535 ℃, operating pressure are the circular granular that under 13MPa, described mixed-powder is a granulated into particle diameter 10～20 μ m (more preferably 13 μ m), by the injection molding temperature of described circular granular, is that 465～490 ℃, pressure are 83～85MPa.
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, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, be incubated 220～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 250～320min.
Further feature is on this basis: described ungrease 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 1～3 ℃/min rises to 400 ℃ from room temperature, insulation 60～120min, with the speed of 1.5～2.5 ℃/min, rise to 600～800 ℃ from 400 ℃, be incubated 180～240min; Described vacuum-sintering condition also includes: vacuum is 10
-4pa～10
-3pa, is warming up to 1800 ℃, is incubated 200min, with stove, is chilled to 200～300 ℃ with 13 ℃/min, then is warming up to 1800 ℃, insulation 230min with 17 ℃/min, with 7 ℃/min, is warming up to 2000～2200 ℃, insulation 300min; Cooling condition after vacuum-sintering also includes: vacuum is 10-4Pa～10-3Pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, is incubated 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, is incubated 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Described heat-treat condition also includes: the speed with 15～30 ℃/min rises to 1000～1250 ℃, is incubated 240～480min, and vacuum is 10
-4pa～10
-3pa, then be cooled to 1000 ℃ with the speed of 5～10 ℃/min, being incubated 90～180min, vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 800 ℃, is incubated 60～120min, and vacuum is 10
-4pa; Speed with 20～30 ℃/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; Optimization of process conditions to pelletize of the present invention, injection moulding, defat, 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 eliminated thermal stress, made organizing of porous tantalum material more even, with the mechanical property that further improves porous tantalum, be all improved as intensity, toughness 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 conforming product rate 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, comprcssive strength can reach 115～130Mpa; It is suitable for substituting the medical embedded material of human body dentale tissue very much.
The specific 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.
Embodiment 1: take paraffin, mean 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.Pelletize: be that 510～520 ℃, operating pressure are under 12～13MPa, described mixed-powder to be a granulated into the circular granular of 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 ℃, pressure are 83～85MPa.Demould time: 6～7S.Ungrease treatment: vacuum 10
-4pa, rises to 400 ℃ with the speed of 1～3 ℃/min from room temperature, is incubated 60～120min, with the speed of 1.5～2.5 ℃/min, rises to 600～800 ℃ from 400 ℃, is incubated 180～240min.Vacuum-sintering: vacuum is 10
-4pa～10
-3pa; with 13 ℃/min, be warming up to 1800 ℃, be incubated 200min, with stove, be chilled to 200～300 ℃; with 17 ℃/min, be warming up to 1800 ℃, insulation 230min again; with 7 ℃/min, be warming up to 2000～2200 ℃, insulation 300min; the protection of sintering process applying argon gas; after taking out product, remove surface dirt and dirt, make porous tantalum finished product.
Inventor detects the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its impurity content is lower than 0.2%, its even pore distribution, density 12.54g/cm
3, porosity 25%, hole average diameter 23 μ m, elastic modelling quantity 5.0GPa, percentage elongation 12.3%, bending strength 172MPa, comprcssive 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, mean diameter are less than 43 microns of oxygen contents and are less than 0.1% tantalum powder and sodium bicarbonate and are mixed into mixed-powder, and wherein polyvinyl alcohol accounts for 6%, sodium bicarbonate accounts for 29%, tantalum powder accounts for 65%, all in volumn concentration.Pelletize: be that 450 ℃, operating pressure are under 15MPa, described mixed-powder to be a granulated into the circular granular of particle diameter 20 μ m in operating temperature.Injection moulding: the temperature that described circular granular is injected into mould is that 540 ℃, pressure are 90MPa.Demould time: 9S.Ungrease treatment: vacuum 10
-4pa, is warming up to 400 ℃, insulation 60min with the heating rate of 1 ℃/min from room temperature; Heating rate with 2.5 ℃/min is warming up to 800 ℃, temperature retention time 180 minutes from 400 ℃ again.Vacuum-sintering: vacuum is 10-4Pa; with 12 ℃/min, be warming up to 1500 ℃, be incubated 200min, with stove, be chilled to 200～300 ℃; with 16 ℃/min, be warming up to 1800 ℃, insulation 220min again; with 5 ℃/min, be warming up to 2000～2200 ℃, insulation 320min; 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 the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its 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, comprcssive 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, mean 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.Pelletize: be that 650 ℃, operating pressure are under 12MPa, described mixed-powder to be a granulated into the circular granular of particle diameter 10 μ m in operating temperature.Injection moulding: the temperature that described circular granular is injected into mould is that 380 ℃, pressure are 72MPa.Demould time: 6S.Ungrease treatment: vacuum 10
-4pa, is warming up to 400 ℃, insulation 120min with the heating rate of 3 ℃/min from room temperature; Heating rate with 1.5 ℃/min is warming up to 750 ℃, temperature retention time 240 minutes from 400 ℃ again.Vacuum-sintering: vacuum is 10
-3pa; with 15 ℃/min, be warming up to 1800 ℃, be incubated 200min, with stove, be chilled to 200～300 ℃; with 19 ℃/min, be warming up to 1600 ℃, insulation 240min again; with 10 ℃/min, be warming up to 2000～2200 ℃, insulation 320min; 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 the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its 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, comprcssive 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 bicarbonate mixed powder are raw material, then process and make through pelletize, injection moulding, the demoulding, ungrease treatment, vacuum-sintering, vacuum annealing.
