CN105056296B - A kind of medical porous tantalum material for substituting dentale and preparation method thereof - Google Patents
A kind of medical porous tantalum material for substituting dentale and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
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- 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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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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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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Abstract
A kind of medical porous tantalum material for substituting dentale and preparation method thereof, mixed-powder is mixed into by tantalum powder and polyvinyl alcohol, sodium acid carbonate, then the mixed-powder is pressed into Organic Foam Material made from shaping, degreasing, sintering, cooling and heat treatment；The compressing pressure used is 50~100Mpa, and the medical porous tantalum material pore diameter of formation is 30~50 μm, and porosity is between 30~38%.Porous tantalum preparation method of the present invention employs pure physical abrasion method so that the content of impurity is extremely low in final porous tantalum material, is effectively improved biocompatibility and biological safety；It can be less than 0.2%, density up to 10.34~11.67g/cm by testing its impurity content3, porosity is up to 30~38%, and pore diameter is up to 30~50 μm；Modulus of elasticity up to 4.5~6.0Gpa, bending strength up to 120~130Mpa, compression strength up to 100~140Mpa, porous tantalum of the present invention be highly suitable for substitute dentale medical embedded material.
Description
The present patent application is application number 201110296545.8, the applying date 2011 year 09 month 29 days, and denomination of invention " replace by one kind
The divisional application of medical porous tantalum material for dentale and preparation method thereof ".
Technical field
The present invention relates to a kind of porous medical metal implanted material and preparation method thereof, is substituted more particularly to one kind fine and close
Medical embedded porous tantalum material of bone tissue and preparation method thereof.
Background technology
Porous medical metal implanted material has treatment bone tissue wound, bone formation necrosis and substitutes fine and close bone tissue such as
The important and special purposes such as dentale, existing common this kind of material have porous metals stainless steel, porous metals titanium etc..As bone group
Knit wound and porous implantation material that bone formation necrosis therapeutic uses, its porosity should be up to 30~80%, and hole is best
All connect and be uniformly distributed, or be allowed to both consistent with the bone growth of human body as needed, alleviate material again in itself
Weight, be adapted to human body implantation use.
And refractory metals tantalum, because it has outstanding biocompatibility, its porous material is expected to foregoing etc. as substituting
Conventional medical metallic biomaterial.Due to metal tantalum to human body it is harmless, nontoxic, have no side effect, and with domestic and international medical science
Rapid development, to tantalum as body implanting material recognize further deeply, people are to human body implantation porous metals tantalum material
The demand of material becomes more and more urgent, requires it also more and more higher.Porous medical embedded metal tantalum is wherein used as, if can have
There is the very high physical and mechanical properties for being uniformly distributed interconnected pore and being adapted with human body, then it is expected to as a kind of new
Bone tissue alternative materials.
Substantially burnt as medical embedded porous metal material just as in general porous metal material with powder
Connection is main processing method, and powder is used with equally distributed porous metal foam structure especially for porosity communication is obtained
It is in the majority to re-sinter abbreviation foam impregnation method for drying after dipping of the metal dust slurry on Organic Foam Material in sintering process.On
Powder sintered obtained porous metal material generally its Metal Mechanic Property be not it is fine, its main cause be in technique such as
What arrange pore-forming medium support and elimination relation, it is metal powder sintered during collapse problem.And known document report
In without well solve method and let alone nature.
It is seldom that the document report of porous tantalum is made using metal powder sintered legal system, is particularly used with obtaining medical embedded material
For the purpose of porous tantalum powder sintering document report almost do not have.That may be referred to is Publication No. CN200510032174,
Title " three-dimensional through hole or some perforations be connected with each other porous metal foam and preparation method thereof " and CN200710152394, name
Claim " a kind of porous foam tungsten and preparation method thereof ".But its porous metals for being obtained or used for filtering material, or
It is to be used for Aero-Space and other high temperature applicationss by the use of rather than as medical metal implanted material, furthermore the porous metals processed
Nor porous tantalum.
On porous tantalum, US5282861 discloses a kind of opening applied to cancellous bone implants, cell and tissue receptor
Hole tantalum material and its preparation.This porous tantalum is made up of pure business tantalum, the carbon that it is obtained with the progress thermal degradation of polyurethane precursor
Skeleton is support, and the carbon skeleton is in multiple dodecahedron, is grid spline structure in it, integrally spreads all over micropore, and porosity can be high
Up to 98%, then the pure tantalum of business is attached on carbon skeleton by the method for chemical vapour deposition, infiltration micro- to form porous metals
Structure, referred to as chemical deposition.The tantalum layer thickness on porous its surface of tantalum material that this method is obtained 40~60 μm it
Between；In whole porous material, tantalum, which weighs about, accounts for 99%, and carbon skeleton weight then accounts for 1% or so.Document further states that this is more
50~70MPa of compression strength of Porous materials, 2.5~3.5GPa of modulus of elasticity, tensile strength 63MPa, amount of plastic deformation 15%.But
It is the porous tantalum using it as medical embedded materials such as fine and close bone tissue such as dentales, the mechanical property such as ductility of its material, resists
Compressive Strength, bending strength etc. have obvious weak point, and influence whether the follow-up processing to porous tantalum material in itself, such as
Cutting of molding part etc..Also such deficiency be present in the product equally obtained in foregoing metal powder sintered method.
