CN103463673B - Method for preparing medical metal implant material multi-hole niobium - Google Patents
Method for preparing medical metal implant material multi-hole niobium Download PDFInfo
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Abstract
Disclosed is a method for preparing medical metal implant material multi-hole niobium. A solution is obtained by adopting polyvinyl alcohol as an organic binding agent and distilled water as a dispersing agent, and mixed with mixed powder of starch and niobium powder with the mean grain size smaller than 43 micrometers and the oxygen content smaller than 0.1% to obtain a niobium powder sizing agent which is poured into an organic foamed body, then, the niobium powder sizing agent is dried, the dispersing agent in the organic foamed body with the poured niobium sizing agent is removed, under the inert gas shielding atmosphere, the ungrease treatment is carried out to remove the organic binding agent and the organic foamed body, sintering is carried out in vacuum to obtain a multi-hole sintering body, and then annealing in the vacuum and conventional postprocessing are carried out to obtain the multi-hole niobium. In the mixed powder of the metal niobium powder and the starch, the content of the starch is 5-10%. The obtained medical metal implant material multi-hole niobium has excellent biological compatibility and biological safety, meanwhile, the multi-hole niobium is of a sintering-neck structure, the mechanical performance like the malleability of the multi-hole niobium is improved, and according to the method, the multi-hole niobium can be conveniently and effectively implanted into medical metal.
Description
The present patent application is application number 201010563420.2, November 29 2010 applying date, the divisional application of denomination of invention " preparation method of medical porous metal implant material ".
Technical field
The present invention relates to the preparation method of medical metal implanted material, be specifically related to a kind of preparation method as medical metal implant material porous niobium, particularly a kind of preparation method being applicable to the porous niobium embedded material at the lighter position of human bearing.
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 common this kind of material has porous metals rustless steel, porous metals titanium etc.As the porous embedded material that osseous tissue wound and bone formation necrosis therapeutic use, its porosity should reach 30 ~ 80%, and hole is preferably all communicated with and is uniformly distributed, or aperture sections 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, implant with applicable human body and use.
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, to niobium going deep into further as body implanting material cognition, the demand of people to human body implantation porous metals niobium material becomes more and more urgent, also more and more higher to its requirement.Wherein as the medical embedded metal niobium of porous, if the very high physical and mechanical properties being uniformly distributed interconnected pore and adapting with human body can be had, then it is the heavy connection constituent material ensureing freshman bone tissue's normal growth.
As medical embedded porous metal material just as porous metal material be main processing method with powder sintering like that substantially, especially obtain porosity communication and equally distributed porous metal structure foam adopt the dipping of the metal dust slurry in powder sintering on Organic Foam Material after drying reburn and tie that to be called for short foam impregnation method in the majority.About powder sintered obtained porosity communication and equally distributed porous metal material usually its Metal Mechanic Property be not very well, its main cause how technique arranges the problem of subsiding in the support of pore-forming medium and elimination relation, metal powder sintered process.And all there is no good solution in known bibliographical information and let alone nature.
Adopt metal powder sintered legal system to make the bibliographical information of porous niobium seldom, particularly almost do not have by the porous niobium powder sintering bibliographical information obtained for the purpose of medical embedded material use.Can reference be publication number be CN200510032174, title " three-dimensional through hole or some perforations are connected with each other porous metal foam and preparation method thereof " and CN200710152394, title " a kind of porous foam tungsten and preparation method thereof ".But its porous metals obtained or for filtering material use, or share for Aero-Space and other high-temperature field but not use as medical metal implanted material, moreover the porous metals processed also non-porous niobium.
At present, directly report is had no using porous niobium as the document of medical embedded material and related manufacturing processes.As everybody knows, metal tantalum and niobium are in of the same clan in the periodic table of elements, and both are adjacent one another are, and therefore the chemical property of the two is extremely similar.And about porous tantalum, US5282861 discloses and is a kind ofly applied to cancellous bone implants, the perforate tantalum material of biological cells and tissues sensor and preparation thereof.This porous tantalum is made up of pure business tantalum, it carries out carbon skeleton that thermal degradation obtains for support with polyurethane precursor, this carbon skeleton is multiple dodecahedron, it is mesh-like structure in it, entirety spreads all over micropore, porosity can up to 98%, then by commercially pure tantalum by the methods combining of chemical vapour deposition, infiltration to carbon skeleton to form porous metals micro structure, referred to as chemical deposition.The tantalum layer thickness on its surface of porous tantalum material that this method obtains is between 40 ~ 60 μm; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight then accounts for about 1%.Document is recorded further, the comprcssive strength 50 ~ 70MPa of this porous material, elastic modelling quantity 2.5 ~ 3.5GPa, tensile strength 63MPa, amount of plastic deformation 15%.Such as, but using its porous tantalum 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 etc. of profiled member.Also all there is such deficiency in the product obtained in aforesaid metal powder sintered method equally.Again due to the limitation of its preparation method, the finished product purity of acquisition is inadequate, has carbon skeleton residue, causes biological safety to reduce.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of medical porous metal implant material of good biocompatibility.The medical metal that the inventive method obtains is implanted porous niobium product and is also had good mechanical property, is specially adapted to the medical embedded material of the lighter part of the human bearing such as frontal bone, facial bone.
