CN102475903A - Preparation method for medical metal implant material porous niobium - Google Patents
Preparation method for medical metal implant material porous niobium Download PDFInfo
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- CN102475903A CN102475903A CN201010563419XA CN201010563419A CN102475903A CN 102475903 A CN102475903 A CN 102475903A CN 201010563419X A CN201010563419X A CN 201010563419XA CN 201010563419 A CN201010563419 A CN 201010563419A CN 102475903 A CN102475903 A CN 102475903A
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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 158
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 81
- 239000010955 niobium Substances 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000007943 implant Substances 0.000 title abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 97
- 238000000034 method Methods 0.000 claims abstract description 68
- 239000006260 foam Substances 0.000 claims abstract description 41
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 35
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 35
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 29
- 229920002472 Starch Polymers 0.000 claims abstract description 28
- 239000008107 starch Substances 0.000 claims abstract description 28
- 235000019698 starch Nutrition 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000137 annealing Methods 0.000 claims abstract description 20
- 239000011812 mixed powder Substances 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 238000009413 insulation Methods 0.000 claims description 47
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 30
- 239000011496 polyurethane foam Substances 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 24
- 230000001476 alcoholic effect Effects 0.000 claims description 21
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 230000014759 maintenance of location Effects 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000012805 post-processing Methods 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 230000011218 segmentation Effects 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 abstract 1
- -1 ductility Chemical compound 0.000 abstract 1
- 238000002513 implantation Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 33
- 238000004891 communication Methods 0.000 description 17
- 238000005452 bending Methods 0.000 description 14
- 229910052715 tantalum Inorganic materials 0.000 description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 239000008187 granular material Substances 0.000 description 9
- 210000000988 bone and bone Anatomy 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000005187 foaming Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229960004756 ethanol Drugs 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000001413 cellular effect Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- 206010028851 Necrosis Diseases 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000017074 necrotic cell death Effects 0.000 description 2
- 231100000957 no side effect Toxicity 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- 230000002742 anti-folding effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 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
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000003054 facial bone Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 210000002454 frontal bone Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 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
- 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
- 229920000642 polymer 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
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 230000008467 tissue growth Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The invention provides a preparation method for a medical metal implant material porous niobium. According to the invention, a solution prepared from ethyl cellulose which is used as an organic binder and anhydrous ethanol which is used as a dispersant and mixed powder prepared from starch and niobium powder which has an average particle size of less than 43 mu m and oxygen content of less than 0.1% are used to prepare niobium powder slurry which is casted and dipped into an organic foam; the organic foam is dried and then is subjected to degreasing under the protection of an inert gas atmosphere and to sintering in vacuum so as to prepare a porous sintered body, sintered niobium powder particles mutually have a sintering neck structure, and after annealing in vacuum and normal post-treatment, porous niobium is prepared; wherein, the content of starch in the mixed powder of metallic niobium powder and starch is 5 to 10%. The medical metal implant material porous niobium prepared in the invention has excellent bio-compatibility and bio-safety; meanwhile, the porous niobium has a sintering neck structure, which enables mechanical properties of the porous niobium like ductility, etc., to be improved; the invention provides a good method for convenient and effective application of porous niobium in the field of medical metal implantation.
Description
Technical field
The present invention relates to the columbic method for preparing of a kind of porous, particularly a kind of method for preparing that is applicable to the porous niobium embedded material at the position that the human bearing is light as medical embedded material.
Background technology
Porous medical metal embedded material has important and special purposes such as treatment osseous tissue wound and bone formation necrosis, and existing common this type 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 uniform distribution, or hole partly is communicated with and uniform distribution as required, makes it that both the osseous tissue growth phase with human body was consistent; Alleviated the weight of material itself again, implanted use to be fit to human body.
And the refractory metal niobium, because it has outstanding bio-compatibility and mechanical property, its porous material is expected to as substituting conventional medical metallic biomaterials such as aforementioned, becomes the biomaterial mainly as bone necrosis's treatment.Since metal niobium to human body harmless, nontoxic, have no side effect; And along with the develop rapidly of domestic and international medical science; As cognitive further the going deep into of body implanting material, the demand that people implant with the porous metals niobium material human body becomes more and more urgent, and is also increasingly high to its requirement to niobium.,, then be the heavy connection constituent material that guarantees freshman bone tissue's normal growth wherein if can have very high uniform distribution interconnected pore and the physical and mechanical properties that adapts with human body as the medical embedded metal niobium of porous.
As medical embedded porous metal material just as the porous metal material that kind be to be main processing method basically with powder sintering, in particular for obtain porosity communication and equally distributed porous metal structure foam adopt the dipping after drying of metal dust slurry on the organic foam body in the powder sintering to reburn to be called for short the foam impregnation method in the majority for knot.About the powder sintered porosity communication that obtains and common its Metal Mechanic Property of equally distributed porous metal material is not fine, and its main cause is how to arrange the support and the problem of eliminating in relation, the metal powder sintered process of subsiding of pore-forming medium on the technology.And all do not have good solution in the known bibliographical information and laissez-faire nature.
Adopt the columbic bibliographical information of metal powder sintered manufactured porous seldom, particularly use porous niobium powder sintering process bibliographical information almost not have as purpose to obtain medical embedded material.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 novel porous foam tungsten and preparation method thereof ".Yet porous metals that it obtained or for filtering material usefulness, or share for Aero-Space and other high-temperature field but not use as the medical metal embedded material, moreover the also non-porous niobium of the porous metals of being processed.