The content of the invention
It is an object of the invention to provide a kind of medical porous tantalum material for being applied to substitute dentale of good biocompatibility.
Another object of the present invention is to provide the preparation method of above-mentioned porous tantalum medical material.
The purpose of the present invention is realized by following technological means：
A kind of medical porous tantalum material for substituting dentale, it is characterised in that：Mixed by tantalum powder with polyvinyl alcohol, sodium acid carbonate
Into mixed-powder, then made from repressed shaping, degreasing, sintering, cooling and heat treatment；It is described it is compressing be will be described mixed
Close powder to be pressed into Organic Foam Material, its pressure is 50~100Mpa, and the medical porous tantalum material pore diameter of formation is 30
~50 μm, porosity is between 30~38%.
In the R＆D process of medical porous tantalum material, syntheti c route is numerous, but inventor creatively proposes use
Fine and close medical porous tantalum implantation material prepared by above-mentioned processing step, 0.2%, its biology can be less than by testing its impurity content
Compatibility is good with biological safety, and density is up to 10.34~11.67g/cm3, for porosity up to 30~38%, pore diameter can
Up to 30~50 μm；Modulus of elasticity up to 4.5~6.0Gpa, bending strength up to 120~130Mpa, compression strength up to 100~
140Mpa, porous tantalum of the present invention are highly suitable for substituting the medical embedded material of dentale.
The average grain diameter for the Ta powder that the present invention uses is less than 43 microns, oxygen content is less than 0.1%, is commercially available prod；
Above-mentioned polyvinyl alcohol, sodium acid carbonate are also commercially available prod.Above-mentioned polyvinyl alcohol mainly plays shaping but it is also equipped with simultaneously
The effect of pore-creating, above-mentioned sodium acid carbonate play pore-creating.Vacuum environment of the present invention preferably uses vacuum as 10-4Pa~10- 3Pa vacuum condition.The above-mentioned preferred polyurethane foam of Organic Foam Material, more preferably 0.48~0.89mm of aperture, density
0.015g/cm3~0.035g/cm3, hardness is more than 50 °, and (most preferably aperture is 0.56~0.72mm, density 0.025g/cm3, firmly
Degree 50 °~80 °) polyurethane foam in.
The inventor in R＆D process further study show that, if controlled in above-mentioned preparation it is bad, though as above institute can be made
State the medical embedded material for being suitable for substituting dentale but product qualification rate is not high：Such as powder pressing forming hardly possible, after pressing portion
Divide and layering, uneven, the technical problems such as degreasing rear portion branch is cracked easily occur.
In order that shaping is easier in powder compaction process, so as to improve yield rate, finished product hole uniformity, make to prepare
Journey is more stable, and the dosage of polyvinyl alcohol is 5~10% in above-mentioned mixed-powder, the dosage of sodium acid carbonate is 20~30%, surplus
(in terms of volumn concentration directly calculated by the situation of final porous tantalum material in terms of volumn concentration for tantalum powder
Unit, the density according further to respective substance in the weighing of above-mentioned mixed-powder calculate its corresponding quality weighing), enter one
Step is preferably that to account for 7~9%, sodium acid carbonate to account for 26~29%, surplus be tantalum powder to polyvinyl alcohol；It is above-mentioned it is compressing during pressure
Power is preferably 70~80Mpa.
In order that idiosome is more stable in skimming processes, reduce the part idiosome deformation easily occurred, aperture is uneven, so as to enter
One step improves yield rate, quality stability, and above-mentioned skimming processes are progressively warming up to 0.5 DEG C/min~3 DEG C/min speed
400~800 DEG C, it is passed through with argon gas and is formed protective atmosphere and be incubated 60min~240min；Further preferably with 2.5~3 DEG C/min
Speed be progressively warming up to 400~800 DEG C, be passed through with argon gas and formed protective atmosphere and be incubated 150min~240min.
The preparation method of the medical porous tantalum material of above-mentioned replacement dentale, formed using die pressing sintering, its feature is
Mixed powder is mixed into tantalum powder and polyvinyl alcohol, sodium bicarbonate powder, the dosage of wherein polyvinyl alcohol accounts for 5~10%, bicarbonate
It is tantalum powder that the dosage of sodium, which accounts for 20~30%, surplus, in terms of volumn concentration；Again by the mixed-powder under 50~100Mpa
It is pressed into shaping in Organic Foam Material, degreasing, vacuum-sintering, cooling and heat treatment and porous tantalum material is made.
