CN103463673A - Method for preparing medical metal implant material multi-hole niobium - Google Patents
Method for preparing medical metal implant material multi-hole niobium Download PDFInfo
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- CN103463673A CN103463673A CN2013104507148A CN201310450714A CN103463673A CN 103463673 A CN103463673 A CN 103463673A CN 2013104507148 A CN2013104507148 A CN 2013104507148A CN 201310450714 A CN201310450714 A CN 201310450714A CN 103463673 A CN103463673 A CN 103463673A
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- niobium
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- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 90
- 239000010955 niobium Substances 0.000 title claims abstract description 90
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007943 implant Substances 0.000 title claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 99
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 30
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920002472 Starch Polymers 0.000 claims abstract description 24
- 239000008107 starch Substances 0.000 claims abstract description 24
- 235000019698 starch Nutrition 0.000 claims abstract description 24
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 239000011812 mixed powder Substances 0.000 claims abstract description 13
- 238000012805 post-processing Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 40
- 238000009413 insulation Methods 0.000 claims description 35
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 32
- 239000011496 polyurethane foam Substances 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- -1 be incubated 90 min Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 7
- 239000011261 inert gas Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 238000004513 sizing Methods 0.000 abstract 3
- 239000011148 porous material Substances 0.000 description 33
- 239000006260 foam Substances 0.000 description 15
- 238000005452 bending Methods 0.000 description 14
- 238000004891 communication Methods 0.000 description 14
- 239000006261 foam material Substances 0.000 description 14
- 229910052715 tantalum Inorganic materials 0.000 description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000008187 granular material Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 210000000988 bone and bone Anatomy 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000005187 foaming Methods 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001413 cellular effect Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 206010028851 Necrosis Diseases 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 210000003054 facial bone Anatomy 0.000 description 2
- 210000002454 frontal bone Anatomy 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000005470 impregnation Methods 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
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- 239000000126 substance Substances 0.000 description 2
- 206010031264 Osteonecrosis Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002742 anti-folding effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 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
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- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000570 polyether 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
- 239000003870 refractory metal Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Abstract
Disclosed is a method for preparing medical metal implant material multi-hole niobium. A solution is obtained by adopting polyvinyl alcohol as an organic binding agent and distilled water as a dispersing agent, and mixed with mixed powder of starch and niobium powder with the mean grain size smaller than 43 micrometers and the oxygen content smaller than 0.1% to obtain a niobium powder sizing agent which is poured into an organic foamed body, then, the niobium powder sizing agent is dried, the dispersing agent in the organic foamed body with the poured niobium sizing agent is removed, under the inert gas shielding atmosphere, the ungrease treatment is carried out to remove the organic binding agent and the organic foamed body, sintering is carried out in vacuum to obtain a multi-hole sintering body, and then annealing in the vacuum and conventional postprocessing are carried out to obtain the multi-hole niobium. In the mixed powder of the metal niobium powder and the starch, the content of the starch is 5-10%. The obtained medical metal implant material multi-hole niobium has excellent biological compatibility and biological safety, meanwhile, the multi-hole niobium is of a sintering-neck structure, the mechanical performance like the malleability of the multi-hole niobium is improved, and according to the method, the multi-hole niobium can be conveniently and effectively implanted into medical metal.
Description
The present patent application is application number 201010563420.2, November 29 2010 applying date, the dividing an application of denomination of invention " preparation method of medical porous metal implant material ".
Technical field
The present invention relates to the preparation method of medical metal implanted material, be specifically related to a kind of preparation method as medical metal implant material porous niobium, particularly a kind of preparation method that is applicable to the porous niobium embedded material at the lighter position of human bearing.
Background technology
The 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 preferably all is communicated with and is uniformly distributed, or hole partly is 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 the refractory metal niobium, because it has outstanding bio-compatibility 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 niobium to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, niobium 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 niobium material human body, also more and more higher to its requirement., as the medical embedded metal niobium 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 basically, in particular for obtain porosity communication and equally distributed porous metal structure foam adopt after the dipping of metal dust slurry on Organic Foam Material in powder sintering drying to reburn to be called for short the foam impregnation method in the majority for knot.About powder sintered obtained porosity communication and equally distributed porous metal material usually its Metal Mechanic Property be not fine, its main cause is the problem of subsiding how arranged on technique in the support of pore-forming medium and elimination relation, metal powder sintered process.And all there is no good solution in known bibliographical information and laissez-faire nature.
Adopt bibliographical information that metal powder sintered legal system makes porous niobium seldom, particularly take and obtain medical embedded material and almost do not have with the porous niobium powder sintering bibliographical information that is purpose.Can reference be that publication number is CN200510032174, title " three-dimensional through hole or part hole are connected with each other porous metal foam 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 niobium of the porous metals of processing.
