CN102475902A - Preparation method of medical porous metal implant material - Google Patents
Preparation method of medical porous metal implant material Download PDFInfo
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- CN102475902A CN102475902A CN2010105634185A CN201010563418A CN102475902A CN 102475902 A CN102475902 A CN 102475902A CN 2010105634185 A CN2010105634185 A CN 2010105634185A CN 201010563418 A CN201010563418 A CN 201010563418A CN 102475902 A CN102475902 A CN 102475902A
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Abstract
A preparation method of a medical porous metal implant material includes steps of mixing solution, prepared by starch which serves as an organic binder and distilled water which serves as a dispersant, with niobium powder of the average particle size smaller than 43 mu m and oxygen content lower than 0.1% to prepare niobium slurry, pouring the niobium slurry into an organic foam body, impregnating the organic foam body until holes of the organic foam body are filled with the niobium slurry, drying and removing the dispersant, removing the organic binder and the organic foam body in a degreasing manner under the protection atmosphere of inert gas, producing a porous sintered body by vacuum sintering, and finally preparing porous niobium after vacuum annealing and conventional post-treatments, wherein the mass percentage concentration of starch solution ranges from 2% to 6%. The porous niobium of the medical metal implant material, which is prepared by the preparation method, has excellent biological compatibility and safety. Meanwhile, since the porous niobium has the sintered neck structure, mechanical properties such as ductility and the like of the porous niobium are improved, and the preparation method is good and convenient for practical application of the porous niobium in medical metal implanting.
Description
Technical field
The present invention relates to a kind of medical metal and implant the method for preparing of porous material, be specifically related to the columbic method for preparing of a kind of porous, relate in particular to a kind of method for preparing that is applicable to the porous niobium embedded material that biocompatibility and safety are good 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 good medical metal of a kind of biocompatibility and biological safety to implant the method for preparing of porous material, the medical metal that the inventive method makes is implanted the porous niobium material and is specially adapted to the medical embedded material as the coupling member of shoulder bone, skull and facial bone tissue injury or defect.
The objective of the invention is to realize through following technical scheme:
A kind of medical metal is implanted the method for preparing of porous material; Adopt foam impregnation method sintering to form; It is characterized in that: be that employing starch is that organic binder bond and distilled water are that solution and the mean diameter that dispersant is mixed with processed niobium powder slurry less than 43 μ m, oxygen content less than 0.1% niobium powder, and be cast in the organic foam body that dipping is filled with niobium powder slurry until 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 on the foam framework that constitutes through agglomerating pure 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; The mass percentage concentration of said amidin is 2～6%.
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 porous niobium that the present invention implants purposes for medical metal finds a kind of practicable method for preparing; The present invention adopts starch as binding agent; Its low price, because starch is the food that people use always, its biological safety of additive when therefore preparing as biomaterial is good; Starch slurry viscosity of the present invention is little; The porosity that starch size floods the sample perforate that is bigger; Sample surfaces after drying is removed dispersant is not prone to the phenomenon in plugging hole crack, moreover starch just can decompose water outlet and carbon dioxide at low temperatures as Organic substance; Improved the purity of sample, made the porous niobium of the medical metal embedded material that makes have superior bio-compatibility and biological safety; But be that the slurry of bonding agent is when being used for infusion process preparation porous niobium medical embedded material with starch; Adhesion in the porous niobium that makes between the niobium powder is less, porosity is bigger; Be prone to make that mechanical property can not get guaranteeing; Make the porous niobium as the medical embedded material purposes not possess practical value, therefore not will consider with starch usually is that bonding agent adopts the porous niobium of immersion process for preparing as medical embedded material.The inventor also finds in research process, 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.But the present invention reasonably cooperates through adopting described technological means; Make that the present invention is that the slurry of bonding agent adopts porous niobium that infusion process makes under the situation that does not influence the common mechanical property that existing porous niobium had with starch; Still can obtain having the porous niobium of sintering neck structure; Mechanical properties such as porous niobium ductility have been improved, for convenience and the application of actual effect of porous niobium in medical metal is implanted provides good method.The porous niobium that adopts method for preparing according to the invention to make is specially adapted to the medical embedded material as the coupling member of the osseous tissue wound of skull, shoulder or bone defect.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.