The average grain diameter of above-mentioned raw materials tantalum powder is less than 0.1% less than 43 microns, oxygen content；Above-mentioned mixed powder is preferably poly- second
It is tantalum powder that enol, which accounts for 7~9%, sodium acid carbonate and accounts for 26~29%, surplus, still more preferably accounts for 8%, bicarbonate for polyvinyl alcohol
It is tantalum powder that sodium, which accounts for 27%, surplus, in terms of volumn concentration.The above-mentioned preferred polyurethane foam of Organic Foam Material, further preferably
For 0.48~0.89mm of aperture, density 0.015g/cm3~0.035g/cm3, hardness be more than 50 ° (most preferably aperture be 0.56~
0.72mm, density 0.025g/cm3, 50 °~80 ° of hardness) polyurethane foam in.
In order that pressing pressure is uniform, not stratified during compacting embryo processed, so that final porous tantalum distribution of pores is more equal
It is even, quality is more stable, the pressure used in above-mentioned pressing process is preferably 70~80Mpa；In above-mentioned skimming processes be preferably with
0.5 DEG C/min~3 DEG C/min speed is progressively warming up to 400~800 DEG C, is passed through with argon gas and is formed protective atmosphere and be incubated
60min~240min, is further preferably progressively warming up to 400~800 DEG C with 2.5~3 DEG C/min speed, and structure is passed through with argon gas
Into protective atmosphere and 150min~240min is incubated, still more preferably 400 are progressively warming up to 2.5 DEG C/min speed~
800 DEG C, it is passed through with argon gas and is formed protective atmosphere and be incubated 220min.
The further feature of another aspect of the present invention is：It is not less than 10 in vacuum-4~10-3Pa, temperature 2000~
2200 DEG C, porous sintered body is made in the soaking time vacuum-sintering of 1~5 hour processing.Sintering process can fill inertia when being incubated
Gas shield replaces vacuum protection；Vacuum annealing processing is finally carried out, wherein vacuum annealing processing refers to after vacuum-sintering
Continue keeping temperature and be in 1000~1250 DEG C, soaking time 1~4 hour, vacuum is not less than 10-4~10-3Pa。
Vacuum-sintering condition also includes：Vacuum is not less than 10-3Pa, with 10~20 DEG C/min heating rate from room temperature
1200 DEG C~1500 DEG C are risen to, after being incubated 1h~2h；2000~2200 DEG C are warming up to the heating rate less than 20 DEG C/min again,
At least it is incubated 2h~4h.
Cooling condition after vacuum-sintering also includes：Vacuum is not less than 10-3Pa is not low with not higher than 25 DEG C/min
Cooldown rate mode is gradually dropped in 10 DEG C/min, sintered porous bodies are segmented with cooling down to 800 DEG C, each section of soaking time 30min
~90min, then cools to normal temperature with the furnace.
Vacuum annealing condition also includes：Vacuum is not less than 10-4Pa, 1000 are risen to the speed not higher than 30 DEG C/min
~1250 DEG C, it is incubated 4h~6h；Again to be segmented soon with the cooldown rate not less than 5 DEG C/min but not higher than 30 DEG C/min after first slow
Room temperature is cooled to, each section of soaking time tapers off and selected no more than in 1.5h~3h.
The characteristics of further on this basis is：The ungrease treatment condition also includes：Progressively it is warming up to 600~
800 DEG C, composition protective atmosphere is specifically passed through with pure argon gas (99.9999%), with 1~3 DEG C/min speed from room temperature liter
To 400 DEG C, 60~120min is incubated, 600~800 DEG C are risen to from 400 DEG C with 1.5~2.5 DEG C/min speed, insulation 180~
240min；The vacuum-sintering condition also includes：1200~1250 DEG C are risen to from room temperature with 10~15 DEG C/min speed, is protected
30~60min of temperature, vacuum 10-4Pa~10-3Pa；1500 DEG C are risen to 10~20 DEG C/min speed, insulation 30~
60min, vacuum 10-4Pa~10-3Pa, 2000~2200 DEG C are risen to 6~20 DEG C/min speed, insulation 120~
240min, vacuum 10-4Pa~10-3Pa；Cooling condition after vacuum-sintering also includes：Vacuum is 10-4Pa~10- 3Pa；1500~1600 DEG C are cooled to 10~20 DEG C/min speed, is incubated 30~60min；With 12~20 DEG C/min speed
1200~1250 DEG C are cooled to, is incubated 60~90min；800 DEG C are cooled to 10~20 DEG C/min speed, it is then cold with stove
But；The vacuum annealing condition also includes：1000~1250 DEG C are risen to 15~30 DEG C/min speed, insulation 240~
480min, vacuum 10-4Pa~10-3Pa, then it is cooled to 1000 DEG C with 5~10 DEG C/min speed, insulation 90~