At present, directly usining porous niobium has no report as the document of medical embedded material and related manufacturing processes.As everybody knows, metal tantalum and niobium are in of the same clan in the periodic table of elements, and both are adjacent one another are, so the chemical property of the two is extremely similar.And, 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 the 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 the 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 the porous metals micro structure, referred to as chemical deposition by the 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 put down in writing, 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 obtained in aforesaid metal powder sintered method.Due to the limitation of its preparation method, the finished product purity of acquisition is inadequate, and the carbon skeleton residue is arranged again, causes biological safety to reduce.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of medical porous metal implant material of good biocompatibility.The medical metal that the inventive method makes is implanted the porous niobium product and is also had mechanical property preferably, is specially adapted to the medical embedded material of the part that the human bearings such as frontal bone, facial bone are lighter.
The inventor finds in research process, selection and occupation mode to organic adhesive in the preparation of medical porous niobium embedded material have exquisite, if improper to its choice and operation, there will be in the porous niobium made the adhesion between the niobium powder little, the porous niobium surface is inhomogeneous as local overstocked or too lax, the problem of series that the porosity of porous niobium is excessive or too small etc., thus make its biocompatibility and mechanical property thereof not reach medical requirement.
The objective of the invention is to realize by following technical measures:
A kind of preparation method of medical metal implant material porous niobium, adopt foam impregnation method sintering to form, it is characterized in that: be that the employing polyvinyl alcohol is that organic binder bond and distilled water are the solution that dispersant is mixed with, be less than 43 μ m with starch and mean diameter, oxygen content is less than the mixed powder of 0.1% niobium powder and makes niobium powder slurry, and be cast in Organic Foam Material, dipping is until the Organic Foam Material hole is filled with niobium powder slurry, then drying is removed the dispersant in the Organic Foam Material that is cast with niobium 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, through the niobium powder of sintering, pile up on the foam framework formed, the niobium powder particles has the sintering neck structure each other, under vacuum, annealing and conventional post processing make porous niobium again, in the mixed powder of described metal niobium powder and starch, content of starch is 5～10%, by weight percentage.
In the preparation method of porous tantalum of the present invention, the mixed powder that adopts niobium powder and starch to form is raw material constituent, can effectively increase porosity and the aperture of the porous niobium made, starch is that people's food commonly used, safety are good simultaneously, starch also easily decomposes, can improve the purity of the porous tantalum material finally made, and therefore can make the porous niobium material made have very superior biocompatibility and safety; But the inventor finds in practice, starch adds in the niobium powder shrinkage factor of material in the time of can not accurately controlling sintering, and the porous niobium material shape of preparing is difficult to be consistent, and mechanical property is bad, can't practical application; The inventor also finds in research process simultaneously, the niobium powder be easy to starch and Organic Foam Material in carbon react, easily make the porous niobium medical embedded material impurity content finally made raise, affect its biocompatibility and biological safety, also its mechanical property is had to considerable influence.Around the problems referred to above, the inventor has launched series of studies, thereby find out other compositions in raw materials as the selection of the selection of organic bonding agent, dispersant and with above being used in conjunction with of mixed powder, all have more exquisite, coordinate follow-up treatment process steps, make the porous tantalum material made not only there is superior biocompatibility and safety, and its shape is consistent, mechanical property is also better, be specially adapted to the medical embedded material at the position that the human bearings such as frontal bone, facial bone are light.Preparation method technique of the present invention is simple, easily control; Whole preparation process is harmless, pollution-free, the nonhazardous dust, and human body is had no side effect.
Above-mentioned Organic Foam Material can adopt the similar substances such as polyurethane foam, polyether ester foam, optimization polyurethane foam of the present invention.Described slurry is poured into a mould, be impregnated in described Organic Foam Material, then after drying is removed the dispersant in the Organic Foam Material that is cast with niobium powder slurry, the porosity of the porous niobium formed is between 55.7～77.7%, hole average diameter 250～500 μ m, form the sintering neck structure between described porous niobium at least 50% niobium powder particles, preferably between at least 80% niobium powder particles, form the sintering neck structure.
Under the bio-compatible implementations guaranteeing medical material porous niobium of the present invention, further improve its mechanical property, be beneficial to the formation of sintering neck structure simultaneously, described slurry is that polyvinyl alcohol is heated to dissolve with distilled water, adopt the polyvinyl alcohol water solution of percentage by weight 2%～8% (preferably 4%～5%) and the mixed powder of described metal niobium powder and starch to make niobium powder slurry, wherein, in the mixed powder of described metal niobium powder and starch, content of starch is preferably 8%, by weight percentage; The described mixed powder that is 2～4 parts (preferably 2.5 parts) by weight adds in the described polyvinyl alcohol water solution that weight is 1 part, stirs and makes starchiness; And to be cast in aperture be 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is more than or equal to 50 °, and (preferably aperture is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness) polyurethane foam in.