Above-mentioned organic foam body can adopt similar substances such as polyurethane foam, polyether ester foam, optimization polyurethane foam of the present invention.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 51.0～77.7%; Hole average diameter 200～500 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 starch is heated to dissolving with distilled water; The preferred amidin and the said metal niobium powder of percentage by weight 5% of adopting processed niobium powder slurry; Wherein, with weight be the metal niobium powder of 3～5 parts (preferred 4 parts) to add weight be in 1 part the said amidin, 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.
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.
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, 3～5 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 1～3 hour, 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 2h at least;
Cooling condition after the vacuum-sintering also includes: vacuum is 1 * 10
-4Pa～1 * 10
-3Pa not to be higher than 25 ℃/min, to be not less than 15 ℃/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 30 ℃/min, insulation 4h～6h; Again with after earlier slow soon to be not less than 10 ℃/min but the cooldown rate segmentation that is not higher than 30 ℃/min is cooled to room temperature, the temperature retention time of each section tapers off and is no more than 1.5 h.
Further characteristics are on this basis: 70～80 ℃ of said vacuum drying baking temperatures, 6～8 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 2～3h, 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 15～20 ℃/min is cooled to 1200～1300 ℃, insulation 0.5～1h; Speed with 18～25 ℃/min is cooled to 600～1000 ℃, insulation 1～1.5h, furnace cooling then; Said vacuum annealing condition also includes: the speed with 22～30 ℃/min rises to 900～1100 ℃, insulation 4～6h, and vacuum is not higher than 1 * 10
-3Pa, the speed with 10～15 ℃/min is cooled to 800 ℃ again, insulation 0.5～1.5h, vacuum is not higher than 1 * 10
-3Pa; Speed with 16～20 ℃/min is cooled to 600 ℃, insulation 0.5～1.5h, 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, the columbic method for preparing of a kind of medical embedded material porous:
A. the preparation of niobium powder slurry: starch is heated to dissolving with distilled water; Be mixed with the amidin of percentage by weight 2～6% (preferred 5%); Stir less than 0.1% metal niobium powder less than 43 μ m, oxygen content with mean diameter and to process starchy niobium powder slurry; Wherein, the weight part ratio of described metal niobium powder and said amidin is 3～5 parts (preferred 4 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 on the foam framework that constitutes through agglomerating pure 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; 70 ℃ of said vacuum drying baking temperatures, 6.5 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 1.5 ℃/min from room temperature; Be incubated 1 hour; Rise to 800 ℃ with the speed of 1.0 ℃/min from 400 ℃, be incubated 2 hours, said vacuum-sintering condition is: the speed with 15 ℃/min rises to 1100 ℃ from room temperature; Insulation 30min, vacuum is 10
-4Pa; Speed with 18 ℃/min rises to 1350 ℃, insulation 30min, and vacuum is 10
-4Pa rises to 1800 ℃ with the speed of 17 ℃/min, insulation 120min, and vacuum is 10
-4Pa; Cooling condition after the vacuum-sintering is: vacuum is 10
-3Pa; Speed with 16 ℃/min is cooled to 1300 ℃, insulation 30min; Speed with 20 ℃/min is cooled to 1100 ℃, insulation 60min; Speed with 18 ℃/min is cooled to 700 ℃, and insulation 60min is furnace cooling then; Said vacuum annealing condition is: the speed with 24 ℃/min rises to 1050 ℃, insulation 240min, and vacuum is 10
-3Pa, the speed with 13 ℃/min is cooled to 800 ℃ again, insulation 60min, vacuum is 10
-3Pa; Speed with 18 ℃/min is cooled to 600 ℃, insulation 60min, vacuum 10
-3Pa; Speed with 25 ℃/min is cooled to room temperature, and vacuum is 10
-3Pa.
