CN103520768B - Preparation method of medical implant material porous niobium - Google Patents
Preparation method of medical implant material porous niobium Download PDFInfo
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Abstract
A preparation method of a medical implant material porous niobium comprises the following steps: preparing ethyl cellulose as an organic binder and absolute ethanol as a dispersant into a solution; mixing the solution with mixed powder composed of starch and niobium powder with the mean particle diameter of less than 43 microns and the oxygen content of less than 0.1% to prepare niobium powder slurry; pouring; dipping in an organic foam; drying, degreasing in an inert gas atmosphere; sintering under vacuum to obtain a porous sintered body having sintering neck structures between the sintered niobium powder particles; and annealing under vacuum; and performing conventional posttreatment to obtain the porous niobium, wherein in the mixed powder of the metal niobium powder and the starch, the starch content is 5-10%. The prepared medical metal implant material porous niobium has excellent biocompatibility and bio-safety; the porous niobium has the sintering neck structures, so that the ductility and other mechanical properties of the porous niobium are improved; and a very good method is provided for convenient and effective application of the porous niobium to medical metal implantation.
Description
The present patent application is application number 201010563419.X, November 29 2010 applying date, the divisional application of denomination of invention " preparation method of medical metal implant material porous niobium ".
Technical field
The present invention relates to a kind of preparation method of the porous niobium as medical embedded material, particularly a kind of preparation method of the porous niobium embedded material that is applicable to the position that human bearing is light.
Background technology
Porous medical metal implanted material has the important and special purposes such as treatment osseous tissue wound and bone formation necrosis, and existing this common class material has porous metals rustless steel, porous metals titanium etc.As the porous embedded material of osseous tissue wound and the use of bone formation necrosis therapeutic, its porosity should reach 30～80%, and hole is preferably all communicated with and is uniformly distributed, or hole part is communicated with and is uniformly distributed as required, make it both consistent with the bone growth of human body, alleviate again the weight of material itself, implanted use to be applicable to human body.
And refractory metal niobium, because it has outstanding bio-compatibility and mechanical property, its porous material is expected to the conventional medical metallic biomaterial such as aforementioned as an alternative, becomes the biomaterial mainly as bone necrosis's treatment.Due to metal niobium to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, niobium is goed deep into as the further of body implanting material cognition, and to human body, implantation becomes more and more urgent by the demand of porous metals niobium material to people, also more and more higher to its requirement., as the medical embedded metal niobium of porous, if can there is the very high physical and mechanical properties that is uniformly distributed interconnected pore and adapts with human body, be wherein the heavy connection constituent material that ensures freshman bone tissue's normal growth.
Just as one porous metal material, be taking powder sintering as main processing method substantially as medical embedded porous metal material, in particular for obtain porosity communication and equally distributed porous metal structure foam adopt metal dust slurry in the powder sintering dipping on Organic Foam Material afterwards the dry knot that reburns to be called for short foam impregnation method in the majority.About powder sintered obtained porosity communication and equally distributed porous metal material conventionally its Metal Mechanic Property be not fine, its main cause is the problem of subsiding how arranging in technique in the support of pore-forming medium and elimination relation, metal powder sintered process.And in known bibliographical information, all there is no good solution and laissez-faire nature.
Adopt metal powder sintered legal system to make the bibliographical information of porous niobium little, particularly to obtain medical embedded material with almost not having as the porous niobium powder sintering bibliographical information of object.Can reference be that publication number is CN200510032174, title " three-dimensional through hole or part hole porous metal foam connected with each other and preparation method thereof " and CN200710152394, title " a kind of porous foam tungsten and preparation method thereof ".But its porous metals that obtain or for filtering material use, or share for Aero-Space and other high-temperature field but not use as medical metal implanted material, moreover also non-porous niobium of the porous metals of processing.
At present, directly using porous niobium as medical embedded material and the document of related manufacturing processes have no report.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, and therefore the chemical property of the two is extremely similar.And about porous tantalum, US5282861 discloses a kind of perforate tantalum material and preparation thereof that is applied to spongy bone implant, cell and organizes sensor.This porous tantalum is made up of pure business tantalum, it carries out carbon skeleton that thermal degradation obtains as support taking polyurethane precursor, this carbon skeleton is multiple dodecahedron, it in it, is mesh-like structure, entirety spreads all over micropore, porosity can be up to 98%, then commercially pure tantalum is attached on carbon skeleton to form porous metals micro structure, referred to as chemical deposition by the method for chemical vapour deposition, infiltration.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtains is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight accounts for 1% left and right.Document is further recorded, the comprcssive strength 50～70MPa of this porous material, elastic modelling quantity 2.5～3.5GPa, tensile strength 63MPa, amount of plastic deformation 15%.But the porous tantalum using it as medical embedded material, the mechanical property of its material is obvious weak point as ductility has, and can have influence on the follow-up processing to porous tantalum material itself, the cutting of such as profiled member etc.Also all there is such deficiency in the same product obtaining in aforesaid metal powder sintered method.Due to the limitation of its preparation method, the finished product purity of acquisition is inadequate, has carbon skeleton residue again, causes biological safety to reduce.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of medical embedded material porous niobium, porous niobium Biocompatibility and biological safety that the inventive method makes are good, also have good mechanical property simultaneously.
