CN102796889B - Preparation method of medical porous tantalum material for replacing weight-bearing bone tissues of human body - Google Patents
Preparation method of medical porous tantalum material for replacing weight-bearing bone tissues of human body Download PDFInfo
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- CN102796889B CN102796889B CN201110295810.0A CN201110295810A CN102796889B CN 102796889 B CN102796889 B CN 102796889B CN 201110295810 A CN201110295810 A CN 201110295810A CN 102796889 B CN102796889 B CN 102796889B
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 38
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 32
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000005238 degreasing Methods 0.000 claims abstract description 3
- 238000009413 insulation Methods 0.000 claims description 41
- 238000010792 warming Methods 0.000 claims description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 17
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 13
- 239000011496 polyurethane foam Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 12
- 239000006261 foam material Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 230000011218 segmentation Effects 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 24
- 239000006260 foam Substances 0.000 abstract description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 22
- 239000011148 porous material Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000001413 cellular effect Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 238000005457 optimization Methods 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects 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
- 238000001914 filtration Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 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
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 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
Classifications
-
- 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
-
- 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
- B22F3/10—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
-
- 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
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- 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)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a preparation method of a medical porous tantalum material for replacing weight-bearing bone tissues of human body. The preparation method comprises the following steps of: dosing polyvinyl alcohol water solution and tantalum powder into slurry; injecting the slurry into organic foam via vibration pressurization; and carrying out the steps of drying, degreasing, sintering, cooling and heat treatment to obtain the medical porous tantalum material, wherein the quality concentration of the polyvinyl alcohol water solution is 2-8%; the vibration frequency is 20-80 times per minute; and the sintering step comprises the following processes of: under the vacuum degree of 10-4Pa-10-3Pa, raising the temperature to 1500-1800 DEG C at a speed of 10-20 DEGC/min, holding the temperature for 120-240min, cooling along a furnace to 200-300 DEG C, raising the temperature to 1500-1800 DEG C at a speed of 10-20 DEG C/min, holding the temperature for 180-240min, raising the temperature to 2000-2200 DEG C at a speed of 5-10 DEG C/min and holding the temperature for 120-360min. The porous tantalum material prepared in the invention is a medical implanting material which is particularly suitable for replacing the weight-bearing bone tissues; and at the same time, the biological compatibility and mechanical property are ensured.
Description
Technical field
The present invention relates to a kind of preparation method of porous medical metal implanted material, particularly relate to a kind of preparation method of medical embedded material porous tantalum of alternative human bearing's osseous tissue.
Background technology
Porous medical metal implanted material has treatment osseous tissue wound, bone formation necrosis and alternative dense bone tissue as important and special purposes such as teeth, and existing this common class material has porous metal stainless steel, porous metal titanium etc.As the porous embedded material of osseous tissue wound and the use of bone formation necrosis therapeutic, its porosity should reach 30～80%, and hole is preferably all communicated with and is uniformly distributed, or make it as required both consistent with the bone growth of human body, alleviate again the weight of material itself, implanted use to be applicable to human body.
And refractory metals tantalum, because it has outstanding biocompatibility, its porous material is expected to the conventional medical metallic biomaterial such as aforementioned as an alternative.Due to metal tantalum to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, tantalum is goed deep into as the further of body implanting material cognition, and to human body, implantation becomes more and more urgent by the demand of porous metal tantalum material to people, also more and more higher to its requirement.Wherein, as the medical embedded metal tantalum of porous, if can have the very high physical and mechanical properties that is uniformly distributed open pore and adapts with human body, it is expected to as a kind of novel osseous tissue equivalent material.
As medical embedded porous metal material just as porous metal material be take powder sintering as main working method like that substantially, in particular for obtain porosity communication and equally distributed porous metal foam structure adopt metal-powder slurry in the powder sintering dipping on Organic Foam Material afterwards the dry knot that reburns to be called for short foam impregnation method in the majority.About powder sintered obtained porous metal material conventionally its Metal Mechanic Property be not fine, its major cause is the problem of subsiding how arranging in technique in the support of pore-forming medium and elimination relation, metal powder sintered process.And in known bibliographical information, all there is no good solution and laissez-faire nature.
