CN102475902B - Preparation method of medical porous metal implant material - Google Patents
Preparation method of medical porous metal implant material Download PDFInfo
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- CN102475902B CN102475902B CN201010563418.5A CN201010563418A CN102475902B CN 102475902 B CN102475902 B CN 102475902B CN 201010563418 A CN201010563418 A CN 201010563418A CN 102475902 B CN102475902 B CN 102475902B
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Abstract
A preparation method of a medical porous metal implant material includes steps of mixing solution, prepared by starch which serves as an organic binder and distilled water which serves as a dispersant, with niobium powder of the average particle size smaller than 43 mu m and oxygen content lower than 0.1% to prepare niobium slurry, pouring the niobium slurry into an organic foam body, impregnating the organic foam body until holes of the organic foam body are filled with the niobium slurry, drying and removing the dispersant, removing the organic binder and the organic foam body in a degreasing manner under the protection atmosphere of inert gas, producing a porous sintered body by vacuum sintering, and finally preparing porous niobium after vacuum annealing and conventional post-treatments, wherein the mass percentage concentration of starch solution ranges from 2% to 6%. The porous niobium of the medical metal implant material, which is prepared by the preparation method, has excellent biological compatibility and safety. Meanwhile, since the porous niobium has the sintered neck structure, mechanical properties such as ductility and the like of the porous niobium are improved, and the preparation method is good and convenient for practical application of the porous niobium in medical metal implanting.
Description
Technical field
The present invention relates to a kind of preparation method of medical porous metal implant material, be specifically related to a kind of preparation method of the porous niobium as medical embedded material, relate in particular to a kind of preparation method that is applicable to biocompatibility and the good porous niobium embedded material of safety.
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.Porous embedded material as 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 is partly communicated with and is uniformly distributed as required, make it both consistent with the bone growth of human body, alleviate again the weight of material itself, to be applicable to human body, implanted use.
And refractory metal niobium, because it has outstanding bio-compatibility and mechanical property, its porous material is expected to the conventional medical metallic biomaterial such as aforementioned as an alternative, becomes the biomaterial mainly as bone necrosis's treatment.Due to metal niobium to human body harmless, nontoxic, have no side effect, and along with the develop rapidly of domestic and international medical science, niobium is goed deep into as the further of body implanting material cognition, and people implant and become more and more urgent by the demand of porous metals niobium material human body, also more and more higher to its requirement., as the medical embedded metal niobium of porous, if can there is the very high physical and mechanical properties that is uniformly distributed interconnected pore and adapts with human body, be wherein the heavy connection constituent material that guarantees freshman bone tissue's normal growth.
As medical embedded porous metal material just as porous metal material be to take powder sintering as main processing method like that substantially, 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 bibliographical information that metal powder sintered legal system makes porous niobium seldom, particularly take and obtain medical embedded material and almost do not have with the porous niobium powder sintering bibliographical information that is 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 ".Yet porous metals that it obtains or for filtering material use, or share for Aero-Space and other high-temperature field but not use as medical metal implanted material, moreover also non-porous niobium of the porous metals of processing.
At present, directly usining porous niobium has no report as the document of medical embedded material and related manufacturing processes.As everybody knows, metal tantalum and niobium are in of the same clan in the periodic table of elements, and both are adjacent one another are, so the chemical property of the two is extremely similar.And about porous tantalum, US5282861 discloses a kind of perforate tantalum material and preparation thereof that is applied to spongy bone implant, cell and organizes sensor.This porous tantalum is made by pure business tantalum, it take polyurethane precursor, and to carry out the carbon skeleton that thermal degradation obtains be support, this carbon skeleton is multiple dodecahedron, it in it, is mesh-like structure, integral body spreads all over micropore, porosity can be up to 98%, then the method by chemical vapour deposition, infiltration is attached on carbon skeleton to form porous metals micro structure, referred to as chemical deposition by commercially pure tantalum.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtains is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight accounts for 1% left and right.Document is further 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, such as cutting of 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 the preparation method of the medical porous metal implant material that a kind of biocompatibility and biological safety are good, the medical metal that the inventive method makes is implanted porous niobium material and is specially adapted to the medical embedded material as the coupling member at shoulder bone, skull and facial bone tissue injury or damaged place.