The present invention selects mean diameter to be less than 431 μ m, oxygen content and is less than the content that 0.1% metal niobium powder contributes to reduce impurity, guarantees that material has mechanical property preferably; The selection aperture is 0.48～0.89mm, density 0.015g/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 niobium.Process conditions have been optimized in the such technical finesse of the present invention, by guaranteeing to implant bio-compatibility and the biological safety of porous niobium material, also are conducive to the formation of sintering neck structure simultaneously.
Sintering neck of the present invention refers to that at high temperature, powder is heated, and between granule, bonds, and is exactly the sintering phenomenon that we often say.Sintering refers to that the process of metallurgical property combination at high temperature occurs between powder particle granule, usually carries out, and realizes by atomic migration under the fusing point of main component constituent element.By microstructure observing, can find that the sintering neck (or claiming the contact neck) of granule contact is grown up, and therefore cause performance variation.Along with the raising of sintering temperature, or the prolongation of sintering time or, to the reasonable control of sintering temperature and sintering time, the sintering neck just can increase gradually, the ratio of sintering neck just can increase, the strength increase of sintered body.Be also that the present invention forms the sintering neck structure also can realize the object of the invention between niobium powder particles partly.
The present invention's further characteristics on the other hand are: dry vacuum keep 1 * 10
-2pa～1Pa vacuum, then, under protective atmosphere, low vacuum is in 1 * 10
-3pa, the ungrease treatment of under 400 ℃～800 ℃ conditions of temperature, being removed organic binder bond and Organic Foam Material; In vacuum, be 1 * 10 again
-4pa～1 * 10
-3pa, 1700～1800 ℃ of temperature, the temperature retention time vacuum-sintering of 3～5 hours is processed and is made porous sintered body.Can also the filling with inert gas protection replace vacuum protection during the sintering process insulation; Finally carry out the vacuum annealing processing, wherein vacuum annealing is processed and to be referred to and continue to keep temperature in 900～1100 ℃ after vacuum-sintering, temperature retention time 2～4 hours, and vacuum is not for higher than 1 * 10
-3pa.
Above-mentioned ungrease treatment condition also includes: the speed with 0.5 ℃/min～3 ℃/min progressively is warming up to 400～800 ℃, with noble gas, as argon passes into, forms protective atmosphere and is incubated 1.5～3h;
The vacuum-sintering condition also includes: vacuum is 1 * 10
-4pa～1 * 10
-3pa, rise to 900 ℃～1400 ℃ with the heating rate of 10～20 ℃/min from room temperature, after insulation 1h～2h; Be warming up to 1700～1800 ℃ with the heating rate lower than 20 ℃/min again, at least be incubated 2h;
Cooling condition after vacuum-sintering also includes: vacuum is 1 * 10
-4pa～1 * 10
-3pa, with not higher than 25 ℃/min, be not less than 15 ℃/min and gradually fall the cooldown rate mode, and to sintered porous bodies segmentation cooling down to 600～800 ℃, each section temperature retention time 0.5～1.5h, then cool to room temperature with the furnace;
The vacuum annealing condition also includes: vacuum is not higher than 1 * 10
-3pa, rise to 900～1100 ℃ with the speed higher than 30 ℃/min not, insulation 4h～6h; After first slow, to be not less than 10 ℃/min but higher than the cooldown rate segmentation of 30 ℃/min, not to be cooled to room temperature soon, the temperature retention time of each section tapers off and is no more than 2h again.
Further characteristics are on this basis: 70～80 ℃ of described vacuum drying baking temperatures, 6～8 hours drying times; Described ungrease treatment condition also includes: progressively be warming up to 400～800 ℃, pass into the formation protective atmosphere with pure argon gas (99.9999%), speed with 1～3 ℃/min rises to 400 ℃ from room temperature, insulation 0.5～1h, rise to 600～800 ℃ with the speed of 0.5～1.5 ℃/min from 400 ℃, be incubated 1～2h; Described vacuum-sintering condition also includes: the speed with 10～15 ℃/min rises to 900～1100 ℃ from room temperature, is incubated 0.5～1h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 10～20 ℃/min rises to 1300～1400 ℃, is incubated 0.5～1h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa, rise to 1700～1800 ℃ with the speed of 6～20 ℃/min, is incubated 2～3h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Cooling condition after vacuum-sintering also includes: vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 15～18 ℃/min is cooled to 1200～1300 ℃, is incubated 0.5～1h; Speed with 18～25 ℃/min is cooled to 600～1000 ℃, is incubated 1～1.5h, then furnace cooling; Described vacuum annealing condition also includes: the speed with 20～30 ℃/min rises to 900～1100 ℃, is incubated 4～6h, and vacuum is not higher than 1 * 10
-3pa, then be cooled to 800 ℃ with the speed of 10～13 ℃/min, being incubated 1～2h, vacuum is not higher than 1 * 10
-3pa; Speed with 13～18 ℃/min is cooled to 600 ℃, is incubated 1～2h, and vacuum is not higher than 1 * 10
-3pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum is not higher than 1 * 10
-3pa.