Inventor finds in research process, selection to organic adhesive in the preparation of medical porous niobium embedded material and occupation mode have exquisite, if improper to its choice and operation, there will be in the porous niobium making the adhesion between niobium powder little, porous niobium surface is inhomogeneous as local overstocked or too lax, the problem of series that the porosity of porous niobium is excessive or too small etc., thus make its biocompatibility and mechanical property thereof not reach medical requirement.
The object of the invention is to realize by following technical measures:
A kind of preparation method of medical embedded material porous niobium, adopt foam impregnation method sintering to form, it is characterized in that: be that employing ethyl cellulose is that organic binder bond and dehydrated alcohol are the solution that dispersant is mixed with, be less than 43 μ m with starch and mean diameter, the mixed powder that oxygen content is less than 0.1% niobium powder composition is mixed and made into niobium powder slurry, and be cast in Organic Foam Material, dipping is until Organic Foam Material hole fills niobium powder slurry, then the dry dispersant of removing in the Organic Foam Material that is cast with niobium powder slurry, under inert gas shielding atmosphere, ungrease treatment is to remove organic binder bond and Organic Foam Material, under vacuum, sintering makes porous sintered body, pile up on the foam framework forming through the niobium powder of sintering, niobium powder particles has sintering neck structure each other, under vacuum, annealing and conventional post processing make porous niobium again, in the mixed powder of described metal niobium powder and starch, content of starch is 5～10%, by weight percentage.
The medical embedded material porous niobium that the inventive method makes, has the foaming structure that hole three-dimensional communication distributes, and has each other sintering neck structure through the niobium powder particles of sintering.The three-dimensional hole that the pore structure that three-dimensional communication of the present invention distributes is not got rid of little part is not communicated with, and it is to belong to negligible that the hole that for example accounts for 1% left and right is not communicated with.Sintering neck of the present invention refers to that at high temperature, powder is heated, and between granule, bonds, and is exactly the sintering phenomenon that we often say.Sintering refers to that the process of metallurgical property combination at high temperature occurs between powder particle granule, conventionally carries out, and realizes by atomic migration under the fusing point of main component constituent element.By microstructure observing, can find that the sintering neck (or claiming contact neck) of granule contact is grown up, and therefore cause performance change.Along with the raising of sintering temperature, or the prolongation of sintering time or the reasonable control to sintering temperature and sintering time, sintering neck just can increase gradually, and the ratio of sintering neck just can increase, the strength increase of sintered body.Also be that the present invention forms sintering neck structure between niobium powder particles partly also can realize the object of the invention.
In preparation method of the present invention, employing ethyl cellulose is organic adhesive, and ethyl cellulose is widely used in pharmaceutical industry, and it has better bio-safety performance; Dehydrated alcohol is dispersant, dehydrated alcohol is volatile, can effectively save drying time, can after having flooded, detect sample interior whether have hollow, thereby can ensure dipping sizing agent quality evenly, also can reduce hydrogen, oxygen content in porous niobium after sintering, thereby reduction impurity content, meanwhile, the porous niobium shape after dipping can be fixed up soon, be not prone to distortion, ensured the stable of sample shape after 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 making, thereby makes the porous niobium Biocompatibility that makes good; In preparation method of the present invention, also adopting the mixed powder of niobium powder and starch composition is raw material constituent, can effectively increase porosity and the aperture of the porous niobium making, starch is that the conventional food of people, safety are good simultaneously, starch also easily decomposes, can improve the purity of the porous niobium material finally making, and therefore the present invention can make the porous niobium material making have very superior biocompatibility and safety; But meanwhile, inventor finds in research process, and slow reaction easily occurs at normal temperatures for ethanol and polymer organic foam, and the internal structure of destructible sample affects the mechanical property of material; When the ethanol in porous niobium is put the heating of stove the inside into without bone dry, because ethanol volume in the time heating expands rapidly, affect purity and the mechanical property of material; Also have porosity and aperture when excessive, can make mechanical property can not be guaranteed, easily making cannot practical application as the porous niobium of medical embedded material purposes; Inventor also finds in research process simultaneously, niobium powder be easy to starch and Organic Foam Material in carbon react, easily make the porous niobium medical embedded material impurity content finally making raise, affect its biocompatibility and biological safety, also its mechanical property is had to considerable influence.Around the problems referred to above, inventor has launched series of studies, thereby find out other compositions in raw materials as the selection of the selection of organic adhesive, dispersant and all have more exquisite above with being used in conjunction with of mixed powder, coordinate follow-up treatment process steps, make the porous niobium material making not only there is superior biocompatibility and safety, and its shape is consistent, mechanical property is also better, be specially adapted to the medical embedded material at the position that the human bearing such as frontal bone, facial bone is light.Meanwhile, described preparation method technique simply, easily control; Whole preparation process is harmless, pollution-free, nonhazardous dust, and human body is had no side effect.