180min, vacuum 10-4Pa~10-3Pa；800 DEG C are cooled to 10~20 DEG C/min speed, is incubated 60~120min,
Vacuum is 10-4Pa；Room temperature, vacuum 10 are cooled to 20~30 DEG C/min speed-4Pa~10-3Pa。
Porous tantalum preparation method of the present invention employs pure physical abrasion method so that the content of impurity in final porous tantalum material
It is extremely low, it is effectively improved biocompatibility and biological safety；, degreasing compressing to the present invention, sintering and annealing steps
Optimization of process conditions so that high yield rate, finished product aperture uniformity are more preferable, make that preparation process is more stable, quality stability is good,
Effectively eliminate thermal stress, make porous tantalum materials microstructure evenly, it is for example strong further to improve the mechanical property of porous tantalum
Degree, toughness are all improved simultaneously, and preparation technology of the present invention make it that product qualified rate is high, production is stable, and product qualification rate can be high
Up to 95%.Porous tantalum finished product even pore distribution produced by the present invention and connection, good biocompatibility, contain by testing its impurity
Amount can be less than 0.2%, density up to 10.34~11.67g/cm3, porosity is up to 30~38%, and pore diameter is up to 30~50
μm；Modulus of elasticity is up to 4.5~6.0Gpa, bending strength up to 120~130Mpa, compression strength up to 100~140Mpa, sheet
Invention porous tantalum is highly suitable for substituting the medical embedded material of dentale.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be that following examples are only used
It is further described in the present invention, it is impossible to be interpreted as limiting the scope of the invention, person skilled in art can
So that some nonessential modifications and adaptations are made to the present invention according to the invention described above content.
A kind of medical porous tantalum material for substituting dentale is specifically forming agent from polyvinyl alcohol, sodium acid carbonate is pore-creating
Agent, mixed powder is mixed into less than 43 microns, tantalum powder of the oxygen content less than 0.1% with average grain diameter, will be mixed under 50~100Mpa
Conjunction powder, which is pressed into Organic Foam Material, to be molded, then is obtained through degreasing, sintering, cooling and heat treatment.The porous tantalum of formation is through inspection
Gaging hole porosity is between 30~38%, 30~50 μm of pore diameter.
More specifically, above-mentioned porous tantalum is by the polyvinyl alcohol of 5~10% (in terms of volumn concentrations), 20~30%
The sodium acid carbonate of (in terms of volumn concentration) and the tantalum powder of surplus are mixed into mixed powder, put it into injection moulding machine and add
It is pressed into polyurethane foam and is molded；It is placed in again in tungsten device and is put into the protection gas that pure argon gas (99.9999%) is passed through composition
Certain temperature is progressively warming up in atmosphere stove, and is incubated and carries out ungrease treatment to remove pore creating material, forming agent and polyurethane foam, its
In argon gas is first passed through before heating to exclude furnace air, the sample furnace cooling after degreasing；For the sample after ungrease treatment
Product are placed in high vacuum high temperature sintering furnace with tungsten device is progressively warming up to 2000~2200 DEG C, and soaking time carries out vacuum in 1~5 hour
Sintering, the vacuum of sintering furnace will at least reach proper level before heating, the sample furnace cooling after vacuum-sintering, cooling
During keep certain vacuum or by certain cooldown rate sub-sectional cooling to keep certain temperature in reasonable time,
Filling with inert gas can be used in insulating process as protective atmosphere.Sample after being cooled down for vacuum-sintering is put with corundum container
Progressively heated up in vacuum annealing furnace, be incubated carry out stress relief annealing process, kept necessarily in annealing furnace before heating
Vacuum, the sample furnace cooling after vacuum annealing processing, certain vacuum is also kept in cooling procedure or by certain cold
But speed sub-sectional cooling, can be using filling with inert gas as guarantor in insulating process to keep certain temperature in reasonable time
Atmosphere is protected, conventional post processing is finally carried out and porous tantalum is made.