Adopt metal powder sintered legal system to make the bibliographical information of porous tantalum little, particularly to obtain medical embedded material with almost not having as the porous tantalum powder sintering bibliographical information of object.Can reference be that publication number is CN200510032174, title " three-dimensional through hole or part hole porous metal foam connected with each other and preparation method thereof " and CN200710152394, title " a kind of porous foam tungsten and preparation method thereof ".But its porous metal that obtain or for filtering material use, or share for aerospace and other high-temperature field but not use as medical metal implanted material, moreover also non-porous tantalum of the porous metal 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 susceptor.This porous tantalum is made up of pure business tantalum, it carries out carbon skeleton that thermal destruction obtains as support take polyurethane precursor, this carbon skeleton is multiple dodecahedron, it in it, is mesh-like structure, entirety spreads all over micropore, porosity can be up to 98%, then commercially pure tantalum is attached on carbon skeleton to form porous metal microstructure, referred to as chemical deposition by the method for chemical vapour deposition, infiltration.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtains is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight accounts for 1% left and right.Document is further recorded, the ultimate compression strength 50～70MPa of this porous material, Young's modulus 2.5～3.5GPa, tensile strength 63MPa, amount of plastic deformation 15%.But using it as dense bone tissue as the porous tantalum of the medical embedded materials such as tooth, 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, the cutting of such as profiled member etc.Also all there is such deficiency in the same product obtaining in aforesaid metal powder sintered method.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of good biocompatibility, medical porous tantalum embedded material that mechanical strength is good, this preparation method is easy and simple to handle, be suitable for commercial scale production.
The object of the invention is to realize by following technique means:
Substitute the preparation method of the medical porous tantalum material of human bearing's osseous tissue, it is characterized in that: the PVOH aqueous solution and tantalum powder are made into slurry, described slurry is injected Organic Foam Material by vibrations pressurizations, then drying, degreasing, sintering, cooling and heat treatment step make medical porous tantalum material; The mass concentration of described polyvinyl alcohol water solution is 2～8%, and described vibration frequency is 20～80 beats/min; Described sintering step is that vacuum tightness is 10
-4pa～10
-3pa, be warming up to 1500～1800 ℃, be incubated 120～240min, be chilled to 200～300 ℃ with stove with 10～20 ℃/min, be warming up to 1500～1800 ℃, insulation 180～240min with 10～20 ℃/min again, be warming up to 2000～2200 ℃, insulation 120～360min with 5～10 ℃/min.
Contriver finds in long-term R & D process, adopts vibrations pressurization of the present invention effectively to avoid tantalum powder to add the dispersiveness easily occurring in cavernous body bad, thereby makes its skewness have a strong impact on the problem of the mechanical property of final porous tantalum material.In the R&D process of medical porous metallic substance, medical porous metallic substance is the material of load bone tissue as an alternative, require that its porosity is large, tissue is just easily grown into like this, thereby good biocompatibility brings into play its effect fully, but porosity is larger, aperture is larger, mechanical property just can not be guaranteed as intensity, toughness; Otherwise mechanical property has been got well and has easily been made that porosity is too small, biocompatibility is bad, the also excessive discomfort that causes of density; The syntheti c route of medical porous tantalum is numerous, but contriver has creatively proposed employing above-mentioned steps, technique is prepared medical porous tantalum embedded material, and the above-mentioned sintering process particularly adopting, makes idiosome become heating element, more even, thorough thereby sintering obtains; Porous tantalum material that it makes through its foreign matter content of test can be lower than 0.2%, its biocompatibility and biological safety good, density reachable 5.00～8.33g/cm
3, porosity can reach 50～70%, and pore diameter can reach 150～500 μ m; Young's modulus can reach that 2.5～4.0Gpa, unit elongation reach 9.3～11.0%, flexural strength can reach 120～150Mpa, ultimate compression strength can reach 80～90Mpa, its biocompatibility, obdurability are close to the characteristic of human bearing's osseous tissue, and the porous tantalum that the present invention makes is suitable for substituting the medical embedded material of load bone tissue very much.Meanwhile, described preparation method's technique simply, easily control; Whole preparation process is harmless, pollution-free, toxicological harmless dust, and human body is had no side effect, and is suitable for commercial scale production.Moreover, in preparation process, preferentially adopt and can all decompose in sintering process, there is no residual reagent and Organic Foam Material etc., will be conducive to guarantee biocompatibility and the biological safety of embedded material.
