CN102796905B - Method for preparing medical porous titanium implant material - Google Patents
Method for preparing medical porous titanium implant material Download PDFInfo
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- CN102796905B CN102796905B CN201110301063.7A CN201110301063A CN102796905B CN 102796905 B CN102796905 B CN 102796905B CN 201110301063 A CN201110301063 A CN 201110301063A CN 102796905 B CN102796905 B CN 102796905B
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract description 10
- 239000007943 implant Substances 0.000 title abstract description 6
- 239000010936 titanium Substances 0.000 title abstract description 5
- 229910052719 titanium Inorganic materials 0.000 title abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 45
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 83
- 229910052715 tantalum Inorganic materials 0.000 claims description 48
- 238000009413 insulation Methods 0.000 claims description 43
- 238000010792 warming Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 22
- 239000011496 polyurethane foam Substances 0.000 claims description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 22
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000006261 foam material Substances 0.000 claims description 16
- 230000014759 maintenance of location Effects 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000012805 post-processing Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000011218 segmentation Effects 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 3
- 239000011148 porous material Substances 0.000 abstract description 24
- 210000000988 bone and bone Anatomy 0.000 abstract description 11
- 238000005187 foaming Methods 0.000 abstract 4
- 238000005238 degreasing Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000001413 cellular effect Effects 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010028851 Necrosis Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 239000006262 metallic foam Substances 0.000 description 2
- 230000017074 necrotic cell death Effects 0.000 description 2
- 231100000957 no side effect Toxicity 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 206010031264 Osteonecrosis Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 208000037816 tissue injury Diseases 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Classifications
-
- 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
- B22F3/1137—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers by coating porous removable preforms
-
- 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
-
- 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
-
- 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
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
-
- 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
- B22F3/24—After-treatment of workpieces or articles
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/08—Methods for forming porous structures using a negative form which is filled and then removed by pyrolysis or dissolution
-
- 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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- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Veterinary Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dermatology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
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Abstract
A method for preparing a medical porous titanium implant material comprise the steps of preparing an organic binding agent and a dispersing agent into a solution, preparing the solution and titanium powder into titanium powder slurry, pouring the titanium powder slurry into an organic foaming body, dipping until the titanium powder slurry is fully filled in a pore of the organic foaming body, drying to remove the dispersing agent in the organic foaming body poured by the titanium powder slurry, degreasing under the protective atmosphere of inert gas to remove the organic binding agent and the organic foaming body, sintering under the vacuum to prepare a porous sintering body, cooling, conducting vacuum annealing and conventional aftertreatment to prepare the porous titanium. In the sintering steps, the vacuum degree is 10<-4>Pa-10<-3>Pa, the temperature is increased to be 1500-1800 DEG C according to the rate of 10-20 DEG C/min, is kept for 120-240min and is cooled to be 200-300 DEG C along with the furnace, then the temperature is increased to be 1500-1800 DEG C according to the rate of 10-20 DEG C/min and is kept for 180-240min, and then the temperature is increased to be 2000-2200 DEG C according to the rate of 5-10 DEG C/min and is kept for 120-360min. The porous titanium material prepared by the invention not only is good in biocompatibility and safety, but also is extremely high in mechanical property and is very suitable for replacing the bone tissue of the bearing part of a human body.
Description
Technical field
The present invention relates to a kind of porous medical metal implanted material, particularly relate to a kind of preparation method that is suitable for the medical porous tantalum embedded material of alternative load-bearing bone tissue.
Background technology
Porous medical metal implanted material has the important and special purposes such as treatment osseous tissue wound and bone formation necrosis, 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 hole is partly communicated with and is uniformly distributed as required, make it 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 and mechanical property, its porous material is expected to the conventional medical metallic biomaterial such as aforementioned as an alternative, becomes the biomaterial mainly as bone necrosis's treatment.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., as the medical embedded metal tantalum of porous, if can there is the very high physical and mechanical properties that is uniformly distributed interconnected pore and adapts with human body, be wherein the heavy connection constituent material that guarantees freshman bone tissue's normal growth.
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 porosity communication and equally distributed 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 the porous tantalum using it as medical embedded material, the mechanical property of its material is obvious weak point as ductility has, 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.Due to the limitation of its preparation method, the finished product purity of acquisition is inadequate, has carbon skeleton residue again, causes biological safety to reduce.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of good biocompatibility, medical porous tantalum embedded material that mechanical strength is high.