To be placed in tungsten crucible to be put into atmosphere furnace to heat up with certain heating rate for ungrease treatment, its
Argon gas or other inert gases are first passed through before heating to exclude furnace air, and temperature control process is from room with suitable heating rate
Temperature rise is to certain temperature, insulation, then heats up, is incubated.Vacuum-sintering processing is carried out for the sample after ungrease treatment, is by it
The maximum sintering temperature progress vacuum burning that with certain heating rate is warming up to tantalum is placed in high vacuum high temperature sintering furnace with tungsten device
Knot, sintering furnace keeps certain vacuum before heating, and such as 1200 DEG C~1250 DEG C are warming up to certain heating rate,
Insulation, keep vacuum；Such as 1250 DEG C~1500 DEG C are warming up to again with certain heating rate, are incubated, then with certain heating
Speed is warming up to the maximum sintering temperature of such as tantalum, insulation, keeps vacuum；Sintering finishes, and keeps vacuum, with certain cooling speed
Rate is cooled to such as 1500 DEG C~1600 DEG C, is incubated, then is cooled to such as 1200 DEG C~1250 DEG C with certain rate of temperature fall, protects
Temperature, such as 800 DEG C also are cooled to certain rate of temperature fall, then furnace cooling.Sample after being cooled down for vacuum-sintering enters
Row vacuum annealing is handled, and is to be placed in it in vacuum annealing furnace with corundum container to be warming up to such as 1000 with certain heating rate
DEG C~1250 DEG C of progress stress relief annealing process, the holding vacuum before heating in annealing furnace, with certain heating rate
1000 DEG C~1250 DEG C are risen to from room temperature, insulation, keeps vacuum；Such as 1000 DEG C are cooled to certain rate of temperature fall again, is protected
Temperature；Such as 800 DEG C are cooled to certain rate of temperature fall again, insulation；Room temperature is also cooled down with certain rate of temperature fall.Finally carry out
Porous tantalum is made in conventional post processing.
Inventor uses metal powder sintered method mainly based on physical abrasion method, has done substantial amounts of theory analysis and experiment
Checking, 0.2%, density can be less than up to 10.34~11.67g/cm by obtaining porous tantalum product by testing its impurity content3, hole
Porosity is up to 30~38%, and pore diameter is up to 30~50 μm；Modulus of elasticity is up to 4.5~6.0Gpa, bending strength up to 120
~130Mpa, compression strength are up to 100~140Mpa.
Embodiment 1：Weigh polyvinyl alcohol, average grain diameter is less than tantalum powder and bicarbonate of 43 microns of oxygen contents less than 0.1%
Sodium is mixed into mixed-powder, and wherein polyvinyl alcohol, which accounts for 8%, sodium acid carbonate and accounts for 27%, tantalum powder, accounts for 65%, with volume basis
Content meter.Extrusion forming：Above-mentioned mixed-powder is pressed into polyurethane foam (aperture in injection moulding machine under 80Mpa
0.48~0.89mm, density 0.015g/cm3~0.035g/cm3, hardness be more than 50 °) in be molded.Ungrease treatment：Vacuum 10- 4Pa, with 2.5 DEG C/min heating rate from room temperature to 400 DEG C, insulation 100min；Again with 2 DEG C/min heating rate from
400 DEG C are warming up to 700 DEG C, soaking time 220 minutes.Vacuum-sintering：Sinter in a vacuum furnace, 2000 DEG C of sintering temperature, insulation 2
Hour, vacuum 10-4Pa, sintering process argon filling gas shielded, surface dirt and dirt are removed after taking out product, obtained sample is again
Carry out routine post-processes to obtain porous tantalum finished product.
Inventor by the standard such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum into
Porous material density, porosity, aperture and the various mechanical properties of product are detected：Its impurity content is less than 0.2%, its hole
It is evenly distributed, density 10.84g/cm3, porosity 35%, 30 μm, modulus of elasticity 5.5GPa of pore mean diameters, bending strength
130MPa, compression strength 140MPa.
Embodiment 2：Weigh polyvinyl alcohol, average grain diameter is less than tantalum powder and bicarbonate of 43 microns of oxygen contents less than 0.1%
Sodium is mixed into mixed-powder, and wherein polyvinyl alcohol, which accounts for 6%, sodium acid carbonate and accounts for 29%, tantalum powder, accounts for 65%, with volume basis
Content meter.Extrusion forming：Above-mentioned mixed-powder is added in injection moulding machine be pressed under 70Mpa aperture for 0.56~
0.72mm, density 0.025g/cm3, it is molded in the polyurethane foam that 50 °~80 ° of hardness.Ungrease treatment：Vacuum 10-4Pa, with 1
DEG C/min heating rate is from room temperature to 400 DEG C, insulation 60min；Risen again with 2.5 DEG C/min heating rate from 400 DEG C
Warm to 800 DEG C, soaking time 180 minutes.Vacuum-sintering：Sinter in a vacuum furnace, 2100 DEG C of sintering temperature, be incubated 4 hours, very
Reciprocal of duty cycle 10-4Pa, sintering process argon filling gas shielded, remove surface dirt after taking out product and dirt, obtained sample are carried out often again
Rule post-process to obtain porous tantalum finished product.
Inventor by the standard such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum into
Porous material density, porosity, aperture and the various mechanical properties of product are detected：Its impurity content is less than 0.2%, its hole
It is evenly distributed, density 10.34g/cm3, porosity 38%, 32 μm, modulus of elasticity 4.5GPa of pore mean diameters, bending strength
123MPa, compression strength 110MPa.