Further feature of the present invention is: adopt its median size to be less than the ta powder that 43 μ m, oxygen level are less than 0.1%, adopting polyvinyl alcohol water solution is that binding agent and water are that dispersion agent and described tantalum powder are made tantalum powder slurry, Organic Foam Material is polyurethane foam, and then vacuum-drying is except anhydrating.It is 10 that vacuum environment of the present invention preferably adopts vacuum tightness
-4pa～10
-3the vacuum condition of Pa.
Wherein, polyvinyl alcohol is heated to dissolve with distilled water, adopt polyvinyl alcohol water solution and the ta powder that mass percent concentration is 4～5% 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 adopt vibrations pressurization (vibration frequency is preferably 60 times/min, pressure is preferably 0.1MPa) to note 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.
Further preferably, above-mentioned tantalum powder slurry vibrations pressurization is injected after Organic Foam Material, also surface uniform spray above-mentioned polyvinyl alcohol water solution, the weight part ratio of quantity for spray and above-mentioned ta powder is 1: 6.
Preferential select median size to be less than 43 μ m, oxygen level 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.
The present invention's further feature is on the other hand: above-mentioned skimming treatment condition also includes: the speed with 0.5 ℃/min～5 ℃/min is progressively warming up to 400～800 ℃, passes into and forms protective atmosphere and be incubated 30min～120min with argon gas;
Vacuum sintering condition also includes: for make idiosome sintering obtain more evenly, thorough, make the medical porous tantalum mechanics of materials intensity that makes higher, it is 10 that above-mentioned sintering step is preferably vacuum tightness
-4pa～10
-3pa, be warming up to 1500～1800 ℃, be incubated 180～200min, be chilled to 200～300 ℃ with stove with 12～15 ℃/min, be warming up to 1500～1800 ℃, insulation 220～240min with 16～19 ℃/min again, be warming up to 2000～2200 ℃, insulation 250～320min with 5～8 ℃/min;
Cooling conditions after vacuum sintering also includes: vacuum tightness is not less than 10
-3pa, with not higher than 25 ℃/min, is not less than 10 ℃/min and gradually falls rate of cooling mode, and to sintered porous bodies segmentation cooling down to 800 ℃, each section of soaking time 30min～90min, then cools to normal temperature with the furnace;
Vacuum annealing condition also includes: vacuum tightness is not less than 10
-4pa, not rise to 1000～1250 ℃ higher than the speed of 30 ℃/min, insulation 4h～6h; Again with after first slow soon to be not less than 5 ℃/min but be not cooled to room temperature higher than the rate of cooling segmentation of 30 ℃/min, the soaking time of each section tapers off and is no more than in 1.5h～3h and selects.
Further feature is on this basis: described vacuum drying vacuum tightness is 10
-2～1Pa, 60～100 ℃ of drying temperatures, 4～8 hours time of drying; Described skimming treatment condition also includes: be progressively warming up to 600～800 ℃; pass into formation protective atmosphere with pure argon gas (99.9999%); 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 also includes: vacuum tightness is 10
-4pa～10
-3pa, is warming up to 1800 ℃, is incubated 200min, is chilled to 200～300 ℃ with stove with 13 ℃/min, then is warming up to 1800 ℃, insulation 230min with 17 ℃/min, is warming up to 2000～2200 ℃, insulation 300min with 7 ℃/min; Cooling conditions after vacuum sintering also includes: vacuum tightness is 10
-4pa～10
-3pa; Be cooled to 1500～1600 ℃ with the speed of 10～20 ℃/min, insulation 30～60min; Be cooled to 1200～1250 ℃ with the speed of 12～20 ℃/min, insulation 60～90min; Be cooled to 800 ℃ with the speed of 10～20 ℃/min, then furnace cooling; Described vacuum annealing condition also includes: rise to 1000～1250 ℃ with the speed of 15～30 ℃/min, and insulation 240～480min, vacuum tightness is 10
-4pa～10
-3pa, then be cooled to 1000 ℃ with the speed of 5～10 ℃/min, insulation 90～180min, vacuum tightness is 10
-4pa～10
-3pa; Be cooled to 800 ℃ with the speed of 10～20 ℃/min, insulation 60～120min, low vacuum is in 10
-4pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum tightness is 10
-4pa～10
-3pa.