Organic Foam Material of the present invention can adopt the similar substance such as polyurethane foam, polyether ester foam, optimization polyurethane foam.Described slurry is poured into a mould, be impregnated in described Organic Foam Material, then after the dry dispersant of removing in the Organic Foam Material that is cast with niobium powder slurry, the porosity of the porous niobium forming is between 59.2～77.7%, hole average diameter 350～500 μ m, between described porous niobium at least 50% niobium powder particles, form sintering neck structure, preferably between at least 80% niobium powder particles, form sintering neck structure.
In order to ensure under the bio-compatible implementations of medical material porous niobium of the present invention, further improve its mechanical property, be beneficial to the formation of sintering neck structure simultaneously, described slurry is that ethyl cellulose dehydrated alcohol is heated to dissolve, adopt the ethyl cellulose alcoholic solution of percentage by weight 1%～4% (preferably 3.5%) and the mixed powder of described metal niobium powder and starch to make niobium powder slurry, wherein, in the mixed powder of described metal niobium powder and starch, content of starch is preferably 6%, by weight percentage; It is, in the described ethyl cellulose alcoholic solution of 1 part, to stir and make starchiness that the described mixed powder that is 1～3 part (preferably 1.5 parts) by weight adds weight; And to be cast in aperture be 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is more than or equal to 50 °, and (preferably aperture is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness) polyurethane foam in.
The present invention selects mean diameter to be less than 43 μ m, oxygen content to be less than the content that 0.1% metal niobium powder contributes to reduce impurity, to ensure that material has good mechanical property; Add starch to be conducive to increase porosity and aperture; Selection aperture is 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than porosity and the pore diameter that the polyurethane foam of 50 ° contributes to ensure porous niobium.Process conditions have been optimized in the such technical finesse of the present invention, by ensureing to implant biocompatibility and the biological safety of porous niobium material, are also conducive to the formation of sintering neck structure simultaneously.
The present invention's further feature is on the other hand: dry vacuum keep 1 × 10
-2pa～1Pa vacuum, then, under protective atmosphere, low vacuum is in 1 × 10
-3pa, the ungrease treatment of removing organic binder bond and Organic Foam Material under 400 DEG C～800 DEG C conditions of temperature; Be 1 × 10 in vacuum again
-4pa～1 × 10
-3pa, 1700～1800 DEG C of temperature, the temperature retention time vacuum-sintering processing of 4～6 hours makes porous sintered body.When sintering process insulation, can also filling with inert gas protection replace vacuum protection; Finally carry out vacuum annealing processing, wherein vacuum annealing processing refers to after vacuum-sintering and to continue to keep temperature in 900～1100 DEG C, temperature retention time 3～6 hours, and vacuum is not for higher than 1 × 10
-3pa.
Above-mentioned ungrease treatment condition also includes: the speed with 0.5 DEG C/min～3 DEG C/min is progressively warming up to 400～800 DEG C, forms protective atmosphere and is incubated 1.5～3h as argon passes into noble gas;
Vacuum-sintering condition also includes: vacuum is 1 × 10
-4pa～1 × 10
-3pa, rises to 900 DEG C～1400 DEG C with the heating rate of 10～20 DEG C/min from room temperature, after insulation 1h～2h; To be warming up to 1700～1800 DEG C lower than the heating rate of 20 DEG C/min, be at least incubated 2～4h again;
Cooling condition after vacuum-sintering also includes: vacuum is 1 × 104Pa～1 × 10
-3pa, with not higher than 15 DEG C/min, is not less than 10 DEG C/min and gradually falls cooldown rate mode, and to sintered porous bodies segmentation cooling down to 600～800 DEG C, each section of temperature retention time 0.5～1.5h, then cools to room temperature with the furnace;
Vacuum annealing condition also includes: vacuum is not higher than 1 × 10
-3pa, not rise to 900～1100 DEG C higher than the speed of 20 DEG C/min, insulation 4h～6h; Again with after first slow soon to be not less than 5 DEG C/min but be not cooled to room temperature higher than the cooldown rate segmentation of 15 DEG C/min, the temperature retention time of each section tapers off and is no more than 3h.