Embodiment 3：Weigh polyvinyl alcohol, average grain diameter is less than tantalum powder and bicarbonate of 43 microns of oxygen contents less than 0.1%
Sodium is mixed into mixed-powder, and wherein polyvinyl alcohol, which accounts for 10%, sodium acid carbonate and accounts for 23%, tantalum powder, accounts for 67%, with volume hundred
Divide content meter.Extrusion forming：Above-mentioned mixed-powder is added in injection moulding machine be pressed under 52Mpa aperture for 0.56~
0.72mm, density 0.025g/cm3, it is molded in the polyurethane foam that 50 °~80 ° of hardness.Ungrease treatment：Vacuum 10-4Pa, with 3
DEG C/min heating rate is from room temperature to 400 DEG C, insulation 120min；Risen again with 1.5 DEG C/min heating rate from 400 DEG C
Warm to 750 DEG C, soaking time 240 minutes.Vacuum-sintering：Sinter in a vacuum furnace, 2200 DEG C of sintering temperature, be incubated 2.5 hours,
Vacuum 10-3Pa, sintering process argon filling gas shielded, cooling are come out of the stove, and remove product surface dust and dirt, obtained sample enter again
Row routine post-processes to obtain porous tantalum finished product.
Inventor by the standard such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum into
Porous material density, porosity, aperture and the various mechanical properties of product are detected：Its impurity content is less than 0.2%, its hole
It is evenly distributed, density 10.67g/cm3, porosity 36%, 34 μm, modulus of elasticity 6.0GPa of pore mean diameters, bending strength
128MPa, compression strength 100MPa.
Embodiment 4：Weigh polyvinyl alcohol, average grain diameter is less than tantalum powder and bicarbonate of 43 microns of oxygen contents less than 0.1%
Sodium is mixed into mixed-powder, and wherein polyvinyl alcohol, which accounts for 5%, sodium acid carbonate and accounts for 30%, tantalum powder, accounts for 65%, with volume basis
Content meter.Extrusion forming：Above-mentioned mixed-powder is added in injection moulding machine be pressed under 96Mpa aperture for 0.56~
0.72mm, density 0.025g/cm3, it is molded in the polyurethane foam that 50 °~80 ° of hardness.Ungrease treatment：Vacuum 10-4Pa, with 2
DEG C/min heating rate is from room temperature to 400 DEG C, insulation 80min；Risen again with 1.5 DEG C/min heating rate from 400 DEG C
Warm to 800 DEG C, soaking time 190 minutes.Vacuum-sintering：Sinter in a vacuum furnace, 2150 DEG C of sintering temperature, be incubated 2 hours, very
Reciprocal of duty cycle 10-4Pa, sintering process argon filling gas shielded, cooling are come out of the stove, and remove product surface dust and dirt, obtained sample are carried out again
Conventional post-processes to obtain porous tantalum finished product.
Inventor by the standard such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum into
Porous material density, porosity, aperture and the various mechanical properties of product are detected：Its impurity content is less than 0.2%, its hole
It is evenly distributed, density 11.17g/cm3, porosity 33%, 40 μm, modulus of elasticity 4.5GPa of pore mean diameters, bending strength
120MPa, compression strength 135MPa.
Embodiment 5：A kind of porous tantalum, it is less than 43 μm, ta powder of the oxygen content less than 0.1%, polyethylene with particle diameter
Alcohol and sodium acid carbonate mixed powder are raw material, then repressed shaping, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing
It is made.
Wherein, polyvinyl alcohol, which accounts for 7%, sodium acid carbonate and accounts for 20%, ta powder, accounts for 73%, in terms of volumn concentration；
It is compressing：Raw material mixed powder end is added in injection moulding machine be pressed under 65Mpa aperture for 0.56~
0.72mm, density 0.025g/cm3, it is molded in the polyurethane foam that 50 °~80 ° of hardness；
Ungrease treatment：Under inert gas shielding atmosphere or vacuum 10-4~10-3Pa, it is warming up to 2.5~3 DEG C/min
400 DEG C~800 DEG C, using argon gas as protective atmosphere, soaking time 150~240 minutes to remove polyvinyl alcohol and carbonic acid therein
Hydrogen sodium；
Vacuum-sintering：Vacuum is less than 10-4Pa~10-3Pa, 2000~2200 DEG C of temperature, soaking time 1~5 hour, burn
Applying argon gas or other inert gas shieldings when knot process is incubated, to obtain porous material；
Vacuum annealing：By the follow-up continuous keeping temperature of vacuum-sintering be in 1000~1250 DEG C, soaking time 1~4 hour,
Vacuum is 10-4~10-3Pa, to carry out stress relief annealing process；Obtained sample carries out conventional post-processing to obtain porous tantalum again
Finished product.
Inventor by the standard such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum into
Porous material density, porosity, aperture and the various mechanical properties of product are detected：Its impurity content is less than 0.2%, its hole
It is evenly distributed, density 10.34g/cm3, porosity 38%, 39 μm, modulus of elasticity 4.9GPa of pore mean diameters, bending strength
122MPa, compression strength 134MPa.