At present, directly do not appear in the newspapers with the document of porous niobium as 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 processed by pure commercial tantalum; It carries out the carbon skeleton that thermal degradation obtains with the polyurethane precursor is support, and this carbon skeleton is multiple dodecahedron, is the mesh-like structure in it; Integral body spreads all over micropore; Porosity can be up to 98%, the method for commercially pure tantalum through chemical vapour deposition, infiltration is attached on the carbon skeleton to form the porous metals micro structure again, abbreviates chemical deposition as.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtained is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight then accounts for about 1%.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 with its porous tantalum as medical embedded material, the mechanical property of its material such as ductility have obvious weak point, can have influence on the follow-up processing to porous tantalum material itself, for example cutting of profiled member etc.Also all there is such deficiency at the product that aforesaid metal powder sintered method obtained equally.Owing to the limitation of its preparation method, the finished product purity of acquisition is not enough, 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 the columbic method for preparing of a kind of medical embedded material porous, porous niobium material biocompatibility and biological safety that the inventive method makes are good, also have mechanical property preferably simultaneously.
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 to its selection and improper use, the adhesion in the porous niobium that can occur making between the niobium powder is little, and the porous niobium surface is inhomogeneous as local overstocked or too lax; The problem of series that the columbic porosity of porous is excessive or too small or the like, thus make its biocompatibility and mechanical property thereof not reach medical requirement.
The objective of the invention is to realize through following technical measures:
The columbic method for preparing of a kind of medical embedded material porous; Adopt foam impregnation method sintering to form, it is characterized in that: be that the employing ethyl cellulose is that organic binder bond and dehydrated alcohol are the solution that dispersant is mixed with, the mixed powder of forming less than 0.1% niobium powder less than 43 μ m, oxygen content with starch and mean diameter is mixed and made into niobium powder slurry; And be cast in the organic foam body; Dipping is filled with niobium powder slurry until organic foam body opening crack, and drying is removed the dispersant in the organic foam body that is cast with niobium powder slurry then, and ungrease treatment is to remove organic binder bond and organic foam body under inert gas shielding atmosphere; Sintering makes porous sintered body under the vacuum; Pile up on the foam framework that constitutes through agglomerating niobium powder, the niobium powder particles has the sintering neck structure each other, and annealing and conventional post processing make the porous niobium under the vacuum again; In the mixed powder of said metal niobium powder and starch, content of starch is 5～10%, by weight percentage.
The medical embedded material porous niobium that the inventive method makes has the foaming structure that the hole three-dimensional communication distributes, and has the sintering neck structure each other through agglomerating niobium powder particles.The pore structure that three-dimensional communication of the present invention distributes does not get rid of seldom that the three-dimensional hole of part is not communicated with, and for example accounting for that hole about 1% is not communicated with is to belong to negligible.Sintering neck of the present invention is meant that at high temperature, powder is heated, and bonds between the granule, is exactly the sintering phenomenon that we often say.Sintering is meant that the bonded process of metallurgical property at high temperature takes place between powder particle granule, carries out, and realize through atomic migration usually under the fusing point of main component constituent element.Observe through microstructure, 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, the perhaps 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, and the intensity of sintered body increases.Also be that the present invention forms the sintering neck structure also can realize the object of the invention between niobium powder particles partly.
In the method for preparing of the present invention, the employing ethyl cellulose is an organic adhesive, and ethyl cellulose is widely used in pharmaceutical industry, and it has better bio-safety performance; Dehydrated alcohol is a dispersant, and dehydrated alcohol is volatile, can save drying time effectively; Can after having flooded, detect sample interior whether have hollow, thereby can guarantee the dipping sizing agent quality evenly, also can reduce hydrogen, oxygen content in the porous niobium behind the sintering; Thereby the reduction impurity content, simultaneously, the porous niobium shape behind the dipping can be fixed up soon; Be not prone to distortion, guaranteed the stable of sample shape behind the sintering, size; The concentration of ethyl cellulose alcoholic solution of the present invention is low, viscosity is also little, and the quality that therefore immerses slurry is few, can improve the porosity of the porous niobium material that makes, thereby make the porous niobium material good biocompatibility that makes; The mixed powder that also adopts niobium powder and starch to form in the method for preparing of the present invention is raw material constituent; Can effectively increase columbic porosity of the porous that makes and aperture; Simultaneously starch is that people food, the safety used always are good; Starch also is prone to decompose, can improve the purity of the porous niobium material that finally makes, so the present invention can make the porous niobium material that makes have very superior biocompatibility and safety; But simultaneously, the inventor finds that in research process ethanol and polymer organic foam are prone to slow reaction takes place at normal temperatures, and the internal structure of destructible sample influences the mechanical property of material; Ethanol in the porous niobium is put the heating of stove the inside into without bone dry, because ethanol volume when heating expands rapidly, influences the purity and the mechanical property of material; When also having porosity and aperture excessive, can make that mechanical property can not get guaranteeing, the feasible easily porous niobium as the medical embedded material purposes can't practical application; The inventor also finds in research process simultaneously; The niobium powder be easy to starch and organic foam body in carbon react; Be prone to make the porous niobium medical embedded material impurity content that finally makes to raise, influence its biocompatibility and biological safety, also its mechanical property is had considerable influence.Around the problems referred to above; The inventor has launched series of studies; Thereby seek out other compositions in the preparation raw material such as organic bonding agent selection, dispersant selection and with all have more exquisitely above being used of mixed powder, cooperate follow-up treatment process steps, make the porous niobium material that makes not only have superior biocompatibility and safety; And its shape is consistent, mechanical property is also better, is specially adapted to the medical embedded material at the light position of human bearings such as frontal bone, facial bone.Simultaneously, simple, the easy control of described method for preparing technology; Whole process of preparation is harmless, pollution-free, the nonhazardous dust, and human body is had no side effect.