Specifically, a kind of preparation method of medical embedded material porous niobium:
A. the preparation of niobium powder slurry: polyvinyl alcohol is heated to dissolve with distilled water, be mixed with the polyvinyl alcohol water solution of percentage by weight 2～8% (preferably 4～5%), being less than with mean diameter mixed powder that 43 μ m, oxygen content are less than 0.1% metal niobium powder and starch stirs and makes starchy niobium powder slurry, wherein, starch accounts for 8% of described mixed powder weight; The weight part ratio of described mixed powder and described polyvinyl alcohol water solution is 2～4 parts (preferably 2.5 parts): 1 part;
B. the preparation of porous niobium: above-mentioned niobium powder slurry is cast in the polyurethane foam Organic Foam Material, dipping is until polyurethane foam Organic Foam Material hole is filled with niobium powder slurry, then drying is removed the dispersant in the Organic Foam Material that is cast with niobium 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, through the niobium powder of sintering, pile up on the foam framework formed, the niobium powder particles has the sintering neck structure each other, then under vacuum annealing and conventional post processing make porous niobium; 75 ℃ of described vacuum drying baking temperatures, 7 hours drying times; Described ungrease treatment condition is: progressively be warming up to 800 ℃; pass into the formation protective atmosphere with pure argon gas (99.9999%); speed with 1 ℃/min rises to 400 ℃ from room temperature; be incubated 0.8 hour; rise to 750 ℃ with the speed of 0.5 ℃/min from 400 ℃, be incubated 1.5 hours, described vacuum-sintering condition is: the speed with 14 ℃/min rises to 1000 ℃ from room temperature; insulation 36min, vacuum is 10
-4pa; Speed with 17 ℃/min rises to 1300 ℃, insulation 30min, and vacuum is 10
-4pa, rise to 1750 ℃ with the speed of 15 ℃/min, insulation 150min, and vacuum is 10
-4pa; Cooling condition after vacuum-sintering is: vacuum is 10
-3pa; Speed with 18 ℃/min is cooled to 1250 ℃, insulation 60min; Speed with 22 ℃/min is cooled to 1000 ℃, insulation 30min; Speed with 24 ℃/min is cooled to 600 ℃, and insulation 30min is furnace cooling then; Described vacuum annealing condition is: the speed with 23 ℃/min rises to 1000 ℃, insulation 270min, and vacuum is 10
-3pa, then be cooled to 800 ℃ with the speed of 12 ℃/min, insulation 120min, vacuum is 10
-3pa; Speed with 16 ℃/min is cooled to 600 ℃, insulation 90min, vacuum 10
-3pa; Speed with 22 ℃/min is cooled to room temperature, and vacuum is 10
-3pa.
The medical embedded material porous niobium made by above-mentioned preparation method can meet the requirement of biocompatibility and biological safety fully, particularly its foam framework is to be piled up and formed by the niobium powder of sintering, the sintering neck structure that the niobium powder particles has has each other greatly improved the mechanical property of this material as ductility, anti-folding anti-bending strength, simultaneously through testing its impurity content lower than 0.4%; This porous niobium finished product even pore distribution and connection, density 1.8～3.8g/cm
3, porosity is between 55.7～77.7.0%, hole average diameter 250～500 μ m; Elastic modelling quantity 0.8～2.0GPa, yield strength 25～60MPa, comprcssive strength 25～65MPa, hardness 100～200MPa, amount of plastic deformation 6.4%～11.3%, tensile strength 15～40MPa, the elongation 6.3%～10.7% of having no progeny; Not only do not affect elastic modelling quantity, yield strength of porous material etc., and be to have improved these performance parameters that porous material is emphasized.And, when carrying out anti-bending test, the fracture rate of the sintering neck formed between each niobium powder particles is less than 45%, the fracture rate of niobium powder particles inside is greater than 55%, further illustrates new product reliability of structure of the present invention.
The accompanying drawing explanation
Fig. 1 is the X-ray diffraction analysis collection of illustrative plates (XRD figure) of the porous niobium for preparing of preparation method of the present invention;
Fig. 2 is the vertical microscope analysis chart of the macrostructure of the porous niobium for preparing of preparation method of the present invention;
Fig. 3 is the scanning electron microscope analysis figure (SEM figure) of the microstructure of the porous niobium for preparing of preparation method of the present invention.
From accompanying drawing, can be observed: 1, porous niobium of the present invention high hole, even pore distribution and connection.Can find out porous niobium three-dimensional communication hole of the present invention from accompanying drawing, this three-dimensional pore space is conducive to that osteoblast adheres to, differentiation and growth, promotes growing into of bone, can strengthen being connected between implant and bone, is beneficial to and realizes biological fixation.2, the mechanical property of porous niobium of the present invention is good.As shown in drawings, the sintering microstructure uniform particles of porous niobium of the present invention, the sintering neck is obvious, has guaranteed good mechanical property, and has good ductility.