The object of the invention is to be achieved through the following technical solutions:
A kind of preparation method of medical porous metal implant material, adopt foam impregnation method sintering to form, it is characterized in that: be that employing starch is that organic binder bond and distilled water are that solution and the mean diameter that dispersant is mixed with is less than 43 μ m, oxygen content is less than 0.1% niobium powder and makes niobium powder slurry, and be cast in Organic Foam Material, dipping is until Organic Foam Material hole is filled with niobium powder slurry, then be dried and remove the dispersant in the Organic Foam Material that is cast with niobium powder slurry, under inert gas shielding atmosphere, ungrease treatment is to remove organic binder bond and Organic Foam Material, under vacuum, sintering makes porous sintered body, through the pure niobium powder of sintering, pile up on the foam framework forming, niobium powder particles has sintering neck structure each other, under vacuum, annealing and conventional post processing make porous niobium again, the mass percentage concentration of described amidin is 2～6%.
Inventor finds in research process, in the preparation of medical porous niobium embedded material, to the selection of organic adhesive 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 present invention is that the porous niobium of medical metal implantation purposes finds a kind of practicable preparation method, the present invention adopts starch as binding agent, its low price, because starch is the conventional foods of people, its biological safety of additive while therefore preparing as biomaterial is good; Starch slurry viscosity of the present invention is little, the porosity that starch size floods the sample perforate is larger, at the dry sample surfaces of removing after dispersant, be not prone to the phenomenon of plugging hole gap, moreover, starch just can decompose water outlet and carbon dioxide at low temperatures as Organic substance, improved the purity of sample, made the porous niobium of the medical metal implanted material that makes there is superior bio-compatibility and biological safety; But when the slurry that the starch of take is bonding agent is prepared porous niobium medical embedded material for infusion process, adhesion in the porous niobium making between niobium powder is less, porosity is larger, easily make mechanical property can not be guaranteed, make do not possess practical value as the porous niobium of medical embedded material purposes, therefore conventionally can not consider to using that starch is as the porous niobium of bonding agent employing infusion process preparation as medical embedded material.In research process, inventor also finds, niobium powder be easy to starch and Organic Foam Material in carbon react, easily make the porous niobium medical embedded material impurity content that finally makes raise, affect its biocompatibility and biological safety.But the present invention is by adopting described technological means reasonably to coordinate, make the present invention take that slurry that starch is bonding agent adopts the porous niobium that infusion process makes in the situation that the common mechanical property that does not affect existing porous niobium and had, still can obtain having the porous niobium of sintering neck structure, the mechanical properties such as porous niobium ductility have been improved, for the convenience of porous niobium in medical metal is implanted and the application of actual effect provide good method.The porous niobium that adopts preparation method of the present invention to make is specially adapted to the medical embedded material as the osseous tissue wound of skull, shoulder or the coupling member at the damaged place of bone.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.
Above-mentioned Organic Foam Material can adopt the similar substances such as polyurethane foam, polyether ester foam, optimization polyurethane foam of the present invention.Described slurry is poured into a mould, be impregnated in described Organic Foam Material, then be dried and remove after the dispersant in the Organic Foam Material that is cast with niobium powder slurry, the porosity of the porous niobium forming is between 51.0～77.7%, hole average diameter 200～500 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 guarantee 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 starch is heated to dissolve with distilled water, preferably adopt amidin and the described metal niobium powder of percentage by weight 5% to make niobium powder slurry, wherein, to add weight be, in the described amidin of 1 part, to stir and make starchiness to the metal niobium powder that is 3～5 parts (preferably 4 parts) by weight; And to be cast in aperture be 0.48～0.89mm, density 0.015 g/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.
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.
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 ℃～800 ℃ conditions of temperature; In vacuum, be 1 * 10 again
-4pa～1 * 10
-3pa, 1700～1800 ℃ of temperature, the temperature retention time vacuum-sintering of 3～5 hours is processed and is made porous sintered body.During sintering process insulation, can also filling with inert gas protection replace vacuum protection; Finally carry out vacuum annealing processing, wherein vacuum annealing is processed and to be referred to and after vacuum-sintering, continue to keep temperature in 900～1100 ℃, temperature retention time 1～3 hour, and vacuum is not for higher than 1 * 10
-3pa.