Organic foam body of the present invention can adopt similar substances such as polyurethane foam, polyether ester foam, optimization polyurethane foam.Said slurry is poured into a mould, impregnated in the said organic foam body; After drying is removed the dispersant in the organic foam body that is cast with niobium powder slurry then; The columbic porosity of porous that forms is between 59.2～77.7%; Hole average diameter 350～500 μ m form the sintering neck structure at least between said porous niobium 50% niobium powder particles, preferably form the sintering neck structure at least between 80% niobium powder particles.
In order to guarantee under the columbic bio-compatible implementations of medical material porous of the present invention; Further improve its mechanical property, be beneficial to the formation of sintering neck structure simultaneously, said slurry is that ethyl cellulose is heated to dissolving with dehydrated alcohol; Adopt the ethyl cellulose alcoholic solution of percentage by weight 1%～4% (preferred 3.5%) and the mixed powder of said metal niobium powder and starch to process niobium powder slurry; Wherein, content of starch is preferably 6% in the mixed powder of said metal niobium powder and starch, by weight percentage; With weight be the said mixed powder of 1～3 part (preferred 1.5 parts) to add weight be in 1 part the said ethyl cellulose alcoholic solution, stir and process starchiness; And to be cast in the aperture be 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, (preferred aperture is 0.56～0.72mm to hardness, density 0.025g/cm more than or equal to 50 °
3, 50 ° ~ 80 ° of hardness) polyurethane foam in.
The present invention selects mean diameter to help to reduce the content of impurity less than 43 μ m, oxygen content less than 0.1% metal niobium powder, guarantees that material has mechanical property preferably; Add starch and help increasing porosity and aperture; The selection aperture is 0.48～0.89mm, density 0.015 g/cm
3~ 0.035g/cm
3, hardness helps to guarantee columbic porosity of porous and pore diameter greater than 50 ° polyurethane foam.Process conditions have been optimized in the such technical finesse of the present invention, with the biocompatibility and the biological safety that guarantee to implant the porous niobium material, also help the formation of sintering neck structure simultaneously.
The present invention's further characteristics on the other hand are: exsiccant vacuum keeps 1 * 10
-2Pa～1Pa vacuum, under protective atmosphere, vacuum is lower than 1 * 10 then
-3Pa, the ungrease treatment of removing organic binder bond and organic foam body under 400 ℃～800 ℃ conditions of temperature; Be 1 * 10 in vacuum again
-4Pa～1 * 10
-3Pa, 1700～1800 ℃ of temperature, 4～6 hours vacuum-sintering of temperature retention time is handled and is made porous sintered body.Can also the filling with inert gas protection replace vacuum protection during the sintering process insulation; Carry out vacuum annealing at last and handle, wherein vacuum annealing is handled and is meant that process vacuum-sintering continued keeps temperature to be in 900～1100 ℃, temperature retention time 3～6 hours, and vacuum is not for being 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 ℃, feeds with noble gas such as argon to constitute protective atmosphere and be incubated 1.5～3h;
The vacuum-sintering condition also includes: vacuum is 1 * 10
-4Pa～1 * 10
-3Pa rises to 900 ℃～1400 ℃ with the heating rate of 10 ~ 20 ℃/min from room temperature, behind insulation 1h～2h; Be warming up to 1700～1800 ℃ with the heating rate that is lower than 20 ℃/min again, be incubated 2～4h at least;
Cooling condition after the vacuum-sintering also includes: vacuum is 1 * 10
-4Pa～1 * 10
-3Pa not to be higher than 15 ℃/min, to be not less than 10 ℃/min and gradually to fall the cooldown rate mode, and sintered porous bodies segmentation cooling is cooled to 600～800 ℃, and each section temperature retention time 0.5～1.5h cools to room temperature then with the furnace;
The vacuum annealing condition also includes: vacuum is not higher than 1 * 10
-3Pa rises to 900～1100 ℃ with the speed that is not higher than 20 ℃/min, insulation 4h～6h; Again with after earlier slow soon to be not less than 5 ℃/min but the cooldown rate segmentation that is not higher than 15 ℃/min is cooled to room temperature, the temperature retention time of each section tapers off and is no more than 3h.
Further characteristics are on this basis: 50～70 ℃ of said vacuum drying baking temperatures, 4～6 hours drying times; Said ungrease treatment condition also includes: progressively be warming up to 400～800 ℃; Feed 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 rises to 600～800 ℃, insulation 1～2h with the speed of 0.5～1.5 ℃/min from 400 ℃; Said vacuum-sintering condition also includes: the speed with 10～15 ℃/min rises to 900～1100 ℃ from room temperature, insulation 0.5～1h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 10～20 ℃/min rises to 1300～1400 ℃, insulation 0.5～1h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa rises to 1700～1800 ℃ with the speed of 6～20 ℃/min, insulation 3～4h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Cooling condition after the vacuum-sintering also includes: vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 13～15 ℃/min is cooled to 1200～1300 ℃, insulation 0.5～1h; Speed with 10～14 ℃/min is cooled to 600～1000 ℃, insulation 1～1.5h, furnace cooling then; Said vacuum annealing condition also includes: the speed with 15～20 ℃/min rises to 900～1100 ℃, insulation 4～6h, and vacuum is not higher than 1 * 10
-3Pa, the speed with 5～7 ℃/min is cooled to 800 ℃ again, insulation 1.5～3h, vacuum is not higher than 1 * 10
-3Pa; Speed with 10～14 ℃/min is cooled to 600 ℃, insulation 1.5～3h, and vacuum is not higher than 1 * 10
-3Pa; Speed with 12～15 ℃/min is cooled to room temperature, and vacuum is not higher than 1 * 10
-3Pa.