Inventor finds in research process, have exquisite to the selection of organic adhesive and occupation mode in the preparation of medical porous niobium embedded material, if improper to its choice and operation, the adhesion that there will be in obtained porous niobium between niobium powder is little, porous niobium surface is uneven as overstocked or too lax in local, 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 be realized by following technical measures:
A kind of preparation method of medical metal implant material porous niobium, foam impregnation method sintering is adopted to form, it is characterized in that: be adopt polyvinyl alcohol be organic binder bond and distilled water to be the solution that dispersant is mixed with, 43 μm are less than with starch and mean diameter, the mixed powder that oxygen content is less than 0.1% niobium powder makes niobium powder slurry, and be cast in Organic Foam Material, dipping is until Organic Foam Material hole fills niobium powder slurry, then drying removes the dispersant be cast with in the Organic Foam Material of niobium powder slurry, under inert gas shielding atmosphere, ungrease treatment is to remove organic binder bond and Organic Foam Material, the obtained porous sintered body of sintering under vacuum, niobium powder through sintering is piled up on the foam framework of formation, niobium powder particles has sintering neck structure each other, under vacuum, annealing and conventional post processing obtain porous niobium again, in the mixed powder of described metal niobium powder and starch, content of starch is 5 ~ 10%, by weight percentage.
In the preparation method of porous tantalum of the present invention, the mixed powder adopting niobium powder and starch to form is raw material constituent, effectively can increase porosity and the aperture of obtained porous niobium, simultaneously starch is that food, safety that people commonly use are good, starch also easily decomposes, can improve the purity of final obtained porous tantalum material, and the porous niobium material obtained therefore can be made to have very superior biocompatibility and safety; But inventor finds in practice, starch adds in niobium powder the shrinkage factor of material when can not accurately control to sinter, and the porous niobium material shape prepared is difficult to be consistent, and mechanical property is bad, cannot practical application; Inventor also finds in research process simultaneously, niobium powder is easy to react with the carbon in starch and Organic Foam Material, easily make final obtained porous niobium medical embedded material impurity content raise, affect its biocompatibility and biological safety, also have considerable influence to its mechanical property.Around the problems referred to above, inventor expands series of studies, thus find out other compositions in raw materials as the selection of organic adhesive, the selection of dispersant and more exquisite with the use of all having with mixed powder above, coordinate follow-up treatment process steps, the porous tantalum material obtained is made not only to have superior biocompatibility and safety, and its shape is consistent, mechanical property is also better, is specially adapted to the medical embedded material at the light position of the human bearing such as frontal bone, facial bone.Preparation method technique of the present invention simply, is easily controlled; Whole preparation process is harmless, pollution-free, nonhazardous dust, has no side effect to human body.
Above-mentioned Organic Foam Material can adopt the similar substance such as polyurethane foam, polyether ester foam, optimization polyurethane foam of the present invention.By described slurry cast, impregnated in described Organic Foam Material, then after dry removing is cast with the dispersant in the Organic Foam Material of niobium powder slurry, the porosity of the porous niobium formed is between 55.7 ~ 77.7%, pore mean diameters 250 ~ 500 μm, form sintering neck structure between described porous niobium at least 50% niobium powder particles, preferably form sintering neck structure between at least 80% niobium powder particles.
In order under the bio-compatible implementations ensureing medical material porous niobium of the present invention, its mechanical property of further raising, be beneficial to the formation of sintering neck structure simultaneously, described slurry is heated to by polyvinyl alcohol distilled water dissolve, the polyvinyl alcohol water solution of percentage by weight 2% ~ 8% (preferably 4% ~ 5%) and the mixed powder of described metal niobium powder and starch is adopted to make niobium powder slurry, wherein, in the mixed powder of described metal niobium powder and starch, content of starch is preferably 8%, by weight percentage; Be that to add weight be in the described polyvinyl alcohol water solution of 1 part for the described mixed powder of 2 ~ 4 parts (preferably 2.5 parts) by weight, stir and make starchiness; And to be cast in aperture be 0.48 ~ 0.89mm, density 0.015g/cm
3~ 0.035g/cm
3, hardness is more than or equal to 50 °, and (preferred aperture is 0.56 ~ 0.72mm, density 0.025g/cm
3, hardness 50 ° ~ 80 °) polyurethane foam in.
The present invention selects that mean diameter is less than 431 μm, the oxygen content metal niobium powder that is less than 0.1% contributes to reducing the content of impurity, ensures that material has good mechanical property; Selection aperture is 0.48 ~ 0.89mm, density 0.015g/cm
3~ 0.035g/cm
3, the polyurethane foam that hardness is greater than 50 ° contributes to the porosity and the pore diameter that ensure porous niobium.The such technical finesse of the present invention optimizes process conditions, will ensure bio-compatibility and the biological safety of implanting porous niobium material, is also conducive to the formation sintering neck structure simultaneously.