The specific embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples only are used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field 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, put into the container that the 240m1 distilled water is housed; Placing it on electric furnace heats and stir makes it to become polyvinyl alcohol water solution.Be less than by 200g balance weighing mean diameter niobium powder 60g and the 5.3g starch that 43 microns, oxygen content are less than 0.1%, add the cooling polyvinyl alcohol water solution of 15m1, be uniformly mixed, make it to become mixed 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 the polyurethane foam hole is filled with slurry, the polyurethane foam that goes out to be filled slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 70 ℃ of baking temperatures, drying time 8h, vacuum keep 1Pa.Ungrease treatment: low vacuum is in 1 * 10
-3pa, 600 ℃ of temperature, temperature retention time 2h.Vacuum-sintering: sintering in vacuum drying oven, 1750 ℃ of sintering temperatures, insulation 3h, vacuum 1 * 10
-3pa～1 * 10
-4pa, the protection of sintering process applying argon gas, remove surface dirt and dirt after the taking-up product, and the sample made carries out conventional post processing again and obtains the porous niobium finished product.
The name hole niobium finished product that adopts said method to make. and have the three-dimensional car of hole to read aloud the truly foam structure of distribution, through the pure niobium powder of sintering, to pile up on the foam framework formed, the niobium powder particles has the sintering neck structure each other.And the sintering neck structure formed between the niobium powder particles in this porous niobium finished product microstructure surpasses 50%.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous niobium finished product detected the inventor: this porous niobium is to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.4% finished product, its even pore distribution and connection, density 2.5g/cm
3, porosity 71%, hole average diameter 300 μ m, elastic modelling quantity 1.5GPa, yield strength 35MPa, comprcssive strength 50MPa, hardness 110MPa, amount of plastic deformation 10.3%, tensile strength 25MPa, the elongation 10.7% of having no progeny; When the method for measuring by the metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 45%, and the fracture rate of granule interior is greater than 55%.
Embodiment 2: weighing polyvinyl alcohol 10g, put into the container that the 200ml distilled water is housed; Placing it on electric furnace heats and stir makes it to become polyvinyl alcohol water solution.Be less than 43 μ m, oxygen content by 200g balance weighing mean diameter and be less than 0.1% niobium powder 40g and the starch of 2.6g, add the 10ml polyvinyl alcohol water solution, be uniformly mixed, make it to become mixed slurry.(average pore size is 0.56mm, density 0.030g/cm to select 10 * 10 * 25mm cellular polyurethane foam
3, hardness 60
0) put into wherein cast, until the polyurethane foam hole is filled with slurry, the polyurethane foam that goes out to be filled slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 70 ℃ of baking temperatures, drying time 6h, vacuum keep 1 * 10
-2pa.Ungrease treatment: low vacuum is in 1 * 10
-3pa, 800 ℃ of temperature, temperature retention time 2h.Vacuum-sintering: sintering in vacuum drying oven, 1800 ℃ of sintering temperatures, be incubated 4 hours, vacuum 1 * 10
-4pa, the protection of sintering process applying argon gas, remove surface dirt and dirt after the taking-up product, and the sample made carries out conventional post processing again and obtains the porous niobium finished product.
The porous niobium finished product that adopts said method to make, have the foaming structure that the hole three-dimensional communication distributes, and through the pure niobium powder of sintering, piles up on the foam framework formed, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure formed between the niobium powder particles in this porous niobium finished product microstructure surpasses 60%.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous niobium finished product detected the inventor: this porous niobium is to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.4% finished product, its even pore distribution and connection, density 3g/cm
3, porosity 65%, hole average diameter 260 μ m, elastic modelling quantity 1.3GPa, yield strength 40MPa, comprcssive strength 50MPa, hardness 150MPa, amount of plastic deformation 10%, tensile strength 30MPa, the elongation 10% of having no progeny; When the method for measuring by the metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 40%, and the fracture rate of granule interior is greater than 60%.
Embodiment 3: weighing polyvinyl alcohol 11g, put into the container that the 220m1 distilled water is housed; Placing it on electric furnace heats and stir makes it to become polyvinyl alcohol water solution.Be less than by 200g balance weighing mean diameter niobium powder 45g and the 2.8g starch that 43 μ m, oxygen content are less than 0.1%, add the 12m1 polyvinyl alcohol water solution, be uniformly mixed, make it to become mixed 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 the polyurethane foam hole is filled with slurry, the polyurethane foam that goes out to be filled niobium powder slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 75 ℃ of baking temperatures, drying time 6h, vacuum keep 1 * 10
-1pa.Ungrease treatment: low vacuum is in 1 * 10
-3pa, 700 ℃ of temperature, temperature retention time 1.5h.Vacuum-sintering: sintering in vacuum drying oven, 1700 ℃ of sintering temperatures, be incubated 3.5 hours, vacuum 1 * 10
-3pa, the protection of sintering process applying argon gas, cooling coming out of the stove, remove product surface dust and dirt, and the sample made carries out conventional post processing again and obtains the porous niobium finished product.