Above-mentioned ungrease treatment condition also includes: the speed with 0.5 ℃/min～3 ℃/min is progressively warming up to 400～800 ℃, with noble gas, as argon passes into, forms protective atmosphere and is incubated 1.5～3h;
Vacuum-sintering condition also includes: vacuum is 1 * 10
-4pa～1 * 10
-3pa, rises to 900 ℃～1400 ℃ with the heating rate of 10 ~ 20 ℃/min from room temperature, after insulation 1h～2h; With the heating rate lower than 20 ℃/min, be warming up to 1700～1800 ℃ again, 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 ℃/min, is not less than 15 ℃/min and gradually falls cooldown rate mode, and to sintered porous bodies segmentation cooling down to 600～800 ℃, 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 ℃ with the speed higher than 30 ℃/min not, insulation 4h～6h; To be not less than 10 ℃/min but not to be cooled to room temperature higher than the cooldown rate segmentation of 30 ℃/min soon after first slow, the temperature retention time of each section tapers off and is no more than 1.5 h again.
Further feature is on this basis: 70～80 ℃ of described vacuum drying baking temperatures, 6～8 hours drying times; Described ungrease treatment condition also includes: be progressively warming up to 400～800 ℃, with pure argon gas (99.9999%), pass into formation protective atmosphere, speed with 1～3 ℃/min rises to 400 ℃ from room temperature, insulation 0.5～1h, speed with 0.5～1.5 ℃/min rises to 600～800 ℃, insulation 1～2h from 400 ℃; Described vacuum-sintering condition also includes: the speed with 10～15 ℃/min rises to 900～1100 ℃ from room temperature, insulation 0.5～1h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 10～20 ℃/min rises to 1300～1400 ℃, insulation 0.5～1h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa, rises to 1700～1800 ℃ with the speed of 6～20 ℃/min, insulation 2～3h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Cooling condition after vacuum-sintering also includes: vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 15～20 ℃/min is cooled to 1200～1300 ℃, insulation 0.5～1h; Speed with 18～25 ℃/min is cooled to 600～1000 ℃, insulation 1～1.5h, then furnace cooling; Described vacuum annealing condition also includes: the speed with 22～30 ℃/min rises to 900～1100 ℃, insulation 4～6h, and vacuum is not higher than 1 * 10
-3pa, then be cooled to 800 ℃ with the speed of 10～15 ℃/min, insulation 0.5～1.5h, vacuum is not higher than 1 * 10
-3pa; Speed with 16～20 ℃/min is cooled to 600 ℃, insulation 0.5～1.5h, and vacuum is not higher than 1 * 10
-3pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum is not higher than 1 * 10
-3pa.
Specifically, a kind of preparation method of medical embedded material porous niobium:
A. the preparation of niobium powder slurry: starch is heated to dissolve with distilled water, be mixed with percentage by weight 2～6%(preferably 5%) amidin, being less than 43 μ m, oxygen content with mean diameter is less than 0.1% metal niobium powder and stirs and make starchy niobium powder slurry, wherein, the weight part ratio of described metal niobium powder and described amidin is 3～5 parts (preferably 4 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 is filled with niobium powder slurry, then be dried and remove the dispersant in the Organic Foam Material that is cast with niobium powder slurry, under inert gas shielding atmosphere, ungrease treatment is to remove organic binder bond and Organic Foam Material, under vacuum, sintering makes porous sintered body, through the pure niobium powder of sintering, pile up on the foam framework forming, niobium powder particles has sintering neck structure each other, under vacuum, annealing and conventional post processing make porous niobium again, 70 ℃ of described vacuum drying baking temperatures, 6.5 hours drying times, described ungrease treatment condition is: be progressively warming up to 800 ℃, with pure argon gas (99.9999%), pass into formation protective atmosphere, speed with 1.5 ℃/min rises to 400 ℃ from room temperature, be incubated 1 hour, with the speed of 1.0 ℃/min, rise to 800 ℃ from 400 ℃, be incubated 2 hours, described vacuum-sintering condition is: the speed with 15 ℃/min rises to 1100 ℃ from room temperature, insulation 30min, vacuum is 10
-4pa, speed with 18 ℃/min rises to 1350 ℃, insulation 30min, and vacuum is 10
-4pa, rises to 1800 ℃ with the speed of 17 ℃/min, insulation 120min, and vacuum is 10
-4pa, cooling condition after vacuum-sintering is: vacuum is 10
-3pa, speed with 16 ℃/min is cooled to 1300 ℃, insulation 30min, speed with 20 ℃/min is cooled to 1100 ℃, insulation 60min, speed with 18 ℃/min is cooled to 700 ℃, and insulation 60min is furnace cooling then, described vacuum annealing condition is: the speed with 24 ℃/min rises to 1050 ℃, insulation 240min, and vacuum is 10
-3pa, then be cooled to 800 ℃ with the speed of 13 ℃/min, insulation 60min, vacuum is 10
-3pa, speed with 18 ℃/min is cooled to 600 ℃, insulation 60min, vacuum 10
-3pa, speed with 25 ℃/min is cooled to room temperature, and vacuum is 10
-3pa.