Sintering neck of the present invention refers to that at high temperature, powder is heated, and bonds between granule, is exactly the sintering phenomenon that we often say.Sintering refers to that the process of metallurgical property combination at high temperature occurs between powder particle granule, usually carries out under the fusing point of main component constituent element, and is realized by atomic migration.By microstructure observing, can find that the sintering neck (or claiming contact neck) of particle contacts is grown up, and therefore cause performance change.Along with the raising of sintering temperature, or the prolongation of sintering time or the conservative control to sintering temperature and sintering time, sintering neck just can increase gradually, and the ratio of sintering neck just can increase, and the intensity of sintered body increases.Also namely the present invention forms sintering neck structure also can realize the object of the invention between niobium powder particles partly.
The present invention's further feature is on the other hand: dry vacuum keeps 1 × 10
-2pa ~ 1Pa vacuum, then under protective atmosphere, low vacuum is in 1 × 10
-3pa, carries out the ungrease treatment removing organic binder bond and Organic Foam Material under temperature 400 DEG C ~ 800 DEG C conditions; Be 1 × 10 in vacuum again
-4pa ~ 1 × 10
-3pa, temperature 1700 ~ 1800 DEG C, the temperature retention time vacuum-sintering process of 3 ~ 5 hours obtains porous sintered body.Filling with inert gas protection vacuum protection can also be replaced during sintering process insulation; Finally carry out vacuum annealing process, wherein vacuum annealing process refers to that after vacuum-sintering, continue maintenance temperature is in 900 ~ 1100 DEG C, temperature retention time 2 ~ 4 hours, and vacuum is not higher than 1 × 10
-3pa.
Above-mentioned ungrease treatment condition also includes: be progressively warming up to 400 ~ 800 DEG C with the speed of 0.5 DEG C/min ~ 3 DEG C/min, is formed protective atmosphere and be incubated 1.5 ~ 3h with noble gas as argon passes into;
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; Again to be warming up to 1700 ~ 1800 DEG C lower than the heating rate of 20 DEG C/min, be at least incubated 2h;
Cooling condition after vacuum-sintering also includes: vacuum is 1 × 10
-4pa ~ 1 × 10
-3pa, with not higher than 25 DEG C/min, is not less than 15 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, rises to 900 ~ 1100 DEG C with the speed not higher than 30 DEG C/min, insulation 4h ~ 6h; Again with after first slow fast be not less than 10 DEG C/min but not higher than the cooldown rate sub-sectional cooling of 30 DEG C/min to room temperature, the temperature retention time of each section tapers off and is no more than 2h.
Further feature is on this basis: described vacuum drying baking temperature 70 ~ 80 DEG C, 6 ~ 8 hours drying times; Described ungrease treatment condition also includes: be progressively warming up to 400 ~ 800 DEG C, formation protective atmosphere is passed into pure argon gas (99.9999%), 400 DEG C are risen to from room temperature with the speed of 1 ~ 3 DEG C/min, insulation 0.5 ~ 1h, 600 ~ 800 DEG C are risen to from 400 DEG C, insulation 1 ~ 2h with the speed of 0.5 ~ 1.5 DEG C/min; Described vacuum-sintering condition also includes: rise to 900 ~ 1100 DEG C with the speed of 10 ~ 15 DEG C/min from room temperature, and insulation 0.5 ~ 1h, 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, and insulation 2 ~ 3h, vacuum is 1 × 10
-4pa ~ 1 × 10
-3pa; Cooling condition after vacuum-sintering also includes: vacuum is 1 × 10
-4pa ~ 1 × 10
-3pa; 1200 ~ 1300 DEG C are cooled to, insulation 0.5 ~ 1h with the speed of 15 ~ 18 DEG C/min; 600 ~ 1000 DEG C are cooled to, insulation 1 ~ 1.5h, then furnace cooling with the speed of 18 ~ 25 DEG C/min; Described vacuum annealing condition also includes: rise to 900 ~ 1100 DEG C with the speed of 20 ~ 30 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 10 ~ 13 DEG C/min, insulation 1 ~ 2h, vacuum is not higher than 1 × 10
-3pa; Be cooled to 600 DEG C with the speed of 13 ~ 18 DEG C/min, insulation 1 ~ 2h, vacuum is not higher than 1 × 10
-3pa; Be cooled to room temperature with the speed of 20 ~ 30 DEG C/min, vacuum is not higher than 1 × 10
-3pa.