Further feature is on this basis: 50～70 DEG C of described vacuum drying baking temperatures, 4～6 hours drying times; Described ungrease treatment condition also includes: be progressively warming up to 400～800 DEG C, pass into formation protective atmosphere with pure argon gas (99.9999%), speed with 1～3 DEG C/min rises to 400 DEG C from room temperature, insulation 0.5～1h, speed with 0.5～1.5 DEG C/min rises to 600～800 DEG C, insulation 1～2h from 400 DEG C; Described vacuum-sintering condition also includes: the speed with 10～15 DEG C/min rises to 900～1100 DEG C from room temperature, insulation 0.5～1h, and vacuum is 1 × 10
-4pa～1 × 10
-3pa; Rise to 1300～1400 DEG C with the speed of 10～20 DEG C/min, insulation 0.5～1h, vacuum is 1 × 10
-4pa～1 × 10
-3pa, rises to 1700～1800 DEG C with the speed of 6～20 DEG C/min, insulation 3～4h, and vacuum is 1 × 10
-4pa～1 × 10
-3pa; Cooling condition after vacuum-sintering also includes: vacuum is 1 × 10
-4pa～1 × 10
-3pa; Be cooled to 1200～1300 DEG C with the speed of 13～15 DEG C/min, insulation 0.5～1h; Be cooled to 600～1000 DEG C with the speed of 10～14 DEG C/min, insulation 1～1.5h, then furnace cooling; Described vacuum annealing condition also includes: rise to 900～1100 DEG C with the speed of 15～20 DEG C/min, and insulation 4～6h, vacuum is not higher than 1 × 10
-3pa, then be cooled to 800 DEG C with the speed of 5～7 DEG C/min, insulation 1.5～3h, vacuum is not higher than 1 × 10
-3pa; Be cooled to 600 DEG C with the speed of 10～14 DEG C/min, insulation 1.5～3h, vacuum is not higher than 1 × 10
-3pa; Speed with 12～15 DEG C/min is cooled to room temperature, and vacuum is not higher than 1 × 10
-3pa.
Specifically, a kind of preparation method of medical embedded material porous niobium:
A. the preparation of niobium powder slurry: ethyl cellulose is heated to dissolve with dehydrated alcohol, be mixed with the ethyl cellulose alcoholic solution of percentage by weight 1～4% (preferably 3.5%), being less than with mean diameter mixed powder that 43 μ m, oxygen content are less than 0.1% metal niobium powder and starch stirs and makes starchy niobium powder slurry, wherein, starch accounts for 6% of described mixed powder weight; The weight part ratio of described mixed powder and described ethyl cellulose alcoholic solution is 1～3 part (preferably 1.5 parts): 1 part;
B. the preparation of porous niobium: above-mentioned niobium powder slurry is cast in polyurethane foam Organic Foam Material, dipping is until polyurethane foam Organic Foam Material hole fills niobium powder slurry, then the dry dispersant of removing in the Organic Foam Material that is cast with niobium powder slurry, under inert gas shielding atmosphere, ungrease treatment is to remove organic binder bond and Organic Foam Material, under vacuum, sintering makes porous sintered body, pile up on the foam framework forming through the niobium powder of sintering, niobium powder particles has sintering neck structure each other, then under vacuum annealing and conventional post processing make porous niobium; 55 DEG C of described vacuum drying baking temperatures, 4.5 hours drying times; Described ungrease treatment condition is: be progressively warming up to 800 DEG C; pass into formation protective atmosphere with pure argon gas (99.9999%); speed with 3 DEG C/min rises to 400 DEG C from room temperature; be incubated 0.5 hour; rise to 600 DEG C with the speed of 1.5 DEG C/min from 400 DEG C, be incubated 1.0 hours, described vacuum-sintering condition is: the speed with 10 DEG C/min rises to 1100 DEG C from room temperature; insulation 60min, vacuum is 10
-3pa; Rise to 1400 DEG C with the speed of 11 DEG C/min, insulation 60min, vacuum is 10
-3pa, rises to 1780 DEG C with the speed of 7 DEG C/min, insulation 240min, and vacuum is 10
-3pa; Cooling condition after vacuum-sintering is: vacuum is 10
-4pa; Be cooled to 1250 DEG C with the speed of 14 DEG C/min, insulation 60min; Be cooled to 900 DEG C with the speed of 11 DEG C/min, insulation 90min; Be cooled to 650 DEG C with the speed of 10 DEG C/min, then furnace cooling of insulation 72min; Described vacuum annealing condition is: rise to 900 DEG C with the speed of 16 DEG C/min, and insulation 360min, vacuum is 10
-4pa, then be cooled to 800 DEG C with the speed of 6 DEG C/min, insulation 180min, vacuum is 10
-4pa; Be cooled to 600 DEG C with the speed of 12 DEG C/min, insulation 180min, vacuum 10
-4pa; Speed with 13 DEG C/min is cooled to room temperature, and vacuum is 10
-4pa.
The medical embedded material porous niobium making by above-mentioned preparation method can meet the requirement of bio-compatibility and biological safety completely, particularly its foam framework is to be piled up and formed by the pure niobium powder of sintering, the sintering neck structure that niobium powder particles has each other has greatly improved the mechanical property of this material as ductility, anti-folding anti-bending strength, simultaneously through testing its impurity content lower than 0.5%; 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 affect elastic modelling quantity, the yield strength etc. of porous material, and be to have improved these performance parameters that porous material is emphasized.And in the time carrying out anti-bending test, the fracture rate of the sintering neck forming between each niobium powder particles is less than 45%, the fracture rate of niobium powder particles inside is greater than 55%, further illustrates new product reliability of structure of the present invention.