The object of the invention is to realize by following technological means:
A kind of method of preparing medical porous tantalum embedded material, adopt foam impregnation method sintering to form, its feature is that the solution and the tantalum powder that with organic binder bond and dispersant, are mixed with make tantalum powder slurry, and be cast in Organic Foam Material, dipping is until Organic Foam Material hole is filled with tantalum powder slurry, then be dried and remove the dispersant in the Organic Foam Material that is cast with tantalum powder slurry, under inert gas shielding atmosphere, ungrease treatment is to remove organic binder bond and Organic Foam Material, under vacuum, sintering makes porous sintered body, cooling, under vacuum, annealing and conventional post processing make porous tantalum again, 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 ℃, insulation 180～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, insulation 120～360min.
The porous tantalum that adopts preparation method of the present invention to make is specially adapted to the coupling member as load-bearing bone tissue injury or the damaged place of bone.Moreover, described preparation method technique simply, easily control; Whole preparation process is harmless, pollution-free, nonhazardous dust, and human body is had no side effect.And preferentially adopt and can all decompose in sintering process in preparation process, there is no residual binding agent, dispersant, Organic Foam Material etc., will be conducive to guarantee biocompatibility and the biological safety of embedded material.
Described organic binder bond preferably polyethylene alcohol, also can adopt the similar substances such as starch, ethyl cellulose; Described dispersant adopts water, dehydrated alcohol etc., wherein preferred water conventionally.Described Organic Foam Material optimization polyurethane foam can be also the similar substances such as polyether ester foam.
Further feature of the present invention is: adopt its mean diameter to be less than the ta powder that 43 μ m, oxygen content are less than 0.1%, adopting polyvinyl alcohol water solution is that binding agent and water are that dispersant and described tantalum powder are made tantalum powder slurry, Organic Foam Material is polyurethane foam, then vacuum drying is except anhydrating, the porosity of the porous tantalum forming is between 50～70%, pore diameter 150～600 μ m.
Wherein, polyvinyl alcohol is heated to dissolve with distilled water, adopt percentage by weight 2～8% (preferably 4～5%) polyvinyl alcohol water solution and ta powder to make tantalum powder slurry, wherein, it is, in the described polyvinyl alcohol water solution of 1 part, to stir and make starchiness that the ta powder that is 6～9 parts (preferably 7 parts) by weight adds weight; And to be cast in aperture be 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °, and (preferably aperture is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness) polyurethane foam in.
Preferential select mean diameter to be less than 43 μ m, oxygen content to be less than the content that 0.1% ta powder contributes to reduce impurity, to guarantee that material has good mechanical property; Selection aperture is 0.48～0.89mm, density 0.025g/cm
3～0.035g/cm
3, hardness is greater than porosity and the pore diameter that the polyurethane foam of 50 ° contributes to guarantee porous tantalum.Process conditions have been optimized in the such technical finesse of the present invention, will guarantee to implant biocompatibility and the biological safety of porous tantalum material.
The present invention's further feature is on the other hand: dry vacuum keep 10
-2～1Pa vacuum, then, under protective atmosphere, for example vacuum 10
-4～10
-3pa, the ungrease treatment of removing organic binder bond and Organic Foam Material under 400 ℃～800 ℃ conditions of temperature; Sintering processes: vacuum is 10
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1600～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, insulation 220～240min again, with 5～8 ℃/min, be warming up to 2000～2200 ℃, insulation 250～320min, during sintering process insulation, can filling with inert gas protection replace vacuum protection; Finally carry out vacuum annealing processing, wherein vacuum annealing is processed and is referred to that continuation keeps temperature in 1000～1250 ℃ after vacuum-sintering, temperature retention time 1～4 hour, and vacuum is lower than 10
-4～10
-3pa.
Above-mentioned ungrease treatment condition also includes: the speed with 0.5 ℃/min～5 ℃/min is progressively warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 30min～120min;
Vacuum-sintering condition is: 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: low vacuum is in 10
-3pa, with not higher than 25 ℃/min, is not less than 10 ℃/min and gradually falls cooldown rate mode, and to sintered porous bodies segmentation cooling down to 800 ℃, each section of temperature retention time 30min～90min, then cools to room temperature with the furnace;
Vacuum annealing condition also includes: low vacuum is in 10
-4pa, rises to 1000～1250 ℃ with the speed higher than 30 ℃/min not, insulation 4h～6h; To be not less than 5 ℃/min but not to be cooled to room temperature higher than the cooldown rate segmentation of 30 ℃/min soon after first slow, the temperature retention time of each section tapers off and is no more than in 1.5h～3h and selects again.