Specifically, a kind of preparation method of medical embedded material porous niobium:
A. the preparation of niobium powder slurry: polyvinyl alcohol distilled water is heated to dissolve, be mixed with the polyvinyl alcohol water solution of percentage by weight 2 ~ 8% (preferably 4 ~ 5%), be less than 43 μm with mean diameter, the oxygen content mixed powder that is less than 0.1% metal niobium powder and starch stirs and make starchy niobium powder slurry, wherein, starch accounts for 8% of described mixed powder weight; The weight part ratio of described mixed powder and described polyvinyl alcohol water solution is 2 ~ 4 parts (preferably 2.5 parts): 1 part;
B. the preparation of porous niobium: above-mentioned niobium powder slurry is cast in polyurethane foam Organic Foam Material, dipping is until polyurethane foam Organic Foam Material hole fills niobium powder slurry, then drying removes the dispersant be cast with in the Organic Foam Material of niobium powder slurry, under inert gas shielding atmosphere, ungrease treatment is to remove organic binder bond and Organic Foam Material, the obtained porous sintered body of sintering under vacuum, niobium powder through sintering is piled up on the foam framework of formation, niobium powder particles has sintering neck structure each other, then under vacuum, annealing and conventional post processing obtain porous niobium; Described vacuum drying baking temperature 75 DEG C, 7 hours drying times; Described ungrease treatment condition is: be progressively warming up to 800 DEG C; formation protective atmosphere is passed into pure argon gas (99.9999%); 400 DEG C are risen to from room temperature with the speed of 1 DEG C/min; be incubated 0.8 hour; rise to 750 DEG C with the speed of 0.5 DEG C/min from 400 DEG C, be incubated 1.5 hours, described vacuum-sintering condition is: rise to 1000 DEG C with the speed of 14 DEG C/min from room temperature; insulation 36min, vacuum is 10
-4pa; Rise to 1300 DEG C with the speed of 17 DEG C/min, insulation 30min, vacuum is 10
-4pa, rises to 1750 DEG C with the speed of 15 DEG C/min, and insulation 150min, vacuum is 10
-4pa; Cooling condition after vacuum-sintering is: vacuum is 10
-3pa; 1250 DEG C are cooled to, insulation 60min with the speed of 18 DEG C/min; 1000 DEG C are cooled to, insulation 30min with the speed of 22 DEG C/min; 600 DEG C are cooled to, insulation 30min then furnace cooling with the speed of 24 DEG C/min; Described vacuum annealing condition is: rise to 1000 DEG C with the speed of 23 DEG C/min, and insulation 270min, vacuum is 10
-3pa, then be cooled to 800 DEG C with the speed of 12 DEG C/min, insulation 120min, vacuum is 10
-3pa; 600 DEG C are cooled to, insulation 90min, vacuum 10 with the speed of 16 DEG C/min
-3pa; Be cooled to room temperature with the speed of 22 DEG C/min, vacuum is 10
-3pa.
The medical embedded material porous niobium obtained by above-mentioned preparation method can meet the requirement of biocompatibility and biological safety completely, particularly its foam framework is piled up by the niobium powder sintered to form, the sintering neck structure that niobium powder particles has each other drastically increases the mechanical property of this material as ductility, anti-folding anti-bending strength, simultaneously through testing its impurity content lower than 0.4%; This porous niobium finished product even pore distribution and be communicated with, density 1.8 ~ 3.8g/cm
3, porosity between 55.7 ~ 77.7.0%, pore mean diameters 250 ~ 500 μm; Elastic modelling quantity 0.8 ~ 2.0GPa, yield strength 25 ~ 60MPa, comprcssive strength 25 ~ 65MPa, hardness 100 ~ 200MPa, amount of plastic deformation 6.4% ~ 11.3%, tensile strength 15 ~ 40MPa, elongation 6.3% ~ 10.7% of having no progeny; Not only do not affect the elastic modelling quantity, yield strength etc. of porous material, and be improve these performance parameters that porous material emphasizes.And when carrying out anti-bending test, the fracture rate of the sintering neck formed between each niobium powder particles is less than 45%, the fracture rate of niobium powder particles inside is greater than 55%, further illustrates new product reliability of structure of the present invention.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction analysis collection of illustrative plates (XRD figure) of porous niobium prepared by preparation method of the present invention;
Fig. 2 is the vertical microscope analysis chart of the macrostructure of porous niobium prepared by preparation method of the present invention;
Fig. 3 is the scanning electron microscope analysis figure (SEM figure) of the microstructure of porous niobium prepared by preparation method of the present invention.
Can be observed from accompanying drawing: 1, porous niobium height hole of the present invention, even pore distribution and be communicated with.Can find out porous niobium three-dimensional communication hole of the present invention from accompanying drawing, this three-dimensional pore space is conducive to osteoblast to be adhered to, breaks up and growth, promotes growing into of bone, can strengthen the connection between implant and bone, be beneficial to and realize 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, ensure that good mechanical property, and has good ductility.
Detailed description of the invention
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that 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 according to the invention described above content to the present invention.
Embodiment 1: weighing polyvinyl alcohol 12.5g, puts into the container that 240m1 distilled water is housed; Placing it in, electric furnace heats and stir makes it to become polyvinyl alcohol water solution.Weigh mean diameter with 200g balance and be less than 43 microns, the oxygen content niobium powder 60g and the 5.3g starch that are less than 0.1%, add the polyvinyl alcohol water solution of 15m1 cooling, 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, hardness 50 °) put into and wherein pour into a mould, until polyurethane foam hole fills slurry, the polyurethane foam going out to be filled slurry by clip puts into porcelain dish.Dry in vacuum drying oven, baking temperature 70 DEG C, drying time 8h, vacuum keeps 1Pa.Ungrease treatment: low vacuum is in 1 × 10
-3pa, temperature 600 DEG C, temperature retention time 2h.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 1750 DEG C, insulation 3h, vacuum 1 × 10
-3pa ~ 1 × 10
-4pa, sintering process applying argon gas is protected, and removes surface dirt and dirt after taking out product, and obtained sample carries out conventional post processing again and obtains porous niobium finished product.