Wherein, polyvinyl alcohol accounts for 7%, sodium bicarbonate accounts for 20%, ta powder accounts for 73%, in volumn concentration;
Pelletize: be that 520 ℃, operating pressure are under 14MPa, described mixed-powder to be a granulated into the circular granular of 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 ℃, pressure are 76MPa.Demould time: 8S;
Subsequently mixed-powder is put into nonoxidizing atmosphere stove and be warming up to 800 ℃ with certain heating rate, protective atmosphere is that 99.999% argon carries out ungrease treatment, its before heating up, first pass into pure argon gas at least 30min to get rid of furnace air, temperature control process: the speed with 1.5 ℃/min rises to 400 ℃ from room temperature, insulation 88min, argon intake 0.5L/min; Speed with 2.0 ℃/min rises to 800 ℃, insulation 195min, argon intake 1L/min from 400 ℃; Powered-down again, the sample furnace cooling after defat, argon intake 1L/min, until close argon while being cooled to room temperature;
For the sample after ungrease treatment, with tungsten device, being placed in vacuum in fine vacuum high temperature sintering furnace is 10
-4pa～10
-3pa, is warming up to 1680 ℃, is incubated 190min, with stove, is chilled to 200～300 ℃ with 13 ℃/min, then is warming up to 1600 ℃, insulation 230min with 17 ℃/min, with 8 ℃/min, is warming up to 2000～2200 ℃, insulation 270min; Sintering is complete, and vacuum 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;
For the cooled sample of vacuum-sintering, with corundum container, be placed in vacuum annealing furnace and with certain heating rate, be warming up to 1250 ℃ and carry out stress relief annealing processing, the vacuum 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 is 10
-4pa～10
-3pa; Speed with 5 ℃/min is cooled to 1000 ℃ again, insulation 180min, and vacuum is 10
-4pa～10
-3pa; Speed with 10 ℃/min is cooled to 800 ℃, insulation 120min, and vacuum is 10
-4pa; Speed with 20 ℃/min is cooled to room temperature, and vacuum is 10
-4pa.Finally carry out conventional post processing and make porous tantalum.
Inventor detects the porous material density of above-mentioned porous tantalum finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its 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, comprcssive strength 123MPa.Through long-term test, this preparation technology's conforming product rate 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 selections to wherein each kind of condition can obtain porous tantalum of the present invention equally.
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 |
| Aperture (μ m) | 20 | 14 | 24 | 18 |
| Elastic modelling quantity (GPa) | 5.4 | 6.0 | 4.6 | 4.9 |
| Bending strength (MPa) | 173 | 176 | 162 | 168 |
| Comprcssive 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 (11)
1. one kind is applicable to substitute the preparation method that human body dentale is organized porous tantalum, tantalum powder and pore creating material, forming agent are mixed into mixed-powder, then through pelletize, be injected into mould molding, the demoulding, defat, sintering and heat treatment and make the medical porous metal implant material that substitutes dentale tissue; It is characterized in that: described pore creating material is one or more in sodium bicarbonate, carbamide, 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 that the speed with 0.5 ℃/min～3 ℃/min is progressively warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 60min～240min, and described sintering step is that vacuum is 10
-4pa～10
-3pa, with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 120～240min, with stove, be chilled to 200～300 ℃, with 10～20 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 120～360min.
2. preparation method as claimed in claim 1, it is characterized in that: described granulation process is to be that 450～650 ℃, 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, the temperature that described circular granular is injected into mould is that 380～540 ℃, pressure are 72～90MPa.