Be wherein the content that contributes to reduce impurity in porous tantalum to vacuum-drying, skimming treatment etc., 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; To the optimization of process conditions of sintering and annealing steps, with the mechanical property that further improves porous tantalum as ductility etc.
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 12.2g, 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.Weigh median size with 200g balance and be less than the tantalum powder 60g that 43 microns, oxygen level are less than 0.1%, add the cooling polyvinyl alcohol water solution of 50ml, be uniformly mixed, make it to become tantalum powder slurry.(mean pore size is 0.48mm, density 0.025g/cm to select 10 × 10 × 30mm cellular polyurethane foam
3, 50 ° of hardness), under 55 times/min, 0.1Mpa, shake pressurization described tantalum powder slurry is poured into wherein.Dry in vacuum drying oven, 60 ℃ of drying temperatures, 8 hours time of drying, vacuum keep 1Pa.Skimming treatment: low vacuum is in 10
-4pa, 600 ℃ of temperature, soaking time 120 minutes.Vacuum sintering: vacuum tightness is 10
-4pa; be warming up to 1800 ℃, be incubated 120min, be chilled to 200～300 ℃ with stove with 10 ℃/min; be warming up to 1800 ℃, insulation 240min with 20 ℃/min again; be warming up to 2000～2200 ℃, insulation 360min with 5 ℃/min; the protection of sintering process applying argon gas; after taking out product, remove surface dirt and dirt, the sample making carries out conventional aftertreatment again and obtains porous tantalum finished product.
Contriver detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its foreign matter content is lower than 0.5% finished product, its even pore distribution and connection, density 6.3g/cm
3, porosity 65%, hole mean diameter 290 μ m, Young's modulus 2.8GPa, flexural strength 124MPa, ultimate compression strength 86Mpa, unit elongation 9.6%.
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.Weigh median size with 200g balance and be less than the tantalum powder 40g that 43 microns, oxygen level are less than 0.1%, add 32ml polyvinyl alcohol water solution, be uniformly mixed, make it to become tantalum powder slurry.(mean pore size is 0.56mm, density 0.030g/cm to select 10 × 10 × 25mm cellular polyurethane foam
3, 60 ° of hardness), under 60 times/min, 0.08Mpa, shake pressurization described tantalum powder slurry is poured into wherein.Dry in vacuum drying oven, 100 ℃ of drying temperatures, 4 hours time of drying, vacuum keep 10
-2pa.Skimming treatment: vacuum tightness 10
-4pa, 800 ℃ of temperature, soaking time 120 minutes.Vacuum sintering: vacuum tightness is 10
-3pa; be warming up to 1500 ℃, be incubated 240min, be chilled to 200～300 ℃ with stove with 20 ℃/min; be warming up to 1500 ℃, insulation 180min with 10 ℃/min again; be warming up to 2000～2200 ℃, insulation 120min with 10 ℃/min; the protection of sintering process applying argon gas; after taking out product, remove surface dirt and dirt, the sample making carries out conventional aftertreatment again and obtains porous tantalum finished product.
Contriver detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its foreign matter content is lower than 0.5% finished product, its even pore distribution and connection, density 6.5g/cm
3, porosity 55%, hole mean diameter 130 μ m, Young's modulus 3.2GPa, flexural strength 142MPa, ultimate compression strength 88Mpa, unit elongation 9.4%.