Adopt the obtained name hole niobium finished product of said method. and have the three-dimensional car of hole to read aloud the truly foam structure of distribution, on the foam framework that the pure niobium powder accumulation through sintering is formed, niobium powder particles has sintering neck structure each other.And the sintering neck structure formed between niobium powder particles in this porous niobium finished product microstructure is more than 50%.
Inventor detects the porous material density of above-mentioned porous niobium finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: this porous niobium is the pore structure with three-dimensional communication distribution, its impurity content lower than 0.4% finished product, its even pore distribution and be communicated with, density 2.5g/cm
3, porosity 71%, pore mean diameters 300 μm, elastic modelling quantity 1.5GPa, yield strength 35MPa, comprcssive strength 50MPa, hardness 110MPa, amount of plastic deformation 10.3%, tensile strength 25MPa, elongation 10.7% of having no progeny; When the method measured by metal bending strength carries out anti-bending test, the fracture rate sintering neck in this porous niobium microstructure is less than 45%, and the fracture rate of granule interior is greater than 55%.
Embodiment 2: weighing polyvinyl alcohol 10g, puts into the container that 200ml distilled water is housed; Placing it in, electric furnace heats and stir makes it to become polyvinyl alcohol water solution.Weigh with 200g balance that mean diameter is less than 43 μm, oxygen content is less than the starch of niobium powder 40g and 2.6g of 0.1%, add 10ml polyvinyl alcohol water solution, be uniformly mixed, make it to become mixed slurry.(average pore size is 0.56mm, density 0.030g/cm to select 10 × 10 × 25mm cellular polyurethane foam
3, hardness 60
0) put into and wherein pour into a mould, until polyurethane foam hole fills slurry, the polyurethane foam going out to be filled slurry by clip puts into porcelain dish.Dry in vacuum drying oven, baking temperature 70 DEG C, drying time 6h, vacuum keeps 1 × 10
-2pa.Ungrease treatment: low vacuum is in 1 × 10
-3pa, temperature 800 DEG C, temperature retention time 2h.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 1800 DEG C, is incubated 4 hours, vacuum 1 × 10
-4pa, sintering process applying argon gas is protected, and removes surface dirt and dirt after taking out product, and obtained sample carries out conventional post processing again and obtains porous niobium finished product.
Adopt the porous niobium finished product that said method is obtained, have the foaming structure of hole three-dimensional communication distribution, on the foam framework that the pure niobium powder accumulation through sintering is formed, niobium powder particles has sintering neck structure each other.And the sintering neck structure formed between niobium powder particles in this porous niobium finished product microstructure is more than 60%.
Inventor detects the porous material density of above-mentioned porous niobium finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: this porous niobium is the pore structure with three-dimensional communication distribution, its impurity content lower than 0.4% finished product, its even pore distribution and be communicated with, density 3g/cm
3, porosity 65%, pore mean diameters 260 μm, elastic modelling quantity 1.3GPa, yield strength 40MPa, comprcssive strength 50MPa, hardness 150MPa, amount of plastic deformation 10%, tensile strength 30MPa, elongation 10% of having no progeny; When the method measured by metal bending strength carries out anti-bending test, the fracture rate sintering neck in this porous niobium microstructure is less than 40%, and the fracture rate of granule interior is greater than 60%.
Embodiment 3: weighing polyvinyl alcohol 11g, puts into the container that 220m1 distilled water is housed; Placing it in, electric furnace heats and stir makes it to become polyvinyl alcohol water solution.Weigh mean diameter with 200g balance and be less than 43 μm, the oxygen content niobium powder 45g and the 2.8g starch that are less than 0.1%, add 12m1 polyvinyl alcohol water solution, be uniformly mixed, make it to become mixed slurry.(average pore size is 0.70mm, density 0.035g/cm to select 8 × 8 × 25mm cellular polyurethane foam
3, hardness 70 °) put into and wherein pour into a mould, until polyurethane foam hole fills slurry, the polyurethane foam going out to be filled niobium powder slurry by clip puts into porcelain dish.Dry in vacuum drying oven, baking temperature 75 DEG C, drying time 6h, vacuum keeps 1 × 10
-1pa.Ungrease treatment: low vacuum is in 1 × 10
-3pa, temperature 700 DEG C, temperature retention time 1.5h.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 1700 DEG C, is incubated 3.5 hours, vacuum 1 × 10
-3pa, sintering process applying argon gas is protected, and cooling is come out of the stove, and removes product surface dust and dirt, and obtained sample carries out conventional post processing again and obtains porous niobium finished product.
Adopt the porous niobium finished product that said method is obtained, have the foaming structure of hole three-dimensional communication distribution, on the foam framework that the pure niobium powder accumulation through sintering is formed, niobium powder particles has sintering neck structure each other.And the sintering neck structure formed between niobium powder particles in this porous niobium finished product microstructure is more than 55%.