Brief description of the drawings
Fig. 1 is the X-ray diffraction analysis collection of illustrative plates (XRD figure) of the porous niobium prepared of preparation method of the present invention;
Fig. 2 is the vertical microscope analysis chart of the macrostructure of the porous niobium prepared of preparation method of the present invention;
Fig. 3 is the scanning electron microscope analysis figure (SEM figure) of the microstructure of the porous niobium prepared of preparation method of the present invention.
Can be observed from accompanying drawing: 1, porous niobium of the present invention high hole, even pore distribution and connection.From accompanying drawing, can find out porous niobium three-dimensional communication hole of the present invention, this three-dimensional pore space is conducive to osteoblast to be adhered to, breaks up and growth, promotes growing into of bone, can strengthen being connected between implant and bone, is beneficial to and realizes biological fixation.2, the mechanical property of porous niobium of the present invention is good.As shown in drawings, the sintering microstructure uniform particles of porous niobium of the present invention, sintering neck is obvious, has ensured good mechanical property, and has good ductility.
Detailed description of the invention
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, 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 ethyl cellulose 8g, put into the container that 240ml dehydrated alcohol is housed; Placing it in heats and stir on electric furnace makes it to become ethyl cellulose alcoholic solution.Weigh mean diameter with 200g balance and be less than niobium powder 60g and the 4g starch that 43 microns, oxygen content are less than 0.1%, add the cooling ethyl cellulose alcoholic solution of 15ml, be uniformly mixed, make it to become mixed slurry.(average pore size is 0.48mm, density 0.025g/cm to select 10 × 10 × 30mm cellular polyurethane foam
3, 50 ° of hardness) and put into wherein cast, until polyurethane foam hole fills slurry, the polyurethane foam that goes out to be filled slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 60 DEG C of baking temperatures, drying time 6h, vacuum keep 1Pa.Ungrease treatment: low vacuum is in 1 × 10
-3pa, 600 DEG C of temperature, temperature retention time 2h.Vacuum-sintering: sintering in vacuum drying oven, 1750 DEG C of sintering temperatures, insulation 4h, vacuum 1 × 10
-3pa～1 × 10
-4pa, the protection of sintering process applying argon gas, removes surface dirt and dirt after taking-up product, and the sample making carries out conventional post processing again and obtains porous niobium finished product.
The porous niobium finished product that adopts said method to make, has the foaming structure that hole three-dimensional communication distributes, and piles up on the foam framework forming through the pure niobium powder of sintering, and niobium powder particles has sintering neck structure each other.And the sintering neck structure forming between niobium powder particles in this porous niobium finished product microstructure exceedes 50%.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous niobium finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: 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 the method for measuring by metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 45%, and the fracture rate of granule interior is greater than 55%.
Embodiment 2: take ethyl cellulose 6g, put into the container that 200ml dehydrated alcohol is housed; Placing it in heats and stir on electric furnace makes it to become ethyl cellulose alcoholic solution.Weigh mean diameter with 200g balance and be less than 43 μ m, oxygen content and be less than 0.1% niobium powder 40g and the starch of 2.15g, add 10ml ethyl cellulose alcoholic solution, be uniformly mixed, make it to become mixed slurry.(average pore size is 0.56mm, density 0.030g/cm to select 10 × 10 × 25mm cellular polyurethane foam
3, 60 ° of hardness) and put into wherein cast, until polyurethane foam hole fills slurry, the polyurethane foam that goes out to be filled slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 70 DEG C of baking temperatures, drying time 4h, vacuum keep 1 × 10
-2pa.Ungrease treatment: low vacuum is in 1 × 10
-3pa, 800 DEG C of temperature, temperature retention time 2.5h.Vacuum-sintering: sintering in vacuum drying oven, 1800 DEG C of sintering temperatures, are incubated 4.5 hours, vacuum 1 × 10
-4pa, the protection of sintering process applying argon gas, removes surface dirt and dirt after taking-up product, and the sample making carries out conventional post processing again and obtains porous niobium finished product.
The porous niobium finished product that adopts said method to make, has the foaming structure that hole three-dimensional communication distributes, and piles up on the foam framework forming through the pure niobium powder of sintering, and niobium powder particles has sintering neck structure each other.And the sintering neck structure forming between niobium powder particles in this porous niobium finished product microstructure exceedes 60%.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous niobium finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: 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 the method for measuring by metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 40%, and the fracture rate of granule interior is greater than 60%.