Specifically, the columbic method for preparing of a kind of medical embedded material porous:
A. the preparation of niobium powder slurry: ethyl cellulose is heated to dissolving with dehydrated alcohol; Be mixed with the ethyl cellulose alcoholic solution of percentage by weight 1～4% (preferred 3.5%); Stir less than the mixed powder of 0.1% metal niobium powder and starch less than 43 μ m, oxygen content with mean diameter and to process starchy niobium powder slurry; Wherein, starch accounts for 6% of said mixed powder weight; The weight part ratio of described mixed powder and said ethyl cellulose alcoholic solution is 1～3 part (preferred 1.5 parts): 1 part;
B. the columbic preparation of porous: above-mentioned niobium powder slurry is cast in the polyurethane foam organic foam body; Dipping is filled with niobium powder slurry until polyurethane foam organic foam body opening crack; Drying is removed the dispersant in the organic foam body that is cast with niobium powder slurry then; Ungrease treatment is to remove organic binder bond and organic foam body under inert gas shielding atmosphere, and sintering makes porous sintered body under the vacuum, piles up through agglomerating niobium powder on the foam framework that constitutes; The niobium powder particles has the sintering neck structure each other, and annealing and conventional post processing make the porous niobium under the vacuum again; 55 ℃ of said vacuum drying baking temperatures, 4.5 hours drying times; Said ungrease treatment condition is: progressively be warming up to 800 ℃, feed constitute protective atmosphere with pure argon gas (99.9999%), rise to 400 ℃ with the speed of 3 ℃/min from room temperature; Be incubated 0.5 hour; Rise to 600 ℃ with the speed of 1.5 ℃/min from 400 ℃, be incubated 1.0 hours, said vacuum-sintering condition is: the speed with 10 ℃/min rises to 1100 ℃ from room temperature; Insulation 60min, vacuum is 10
-3Pa; Speed with 11 ℃/min rises to 1400 ℃, insulation 60min, and vacuum is 10
-3Pa rises to 1780 ℃ with the speed of 7 ℃/min, insulation 240min, and vacuum is 10
-3Pa; Cooling condition after the vacuum-sintering is: vacuum is 10
-4Pa; Speed with 14 ℃/min is cooled to 1250 ℃, insulation 60min; Speed with 11 ℃/min is cooled to 900 ℃, insulation 90min; Speed with 10 ℃/min is cooled to 650 ℃, and insulation 72min is furnace cooling then; Said vacuum annealing condition is: the speed with 16 ℃/min rises to 900 ℃, insulation 360min, and vacuum is 10
-4Pa, the speed with 6 ℃/min is cooled to 800 ℃ again, insulation 180min, vacuum is 10
-4Pa; Speed with 12 ℃/min is cooled to 600 ℃, insulation 180min, vacuum 10
-4Pa; Speed with 13 ℃/min is cooled to room temperature, and vacuum is 10
-4Pa.
The medical embedded material porous niobium that makes through above-mentioned method for preparing can satisfy the requirement of bio-compatibility and biological safety fully; Particularly its foam framework is to be piled up by agglomerating pure niobium powder to constitute; The sintering neck structure that the niobium powder particles has has each other greatly improved mechanical property such as the ductility of this material, anti-folding anti-bending strength, is lower than 0.5% through its impurity content of test simultaneously; This porous niobium finished product even pore distribution and connection, density 1.5～3.8g/cm
3, porosity is between 59.2～77.7.0%, hole average diameter 350～500 μ m; Elastic modelling quantity 0.6～2.0GPa, yield strength 30～60MPa, comprcssive strength 25～60MPa, hardness 100～160MPa, amount of plastic deformation 6.4%～11.3%, tensile strength 15～35MPa, the elongation 6.3%～10.7% of having no progeny; Not only do not influence elastic modelling quantity, yield strength of porous material etc., and be to have improved these performance parameters that porous material is stressed.And when carrying out anti-bending test, the fracture rate of the sintering neck that forms between each niobium powder particles is less than 45%, and the fracture rate of niobium powder particles inside further illustrates new product reliability of structure of the present invention greater than 55%.
Description of drawings
Fig. 1 is the columbic X-ray diffraction analysis collection of illustrative plates of porous (XRD figure) of method for preparing preparation according to the invention;
Fig. 2 is the vertical microscope analysis chart of the columbic macrostructure of porous of method for preparing preparation according to the invention;
Fig. 3 is the scanning electron microscope analysis figure (SEM figure) of the columbic microstructure of porous of method for preparing preparation according to the invention.
Can be observed from accompanying drawing: 1, porous niobium high hole, even pore distribution and connection according to the invention.From accompanying drawing, can find out porous niobium three-dimensional communication hole of the present invention, this three-dimensional pore space helps that osteoblast adheres to, differentiation and growth, promotes growing into of bone, can strengthen being connected between implant and the bone, is beneficial to the realization biological fixation.2, the columbic mechanical property of porous according to the invention is good.Shown in accompanying drawing, the columbic sintering microstructure of porous of the present invention uniform particles, the sintering neck is obvious, has guaranteed the good mechanical performance, and has good ductility.