Inventor detects the porous material density of above-mentioned porous niobium finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: this porous niobium is the pore structure with three-dimensional communication distribution, its impurity content lower than 0.4% finished product, its even pore distribution and be communicated with, density 3.6g/cm
3, porosity 61%, pore mean diameters 300 μm, elastic modelling quantity 1.0GPa, yield strength 30MPa, comprcssive strength 35MPa, hardness 150MPa, amount of plastic deformation 9.2%, tensile strength 25MPa, elongation 9.5% of having no progeny; When the method measured by metal bending strength carries out anti-bending test, the fracture rate sintering neck in this porous niobium microstructure is less than 35%, and the fracture rate of granule interior is greater than 65%.
Embodiment 4: weighing polyvinyl alcohol 12g, puts into the container that 230ml distilled water is housed; Placing it in, electric furnace heats and stir makes it to become polyvinyl alcohol water solution.Weigh mean diameter with 200g balance and be less than 43 μm, the oxygen content niobium powder 50g and the 3.5g starch that are less than 0.1%, add 13ml polyvinyl alcohol water solution, be uniformly mixed, make it to become mixed slurry.(aperture is 0.60mm, density 0.027g/cm to select 12 × 12 × 30mm cellular polyurethane foam
3, hardness 80 °) put into and wherein pour into a mould, until polyurethane foam hole fills slurry, the polyurethane foam going out to be filled slurry by clip puts into porcelain dish.Dry in vacuum drying oven, baking temperature 70 DEG C, drying time 6.5h, vacuum keeps 1Pa.Ungrease treatment: vacuum 1 × 10
-4pa ~ 1 × 10
-3pa, temperature 500 DEG C, temperature retention time 2h.Vacuum-sintering: sinter in a vacuum furnace, sintering temperature 1750 DEG C, is incubated 4 hours, vacuum 1 × 10
-4pa, sintering process applying argon gas is protected, and cooling is come out of the stove, and removes product surface dust and dirt, and obtained sample carries out conventional post processing again and obtains porous niobium finished product.
Adopt the porous niobium finished product that said method is obtained, have the foaming structure of hole three-dimensional communication distribution, on the foam framework that the pure niobium powder accumulation through sintering is formed, niobium powder particles has sintering neck structure each other.And the sintering neck structure formed between niobium powder particles in this porous niobium finished product microstructure is more than 70%.
Inventor detects the porous material density of above-mentioned porous niobium finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: this porous niobium is the pore structure with three-dimensional communication distribution, its impurity content lower than 0.4% finished product, its even pore distribution and be communicated with, density 2.2g/cm
3, porosity 74%, pore mean diameters 400 μm, elastic modelling quantity 1.5GPa, yield strength 30MPa, comprcssive strength 35MPa, hardness 100MPa, amount of plastic deformation 10.3%, tensile strength 32MPa, elongation 10.6% of having no progeny; When the method measured by metal bending strength carries out anti-bending test, the fracture rate sintering neck in this porous niobium microstructure is less than 43%, and the fracture rate of granule interior is greater than 57%.
Embodiment 5: a kind of porous niobium, it with particle diameter be less than 43 μm, oxygen content be less than 0.1% metal niobium powder and starch for raw material, adopt percentage by weight to be that 2 ~ 8% polyvinyl alcohol water solutions make mixed slurry, and be cast in polyurethane foam carrier; Then vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing are obtained.
Wherein, the polyurethane foam selected, its aperture is 0.48 ~ 0.89mm, density 0.015g/cm
3~ 0.035g/cm
3, hardness is greater than 50 °;
Vacuum drying: vacuum keeps 10
-2~ 1Pa, to remove the moisture filled in the polyurethane foam of slurry;
Ungrease treatment: under inert gas shielding atmosphere or low vacuum in 1 × 10
-3pa, temperature 400 DEG C ~ 800 DEG C, and temperature retention time 1.5 ~ 3 hours is with removing polyvinyl alcohol wherein and polyurethane foam;
Vacuum-sintering: vacuum 1 × 10
-4pa ~ 1 × 10
-3pa, temperature 1700 ~ 1800 DEG C, temperature retention time 3 ~ 5 hours, applying argon gas or other inert gas shielding during sintering process insulation, to obtain porous material;
Vacuum annealing: continue to keep temperature to be in 900 ~ 1100 DEG C after vacuum-sintering, temperature retention time 4 ~ 4 hours, low vacuum is in 1 × 10
-3pa, to carry out stress relief annealing process; Obtained sample 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 adopting said method obtained, have the foaming structure of hole three-dimensional communication distribution, and on the foam framework that the pure niobium powder accumulation through sintering is formed, niobium powder particles has sintering neck structure each other.And the sintering neck structure formed between niobium powder particles in this porous niobium finished product microstructure is more than 80%.