3. preparation method as claimed in claim 1 or 2, is characterized in that: in described mixed-powder, the consumption of forming agent is 5～10%, the consumption of pore creating material is 20～30%, surplus is tantalum powder, in volumn concentration; Described demould time is 6～9S.
4. preparation method as claimed in claim 3, is characterized in that: described forming agent is that paraffin accounts for 7～9%, pore creating material is that ethyl cellulose accounts for 26～29%, surplus is tantalum powder, all in volumn concentration.
5. preparation method as claimed in claim 4, is characterized in that: described paraffin accounts for 8%, ethyl cellulose accounts for 27%, surplus is tantalum powder, all in volumn concentration; Described demould time is 7S.
6. preparation method as claimed in claim 1 or 2, it is characterized in that: in the preparation of the porous tantalum material of described alternative dentale tissue, skimming processes is that speed with 1～3 ℃/min rises to 400 ℃ from room temperature, insulation 60～120min, with the speed of 1.5～2.5 ℃/min, rise to 600～800 ℃ from 400 ℃, be incubated 180～240min; The temperature of described granulation process is that 510～535 ℃, operating pressure are under 13MPa, described mixed-powder to be a granulated into the circular granular of particle diameter 10～20 μ m, by the injection molding temperature of described circular granular, is that 465～490 ℃, pressure are 83～85MPa.
7. preparation method as claimed in claim 4, it is characterized in that: in the preparation of the porous tantalum material of described alternative dentale tissue, skimming processes is that speed with 1～3 ℃/min rises to 400 ℃ from room temperature, insulation 60～120min, with the speed of 1.5～2.5 ℃/min, rise to 600～800 ℃ from 400 ℃, be incubated 180～240min; The temperature of described granulation process is that 510～535 ℃, operating pressure are under 13MPa, described mixed-powder to be a granulated into the circular granular of particle diameter 10～20 μ m, by the injection molding temperature of described circular granular, is that 465～490 ℃, pressure are 83～85MPa.
8. preparation method as claimed in claim 1 or 2, is characterized in that: described vacuum-sintering step is that vacuum is 10
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, be incubated 220～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 250～320min.
9. preparation method as claimed in claim 3, is characterized in that: described vacuum-sintering step is that vacuum is 10
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, be incubated 220～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 250～320min.
10. the preparation method as described in claim 4 or 7, is characterized in that: described vacuum-sintering step is that vacuum is 10
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1500～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, be incubated 220～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, be incubated 250～320min.
11. preparation methoies as claimed in claim 7, is characterized in that: described vacuum-sintering condition also includes: vacuum is 10
-4pa～10
-3pa, is warming up to 1800 ℃, is incubated 200min, with stove, is chilled to 200～300 ℃ with 13 ℃/min, then is warming up to 1800 ℃, insulation 230min with 17 ℃/min, with 7 ℃/min, is warming up to 2000～2200 ℃, insulation 300min; Cooling condition after vacuum-sintering also includes: vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, is incubated 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, is incubated 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Described heat-treat condition also includes: the speed with 15～30 ℃/min rises to 1000～1250 ℃, is incubated 240～480min, and vacuum is 10
-4pa～10
-3pa, then be cooled to 1000 ℃ with the speed of 5～10 ℃/min, being incubated 90～180min, vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 800 ℃, is incubated 60～120min, and vacuum is 10
-4pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum is 10
-4pa～10
-3pa.
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| CN201110295867.0A CN102796893B (en) | 2011-09-29 | 2011-09-29 | Preparation method of porous tantalum applicable to replacing human dentale tissue |
| CN201410110916.2A CN103846443B (en) | 2011-09-29 | 2011-09-29 | A kind of porous tantalum being applicable to alternative human dentale tissue |
| CN201410110740.0A CN103849792B (en) | 2011-09-29 | 2011-09-29 | A kind of porous tantalum being applicable to alternative human dentale tissue |
| PCT/CN2012/082344 WO2013044857A1 (en) | 2011-09-29 | 2012-09-28 | Preparation method for porous tantalum for human dental bone tissue replacement |
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| CN201410110916.2A Division CN103846443B (en) | 2011-09-29 | 2011-09-29 | A kind of porous tantalum being applicable to alternative human dentale tissue |
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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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|---|---|
| CN103849792A (en) | 2014-06-11 |
| CN103846443B (en) | 2015-10-07 |
| CN102796893A (en) | 2012-11-28 |
| CN103846443A (en) | 2014-06-11 |
| CN103849792B (en) | 2015-11-25 |
| WO2013044857A1 (en) | 2013-04-04 |
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