Further feature is on this basis: 60～100 ℃ of described vacuum drying baking temperatures, 4～8 hours drying times; Described ungrease treatment condition also includes: be progressively warming up to 600～800 ℃; with pure argon gas (99.9999%), pass into formation protective atmosphere; speed with 1～5 ℃/min rises to 400 ℃ from room temperature; insulation 30～60min; speed with 0.5～1.5 ℃/min rises to 600～800 ℃ from 400 ℃; insulation 60～120min, described vacuum-sintering condition is: reciprocal of duty cycle 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 ℃, insulation 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, insulation 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Described vacuum annealing condition also includes: the speed with 15～30 ℃/min rises to 1000～1250 ℃, insulation 240～480min, and vacuum is 10
-4pa～10
-3pa, then be cooled to 1000 ℃ with the speed of 5～10 ℃/min, insulation 90～180min, vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 800 ℃, insulation 60～120min, and low vacuum is in 10
-4pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum is 10
-4pa～10
-3pa.
To vacuum drying, ungrease treatment etc., be wherein the content that contributes to reduce impurity in porous tantalum, improve biocompatibility and biological safety is good and mechanical property; The problem of subsiding that is difficult for to the optimization of Organic Foam Material material with foam framework in solution sintering process; Optimization of process conditions to sintering and annealing steps, the mechanical property that further improves porous tantalum as ductility, reduce the fracture rate of sintering neck.
The porous tantalum material that said method makes, through testing its impurity content lower than 0.5%; This porous tantalum finished product even pore distribution and connection, density 5.00～8.33g/cm
3, porosity 50～70%, pore diameter 150～600 μ m, elastic modelling quantity 2.5～4.0GPa, bending strength 130～150MPa, comprcssive strength 75～88MPa, percentage elongation 9.3%～10.2%.Porous tantalum material of the present invention not only biocompatibility, safety is good, and the special intensity of mechanical property is high, is suitable for very much substituting the osseous tissue at human bearing position.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope analysis figure (SEM figure) of the porous tantalum structure prepared of preparation method of the present invention;
From accompanying drawing, can be observed: the high hole of porous tantalum of the present invention, even pore distribution is communicated with.From accompanying drawing, can find out that porous tantalum of the present invention interconnected pore is conducive to that osteoblast adheres to, differentiation and growth, promote growing into of bone, can strengthen being connected between implant and bone, be beneficial to and realize biological fixation.
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: weighing polyvinyl alcohol 12.5g, puts into the container that 240ml distilled water is housed; Placing it in heats and stir on electric furnace makes it to become polyvinyl alcohol water solution.With 200g balance, weigh mean diameter and be less than the tantalum powder 60g that 43 microns, oxygen content are less than 0.1%, add the cooling polyvinyl alcohol water solution of 50ml, be uniformly mixed, make it to become tantalum powder slurry.(average pore size is 0.48mm, density 0.025g/cm to select 10 * 10 * 30mm cellular polyurethane foam
3, 50 ° of hardness) and put into wherein cast, until polyurethane foam hole is filled with tantalum powder slurry, the polyurethane foam that goes out to be filled tantalum powder slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 60 ℃ of baking temperatures, 8 hours drying times, vacuum keep 1Pa.Ungrease treatment: low vacuum is in 10
-4pa, 600 ℃ of temperature, temperature retention time 120 minutes.Vacuum-sintering: described sintering step is that 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; The protection of sintering process applying argon gas, removes surface dirt and dirt after taking-up product, 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 0.5% finished product, its even pore distribution and connection, density 6.7g/cm
3, porosity 56%, hole average diameter 300 μ m, elastic modelling quantity 3.0GPa, bending strength 150MPa, comprcssive strength 82MPa, percentage elongation 9.8%.