The medical embedded material porous niobium that above-mentioned preparation method makes 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 0.3%; This porous niobium finished product even pore distribution and connection, density 2.0～4.2g/cm
3, porosity is between 51.0～77.7%, hole average diameter 200～500 μ m; Elastic modelling quantity 0.8～2.0GPa, yield strength 35～60MPa, comprcssive strength 35～65MPa, hardness 100～200MPa, amount of plastic deformation 9.4%～17.3%, tensile strength 20～45 MPa, the elongation 9.3%～14.7% of having no progeny; Not only do not affect elastic modelling quantity, yield strength of porous material etc., and be to have improved these performance parameters that porous material is emphasized.And when carrying out anti-bending test, the fracture rate of the sintering neck 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.
Accompanying drawing explanation
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.
From accompanying drawing, can be observed: 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 that osteoblast adheres to, differentiation and growth, promotes growing into of bone, can strengthen being connected between implant and bone, is beneficial to and realizes biological fixation.2, the mechanical property of porous niobium of the present invention is good.As shown in drawings, the sintering microstructure uniform particles of porous niobium of the present invention, sintering neck is obvious, has guaranteed good mechanical property, and has good ductility.
The specific embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples 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 starch 8g, put into the container that 240ml distilled water is housed; Placing it in heats and stir on electric furnace makes it to become amidin.With 200g balance, weigh mean diameter and be less than the niobium powder 60g that 43 microns, oxygen content are less than 0.1%, add the cooling amidin of 15ml, be uniformly mixed, make it to become niobium powder slurry.(average pore size is 0.48mm, density 0.025g/cm to select 10 * 10 * 30mm cellular polyurethane foam
3, 50 ° of hardness) and put into wherein cast, until polyurethane foam hole is filled with niobium powder 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, 70 ℃ of baking temperatures, drying time 8h, vacuum keep 1Pa.Ungrease treatment: low vacuum is in 1 * 10
-3pa, 600 ℃ of temperature, temperature retention time 2h.Vacuum-sintering: sintering in vacuum drying oven, 1750 ℃ of sintering temperatures, insulation 3h, vacuum 1 * 10
-3pa ~ 1 * 10
-4pa, the protection of sintering process applying argon gas, 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 through the pure niobium powder of sintering, piles up on the foam framework forming, 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 surpasses 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 to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.3% finished product, its even pore distribution and connection, density 2.5g/cm
3, porosity 71%, hole average diameter 300 μ m, elastic modelling quantity 2.0GPa, yield strength 35MPa, comprcssive strength 50MPa, hardness 110MPa, amount of plastic deformation 17.3%, tensile strength 45MPa, the elongation 14.7% of having no progeny; When 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 starch 5g, put into the container that 200ml distilled water is housed; Placing it in heats and stir on electric furnace makes it to become amidin.With 200g balance, weigh mean diameter and be less than the niobium powder 40g that 43 μ m, oxygen content are less than 0.1%, add 10ml amidin, be uniformly mixed, make it to become niobium powder slurry.(average pore size is 0.56mm, density 0.030g/cm to select 10 * 10 * 25mm cellular polyurethane foam
3, hardness 60
0) put into wherein cast, until polyurethane foam hole is filled with niobium powder 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, 80 ℃ of baking temperatures, drying time 4h, vacuum keep 1 * 10
-2pa.Ungrease treatment: low vacuum is in 1 * 10
-3pa, 800 ℃ of temperature, temperature retention time 6h.Vacuum-sintering: sintering in vacuum drying oven, 1800 ℃ of sintering temperatures, are incubated 4 hours, vacuum 1 * 10
-4pa, the protection of sintering process applying argon gas, 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 through the pure niobium powder of sintering, piles up on the foam framework forming, 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 surpasses 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 to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.3% finished product, its even pore distribution and connection, density 3g/cm
3, porosity 65%, hole average diameter 200 μ m, elastic modelling quantity 1.5GPa, yield strength 50MPa, comprcssive strength 60MPa, hardness 150MPa, amount of plastic deformation 17%, tensile strength 40MPa, the elongation 14% of having no progeny; When 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 starch 6g, put into the container that 220ml distilled water is housed; Placing it in heats and stir on electric furnace makes it to become amidin.With 200g balance, weigh mean diameter and be less than the niobium powder 45g that 43 μ m, oxygen content are less than 0.1%, add 12ml amidin, be uniformly mixed, make it to become niobium powder slurry.(average pore size is 0.70mm, density 0.035g/cm to select 8 * 8 * 25mm cellular polyurethane foam