The specific embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present 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: take by weighing ethyl cellulose 8g, put into the container that the 240ml dehydrated alcohol is housed; Placing it in heats on the electric furnace and stir makes it to become the ethyl cellulose alcoholic solution.With 200g balance weighing mean diameter less than 43 microns, oxygen content less than 0.1% niobium powder 60g and 4g starch, add the refrigerative ethyl cellulose alcoholic solution of 15ml, mix, make it to become mixed slurry.(average pore size is 0.48mm, density 0.025g/cm to select 10 * 10 * 30mm cellular polyurethane foam for use
3, 50 ° of hardness) and put into wherein cast, fill with slurry until the polyurethane foam hole, the polyurethane foam that goes out to be filled slurry with clip is put into porcelain dish.Dry in vacuum drying oven, 60 ℃ of baking temperatures, drying time 6h, vacuum keeps 1Pa.Ungrease treatment: vacuum is lower than 1 * 10
-3Pa, 600 ℃ of temperature, temperature retention time 2h.Vacuum-sintering: sintering in vacuum drying oven, 1750 ℃ of sintering temperatures, insulation 4h, vacuum 1 * 10
-3Pa ~ 1 * 10
-4Pa, the protection of sintering process applying argon gas is removed surface dirt and dirt behind the taking-up product, and the sample that makes carries out conventional post processing again and gets porous niobium finished product.
The porous niobium finished product that adopts said method to make has the foaming structure that the hole three-dimensional communication distributes, and piles up on the foam framework that constitutes through agglomerating pure niobium powder, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the niobium powder particles in this porous niobium finished product microstructure surpasses 50%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous niobium finished product: this porous niobium is to have the pore structure that three-dimensional communication distributes; Its impurity content is lower than 0.5% finished product; Its even pore distribution and connection, density 2.5g/cm
3, porosity 71%, hole average diameter 350 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 carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 45% in this porous niobium microstructure, and the fracture rate of granule interior is greater than 55%.
Embodiment 2: take by weighing ethyl cellulose 6g, put into the container that the 200ml dehydrated alcohol is housed; Placing it in heats on the electric furnace and stir makes it to become the ethyl cellulose alcoholic solution.With 200g balance weighing mean diameter less than 43 μ m, oxygen content less than 0.1% niobium powder 40g and the starch of 2.15g, add 10ml ethyl cellulose alcoholic solution, mix, make it to become mixed slurry.(average pore size is 0.56mm, density 0.030g/cm to select 10 * 10 * 25mm cellular polyurethane foam for use
3, hardness 60
0) put into wherein cast, fill with slurry until the polyurethane foam hole, the polyurethane foam that goes out to be filled slurry with clip is put into porcelain dish.Dry in vacuum drying oven, 70 ℃ of baking temperatures, drying time 4h, vacuum keeps 1 * 10
-2Pa.Ungrease treatment: vacuum is lower than 1 * 10
-3Pa, 800 ℃ of temperature, temperature retention time 2.5h.Vacuum-sintering: sintering in vacuum drying oven, 1800 ℃ of sintering temperatures are incubated 4.5 hours, vacuum 1 * 10
-4Pa, the protection of sintering process applying argon gas is removed surface dirt and dirt behind the taking-up product, and the sample that makes carries out conventional post processing again and gets porous niobium finished product.
The porous niobium finished product that adopts said method to make has the foaming structure that the hole three-dimensional communication distributes, and piles up on the foam framework that constitutes through agglomerating pure niobium powder, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the niobium powder particles in this porous niobium finished product microstructure surpasses 60%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous niobium finished product: this porous niobium is to have the pore structure that three-dimensional communication distributes; Its impurity content is lower than 0.5% finished product; Its even pore distribution and connection, density 3g/cm
3, porosity 65%, hole average diameter 360 μ m, elastic modelling quantity 1.3GPa, yield strength 30MPa, comprcssive strength 40MPa, hardness 150MPa, amount of plastic deformation 10%, tensile strength 30MPa, the elongation 10% of having no progeny; When carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 40% in this porous niobium microstructure, and the fracture rate of granule interior is greater than 60%.
Embodiment 3: take by weighing ethyl cellulose 9g, put into the container that the 220ml dehydrated alcohol is housed; Placing it in heats on the electric furnace and stir makes it to become the ethyl cellulose alcoholic solution.With 200g balance weighing mean diameter less than 43 μ m, oxygen content less than 0.1% niobium powder 45g and 2.5g starch, add 12ml ethyl cellulose alcoholic solution, mix, make it to become mixed slurry.(average pore size is 0.70mm, density 0.035g/cm to select 8 * 8 * 25mm cellular polyurethane foam for use
3, 70 ° of hardness) and put into wherein cast, fill with slurry until the polyurethane foam hole, the polyurethane foam that goes out to be filled niobium powder slurry with clip is put into porcelain dish.Dry in vacuum drying oven, 68 ℃ of baking temperatures, drying time 6h, vacuum keeps 1 * 10
-1Pa.Ungrease treatment: vacuum is lower than 1 * 10
-3Pa, 700 ℃ of temperature, temperature retention time 1.5h.Vacuum-sintering: sintering in vacuum drying oven, 1700 ℃ of sintering temperatures are incubated 5.5 hours, vacuum 1 * 10
-3Pa, the protection of sintering process applying argon gas, cooling is come out of the stove, and removes product surface dust and dirt, and the sample that makes carries out conventional post processing again and gets porous niobium finished product.