The medical embedded material porous niobium that above-mentioned method for preparing makes 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 0.3% through its impurity content of test simultaneously; This porous niobium finished product even pore distribution and connection, density 2.0～4.2g/cm
3, porosity is between 51.0～77.7%, hole average diameter 200～500 μ m; Elastic modelling quantity 0.8～2.0GPa, yield strength 35～60MPa, comprcssive strength 35～65MPa, hardness 100～200MPa, amount of plastic deformation 9.4%～17.3%, tensile strength 20～45 MPa, the elongation 9.3%～14.7% 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 starch 8g, put into the container that the 240ml distilled water is housed; Placing it in heats on the electric furnace and stir makes it to become amidin.With 200g balance weighing mean diameter less than 43 microns, oxygen content less than 0.1% niobium powder 60g, add 15ml cooled starch aqueous solution, mix, make it to become niobium powder 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 niobium powder 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, 70 ℃ of baking temperatures, drying time 8h, 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 3h, 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 0.3% finished product; Its even pore distribution and connection, density 2.5g/cm
3, porosity 71%, hole average diameter 300 μ m, elastic modelling quantity 2.0GPa, yield strength 35MPa, comprcssive strength 50MPa, hardness 110MPa, amount of plastic deformation 17.3%, tensile strength 45MPa, the elongation 14.7% 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 starch 5g, put into the container that the 200ml distilled water is housed; Placing it in heats on the electric furnace and stir makes it to become amidin.With 200g balance weighing mean diameter less than 43 μ m, oxygen content less than 0.1% niobium powder 40g, add the 10ml amidin, mix, make it to become niobium powder 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 niobium powder 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, 80 ℃ 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 6h.Vacuum-sintering: sintering in vacuum drying oven, 1800 ℃ of sintering temperatures are incubated 4 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 0.3% finished product; Its even pore distribution and connection, density 3g/cm
3, porosity 65%, hole average diameter 200 μ m, elastic modelling quantity 1.5GPa, yield strength 50MPa, comprcssive strength 60MPa, hardness 150MPa, amount of plastic deformation 17%, tensile strength 40MPa, the elongation 14% 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 starch 6g, put into the container that the 220ml distilled water is housed; Placing it in heats on the electric furnace and stir makes it to become amidin.With 200g balance weighing mean diameter less than 43 μ m, oxygen content less than 0.1% niobium powder 45g, add the 12ml amidin, mix, make it to become niobium powder 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 niobium powder 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, 78 ℃ 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 3.5 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 0.3% finished product; Its even pore distribution and connection, density 4.2g/cm
3, porosity 51%, hole average diameter 300 μ m, elastic modelling quantity 1.0GPa, yield strength 50MPa, comprcssive strength 40MPa, hardness 150MPa, amount of plastic deformation 17.2%, tensile strength 35MPa, the elongation 14.5% 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 starch 7g, put into the container that the 230ml distilled water is housed; Placing it in heats on the electric furnace and stir makes it to become amidin.With 200g balance weighing mean diameter less than 43 μ m, oxygen content less than 0.1% niobium powder 50g, add the 13ml amidin, mix, make it to become niobium powder 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 niobium powder 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, 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 2h.Vacuum-sintering: sintering in vacuum drying oven, 1750 ℃ of sintering temperatures are incubated 4 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 50MPa, comprcssive strength 60MPa, hardness 100MPa, amount of plastic deformation 17.3%, tensile strength 42MPa, the elongation 14.6% 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 with particle diameter, adopting percentage by weight is that 2～6% amidins are processed niobium powder 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 moisture in the polyurethane foam of filling with niobium powder 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 starch 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 are to obtain porous material;