3, 70 ° of hardness) and put into wherein cast, until polyurethane foam hole is filled with niobium powder 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, 78 ℃ of baking temperatures, drying time 6h, vacuum keep 1 * 10
-1pa.Ungrease treatment: low vacuum is in 1 * 10
-3pa, 700 ℃ of temperature, temperature retention time 1.5h.Vacuum-sintering: sintering in vacuum drying oven, 1700 ℃ of sintering temperatures, are incubated 3.5 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 through the pure niobium powder of sintering, piles up on the foam framework forming, 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 surpasses 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 to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.3% finished product, its even pore distribution and connection, density 4.2g/cm
3, porosity 51%, hole average diameter 300 μ m, elastic modelling quantity 1.0GPa, yield strength 50MPa, comprcssive strength 40MPa, hardness 150MPa, amount of plastic deformation 17.2%, tensile strength 35MPa, the elongation 14.5% of having no progeny; When 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 starch 7g, put into the container that 230ml distilled water is housed; Placing it in heats and stir on electric furnace makes it to become amidin.With 200g balance, weigh mean diameter and be less than the niobium powder 50g that 43 μ m, oxygen content are less than 0.1%, add 13ml amidin, be uniformly mixed, make it to become niobium powder 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 is filled with niobium powder 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, 70 ℃ of baking temperatures, drying time 5h, vacuum keep 1Pa.Ungrease treatment: vacuum 1 * 10
-4pa～1 * 10
-3pa, 500 ℃ of temperature, temperature retention time 2h.Vacuum-sintering: sintering in vacuum drying oven, 1750 ℃ of sintering temperatures, are incubated 4 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 through the pure niobium powder of sintering, piles up on the foam framework forming, 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 surpasses 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 to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.5% finished product, its even pore distribution and connection, density 2.2g/cm
3, porosity 74%, hole average diameter 400 μ m, elastic modelling quantity 1.5GPa, yield strength 50MPa, comprcssive strength 60MPa, hardness 100MPa, amount of plastic deformation 17.3%, tensile strength 42MPa, the elongation 14.6% of having no progeny; When 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, and it be take particle diameter and is less than 43 μ m, oxygen content to be less than 0.1% metal niobium powder be raw material, and adopting percentage by weight is that 2～6% amidins are made niobium powder 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 0.015 g/cm
3～0.035g/cm
3, hardness is greater than 50 °;
Vacuum drying: vacuum keep 10
-2～1Pa, to remove the moisture in the polyurethane foam of filling with niobium powder slurry;
Ungrease treatment: under inert gas shielding atmosphere or low vacuum in 1 * 10
-3pa, 400 ℃～800 ℃ of temperature, and temperature retention time 1.5～3 hours is to remove starch and polyurethane foam wherein;
Vacuum-sintering: vacuum 1 * 10
-4pa～1 * 10
-3pa, 1700～1800 ℃ of temperature, temperature retention time 3～5 hours, applying argon gas or other inert gas shielding during sintering process insulation, to obtain porous material;
Vacuum annealing: after vacuum-sintering, continue to keep temperature in 900～1100 ℃, temperature retention time 1～3 hour, low vacuum is in 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 through the pure niobium powder of sintering, pile up on the foam framework forming, 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 surpasses 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 to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.3% finished product, its even pore distribution and connection,, density 2.0～4.2g/cm
3, porosity is between 51.0～77.7%, hole average diameter 200～500 μ m; Elastic modelling quantity 0.8～2.0GPa, yield strength 35～60MPa, comprcssive strength 35～65MPa, hardness 100～200MPa, amount of plastic deformation 9.4%～17.3%, tensile strength 20～45 MPa, the elongation 9.3%～14.7% of having no progeny; When 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, and it be take particle diameter and is less than 43 μ m, oxygen content to be less than 0.1% metal niobium powder be raw material, and the amidin of take is made niobium powder slurry as binder solution, and to be cast in its aperture be 0.56～0.72mm, density 0.025～0.035g/cm
3, in the polyurethane foam carrier that hardness is 50 °～80 °; Then vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make.