The porous niobium finished product that adopts said method to make has the foaming structure that the hole three-dimensional communication distributes, and piles up on the foam framework that constitutes through agglomerating pure niobium powder, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the niobium powder particles in this porous niobium finished product microstructure surpasses 55%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous niobium finished product: this porous niobium is to have the pore structure that three-dimensional communication distributes; Its impurity content is lower than 0.5% finished product; Its even pore distribution and connection, density 3.4g/cm
3, porosity 61%, hole average diameter 400 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 carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 35% in this porous niobium microstructure, and the fracture rate of granule interior is greater than 65%.
Embodiment 4: take by weighing ethyl cellulose 7g, put into the container that the 230ml dehydrated alcohol is housed; Placing it in heats on the electric furnace and stir makes it to become the ethyl cellulose alcoholic solution.With 200g balance weighing mean diameter less than 43 μ m, oxygen content less than 0.1% niobium powder 50g and 4.5g starch, add 13ml ethyl cellulose alcoholic solution, mix, make it to become mixed slurry.(aperture is 0.60mm, density 0.027g/cm to select 12 * 12 * 30mm cellular polyurethane foam for use
3, 80 ° of hardness) and put into wherein cast, fill with slurry until the polyurethane foam hole, the polyurethane foam that goes out to be filled slurry with clip is put into porcelain dish.Dry in vacuum drying oven, 70 ℃ of baking temperatures, drying time 5h, vacuum keeps 1Pa.Ungrease treatment: vacuum 1 * 10
-4Pa～1 * 10
-3Pa, 500 ℃ of temperature, temperature retention time 3h.Vacuum-sintering: sintering in vacuum drying oven, 1750 ℃ of sintering temperatures are incubated 4.5 hours, vacuum 1 * 10
-4Pa, the protection of sintering process applying argon gas, cooling is come out of the stove, and removes product surface dust and dirt, and the sample that makes carries out conventional post processing again and gets porous niobium finished product.
The porous niobium finished product that adopts said method to make has the foaming structure that the hole three-dimensional communication distributes, and piles up on the foam framework that constitutes through agglomerating pure niobium powder, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the niobium powder particles in this porous niobium finished product microstructure surpasses 70%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous niobium finished product: this porous niobium is to have the pore structure that three-dimensional communication distributes; Its impurity content is lower than 0.5% 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 carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 43% in this porous niobium microstructure, and the fracture rate of granule interior is greater than 57%.
Embodiment 5: a kind of porous niobium, and it is raw material less than 43 μ m, oxygen content less than 0.1% metal niobium powder and starch with particle diameter, adopting percentage by weight is that 1～4% ethyl cellulose alcoholic solution is processed mixed slurry, and is cast in the polyurethane foam carrier; Vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make then.
Wherein, the polyurethane foam of selecting for use, its aperture is 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, hardness is greater than 50 °;
Vacuum drying: vacuum keeps 10
-2～1Pa is to remove the ethanol in the polyurethane foam of filling with slurry;
Ungrease treatment: under inert gas shielding atmosphere or vacuum be lower than 1 * 10
-3Pa, 400 ℃～800 ℃ of temperature, and temperature retention time 1.5～3 hours is to remove ethyl cellulose and polyurethane foam wherein;
Vacuum-sintering: vacuum 1 * 10
-4Pa～1 * 10
-3Pa, 1700～1800 ℃ of temperature, temperature retention time 4～6 hours, applying argon gas or other inert gas shielding during the sintering process insulation are to obtain porous material;
Vacuum annealing: keep temperature to be in 900～1100 ℃ through the vacuum-sintering continued, temperature retention time 3～6 hours, vacuum is not higher than 1 * 10
-3Pa handles to carry out stress relief annealing; The sample that makes carries out conventional post processing again and gets 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 pile up on the foam framework that constitutes through agglomerating pure niobium powder, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the niobium powder particles in this porous niobium finished product microstructure surpasses 80%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous niobium finished product: this porous niobium is to have the pore structure that three-dimensional communication distributes; Its impurity content is lower than 0.5% finished product; Its even pore distribution and connection, density 1.5～3.8g/cm
3, porosity is between 59.2～77.7%, hole average diameter 350～500 μ m; Elastic modelling quantity 0.6～2.0GPa, yield strength 30～60MPa, comprcssive strength 25～60MPa, hardness 100～160MPa, amount of plastic deformation 6.4%～11.3%, tensile strength 15～35MPa, the elongation 6.3%～10.7% of having no progeny; When carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 45% in this porous niobium microstructure, and the fracture rate of granule interior is greater than 55%.
Embodiment 6: a kind of porous niobium; It is raw material less than 43 μ m, oxygen content less than 0.1% metal niobium powder and starch with particle diameter; With the ethyl cellulose alcoholic solution is that binder solution is processed niobium powder slurry, 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 °; Vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make then.