Embodiment 2: weighing polyvinyl alcohol 10g, puts into the container that 200ml distilled water is housed; Placing it in heats and stir on electric furnace makes it to become polyvinyl alcohol water solution.With 200g balance, weigh mean diameter and be less than the tantalum powder 40g that 43 microns, oxygen content are less than 0.1%, add 32ml polyvinyl alcohol water solution, be uniformly mixed, make it to become tantalum powder slurry.(average pore size is 0.56mm, density 0.030g/cm to select 10 * 10 * 25mm cellular polyurethane foam
3, 60 ° of hardness) and put into wherein cast, until polyurethane foam hole is filled with tantalum powder slurry, the polyurethane foam that goes out to be filled tantalum powder slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 100 ℃ of baking temperatures, 4 hours drying times, vacuum keep 10
-2pa.Ungrease treatment: vacuum 10
-4pa, 800 ℃ of temperature, temperature retention time 120 minutes.Vacuum-sintering: described sintering step is that vacuum is 10
-4pa～10
-3pa; with 10 ℃/min, be warming up to 1600 ℃, be incubated 240min, with stove, be chilled to 200～300 ℃; with 20 ℃/min, be warming up to 1500 ℃, insulation 180min again; with 5 ℃/min, be warming up to 2000～2200 ℃, insulation 360min; 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 0.5% finished product, its even pore distribution and connection, density 8.0g/cm
3, porosity 66%, hole average diameter 400 μ m, elastic modelling quantity 3.5GPa, bending strength 140MPa, comprcssive strength 75MPa, percentage elongation 10.1%.
Embodiment 3: weighing polyvinyl alcohol 11g, puts into the container that 220ml distilled water is housed; Placing it in heats and stir on electric furnace makes it to become polyvinyl alcohol water solution.With 200g balance, weigh mean diameter and be less than the tantalum powder 45g that 43 microns, oxygen content are less than 0.1%, add 36ml polyvinyl alcohol water solution, be uniformly mixed, make it to become tantalum powder slurry.(average pore size is 0.70mm, density 0.035g/cm to select 8 * 8 * 25mm cellular polyurethane foam
3, 70 ° of hardness) and put into wherein cast, until polyurethane foam hole is filled with tantalum powder slurry, the polyurethane foam that goes out to be filled tantalum powder slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 80 ℃ of baking temperatures, 6 hours drying times, vacuum keep 10
-1pa.Ungrease treatment: vacuum 10
-3pa, 700 ℃ of temperature, temperature retention time 90 minutes.Vacuum-sintering: described sintering step is that vacuum is 10
-4pa～10
-3pa; with 20 ℃/min, be warming up to 1800 ℃, be incubated 120min, with stove, be chilled to 200～300 ℃; with 10 ℃/min, be warming up to 1800 ℃, insulation 240min again; with 10 ℃/min, be warming up to 2000～2200 ℃, insulation 120min; 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 0.5% finished product, its even pore distribution and connection, density 5.0g/cm
3, porosity 70%, hole average diameter 450 μ m, elastic modelling quantity 5.5GPa, bending strength 130MPa, comprcssive strength 86MPa, percentage elongation 9.5%.
Embodiment 4: weighing polyvinyl alcohol 12g, puts into the container that 230ml distilled water is housed; Placing it in heats and stir on electric furnace makes it to become polyvinyl alcohol water solution.With 200g balance, weigh mean diameter and be less than the tantalum powder 50g that 43 microns, oxygen content are less than 0.1%, add 40ml polyvinyl alcohol water solution, be uniformly mixed, make it to become tantalum powder slurry.(aperture is 0.60mm, density 0.027g/cm to select 12 * 12 * 30mm cellular polyurethane foam
3, 80 ° of hardness) and put into wherein cast, until polyurethane foam hole is filled with tantalum powder slurry, the polyurethane foam that goes out to be filled tantalum powder slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 90 ℃ of baking temperatures, 5 hours drying times, vacuum keep 1Pa.Ungrease treatment: vacuum 10
-4～10
-3pa, 500 ℃ of temperature, temperature retention time 120 minutes.Vacuum-sintering: described sintering step is that vacuum is 10
-4pa～10
-3pa; with 13 ℃/min, be warming up to 1700 ℃, be incubated 210min, with stove, be chilled to 200～300 ℃; with 15 ℃/min, be warming up to 1600 ℃, insulation 210min again; with 8 ℃/min, be warming up to 2000～2200 ℃, insulation 260min; 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 0.5% finished product, its even pore distribution and connection, density 8.33g/cm
3, porosity 50%, hole average diameter 350 μ m, elastic modelling quantity 2.7GPa, bending strength 142MPa, comprcssive strength 81MPa, percentage elongation 9.8%.