The porous niobium finished product that adopts said method to make, have the foaming structure that the hole three-dimensional communication distributes, and through the pure niobium powder of sintering, piles up on the foam framework formed, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure formed between the niobium powder particles in this porous niobium finished product microstructure surpasses 55%.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous niobium finished product detected the inventor: this porous niobium is to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.4% finished product, its even pore distribution and connection, density 3.6g/cm
3, porosity 61%, hole average diameter 300 μ m, elastic modelling quantity 1.0GPa, yield strength 30MPa, comprcssive strength 35MPa, hardness 150MPa, amount of plastic deformation 9.2%, tensile strength 25MPa, the elongation 9.5% of having no progeny; When the method for measuring by the metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 35%, and the fracture rate of granule interior is greater than 65%.
Embodiment 4: weighing polyvinyl alcohol 12g, put into the container that the 230ml distilled water is housed; Placing it on electric furnace heats and stir makes it to become polyvinyl alcohol water solution.Be less than by 200g balance weighing mean diameter niobium powder 50g and the 3.5g starch that 43 μ m, oxygen content are less than 0.1%, add the 13ml polyvinyl alcohol water solution, be uniformly mixed, make it to become mixed 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 the polyurethane foam hole is filled with slurry, the polyurethane foam that goes out to be filled slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 70 ℃ of baking temperatures, drying time 6.5h, vacuum keep 1Pa.Ungrease treatment: vacuum 1 * 10
-4pa～1 * 10
-3pa, 500 ℃ of temperature, temperature retention time 2h.Vacuum-sintering: sintering in vacuum drying oven, 1750 ℃ of sintering temperatures, be incubated 4 hours, vacuum 1 * 10
-4pa, the protection of sintering process applying argon gas, cooling coming out of the stove, remove product surface dust and dirt, and the sample made carries out conventional post processing again and obtains the porous niobium finished product.
The porous niobium finished product that adopts said method to make, have the foaming structure that the hole three-dimensional communication distributes, and through the pure niobium powder of sintering, piles up on the foam framework formed, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure formed between the niobium powder particles in this porous niobium finished product microstructure surpasses 70%.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous niobium finished product detected the inventor: this porous niobium is to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.4% finished product, its even pore distribution and connection, density 2.2g/cm
3, porosity 74%, hole average diameter 400 μ m, elastic modelling quantity 1.5GPa, yield strength 30MPa, comprcssive strength 35MPa, hardness 100MPa, amount of plastic deformation 10.3%, tensile strength 32MPa, the elongation 10.6% of having no progeny; When the method for measuring by the metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 43%, and the fracture rate of granule interior is greater than 57%.
Embodiment 5: a kind of porous niobium, and it be take particle diameter and is less than 43 μ m, oxygen content to be less than 0.1% metal niobium powder and starch be raw material, and adopting percentage by weight is that 2～8% polyvinyl alcohol water solutions are made mixed slurry, 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 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °;
Vacuum drying: vacuum keep 10
-2～1Pa, to remove the moisture in the polyurethane foam of filling with slurry;
Ungrease treatment: under inert gas shielding atmosphere or low vacuum in 1 * 10
-3pa, 400 ℃～800 ℃ of temperature, and temperature retention time 1.5～3 hours is to remove polyvinyl alcohol and polyurethane foam wherein;
Vacuum-sintering: vacuum 1 * 10
-4pa～1 * 10
-3pa, 1700～1800 ℃ of temperature, temperature retention time 3～5 hours, applying argon gas or other inert gas shielding during the sintering process insulation, to obtain porous material;
Vacuum annealing: after vacuum-sintering, continue to keep temperature in 900～1100 ℃, temperature retention time 4～4 hours, low vacuum is in 1 * 10
-3pa, to carry out the stress relief annealing processing; The sample made carries out conventional post processing again and obtains the porous niobium finished product.
In conjunction with each accompanying drawing, we can find out the porous niobium finished product that adopts said method to make, and have the foaming structure that the hole three-dimensional communication distributes, and through the pure niobium powder of sintering, pile up on the foam framework formed, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure formed between the niobium powder particles in this porous niobium finished product microstructure surpasses 80%.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous niobium finished product detected the inventor: this porous niobium is to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.4% finished product, its even pore distribution and connection, density 1.8～3.8g/cm
3, porosity is between 55.7～77.7%, hole average diameter 250～500 μ m; Elastic modelling quantity 0.8～2.0GPa, yield strength 25～60MPa, comprcssive strength 25～65MPa, hardness 100～200MPa, amount of plastic deformation 6.4%～11.3%, tensile strength 15～40MPa, the elongation 6.3%～10.7% of having no progeny; When the method for measuring by the metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 45%, and the fracture rate of granule interior is greater than 55%.