Wherein, using dehydrated alcohol to be heated to dissolving ethyl cellulose, to be mixed with percentage by weight be 3.5% ethyl cellulose alcoholic solution; Then with weight be 1～3 part metal niobium powder to add cooled weight be in 1 part the said ethyl cellulose alcoholic solution, stir and process starchiness; Again above-mentioned polyurethane foam is put into and be starchy niobium powder slurry and flood repeatedly until the polyurethane foam hole and fill with;
Vacuum drying is removing the ethanol in the polyurethane foam of filling with niobium powder slurry, and vacuum keeps 1Pa, 50～70 ℃ of baking temperatures, drying time 4～6h;
The dried polyurethane foam of against vacuum places the tungsten device to put 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, feed earlier 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, and argon feeds speed 0.5L/min; Speed with 0.5 ℃/min rises to 800 ℃, insulation 2h, argon feeding speed 1L/min from 400 ℃; Powered-down again, the sample furnace cooling after the defat, argon feeds speed 1L/min, when being cooled to room temperature, closes argon;
Place with the tungsten device for the sample after the ungrease treatment to be warming up to 1800 ℃ with certain heating rate in the fine vacuum high temperature sintering furnace and to carry out vacuum-sintering, the vacuum of sintering furnace will reach 1 * 10 at least before heating up
-3Pa rises 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 3h, and vacuum is 1 * 10
-3Pa; Sintering finishes, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 15 ℃/min is cooled to 1300 ℃, insulation 1h; Speed with 14 ℃/min is cooled to 800 ℃, insulation 1.5h, furnace cooling then;
The cooled sample of against vacuum sintering places vacuum annealing furnace to be warming up to 1000 ℃ with certain heating rate with the corundum container to carry out stress relief annealing and handle, and the vacuum before heating up in the annealing furnace will reach 1 * 10 at least
-3Pa rises to 1000 ℃ with the speed of 15 ℃/min from room temperature, insulation 4h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 5 ℃/min is cooled to 800 ℃ again, insulation 3h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 10 ℃/min is cooled to 600 ℃, insulation 2h, and vacuum is 1 * 10
-4Pa; Speed with 15 ℃/min is cooled to room temperature, and vacuum is 1 * 10
-4Pa.Carry out conventional post processing at last and make the 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 piles up on the foam framework that constitutes through agglomerating pure niobium powder, and the niobium powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the niobium powder particles in this porous niobium finished product microstructure surpasses 80%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous niobium finished product: this porous niobium is to have the pore structure that three-dimensional communication distributes; Its impurity content is lower than 0.5% finished product; Its even pore distribution and connection, density 2.45g/cm
3, porosity 72.5%, hole average diameter 350 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 carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 40% in this porous niobium microstructure, and the fracture rate of granule interior is greater than 60%.
In the method that the foregoing description 6 provides, we can also do other to wherein each kind of condition and select can obtain equally porous niobium of the present invention.In following embodiment, if do not specify that the parameters condition is all identical with previous embodiment 6 in the table.
Gained porous niobium finished product is pressed preceding method and is detected:
Claims (7)
1. columbic method for preparing of medical embedded material porous; Adopt foam impregnation method sintering to form, it is characterized in that: be that the employing ethyl cellulose is that organic binder bond and dehydrated alcohol are the solution that dispersant is mixed with, the mixed powder of forming less than 0.1% niobium powder less than 43 μ m, oxygen content with starch and mean diameter is mixed and made into niobium powder slurry; And be cast in the organic foam body; Dipping is filled with niobium powder slurry until organic foam body opening crack, and drying is removed the dispersant in the organic foam body that is cast with niobium powder slurry then, and ungrease treatment is to remove organic binder bond and organic foam body under inert gas shielding atmosphere; Sintering makes porous sintered body under the vacuum; Pile up on the foam framework that constitutes through agglomerating niobium powder, the niobium powder particles has the sintering neck structure each other, and annealing and conventional post processing make the porous niobium under the vacuum again; In the mixed powder of said metal niobium powder and starch, content of starch is 5～10%, by weight percentage.
2. method for preparing as claimed in claim 1 is characterized in that: described organic foam body is a polyurethane foam; Said slurry is poured into a mould, impregnated in the said organic foam body; After drying is removed the dispersant in the organic foam body that is cast with niobium powder slurry then; The columbic porosity of porous that forms is between 59.2～77.7%; Hole average diameter 350～500 μ m form the sintering neck structure at least between said porous niobium 50% niobium powder particles.
3. according to claim 1 or claim 2 method for preparing; It is characterized in that: said slurry is that ethyl cellulose is heated to dissolving with dehydrated alcohol; Adopt the ethyl cellulose alcoholic solution of percentage by weight 1%～4% and the mixed powder of said metal niobium powder and starch to process niobium powder slurry; Wherein, content of starch is 6% in the mixed powder of said metal niobium powder and starch, by weight percentage; With weight be 1～3 part said mixed powder to add weight be in 1 part the said ethyl cellulose alcoholic solution, stir and process starchiness; And to be cast in the aperture be 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, hardness is more than or equal in 50 ° the polyurethane foam.
4. method for preparing as claimed in claim 3 is characterized in that: the weight part ratio of said mixed powder and ethyl cellulose alcoholic solution is 1.5:1; The aperture of said polyurethane foam is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness; The mass percentage concentration of said ethyl cellulose alcoholic solution is 3.5%.
5. like each described method for preparing of claim 1～4, it is characterized in that: said exsiccant vacuum keeps 1 * 10
-2Pa～1Pa vacuum, under protective atmosphere, vacuum is lower than 1 * 10 then
-3Pa, the ungrease treatment of removing organic binder bond and organic foam body under 400 ℃～800 ℃ conditions of temperature; Be 1 * 10 in vacuum again
-4Pa～1 * 10
-3Pa, 1700～1800 ℃ of temperature, 4～6 hours vacuum-sintering of temperature retention time is handled and is made porous sintered body, can also the filling with inert gas protection replace vacuum protection during the sintering process insulation; Carry out vacuum annealing at last and handle, wherein vacuum annealing is handled and is meant that process vacuum-sintering continued keeps temperature to be in 900～1100 ℃, temperature retention time 3～6 hours, and vacuum is not for being higher than 1 * 10
-3Pa.