Embodiment 3: take ethyl cellulose 9g, put into the container that 220ml dehydrated alcohol is housed; Placing it in heats and stir on electric furnace makes it to become ethyl cellulose alcoholic solution.Weigh mean diameter with 200g balance and be less than niobium powder 45g and the 2.5g starch that 43 μ m, oxygen content are less than 0.1%, add 12ml ethyl cellulose alcoholic solution, be uniformly mixed, make it to become mixed slurry.(average pore size is 0.70mm, density 0.035g/cm to select 8 × 8 × 25mm cellular polyurethane foam
3, 70 ° of hardness) and put into wherein cast, until polyurethane foam hole fills slurry, the polyurethane foam that goes out to be filled niobium powder slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 68 DEG C of baking temperatures, drying time 6h, vacuum keep 1 × 10
-1pa.Ungrease treatment: low vacuum is in 1 × 10
-3pa, 700 DEG C of temperature, temperature retention time 1.5h.Vacuum-sintering: sintering in vacuum drying oven, 1700 DEG C of sintering temperatures, are incubated 5.5 hours, vacuum 1 × 10
-3pa, the protection of sintering process applying argon gas, cooling coming out of the stove, removes product surface dust and dirt, and the sample making carries out conventional post processing again and obtains porous niobium finished product.
The porous niobium finished product that adopts said method to make, has the foaming structure that hole three-dimensional communication distributes, and piles up on the foam framework forming through the pure niobium powder of sintering, and niobium powder particles has sintering neck structure each other.And the sintering neck structure forming between niobium powder particles in this porous niobium finished product microstructure exceedes 55%.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous niobium finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: 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 the method for measuring by metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 35%, and the fracture rate of granule interior is greater than 65%.
Embodiment 4: take ethyl cellulose 7g, put into the container that 230ml dehydrated alcohol is housed; Placing it in heats and stir on electric furnace makes it to become ethyl cellulose alcoholic solution.Weigh mean diameter with 200g balance and be less than niobium powder 50g and the 4.5g starch that 43 μ m, oxygen content are less than 0.1%, add 13ml ethyl cellulose alcoholic solution, be uniformly mixed, make it to become mixed slurry.(aperture is 0.60mm, density 0.027g/cm to select 12 × 12 × 30mm cellular polyurethane foam
3, 80 ° of hardness) and put into wherein cast, until polyurethane foam hole fills slurry, the polyurethane foam that goes out to be filled slurry by clip is put into porcelain dish.Dry in vacuum drying oven, 70 DEG C of baking temperatures, drying time 5h, vacuum keep 1Pa.Ungrease treatment: vacuum 1 × 10
-4pa～1 × 10
-3pa, 500 DEG C of temperature, temperature retention time 3h.Vacuum-sintering: sintering in vacuum drying oven, 1750 DEG C of sintering temperatures, are incubated 4.5 hours, vacuum 1 × 10
-4pa, the protection of sintering process applying argon gas, cooling coming out of the stove, removes product surface dust and dirt, and the sample making carries out conventional post processing again and obtains porous niobium finished product.
The porous niobium finished product that adopts said method to make, has the foaming structure that hole three-dimensional communication distributes, and piles up on the foam framework forming through the pure niobium powder of sintering, and niobium powder particles has sintering neck structure each other.And the sintering neck structure forming between niobium powder particles in this porous niobium finished product microstructure exceedes 70%.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous niobium finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: 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 the method for measuring by metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 43%, and the fracture rate of granule interior is greater than 57%.
Embodiment 5: a kind of porous niobium, it is less than 43 μ m, oxygen content taking particle diameter and is less than 0.1% metal niobium powder and starch as raw material, and adopting percentage by weight is that 1～4% ethyl cellulose alcoholic solution is made mixed slurry, and is cast in polyurethane foam carrier; Then vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, the polyurethane foam of selecting, its aperture is 0.48～0.89mm, density 0.015g/cm
3～0.035g/cm
3, hardness is greater than 50 °;
Vacuum drying: vacuum keep 10
-2～1Pa, to remove the ethanol in the polyurethane foam that fills slurry;
Ungrease treatment: under inert gas shielding atmosphere or low vacuum in 1 × 10
-3pa, 400 DEG C～800 DEG C 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 DEG C of temperature, temperature retention time 4～6 hours, applying argon gas or other inert gas shielding when sintering process insulation, to obtain porous material;
Vacuum annealing: after vacuum-sintering, continue to keep temperature in 900～1100 DEG C, temperature retention time 3～6 hours, vacuum is not higher than 1 × 10
-3pa, to carry out stress relief annealing processing; The sample making carries out conventional post processing again and obtains 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 hole three-dimensional communication distributes, and pile up on the foam framework forming through the pure niobium powder of sintering, and niobium powder particles has sintering neck structure each other.And the sintering neck structure forming between niobium powder particles in this porous niobium finished product microstructure exceedes 80%.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous niobium finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: 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 the method for measuring by metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 45%, and the fracture rate of granule interior is greater than 55%.