Inventor detects the porous material density of above-mentioned porous niobium finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: this porous niobium is the pore structure with three-dimensional communication distribution, its impurity content lower than 0.4% finished product, its even pore distribution and be communicated with, density 1.8 ~ 3.8g/cm
3, porosity between 55.7 ~ 77.7%, pore mean diameters 250 ~ 500 μm; Elastic modelling quantity 0.8 ~ 2.0GPa, yield strength 25 ~ 60MPa, comprcssive strength 25 ~ 65MPa, hardness 100 ~ 200MPa, amount of plastic deformation 6.4% ~ 11.3%, tensile strength 15 ~ 40MPa, elongation 6.3% ~ 10.7% of having no progeny; When the method measured by metal bending strength carries out anti-bending test, the fracture rate sintering neck in this porous niobium microstructure is less than 45%, and the fracture rate of granule interior is greater than 55%.
Embodiment 6: a kind of porous niobium, it with particle diameter be less than 43 μm, oxygen content be less than 0.1% metal niobium powder and starch for raw material, be that binder solution makes niobium powder slurry with polyvinyl alcohol water 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 are obtained.
Wherein, polyvinyl alcohol distilled water being heated to dissolving, to be mixed with percentage by weight be 4 ~ 5% polyvinyl alcohol water solutions; Then be that to add cooled weight be in the described polyvinyl alcohol water solution of 1 part for the metal niobium powder of 2 ~ 4 parts by weight, stir and make starchiness; Above-mentioned polyurethane foam being put into floods until polyurethane foam hole fills in starchy niobium powder slurry repeatedly again;
Vacuum drying is to remove the moisture that fills in the polyurethane foam of niobium powder slurry, and vacuum keeps 1Pa, baking temperature 70 ~ 80 DEG C, drying time 6 ~ 8h;
Tungsten device is placed in for the polyurethane foam after vacuum drying put into nonoxidizing atmosphere stove and be warming up to 800 DEG C with certain heating rate, protective atmosphere is that 99.999% argon carries out ungrease treatment, its intensification before first pass into argon at least 0.5h to get rid of furnace air, temperature control process: rise to 400 DEG C from room temperature with the speed of 1 DEG C/min, 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 when being cooled to room temperature;
To be placed in tungsten device for the sample after ungrease treatment and to be warming up to 1800 DEG C with certain heating rate in fine vacuum high temperature sintering furnace and to carry out vacuum-sintering, 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, and insulation 0.5h, 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 2h, vacuum is 1 × 10
-3pa; Sinter complete, vacuum is 1 × 10
-4pa ~ 1 × 10
-3pa; 1300 DEG C are cooled to, insulation 1h with the speed of 15 DEG C/min; 800 DEG C are cooled to, insulation 1.5h, then furnace cooling with the speed of 20 DEG C/min;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with corundum container to be warming up to 1000 DEG C with certain heating rate and to carry out stress relief annealing process, the vacuum before heating up in annealing furnace at least will reach 1 × 10
-3pa, rises to 1000 DEG C with the speed of 25 DEG C/min from room temperature, and insulation 4h, vacuum is 1 × 10
-4pa ~ 1 × 10
-3pa; Be cooled to 800 DEG C with the speed of 12 DEG C/min again, insulation 2h, vacuum is 1 × 10
-4pa ~ 1 × 10
-3pa; Be cooled to 600 DEG C with the speed of 14 DEG C/min, insulation 2h, vacuum is 1 × 10
-4pa; Be cooled to room temperature with the speed of 20 DEG C/min, vacuum is 1 × 10
-4pa.Finally carry out conventional post processing and obtain porous niobium.
The porous niobium finished product adopting said method to obtain has the foaming structure of hole three-dimensional communication distribution, and the pure niobium powder through sintering is piled up on the foam framework of formation, and niobium powder particles has sintering neck structure each other.And the sintering neck structure formed between niobium powder particles in this porous niobium finished product microstructure is more than 80%.
Inventor detects the porous material density of above-mentioned porous niobium finished product, porosity, aperture and various mechanical property by standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001: this porous niobium is the pore structure with three-dimensional communication distribution, its impurity content lower than 0.4% finished product, its even pore distribution and be communicated with, density 2.45g/cm
3, porosity 72.5%, pore mean diameters 300 μm, elastic modelling quantity 1.5GPa, yield strength 45MPa, comprcssive strength 50MPa, hardness 130MPa, amount of plastic deformation 9.4%, tensile strength 27MPa, elongation 9.7% of having no progeny; When the method measured by metal bending strength carries out anti-bending test, the fracture rate sintering neck in this porous niobium microstructure is less than 40%, and the fracture rate of granule interior is greater than 60%.
In the method that above-described embodiment 6 provides, we can also do other selection to wherein each kind of condition can obtain porous niobium of the present invention equally.In the following embodiments, if not otherwise specified, in table parameters condition all with aforementioned
Embodiment 6 is identical.