Embodiment 6: a kind of porous niobium, it be take particle diameter and is less than 43 μ m, oxygen content to be less than 0.1% metal niobium powder and starch be raw material, the polyvinyl alcohol water solution of take is made niobium powder slurry as binder solution, and to be cast in its aperture be 0.56～0.72mm, density 0.025～0.035g/cm
3, in the polyurethane foam carrier that hardness is 50 °～80 °; Then vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, polyvinyl alcohol is heated to dissolve to be mixed with percentage by weight be 4～5% polyvinyl alcohol water solutions with distilled water; Then the metal niobium powder that is 2～4 parts by weight adds in the described polyvinyl alcohol water solution that cooled weight is 1 part, stirs and makes starchiness; Again above-mentioned polyurethane foam is put into and be starchy niobium powder slurry and repeatedly flood until the polyurethane foam hole is filled with;
Vacuum drying to be to remove the moisture in the polyurethane foam of filling with niobium powder slurry, vacuum keep 1Pa, 70～80 ℃ of baking temperatures, drying time 6～8h;
Being placed in the tungsten device for the polyurethane foam after vacuum drying puts into the nonoxidizing atmosphere stove and is warming up to 800 ℃ with certain heating rate, protective atmosphere is that 99.999% argon carries out ungrease treatment, its before heating up, first pass into argon at least 0.5h to get rid of furnace air, the temperature control process: the speed with 1 ℃/min rises to 400 ℃ from room temperature, insulation 0.5h, argon passes into speed 0.5L/min; Rise to 800 ℃ with the speed of 0.5 ℃/min from 400 ℃, insulation 2h, argon passes into speed 1L/min; Powered-down again, the sample furnace cooling after defat, argon passes into speed 1L/min, until close argon while being cooled to room temperature;
Be placed in and be warming up to 1800 ℃ with certain heating rate in the fine vacuum high temperature sintering furnace and carry out vacuum-sintering with the tungsten device for the sample after ungrease treatment, before heating up, the vacuum of sintering furnace at least will reach 1 * 10
-3pa, rise to 900 ℃ with the speed of 10～15 ℃/min from room temperature, insulation 0.5h, and vacuum is 1 * 10
-4pa; Speed with 10 ℃/min rises to 1300 ℃, insulation 0.5h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 6 ℃/min rises to 1800 ℃, insulation 2h, and vacuum is 1 * 10
-3pa; Sintering is complete, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 15 ℃/min is cooled to 1300 ℃, insulation 1h; Speed with 20 ℃/min is cooled to 800 ℃, insulation 1.5h, then furnace cooling;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with the corundum container and be warming up to 1000 ℃ with certain heating rate and carry out the stress relief annealing processing, the vacuum before heating up in annealing furnace at least will reach 1 * 10
-3pa, rise to 1000 ℃ with the speed of 25 ℃/min from room temperature, insulation 4h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 12 ℃/min is cooled to 800 ℃ again, insulation 2h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 14 ℃/min is cooled to 600 ℃, insulation 2h, and vacuum is 1 * 10
-4pa; Speed with 20 ℃/min is cooled to room temperature, and vacuum is 1 * 10
-4pa.Finally carry out conventional post processing and make porous niobium.
The porous niobium finished product that adopts said method to make has the foaming structure that the hole three-dimensional communication distributes, and through the pure niobium powder of sintering, piles up on the foam framework formed, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure formed between the niobium powder particles in this porous niobium finished product microstructure surpasses 80%.
By standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001, porous material density, porosity, aperture and the various mechanical property to above-mentioned porous niobium finished product detected the inventor: this porous niobium is to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.4% finished product, its even pore distribution and connection, density 2.45g/cm
3, porosity 72.5%, hole average diameter 300 μ m, elastic modelling quantity 1.5GPa, yield strength 45MPa, comprcssive strength 50MPa, hardness 130MPa, amount of plastic deformation 9.4%, tensile strength 27MPa, the elongation 9.7% of having no progeny; When the method for measuring by the metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 40%, and the fracture rate of granule interior is greater than 60%.
In the method provided at above-described embodiment 6, we can also do other selection to wherein each kind of condition can obtain porous niobium of the present invention equally.In the following embodiments, if not otherwise specified, in table, the parameters condition is all with aforementioned
Embodiment 6 is identical.