Embodiment 6: a kind of porous niobium, it is less than 43 μ m, oxygen content taking particle diameter and is less than 0.1% metal niobium powder and starch as raw material, make niobium powder slurry taking ethyl cellulose alcoholic solution as binder solution, and to be cast in its aperture be 0.56～0.72mm, density 0.025～0.035g/cm
3, in the polyurethane foam carrier that hardness is 50 °～80 °; Then vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, ethyl cellulose is heated to dissolve to be mixed with percentage by weight be 3.5% ethyl cellulose alcoholic solution with dehydrated alcohol; Then be that to add cooled weight be, in the described ethyl cellulose alcoholic solution of 1 part, to stir and make starchiness for the metal niobium powder of 1～3 part by weight; Again above-mentioned polyurethane foam is put into and be starchy niobium powder slurry and repeatedly flood until polyurethane foam hole fills;
Vacuum drying to be to remove the ethanol in the polyurethane foam that fills niobium powder slurry, vacuum keep 1Pa, 50～70 DEG C of baking temperatures, drying time 4～6h;
Being placed in tungsten device for the polyurethane foam after vacuum drying puts into nonoxidizing atmosphere stove and is warming up to 800 DEG C with certain heating rate, protective atmosphere is that 99.999% argon carries out ungrease treatment, its heat up before first pass into argon at least 0.5h with get rid of furnace air, temperature control process: the speed with 1 DEG C/min rises to 400 DEG C from room temperature, insulation 0.5h, argon passes into speed 0.5L/min; Rise to 800 DEG C with the speed of 0.5 DEG C/min from 400 DEG C, insulation 2h, argon passes into speed 1L/min; Powered-down again, the sample furnace cooling after defat, argon passes into speed 1L/min, until close argon while being cooled to room temperature;
Be placed in and in fine vacuum high temperature sintering furnace, be warming up to 1800 DEG C with certain heating rate and carry out vacuum-sintering with tungsten device for the sample after ungrease treatment, before heating up, the vacuum of sintering furnace at least will reach 1 × 10
-3pa, rises to 900 DEG C with the speed of 10～15 DEG C/min from room temperature, insulation 0.5h, and vacuum is 1 × 10
-4pa; Rise to 1300 DEG C with the speed of 10 DEG C/min, insulation 0.5h, vacuum is 1 × 10
-4pa～1 × 10
-3pa; Rise to 1800 DEG C with the speed of 6 DEG C/min, insulation 3h, vacuum is 1 × 10
-3pa; Sintering is complete, and vacuum is 1 × 10
-4pa～1 × 10
-3pa; Be cooled to 1300 DEG C with the speed of 15 DEG C/min, insulation 1h; Be cooled to 800 DEG C with the speed of 14 DEG C/min, insulation 1.5h, then furnace cooling;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with corundum container and be warming up to 1000 DEG C with certain heating rate and carry out stress relief annealing processing, the vacuum before heating up in annealing furnace at least will reach 1 × 10
-3pa, rises to 1000 DEG C with the speed of 15 DEG C/min from room temperature, insulation 4h, and vacuum is 1 × 10
-4pa～1 × 10
-3pa; Be cooled to 800 DEG C with the speed of 5 DEG C/min again, insulation 3h, vacuum is 1 × 10
-4pa～1 × 10
-3pa; Be cooled to 600 DEG C with the speed of 10 DEG C/min, insulation 2h, vacuum is 1 × 10
-4pa; Speed with 15 DEG C/min is cooled to room temperature, and vacuum is 1 × 10
-4pa.Finally carry out conventional post processing and make porous niobium.
The porous niobium finished product that adopts said method to make has the foaming structure that hole three-dimensional communication distributes, and piles up on the foam framework forming through the pure niobium powder of sintering, and niobium powder particles has sintering neck structure each other.And the sintering neck structure forming between niobium powder particles in this porous niobium finished product microstructure exceedes 80%.
Inventor detects by porous material density, porosity, aperture and the various mechanical property of standard to above-mentioned porous niobium finished product such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: 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 the method for measuring by metal bending strength is carried out anti-bending test, in this porous niobium microstructure, the fracture rate of sintering neck is less than 40%, and the fracture rate of granule interior is greater than 60%.
In the method providing at above-described embodiment 6, we can also do other to wherein each kind of condition and select can obtain equally porous niobium of the present invention.In the following embodiments, if not otherwise specified, in table, parameters condition is all identical with previous embodiment 6.