Embodiment 6：A kind of porous tantalum, it is less than 43 μm, ta powder of the oxygen content less than 0.1%, polyethylene with particle diameter
Alcohol and sodium acid carbonate mixed powder are raw material, then repressed shaping, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing
It is made.
Wherein, polyvinyl alcohol, which accounts for 7%, sodium acid carbonate and accounts for 20%, ta powder, accounts for 73%, in terms of volumn concentration；
It is compressing：Raw material mixed powder end is added in injection moulding machine be pressed under 65Mpa aperture for 0.56~
0.72mm, density 0.025g/cm3, it is molded in the polyurethane foam that 50 °~80 ° of hardness；
Mixed-powder is put into nonoxidizing atmosphere stove after compressing and is warming up to 800 DEG C with certain heating rate, is protected
It is that 99.999% argon gas carries out ungrease treatment to protect atmosphere, and it is first passed through pure argon gas at least 30min to exclude stove before heating
Interior air, temperature control process：400 DEG C are risen to from room temperature with 1.5 DEG C/min speed, is incubated 88min, argon gas intake 0.5L/
min；800 DEG C are risen to from 400 DEG C with 2.0 DEG C/min speed, is incubated 195min, argon gas intake 1L/min；Turn off power supply,
Sample furnace cooling after degreasing, argon gas intake 1L/min, until closing argon gas when being cooled to room temperature；
It is placed in high vacuum high temperature sintering furnace with tungsten device for the sample after ungrease treatment and is heated up with certain heating rate
To 2200 DEG C of progress vacuum-sinterings, the vacuum of sintering furnace will at least reach 10 before heating-4Pa, with 10~15 DEG C/min's
Speed rises to 1200 DEG C from room temperature, is incubated 30min, vacuum 10-4Pa；1500 DEG C are risen to 10 DEG C/min speed, insulation
30min, vacuum 10-4Pa~10-3Pa；2200 DEG C are risen to 6 DEG C/min speed, is incubated 120min, vacuum 10- 3Pa；Sintering finishes, vacuum 10-3Pa, 1600 DEG C are cooled to 10~15 DEG C/min speed, is incubated 30min；With 12 DEG C/
Min speed is cooled to 1200 DEG C, is incubated 60min；800 DEG C are cooled to 10 DEG C/min speed, then furnace cooling；
Sample after being cooled down for vacuum-sintering is placed in vacuum annealing furnace with certain heating rate liter with corundum container
For temperature to 1250 DEG C of progress stress relief annealing process, the vacuum before heating in annealing furnace will at least reach 10-4Pa, with 15
DEG C/min speed rises to 1250 DEG C from room temperature, it is incubated 240min, vacuum 10-4Pa~10-3Pa；Again with 5 DEG C/min speed
Rate is cooled to 1000 DEG C, is incubated 180min, vacuum 10-4Pa~10-3Pa；800 DEG C are cooled to 10 DEG C/min speed,
It is incubated 120min, vacuum 10-4Pa；Room temperature, vacuum 10 are cooled to 20 DEG C/min speed-4Pa.Finally carry out normal
Porous tantalum is made in rule post processing.
Inventor by the standard such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum into
Porous material density, porosity, aperture and the various mechanical properties of product are detected：Its impurity content is less than 0.2%, its hole
It is evenly distributed, density 11.67g/cm3, porosity 30%, 50 μm, modulus of elasticity 5.8GPa of pore mean diameters, bending strength
127MPa, compression strength 133MPa.The preparation technology product qualification rate is up to 93.4%.
In the method that above-described embodiment 6 provides, we can also make other to various conditions therein and select same energy
Obtain porous tantalum of the present invention.