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.Weigh median size with 200g balance and be less than the tantalum powder 45g that 43 microns, oxygen level are less than 0.1%, add 36ml polyvinyl alcohol water solution, be uniformly mixed, make it to become tantalum powder slurry.(mean pore size is 0.70mm, density 0.035g/cm to select 8 × 8 × 25mm cellular polyurethane foam
3, 70 ° of hardness), under 80 times/min, 0.2Mpa, shake pressurization described tantalum powder slurry is poured into wherein.Dry in vacuum drying oven, 80 ℃ of drying temperatures, 6 hours time of drying, vacuum keep 10
-1pa.Skimming treatment: vacuum tightness 10
-3pa, 700 ℃ of temperature, soaking time 90 minutes.Vacuum sintering: vacuum tightness is 10
-4pa; be warming up to 1600 ℃, be incubated 180min, be chilled to 200～300 ℃ with stove with 12 ℃/min; be warming up to 1700 ℃, insulation 220min with 19 ℃/min again; be warming up to 2000～2200 ℃, insulation 320min with 8 ℃/min; the protection of sintering process applying argon gas; after taking out product, remove surface dirt and dirt, the sample making carries out conventional aftertreatment again and obtains porous tantalum finished product.
Contriver detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its foreign matter content is lower than 0.5% finished product, its even pore distribution and connection, density 6.5g/cm
3, porosity 55%, hole mean diameter 130 μ m, Young's modulus 3.2GPa, flexural strength 133MPa, ultimate compression strength 85Mpa, unit elongation 9.4%.
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.Weigh median size with 200g balance and be less than the tantalum powder 50g that 43 microns, oxygen level 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), under 23 times/min, 0.1Mpa, shake pressurization described tantalum powder slurry is poured into wherein.Dry in vacuum drying oven, 90 ℃ of drying temperatures, 5 hours time of drying, vacuum keep 1Pa.Skimming treatment: vacuum tightness 10
-4～10
-3pa, 500 ℃ of temperature, soaking time 120 minutes.Vacuum sintering: vacuum tightness is 10
-4pa; be warming up to 1700 ℃, be incubated 200min, be chilled to 200～300 ℃ with stove with 15 ℃/min; be warming up to 1650 ℃, insulation 190min with 16 ℃/min again; be warming up to 2000～2200 ℃, insulation 250min with 6 ℃/min; the protection of sintering process applying argon gas; after taking out product, remove surface dirt and dirt, the sample making carries out conventional aftertreatment again and obtains porous tantalum finished product.
Contriver detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its foreign matter content is lower than 0.5% finished product, its even pore distribution and connection, density 7.5g/cm
3, porosity 63%, hole mean diameter 250 μ m, Young's modulus 3.6GPa, flexural strength 122MPa, ultimate compression strength 70Mpa, unit elongation 10.2%.
Embodiment 5: a kind of porous tantalum, it is less than 43 μ m, oxygen level take particle diameter and is less than 0.1% ta powder as raw material, make tantalum powder slurry take polyvinyl alcohol water solution as binder solution, and vibrations add pressure injection in polyurethane foam carrier, then at the above-mentioned polyvinyl alcohol water solution of surface spraying; Carrying out vacuum-drying, skimming treatment, vacuum sintering, vacuum annealing and conventional aftertreatment makes again.
Wherein, the polyurethane foam of selecting, its aperture is 0.72～0.56mm, density 0.025g/cm
3, 50 °～80 ° of hardness;
Vibrations pressurization: 23 times/min of frequency, 0.1Mpa;
Vacuum-drying: vacuum keep 10
-2～1Pa, to remove the moisture in the polyurethane foam that fills tantalum powder slurry;
Skimming treatment: under protection of inert gas atmosphere or vacuum tightness 10
-4～10
-3pa, 400 ℃～800 ℃ of temperature, and soaking time 30～120 minutes is to remove polyvinyl alcohol and polyurethane foam wherein;
Vacuum sintering: vacuum tightness is 10
-4pa, is warming up to 1800 ℃, is incubated 200min, is chilled to 200～300 ℃ with stove with 13 ℃/min, then is warming up to 1700 ℃, insulation 230min with 17 ℃/min, is warming up to 2000～2200 ℃, insulation 300min, the protection of sintering process applying argon gas with 7 ℃/min;
Vacuum annealing: after vacuum sintering, continue to keep temperature in 1000～1250 ℃, soaking time 1～4 hour, vacuum tightness is 10
-4～10
-3pa, to carry out stress relief annealing processing; The sample making carries out conventional aftertreatment again and obtains porous tantalum finished product.
Contriver detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous tantalum finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: its foreign matter content is lower than 0.5% finished product, its even pore distribution and connection, density 7.6g/cm
3, porosity 67%, hole mean diameter 400 μ m, Young's modulus 3.2GPa, flexural strength 150MPa, ultimate compression strength 90Mpa, unit elongation 10.0%.