6. method for preparing as claimed in claim 5; It is characterized in that: said ungrease treatment condition also includes: the speed with 0.5 ℃/min～3 ℃/min progressively is warming up to 400～800 ℃, feeds with noble gas such as argon to constitute protective atmosphere and be incubated 1.5～3h;
The vacuum-sintering condition also includes: vacuum is 1 * 10
-4Pa～1 * 10
-3Pa rises to 900 ℃～1400 ℃ with the heating rate of 10 ~ 20 ℃/min from room temperature, behind insulation 1h～2h; Be warming up to 1700～1800 ℃ with the heating rate that is lower than 20 ℃/min again, be incubated 2～4h at least;
Cooling condition after the vacuum-sintering also includes: vacuum is 1 * 10
-4Pa～1 * 10
-3Pa not to be higher than 15 ℃/min, to be not less than 10 ℃/min and gradually to fall the cooldown rate mode, and sintered porous bodies segmentation cooling is cooled to 600～800 ℃, and each section temperature retention time 0.5～1.5h cools to room temperature then with the furnace;
The vacuum annealing condition also includes: vacuum is not higher than 1 * 10
-3Pa rises to 900～1100 ℃ with the speed that is not higher than 20 ℃/min, insulation 4h～6h; Again with after earlier slow soon to be not less than 5 ℃/min but the cooldown rate segmentation that is not higher than 15 ℃/min is cooled to room temperature, the temperature retention time of each section tapers off and is no more than 3h.
7. method as claimed in claim 6 is characterized in that: 50～70 ℃ of said vacuum drying baking temperatures, 4～6 hours drying times; Said ungrease treatment condition also includes: progressively be warming up to 400～800 ℃; With purity is that 99.9999% argon feeds the formation protective atmosphere; Speed with 1～3 ℃/min rises to 400 ℃ from room temperature; Insulation 0.5～1h rises to 600～800 ℃, insulation 1～2h with the speed of 0.5～1.5 ℃/min from 400 ℃; Said vacuum-sintering condition also includes: the speed with 10～15 ℃/min rises to 900～1100 ℃ from room temperature, insulation 0.5～1h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 10～20 ℃/min rises to 1300～1400 ℃, insulation 0.5～1h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa rises to 1700～1800 ℃ with the speed of 6～20 ℃/min, insulation 3～4h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Cooling condition after the vacuum-sintering also includes: vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 13～15 ℃/min is cooled to 1200～1300 ℃, insulation 0.5～1h; Speed with 10～14 ℃/min is cooled to 600～1000 ℃, insulation 1～1.5h, furnace cooling then; Said vacuum annealing condition also includes: the speed with 15～20 ℃/min rises to 900～1100 ℃, insulation 4～6h, and vacuum is not higher than 1 * 10
-3Pa, the speed with 5～7 ℃/min is cooled to 800 ℃ again, insulation 1.5～3h, vacuum is not higher than 1 * 10
-3Pa; Speed with 10～14 ℃/min is cooled to 600 ℃, insulation 1.5～3h, and vacuum is not higher than 1 * 10
-3Pa; Speed with 12～15 ℃/min is cooled to room temperature, and vacuum is not higher than 1 * 10
-3Pa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010563419.XA CN102475903B (en) | 2010-11-29 | 2010-11-29 | Preparation method for medical metal implant material porous niobium |
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Cited By (4)
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| CN102864322A (en) * | 2012-09-10 | 2013-01-09 | 西安工程大学 | Method for preparing high-porosity material by formed knitting technology |
| CN103805798A (en) * | 2014-02-20 | 2014-05-21 | 中南大学 | Porous tantalum-niobium alloy and preparation method thereof |
| WO2017028771A1 (en) * | 2015-08-18 | 2017-02-23 | 重庆润泽医药有限公司 | Porous material |
| WO2017050134A1 (en) * | 2015-09-21 | 2017-03-30 | 重庆润泽医药有限公司 | Use of porous material |
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| CN101195048A (en) * | 2006-12-08 | 2008-06-11 | 许才德 | Compound medicament washing bracket and method for preparing the same |
| CN101448534A (en) * | 2006-05-17 | 2009-06-03 | 生物技术公司 | Anisotropic nanoporous coatings for medical implants |
| CN101660076A (en) * | 2009-10-14 | 2010-03-03 | 北京师范大学 | Macro mesh structural porous tantalum prepared by dipping and sintering organic foams |
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| US20050048193A1 (en) * | 2001-02-19 | 2005-03-03 | Isotis N.V. | Porous metals and metal coatings for implants |
| CN101448534A (en) * | 2006-05-17 | 2009-06-03 | 生物技术公司 | Anisotropic nanoporous coatings for medical implants |
| CN101195048A (en) * | 2006-12-08 | 2008-06-11 | 许才德 | Compound medicament washing bracket and method for preparing the same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102864322A (en) * | 2012-09-10 | 2013-01-09 | 西安工程大学 | Method for preparing high-porosity material by formed knitting technology |
| CN102864322B (en) * | 2012-09-10 | 2014-07-30 | 西安工程大学 | Method for preparing high-porosity material by formed knitting technology |
| CN103805798A (en) * | 2014-02-20 | 2014-05-21 | 中南大学 | Porous tantalum-niobium alloy and preparation method thereof |
| WO2017028771A1 (en) * | 2015-08-18 | 2017-02-23 | 重庆润泽医药有限公司 | Porous material |
| US10597755B2 (en) | 2015-08-18 | 2020-03-24 | Chongqing Runze Pharmaceutical Co., Ltd. | Porous material |
| WO2017050134A1 (en) * | 2015-09-21 | 2017-03-30 | 重庆润泽医药有限公司 | Use of porous material |
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