Gained porous tantalum finished product is detected by preceding method：
| Embodiment | 7 | 8 | 9 | 10 | 11 | 12 | 13 |
| Density (g/cm3) | 11.34 | 10.34 | 10.67 | 11.67 | 11.17 | 11.0 | 10.50 |
| Porosity (%) | 32 | 38 | 36 | 30 | 33 | 34 | 37 |
| Aperture (μm) | 44 | 50 | 48 | 35 | 37 | 30 | 40 |
| Modulus of elasticity (GPa) | 4.7 | 4.3 | 4.9 | 5.8 | 5.5 | 6.0 | 5.2 |
| Bending strength (MPa) | 120 | 122 | 125 | 128 | 124 | 130 | 121 |
| Compression strength (MPa) | 123 | 100 | 115 | 118 | 128 | 140 | 135 |
Claims (5)
1. a kind of medical porous tantalum material for substituting dentale, formed using die pressing sintering, it is characterised in that：With tantalum powder and poly- second
Enol, sodium bicarbonate powder are mixed into mixed powder, the dosage of wherein polyvinyl alcohol account for 5~10%, sodium acid carbonate dosage account for 20~
30%th, surplus is tantalum powder, in terms of volumn concentration；It is 0.56~0.72mm to be pressed into aperture under 50~100Mpa again, close
Spend 0.025g/cm3, in the polyurethane foam of hardness 500~800 shaping, degreasing, vacuum-sintering, cooling and heat treatment be made more
Hole tantalum material；
The skimming processes are progressively to be warming up to 400~800 DEG C with 0.5 DEG C/min~3 DEG C/min speed, and structure is passed through with argon gas
Into protective atmosphere and it is incubated 60min~240min；
The vacuum-sintering condition is：Vacuum is not less than 10-3Pa, risen to 10~20 DEG C/min heating rate from room temperature
1200 DEG C~1500 DEG C, after being incubated 1h~2h；2000~2200 DEG C are warming up to the heating rate less than 20 DEG C/min again, extremely
2h is incubated less；
Cooling condition after the vacuum-sintering is：Vacuum is not less than 10-3Pa, with not higher than 25 DEG C/min, not less than 10 DEG C/
Cooldown rate mode gradually drops in min, and sintered porous bodies are segmented with cooling down to 800 DEG C, and each section of soaking time 30min~
90min, then cool to normal temperature with the furnace；
Heat treatment condition is：Vacuum is not less than 10-4Pa, 1000~1250 DEG C are risen to the speed not higher than 30 DEG C/min, is protected
Warm 4h~6h；Again with after first slow soon with the cooldown rate sub-sectional cooling not less than 5 DEG C/min but not higher than 30 DEG C/min to room temperature,
Each section of soaking time tapers off and selected in 1.5h~3h.
2. the medical porous tantalum material of the replacement dentale as described in claim 1, the skimming processes are with 2.5~3 DEG C/min
Speed be progressively warming up to 400~800 DEG C, be passed through with argon gas and formed protective atmosphere and be incubated 150min~240min.
3. the medical porous tantalum material of the replacement dentale as described in claim 1, it is characterised in that：Gather in the mixed-powder
It is tantalum powder that vinyl alcohol, which accounts for 7~9%, sodium acid carbonate and accounts for 26~29%, surplus, in terms of volumn concentration；The compressing process
In pressure be 70~80Mpa.
4. the medical porous tantalum material of the replacement dentale as described in claim 1,2 or 3, it is characterised in that：The raw material tantalum
The average grain diameter of powder is less than 0.1% less than 43 microns, oxygen content；The mixed powder accounts for 7~9%, sodium acid carbonate for polyvinyl alcohol and accounted for
26~29%, surplus is tantalum powder, in terms of volumn concentration.
5. the medical porous tantalum material of the replacement dentale as described in claim 1,2 or 3, it is characterised in that：The mixed powder
It is tantalum powder to account for 8%, sodium acid carbonate to account for 27%, surplus for polyvinyl alcohol, in terms of volumn concentration.
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| CN107745126B (en) * | 2017-09-30 | 2020-01-31 | 中国振华（集团）新云电子元器件有限责任公司 | method for improving internal porosity of sintered tantalum block |
| CN113102753B (en) * | 2020-01-13 | 2023-01-13 | 天津大学 | Indirect 3D printing tungsten-based alloy part degreasing sintering method |
| CN114855024B (en) * | 2022-05-10 | 2023-08-01 | 南方科技大学 | Porous tantalum medical implant material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250638A (en) * | 2007-02-21 | 2008-08-27 | 德普伊产品公司 | Porous metal foam structures and methods |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
| 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. |
| CN101811189A (en) * | 2008-08-27 | 2010-08-25 | 德普伊产品公司 | Mixtures for forming porous constructs |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2190197A (en) * | 1996-02-27 | 1997-09-16 | Astro Met, Inc. | Porous materials and method for producing |
| EP1362129A1 (en) * | 2001-02-19 | 2003-11-19 | IsoTis N.V. | Porous metals and metal coatings for implants |
| 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 |
| US7635447B2 (en) * | 2006-02-17 | 2009-12-22 | Biomet Manufacturing Corp. | Method and apparatus for forming porous metal implants |
| BRPI0806916A2 (en) * | 2007-01-19 | 2014-04-29 | Cinv Ag | NON-DEGRADABLE POROUS IMPLANT MADE BY DUST |
| CN101660076A (en) * | 2009-10-14 | 2010-03-03 | 北京师范大学 | Macro mesh structural porous tantalum prepared by dipping and sintering organic foams |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250638A (en) * | 2007-02-21 | 2008-08-27 | 德普伊产品公司 | Porous metal foam structures and methods |
| 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. |
| CN101811189A (en) * | 2008-08-27 | 2010-08-25 | 德普伊产品公司 | Mixtures for forming porous constructs |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
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| CN104940991A (en) | 2015-09-30 |
| CN104940991B (en) | 2017-06-16 |
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