In the method providing at above-described embodiment 5, we can also do other to wherein each kind of condition and select can obtain equally porous tantalum of the present invention.
Gained porous tantalum finished product is pressed preceding method and is detected:
| Embodiment | 6 | 7 | 8 | 9 |
| Density (g/cm 3) | 5.36 | 5.02 | 6.73 | 8.33 |
| Porosity (%) | 61 | 70 | 55 | 64 |
| (μ m) in aperture | 161 | 338 | 240 | 467 |
| Young's modulus (GPa) | 2.6 | 3.6 | 4.0 | 2.9 |
| Flexural strength (MPa) | 123 | 145 | 137 | 129 |
| Ultimate compression strength (MPa) | 80 | 83 | 90 | 86 |
| Unit elongation (%) | 9.3 | 10.8 | 11.0 | 9.7 |
Claims (10)
1. substitute the preparation method of the medical porous tantalum material of human bearing's osseous tissue, it is characterized in that: polyvinyl alcohol water solution and tantalum powder are made into slurry, described slurry is injected Organic Foam Material by vibrations pressurizations, then drying, degreasing, sintering, cooling and heat treatment step make medical porous tantalum material; The mass concentration of described polyvinyl alcohol water solution is 2～8%, and described vibration frequency is 20～80 beats/min; Described sintering step is that vacuum tightness is 10
-4pa～10
-3pa, be warming up to 1500～1800 ℃, be incubated 120～240min, be chilled to 200～300 ℃ with stove with 10～20 ℃/min, be warming up to 1500～1800 ℃, insulation 180～240min with 10～20 ℃/min again, be warming up to 2000～2200 ℃, insulation 120～360min with 5～10 ℃/min.
2. preparation method as claimed in claim 1, is characterized in that: described tantalum powder is that median size is less than the ta powder that 43 μ m, oxygen level are less than 0.1%, and described Organic Foam Material is aperture 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, the polyurethane foam that hardness is greater than 50 °.
3. preparation method as claimed in claim 2, is characterized in that: the mass percent concentration of described polyvinyl alcohol water solution is 4～5%, and the weight part ratio of ta powder and described polyvinyl alcohol water solution is 6～9:1.
4. preparation method as claimed in claim 3, is characterized in that: described vibration frequency is that 60 times/min, pressure are 0.1Mpa; Described polyurethane foam is aperture 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness; The weight part ratio of ta powder and described polyvinyl alcohol water solution is 7:1.
5. preparation method as claimed in claim 1 or 2, is characterized in that: above-mentioned tantalum powder slurry vibrations pressurization is injected after Organic Foam Material, also surface uniform spray described polyvinyl alcohol water solution, the weight part ratio of quantity for spray and described tantalum powder is 1:6.
6. preparation method as claimed in claim 3, is characterized in that: above-mentioned tantalum powder slurry vibrations pressurization is injected after Organic Foam Material, also surface uniform spray described polyvinyl alcohol water solution, the weight part ratio of quantity for spray and described tantalum powder is 1:6.
7. preparation method as claimed in claim 4, is characterized in that: above-mentioned tantalum powder slurry vibrations pressurization is injected after Organic Foam Material, also surface uniform spray described polyvinyl alcohol water solution, the weight part ratio of quantity for spray and described ta powder is 1:6.
8. preparation method as claimed in claim 1 or 2, is characterized in that: described being dried is in vacuum tightness 10
-2under～1Pa, carry out;
Described skimming treatment condition also includes: the speed with 0.5 ℃/min～5 ℃/min is progressively warming up to 400～800 ℃, passes into and forms protective atmosphere and be incubated 30min～120min with argon gas;
Vacuum sintering condition also includes: 10
-4pa～10
-3pa, be warming up to 1500～1800 ℃, be incubated 180～200min, be chilled to 200～300 ℃ with stove with 12～15 ℃/min, be warming up to 1500～1800 ℃, insulation 220～240min with 16～19 ℃/min again, be warming up to 2000～2200 ℃, insulation 250～320min with 5～8 ℃/min;
Cooling conditions after vacuum sintering also includes: vacuum tightness is not less than 10
-3pa, with not higher than 25 ℃/min, is not less than 10 ℃/min and gradually falls rate of cooling mode, and to sintered porous bodies segmentation cooling down to 800 ℃, each section of soaking time 30min～90min, then cools to normal temperature with the furnace;
Vacuum annealing condition also includes: vacuum tightness is not less than 10
-4pa, not rise to 1000～1250 ℃ higher than the speed of 30 ℃/min, insulation 4h～6h; Again with after first slow soon to be not less than 5 ℃/min but be not cooled to room temperature higher than the rate of cooling segmentation of 30 ℃/min, the soaking time of each section tapers off and selects in 1.5 h～3h.