Gained porous niobium finished product is pressed preceding method and is detected:
| Embodiment | 7 | 8 | 9 | 10 | 11 | 12 | 13 |
| Density (g/cm 3) | 3.7 | 3.5 | 3.0 | 3.2 | 2.7 | 2.2 | 1.6 |
| Porosity (%) | 57 | 60 | 63 | 74 | 69 | 65 | 81 |
| (μ m) for pore diameter | 280 | 300 | 320 | 400 | 380 | 350 | 450 |
| Elastic modelling quantity (GPa) | 1.3 | 1.6 | 1.4 | 1.8 | 1.1 | 1.0 | 0.8 |
| Yield strength (MPa) | 45 | 54 | 52 | 50 | 55 | 40 | 35 |
| Comprcssive strength (MPa) | 45 | 55 | 52 | 49 | 56 | 42 | 38 |
| Hardness (MPa) | 130 | 150 | 140 | 140 | 160 | 120 | 100 |
| Amount of plastic deformation (%) | 10.22 | 10.20 | 10.25 | 10.30 | 9.28 | 9.29 | 8.30 |
| Tensile strength (MPa) | 25 | 30 | 28 | 34 | 22 | 20 | 17 |
| The elongation (%) of having no progeny | 10.70 | 10.60 | 10.50 | 10.65 | 9.55 | 9.75 | 8.80 |
| Sintering neck fracture rate (%) | 55 | 53 | 48 | 50 | 53 | 58 | 47 |
| Granule interior fracture rate (%) | 50 | 47 | 52 | 47 | 45 | 42 | 53 |
Claims (1)
1. the preparation method of a medical embedded material porous niobium, it is characterized in that: be less than 41 μ m, oxygen content taking particle diameter and be less than 0.1% metal niobium powder and starch as raw material, make niobium powder slurry taking ethyl cellulose alcoholic solution as binder solution, and to be cast in its aperture be 0.85mm, density 0.032g/cm
3, in the polyurethane foam carrier that hardness is 52 °; Then vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing;
Wherein, ethyl cellulose is heated to dissolve with dehydrated alcohol the ethyl cellulose alcoholic solution that is mixed with 3g/100ml; Then be that to add cooled weight be, in the described ethyl cellulose alcoholic solution of 1 part, to stir and make starchiness for the mixed powder of the metal niobium powder of 1.5 parts and starch by weight; Again above-mentioned polyurethane foam is put into and be starchy niobium powder slurry and repeatedly flood until polyurethane foam hole fills;
Vacuum drying to be to remove the ethanol in the polyurethane foam that fills niobium powder slurry, vacuum keep 0.1Pa, 55 DEG C of baking temperatures, drying time 4.5h;
Being placed in tungsten device for the polyurethane foam after vacuum drying puts into nonoxidizing atmosphere stove and is warming up to 600 DEG C with certain heating rate; protective atmosphere is that 99.999% argon carries out ungrease treatment; at least 0.5h is to get rid of furnace air before heating up, first to pass into argon, and defat atmosphere is 1 × 10
-4pa～1 × 10
-3pa, temperature control process: the speed with 3.0 DEG C/min rises to 400 DEG C from room temperature, insulation 0.5h, argon passes into speed 0.5L/min; Rise to 600 DEG C with the speed of 1.5 DEG C/min from 400 DEG C, insulation 1h, argon passes into speed 1L/min; Powered-down again, the sample furnace cooling after defat, argon passes into speed 1L/min, until close argon while being cooled to room temperature;
Be placed in and in fine vacuum high temperature sintering furnace, be warming up to 1780 DEG C with certain heating rate and carry out vacuum-sintering with tungsten device for the sample after ungrease treatment, before heating up, the vacuum of sintering furnace at least will reach 1 × 10
-3pa, sintering atmosphere is 1 × 10
-4pa～1 × 10
-3pa, rises to 1100 DEG C with the speed of 10 DEG C/min from room temperature, insulation 60min, and vacuum is 1 × 10
-3pa; Rise to 1400 DEG C with the speed of 11 DEG C/min, insulation 60min; Rise to 1780 DEG C with the speed of 7 DEG C/min, insulation 240min, vacuum is 1 × 10
-3pa; After sintering, cooling vacuum degree is 1 × 10
-4pa～1 × 10
-3pa; Be cooled to 1250 DEG C with the speed of 14 DEG C/min, insulation 1h; Be cooled to 900 DEG C with the speed of 11 DEG C/min, insulation 1.5h; Be cooled to 650 DEG C with the speed of 10 DEG C/min, insulation 72min, then furnace cooling;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with corundum container and be warming up to 900 DEG C with certain heating rate and carry out stress relief annealing processing, the vacuum before heating up in annealing furnace at least will reach 1 × 10
-3pa, de-fire of moxibustion atmosphere is 1 × 10
-4pa, rises to 900 DEG C with the speed of 16 DEG C/min from room temperature, insulation 360min; Be cooled to 800 DEG C with the speed of 6 DEG C/min again, insulation 180min; Be cooled to 600 DEG C with the speed of 12 DEG C/min, insulation 180min; Speed with 13 DEG C/min is cooled to room temperature, finally carries out conventional post processing and makes porous niobium.
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| CN1936045A (en) * | 2005-09-22 | 2007-03-28 | 中南大学 | Three-dimensional through-hole or part-hole interconnecting porous metal foam and its preparing method |
| CN101448534A (en) * | 2006-05-17 | 2009-06-03 | 生物技术公司 | Anisotropic nanoporous coatings for medical implants |
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