Gained porous niobium finished product is pressed preceding method and is detected:
| Embodiment | 7 | 8 | 9 | 10 | 11 | 12 | 13 |
| Density (g/cm 3) | 3.8 | 3.5 | 2.4 | 2.7 | 2.2 | 2.0 | 1.9 |
| Porosity (%) | 56 | 60 | 68 | 74 | 72 | 77 | 78 |
| Pore diameter (μm) | 230 | 260 | 350 | 420 | 400 | 410 | 480 |
| Elastic modelling quantity (GPa) | 1.3 | 1.6 | 1.4 | 1.8 | 1.2 | 0.9 | 0.7 |
| Yield strength (MPa) | 48 | 53 | 50 | 56 | 46 | 43 | 35 |
| Comprcssive strength (MPa) | 50 | 55 | 52 | 60 | 48 | 45 | 38 |
| Hardness (MPa) | 160 | 140 | 140 | 150 | 130 | 100 | 120 |
| Amount of plastic deformation (%) | 10.30 | 11.20 | 10.25 | 10.22 | 9.28 | 8.29 | 9.30 |
| Tensile strength (MPa) | 25 | 30 | 28 | 34 | 22 | 20 | 18 |
| To have no progeny elongation (%) | 10.70 | 11.60 | 10.50 | 10.65 | 9.55 | 9.75 | 9.80 |
| Sintering neck fracture rate (%) | 45 | 48 | 50 | 55 | 58 | 59 | 60 |
| Granule interior fracture rate (%) | 55 | 52 | 50 | 45 | 42 | 41 | 40 |
Claims (1)
1. the preparation method of a medical metal implant material porous niobium, it is characterized in that: with particle diameter be less than 41 μm, oxygen content be less than 0.1% metal niobium powder and starch for raw material, in the mixed powder of described metal niobium powder and starch, content of starch is 5-10%, by weight percentage, be that binder solution makes niobium powder slurry with polyvinyl alcohol water solution, and to be cast in its aperture be 0.85mm, density 0.032g/cm
3, in the polyurethane foam carrier that hardness is 52 °; Then vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing;
Wherein, polyvinyl alcohol distilled water is heated to dissolving and is mixed with 5g/100ml polyvinyl alcohol water solution; Then be that to add cooled weight be in the described polyvinyl alcohol water solution of 1 part for the metal niobium powder of 2.5 parts and the mixed powder of starch by weight, stir and make starchiness; Above-mentioned polyurethane foam being put into floods until polyurethane foam hole fills in starchy niobium powder slurry repeatedly again;
Vacuum drying is to remove the moisture that fills in the polyurethane foam of niobium powder slurry, and vacuum keeps 0.1Pa, baking temperature 75 DEG C, drying time 7.0h;
Tungsten device is placed in for the polyurethane foam after vacuum drying put into nonoxidizing atmosphere stove and be warming up to 750 DEG C with certain heating rate; protective atmosphere is that 99.999% argon carries out ungrease treatment; it first passed into argon before intensification, and at least 0.5h is to get rid of furnace air, and defat atmosphere is 1 × 10
-4pa ~ 1 × 10
-3pa, temperature control process: rise to 400 DEG C from room temperature with the speed of 1 DEG C/min, insulation 48min, argon passes into speed 0.5L/min; Rise to 750 DEG C with the speed of 0.5 DEG C/min from 400 DEG C, be incubated 90 min, argon passes into speed 1L/min; Powered-down again, the sample furnace cooling after defat, argon passes into speed 1L/min, until close argon when being cooled to room temperature;
Sample after ungrease treatment is placed in tungsten device and is warming up to 1750 DEG C with certain heating rate in fine vacuum high temperature sintering furnace and carries out vacuum-sintering, sintering atmosphere 1 × 10
-4pa ~ 1 × 10
-3pa, rises to 1000 DEG C with the speed of 14 DEG C/min from room temperature, and insulation 36min, vacuum is 1 × 10
-3pa; 1300 DEG C are risen to, insulation 30min with the speed of 17 DEG C/min; Rise to 1750 DEG C with the speed of 15 DEG C/min, insulation 150min, vacuum is 1 × 10
-3pa; After sintering, cooling vacuum degree is 1 × 10
-4pa ~ 1 × 10
-3pa; 1250 DEG C are cooled to, insulation 60min with the speed of 18 DEG C/min; 1000 DEG C are cooled to, insulation 30min with the speed of 22 DEG C/min; 600 DEG C are cooled to, insulation 30min then furnace cooling with the speed of 24 DEG C/min;
Be placed in vacuum annealing furnace for the cooled sample of vacuum-sintering with corundum container to be warming up to 1000 DEG C with certain heating rate and to carry out stress relief annealing process, annealing vacuum is 1 × 10
-3pa, rises to 1000 DEG C with the speed of 23 DEG C/min from room temperature, insulation 270min; 800 DEG C are cooled to again, insulation 2h with the speed of 12 DEG C/min; 600 DEG C are cooled to, insulation 90min with the speed of 16 DEG C/min; Be cooled to room temperature with the speed of 22 DEG C/min, finally carry out conventional post processing and obtain porous niobium.
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| WO1997031738A1 (en) * | 1996-02-27 | 1997-09-04 | Astro Met, Inc. | Porous materials and method for producing |
| CN101448534A (en) * | 2006-05-17 | 2009-06-03 | 生物技术公司 | Anisotropic nanoporous coatings for medical implants |
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