9. preparation method as claimed in claim 7, is characterized in that: described skimming treatment condition also includes: the speed with 0.5 ℃/min～5 ℃/min is progressively warming up to 400～800 ℃, passes into and forms protective atmosphere and be incubated 30min～120min with argon gas;
Vacuum sintering condition also includes: vacuum tightness is 10
-4pa～10
-3pa, is warming up to 1800 ℃, is incubated 200min, is chilled to 200～300 ℃ with stove with 13 ℃/min, then is warming up to 1800 ℃, insulation 230min with 17 ℃/min, is warming up to 2000～2200 ℃, insulation 300min with 7 ℃/min;
Cooling conditions after vacuum sintering also includes: vacuum tightness is not less than 10
-3pa, with not higher than 25 ℃/min, is not less than 10 ℃/min and gradually falls rate of cooling mode, and to sintered porous bodies segmentation cooling down to 800 ℃, each section of soaking time 30min～90min, then cools to normal temperature with the furnace;
Vacuum annealing condition also includes: vacuum tightness is not less than 10
-4pa, not rise to 1000～1250 ℃ higher than the speed of 30 ℃/min, insulation 4h～6h; Again with after first slow soon to be not less than 5 ℃/min but be not cooled to room temperature higher than the rate of cooling segmentation of 30 ℃/min, the soaking time of each section tapers off and selects in 1.5 h～3h.
10. preparation method as claimed in claim 1, is characterized in that: vacuum drying vacuum tightness is 10
-2～1Pa, 60～100 ℃ of drying temperatures, 4～8 hours time of drying; Skimming treatment condition also includes: be progressively warming up to 600～800 ℃, pass into formation protective atmosphere with 99.9999% pure argon gas, 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 ℃, insulation 60～120min from 400 ℃; Vacuum sintering condition also includes: vacuum tightness is 10
-4pa～10
-3pa, is warming up to 1800 ℃, is incubated 200min, is chilled to 200～300 ℃ with stove with 13 ℃/min, then is warming up to 1800 ℃, insulation 230min with 17 ℃/min, is warming up to 2000～2200 ℃, insulation 300min with 7 ℃/min; Cooling conditions after vacuum sintering also includes: vacuum tightness is 10
-4pa～10
-3pa; Be cooled to 1500～1600 ℃ with the speed of 10～20 ℃/min, insulation 30～60min; Be cooled to 1200～1250 ℃ with the speed of 12～20 ℃/min, insulation 60～90min; Be cooled to 800 ℃ with the speed of 10～20 ℃/min, then furnace cooling; Vacuum annealing condition also includes: rise to 1000～1250 ℃ with the speed of 15～30 ℃/min, and insulation 240～480min, vacuum tightness is 10
-4pa～10
-3pa, then be cooled to 1000 ℃ with the speed of 5～10 ℃/min, insulation 90～180min, vacuum tightness is 10
-4pa～10
-3pa; Be cooled to 800 ℃ with the speed of 10～20 ℃/min, insulation 60～120min, low vacuum is in 10
-4pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum tightness is 10
-4pa～10
-3pa.
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| CN201110295810.0A CN102796889B (en) | 2011-09-29 | 2011-09-29 | Preparation method of medical porous tantalum material for replacing weight-bearing bone tissues of human body |
| PCT/CN2012/082212 WO2013044831A1 (en) | 2011-09-29 | 2012-09-27 | Preparation method for medical porous tantalum material for human weight-bearing bone tissue replacement |
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