Embodiment 5: a kind of porous tantalum, and it be take particle diameter and is less than 43 μ m, oxygen content to be less than 0.1% ta powder be raw material, and the polyvinyl alcohol water solution of take is made tantalum powder slurry as binder solution, and is cast in polyurethane foam carrier; Then vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, the polyurethane foam of selecting, its aperture is 0.72～0.56mm, density 0.025g/cm
3, 50 °～80 ° of hardness;
Vacuum drying: vacuum keep 10
-2～1Pa, to remove the moisture in the polyurethane foam of filling with tantalum powder slurry;
Ungrease treatment: under inert gas shielding atmosphere or vacuum 10
-4～10
-3pa, 400 ℃～800 ℃ of temperature, and temperature retention time 30～120 minutes is to remove polyvinyl alcohol and polyurethane foam wherein;
Vacuum-sintering: described sintering step is that vacuum is 10
-4pa～10
-3pa, is warming up to 1650 ℃, is incubated 190min, with stove, is chilled to 200～300 ℃ with 16 ℃/min, then is warming up to 1800 ℃, insulation 200min with 18 ℃/min, with 6 ℃/min, is warming up to 2000～2200 ℃, insulation 270min;
Vacuum annealing: after vacuum-sintering, continue to keep temperature in 1000～1250 ℃, temperature retention time 1～4 hour, vacuum is 10
-4～10
-3pa, to carry out stress relief annealing processing; 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 0.5% finished product, its even pore distribution and connection, density 6.3g/cm
3, porosity 62%, hole average diameter 220 μ m, elastic modelling quantity 3.3GPa, bending strength 136MPa, comprcssive strength 84MPa, percentage elongation 10.2%.
In the method providing at above-described embodiment 5, 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 | 6 | 7 | 8 |
| Density (g/cm 3) | 6.9 | 7.5 | 7.8 |
| Porosity (%) | 50 | 64 | 70 |
| Aperture (μ m) | 170 | 410 | 280 |
| Elastic modelling quantity (GPa) | 2.6 | 3.5 | 4.0 |
| Bending strength (MPa) | 140 | 130 | 150 |
| Comprcssive strength (MPa) | 80 | 88 | 76 |
| Percentage elongation (%) | 9.5 | 9.8 | 10.0 |
Claims (6)
1. a method of preparing medical porous tantalum embedded material, adopt foam impregnation method sintering to form, it is characterized in that: the solution being mixed with organic binder bond and dispersant and tantalum powder are made tantalum powder slurry, and be cast in Organic Foam Material, dipping is until Organic Foam Material hole is filled with tantalum powder slurry, then be dried and remove the dispersant in the Organic Foam Material that is cast with tantalum powder slurry, under inert gas shielding atmosphere, ungrease treatment is to remove organic binder bond and Organic Foam Material, under vacuum, sintering makes porous sintered body, cooling, anneal under vacuum again heat treatment and conventional post processing makes porous tantalum, 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 ℃, insulation 180～240min again, with 5～10 ℃/min, be warming up to 2000～2200 ℃, insulation 120～360min.
2. the method for claim 1, is characterized in that: described tantalum powder is that mean diameter is less than the ta powder that 43 μ m, oxygen content are less than 0.1%; Described organic binder bond is polyvinyl alcohol, and described dispersant is water, is mixed with polyvinyl alcohol water solution and described tantalum powder and makes tantalum powder slurry; Described Organic Foam Material is aperture 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, hardness is more than or equal to 50
0polyurethane foam.
3. method as claimed in claim 2, is characterized in that: the weight percent concentration of described polyvinyl alcohol water solution is 2～8%; It is 6～9 parts that described tantalum powder and polyvinyl alcohol water solution obtain weight part ratio: 1 part; Described polyurethane foam aperture is 0.56～0.72mm, density 0.025g/cm
3, hardness 50
0～80
0.
4. the method as described in claim 1,2 or 3, is characterized in that: described dry vacuum keep 10
-2～1Pa vacuum, then under protective atmosphere, vacuum 10
-4～10
-3pa, the ungrease treatment of removing organic binder bond and Organic Foam Material under 400 ℃～800 ℃ conditions of temperature; Sintering processes: vacuum is 10
-4pa～10
-3pa, with 12～15 ℃/min, be warming up to 1600～1800 ℃, be incubated 180～200min, with stove, be chilled to 200～300 ℃, with 16～19 ℃/min, be warming up to 1500～1800 ℃, insulation 220～240min again, with 5～8 ℃/min, be warming up to 2000～2200 ℃, insulation 250～320min; Finally carry out vacuum annealing heat treatment, vacuum annealing heat treatment refers to and after vacuum-sintering, continues to keep temperature in 1000～1250 ℃, temperature retention time 1～4 hour, and vacuum is 10
-4～10
-3pa.