Vacuum annealing: keep temperature to be in 900～1100 ℃ through the vacuum-sintering continued, temperature retention time 1～3 hour, vacuum is lower 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 0.3% finished product; Its even pore distribution and connection;, density 2.0～4.2g/cm
3, porosity is between 51.0～77.7%, hole average diameter 200～500 μ m; Elastic modelling quantity 0.8～2.0GPa, yield strength 35～60MPa, comprcssive strength 35～65MPa, hardness 100～200MPa, amount of plastic deformation 9.4%～17.3%, tensile strength 20～45 MPa, the elongation 9.3%～14.7% 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 with particle diameter, is that binder solution is processed niobium powder slurry with the amidin, 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, starch is heated to dissolving with distilled water and is mixed with percentage by weight 5% amidin; Then with weight be 3～5 parts metal niobium powder to add cooled weight be in 1 part the said amidin, 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 moisture in the polyurethane foam of filling with niobium powder slurry, and vacuum keeps 1Pa, 70～80 ℃ of baking temperatures, drying time 6～8h;
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 2h, 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 20 ℃/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 22 ℃/min from room temperature, insulation 4h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 15 ℃/min is cooled to 800 ℃ again, insulation 1.5h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 16 ℃/min is cooled to 600 ℃, insulation 1h, and vacuum is 1 * 10
-4Pa; Speed with 20 ℃/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 0.3% 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 55MPa, comprcssive strength 60MPa, hardness 130MPa, amount of plastic deformation 11.4%, tensile strength 37MPa, the elongation 14.7% 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. a medical metal is implanted the method for preparing of porous material; Adopt foam impregnation method sintering to form; It is characterized in that: be that employing starch is that organic binder bond and distilled water are that solution and the mean diameter that dispersant is mixed with processed niobium powder slurry less than 43 μ m, oxygen content less than 0.1% niobium powder, and be cast in the organic foam body that dipping is filled with niobium powder slurry until 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 on the foam framework that constitutes through agglomerating pure 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; The mass percentage concentration of said amidin is 2～6%.
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 tantalum powder slurry then; The columbic porosity of porous that forms is between 51.0～77.7%; Hole average diameter 200～500 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 starch is heated to dissolving with distilled water; Adopt the amidin and the said metal niobium powder of percentage by weight 5% to process niobium powder slurry; Wherein, with weight be 3～5 parts metal niobium powder to add weight be in 1 part the said amidin, 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 metal niobium powder and amidin is 4:1; The aperture of said polyurethane foam is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness.
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, 3～5 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 1～3 hour, 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 2h at least;
Cooling condition after the vacuum-sintering also includes: vacuum is 1 * 10
-4Pa～1 * 10
-3Pa not to be higher than 25 ℃/min, to be not less than 15 ℃/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 30 ℃/min, insulation 4h～6h; Again with after earlier slow soon to be not less than 10 ℃/min but the cooldown rate segmentation that is not higher than 30 ℃/min is cooled to room temperature, the temperature retention time of each section tapers off and is no more than 1.5 h.
7. method as claimed in claim 6 is characterized in that: 70～80 ℃ of said vacuum drying baking temperatures, 6～8 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 2～3h, 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 15～20 ℃/min is cooled to 1200～1300 ℃, insulation 0.5～1h; Speed with 18～25 ℃/min is cooled to 600～1000 ℃, insulation 1～1.5h, furnace cooling then; Said vacuum annealing condition also includes: the speed with 22～30 ℃/min rises to 900～1100 ℃, insulation 4～6h, and vacuum is not higher than 1 * 10
-3Pa, the speed with 10～15 ℃/min is cooled to 800 ℃ again, insulation 0.5～1.5h, vacuum is not higher than 1 * 10
-3Pa; Speed with 16～20 ℃/min is cooled to 600 ℃, insulation 0.5～1.5h, 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.
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