Gained porous niobium finished product is pressed preceding method and is detected:
| Embodiment | 7 | 8 | 9 | 10 | 11 | 12 | 13 |
| Density (g/cm 3) | 3.8 | 3.5 | 2.4 | 2.7 | 2.2 | 2.0 | 1.9 |
| Porosity (%) | 56 | 60 | 68 | 74 | 72 | 77 | 78 |
| Pore diameter (μ m) | 230 | 260 | 350 | 420 | 400 | 410 | 480 |
| Elastic modelling quantity (GPa) | 1.3 | 1.6 | 1.4 | 1.8 | 1.2 | 0.9 | 0.7 |
| Yield strength (MPa) | 48 | 53 | 50 | 56 | 46 | 43 | 35 |
| Comprcssive strength (MPa) | 50 | 55 | 52 | 60 | 48 | 45 | 38 |
| Hardness (MPa) | 160 | 140 | 140 | 150 | 130 | 100 | 120 |
| Amount of plastic deformation (%) | 10.30 | 11.20 | 10.25 | 10.22 | 9.28 | 8.29 | 9.30 |
| Tensile strength (MPa) | 25 | 30 | 28 | 34 | 22 | 20 | 18 |
| The elongation (%) of having no progeny | 10.70 | 11.60 | 10.50 | 10.65 | 9.55 | 9.75 | 9.80 |
| Sintering neck fracture rate (%) | 45 | 48 | 50 | 55 | 58 | 59 | 60 |
| Granule interior fracture rate (%) | 55 | 52 | 50 | 45 | 42 | 41 | 40 |
Claims (1)
1. the preparation method of a medical metal implant material porous niobium, it is characterized in that: the particle diameter of take is less than 41 μ m, oxygen content, and to be less than 0.1% metal niobium powder and starch be raw material, the polyvinyl alcohol water solution of take is made niobium powder slurry as binder solution, and to be cast in its aperture be 0.85mm, density 0.032g/cm
3, in the polyurethane foam carrier that hardness is 52 °; Then vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing;
Wherein, polyvinyl alcohol is heated to dissolving with distilled water and is mixed with the 5g/100ml polyvinyl alcohol water solution; The mixed powder of the metal niobium powder that is then 2.5 parts of left and right by weight and starch adds in the described polyvinyl alcohol water solution that cooled weight is 1 part of left and right, stirs and makes starchiness; Again above-mentioned polyurethane foam is put into and be starchy niobium powder slurry and repeatedly flood until the polyurethane foam hole is filled with;
Vacuum drying to be to remove the moisture in the polyurethane foam of filling with niobium powder slurry, vacuum keep 0.1Pa, 75 ℃ of baking temperatures, drying time 7.0h;
Being placed in the tungsten device for the polyurethane foam after vacuum drying puts into the nonoxidizing atmosphere stove and is warming up to 800 ℃ with certain heating rate; protective atmosphere is that 99.999% argon carries out ungrease treatment; it first passed into argon before heating up, and at least 0.5h is to get rid of furnace air, and defat atmosphere is 1 * 10
-4pa～1 * 10
-3pa, the temperature control process: the speed with 1 ℃/min rises to 400 ℃ from room temperature, insulation 48min, argon passes into speed 0.5L/min; Rise to 750 ℃ with the speed of 0.5 ℃/min from 400 ℃, be incubated 90 min, argon passes into speed 1L/min; Powered-down again, the sample furnace cooling after defat, argon passes into speed 1L/min, until close argon while being cooled to room temperature;
Be placed in and be warming up to 1800 ℃ with certain heating rate in the fine vacuum high temperature sintering furnace and carry out vacuum-sintering, sintering atmosphere 1 * 10 with the tungsten device for the sample after ungrease treatment
-4pa～1 * 10
-3pa, rise to 1000 ℃ with the speed of 14 ℃/min from room temperature, insulation 36min, and vacuum is 1 * 10
-3pa; Speed with 17 ℃/min rises to 1300 ℃, insulation 30min; Speed with 15 ℃/min rises to 1750 ℃, insulation 150min, and vacuum is 1 * 10
-3pa; After sintering, the cooling vacuum degree is 1 * 10
-4pa～1 * 10
-3pa; Speed with 18 ℃/min is cooled to 1250 ℃, insulation 60min; Speed with 22 ℃/min is cooled to 1000 ℃, insulation 30min; Speed with 24 ℃/min is cooled to 600 ℃, and insulation 30min is furnace cooling then;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with the corundum container and be warming up to 1000 ℃ with certain heating rate and carry out the stress relief annealing processing, annealing vacuum is 1 * 10
-3pa, rise to 1000 ℃ with the speed of 23 ℃/min from room temperature, insulation 270min; Speed with 12 ℃/min is cooled to 800 ℃ again, insulation 2h; Speed with 16 ℃/min is cooled to 600 ℃, insulation 90min; Speed with 22 ℃/min is cooled to room temperature, finally carries out conventional post processing and makes porous niobium.
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| CN106466494A (en) * | 2015-08-18 | 2017-03-01 | 重庆润泽医药有限公司 | A kind of porous material and preparation method |
| CN106466494B (en) * | 2015-08-18 | 2020-09-15 | 重庆润泽医药有限公司 | Porous material and preparation method thereof |
| US10835641B2 (en) | 2015-08-18 | 2020-11-17 | Chongqing Runze Pharmaceuticals Co., Ltd. | Porous material and preparation method thereof |
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