5. the method as described in claim 1,2 or 3, is characterized in that: described ungrease treatment condition is: the speed with 0.5 ℃/min～5 ℃/min is progressively warming up to 400～800 ℃, with argon, passes into and forms protective atmosphere and be incubated 30min～120min;
Vacuum-sintering condition is: 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 is: low vacuum is in 10
-3pa, with not higher than 25 ℃/min, is not less than 10 ℃/min and gradually falls cooldown rate mode, and to sintered porous bodies segmentation cooling down to 800 ℃, each section of temperature retention time 30min～90min, then cools to room temperature with the furnace;
Vacuum annealing heat-treat condition is: low vacuum is in 10
-4pa, rises to 1000～1250 ℃ with the speed higher than 30 ℃/min not, insulation 4h～6h; To be not less than 5 ℃/min but not to be cooled to room temperature higher than the cooldown rate segmentation of 30 ℃/min soon after first slow, the temperature retention time of each section tapers off and is no more than 3h again.
6. the method as described in claim 1,2 or 3, is characterized in that: 60～100 ℃ of described dry baking temperatures, 4～8 hours drying times; Described ungrease treatment condition is: be progressively warming up to 600～800 ℃; pure argon gas with 99.9999% passes into formation protective atmosphere; speed with 1～5 ℃/min rises to 400 ℃ from room temperature; insulation 30～60min; speed with 0.5～1.5 ℃/min rises to 600～800 ℃ from 400 ℃; insulation 60～120min, vacuum-sintering condition is: 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 is: vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 1500～1600 ℃, insulation 30～60min; Speed with 12～20 ℃/min is cooled to 1200～1250 ℃, insulation 60～90min; Speed with 10～20 ℃/min is cooled to 800 ℃, then furnace cooling; Vacuum annealing heat-treat condition is: the speed with 15～30 ℃/min rises to 1000～1250 ℃, insulation 240～480min, and vacuum is 10
-4pa～10
-3pa, then be cooled to 1000 ℃ with the speed of 5～10 ℃/min, insulation 90～180min, vacuum is 10
-4pa～10
-3pa; Speed with 10～20 ℃/min is cooled to 800 ℃, insulation 60～120min, and low vacuum is in 10
-4pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum is 10
-4pa～10
-3pa.
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|---|---|---|---|
| CN201110301063.7A CN102796905B (en) | 2011-09-29 | 2011-09-29 | Method for preparing medical porous titanium implant material |
| PCT/CN2012/082230 WO2013044834A1 (en) | 2011-09-29 | 2012-09-27 | Preparation method for medical porous tantalum implant material |
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|---|---|---|---|
| CN201110301063.7A CN102796905B (en) | 2011-09-29 | 2011-09-29 | Method for preparing medical porous titanium implant material |
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| CN102796905B true CN102796905B (en) | 2014-05-07 |
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Citations (2)
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|---|---|---|---|---|
| US5282861A (en) * | 1992-03-11 | 1994-02-01 | Ultramet | Open cell tantalum structures for cancellous bone implants and cell and tissue receptors |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
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| US7635447B2 (en) * | 2006-02-17 | 2009-12-22 | Biomet Manufacturing Corp. | Method and apparatus for forming porous metal implants |
| 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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2011
- 2011-09-29 CN CN201110301063.7A patent/CN102796905B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5282861A (en) * | 1992-03-11 | 1994-02-01 | Ultramet | Open cell tantalum structures for cancellous bone implants and cell and tissue receptors |
| CN101549175A (en) * | 2009-05-15 | 2009-10-07 | 中南大学 | Method for preparation of pore heterogeneous distribution bionic bone material |
Non-Patent Citations (2)
| Title |
|---|
| 烧结温度对泡沫铌力学性能及微观组织的影响;节云峰等;《中国有色金属学报》;20101031;第20卷(第10期);第2014-2018页 * |
| 节云峰等.烧结温度对泡沫铌力学性能及微观组织的影响.《中国有色金属学报》.2010,第20卷(第10期),第2014-2018页. |
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