Wherein, starch is heated to dissolving with distilled water and is mixed with percentage by weight 5% amidin; Then by weight, be that to add cooled weight be, in the described amidin of 1 part, to stir and make starchiness for the metal niobium powder of 3～5 parts; Again above-mentioned polyurethane foam is put into and be starchy niobium powder slurry and repeatedly flood until polyurethane foam hole is filled with;
Vacuum drying to be to remove the moisture in the polyurethane foam of filling with niobium powder slurry, vacuum keep 1Pa, 70～80 ℃ of baking temperatures, drying time 6～8h;
For the polyurethane foam after vacuum drying, being placed in tungsten device puts into nonoxidizing atmosphere stove and is warming up to 800 ℃ with certain heating rate, protective atmosphere is that 99.999% argon carries out ungrease treatment, its before heating up, first pass into argon at least 0.5h to get rid of furnace air, temperature control process: the speed with 1 ℃/min rises to 400 ℃ from room temperature, insulation 0.5h, argon passes into speed 0.5L/min; With the speed of 0.5 ℃/min, rise to 800 ℃ from 400 ℃, insulation 2h, argon passes into speed 1L/min; Powered-down again, the sample furnace cooling after defat, argon passes into speed 1L/min, until close argon while being cooled to room temperature;
For the sample after ungrease treatment, with tungsten device, be placed in and in fine vacuum high temperature sintering furnace, with certain heating rate, be warming up to 1800 ℃ and carry out vacuum-sintering, before heating up, the vacuum of sintering furnace at least will reach 1 * 10
-3pa, rises to 900 ℃ with the speed of 10～15 ℃/min from room temperature, insulation 0.5h, and vacuum is 1 * 10
-4pa; Speed with 10 ℃/min rises to 1300 ℃, insulation 0.5h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 6 ℃/min rises to 1800 ℃, insulation 2h, and vacuum is 1 * 10
-3pa; Sintering is complete, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 15 ℃/min is cooled to 1300 ℃, insulation 1h; Speed with 20 ℃/min is cooled to 800 ℃, insulation 1.5h, then furnace cooling;
For the cooled sample of vacuum-sintering, with corundum container, be placed in vacuum annealing furnace and with certain heating rate, be warming up to 1000 ℃ 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 ℃ with the speed of 22 ℃/min from room temperature, insulation 4h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 15 ℃/min is cooled to 800 ℃ again, insulation 1.5h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 16 ℃/min is cooled to 600 ℃, insulation 1h, and vacuum is 1 * 10
-4pa; Speed with 20 ℃/min is cooled to room temperature, and vacuum is 1 * 10
-4pa.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 through the pure niobium powder of sintering, piles up on the foam framework forming, 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 surpasses 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 to have the pore structure that three-dimensional communication distributes, its impurity content is lower than 0.3% finished product, its even pore distribution and connection, density 2.45g/cm
3, porosity 72.5%, hole average diameter 300 μ m, elastic modelling quantity 1.5GPa, yield strength 55MPa, comprcssive strength 60MPa, hardness 130MPa, amount of plastic deformation 11.4%, tensile strength 37MPa, the elongation 14.7% of having no progeny; When 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 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 is all identical with previous embodiment 6.
Gained porous niobium finished product is pressed preceding method and is detected:
Claims (6)
1. the preparation method of a medical porous metal implant material, adopt foam impregnation method sintering to form, it is characterized in that: be that to adopt starch be that organic binder bond and distilled water are that the solution that is mixed with of dispersant and mean diameter are less than 43 μ m, oxygen content and are less than 0.1% niobium powder and make niobium powder slurry, and be cast in Organic Foam Material, dipping is until Organic Foam Material hole is filled with niobium powder slurry, then 1 * 10
-2under Pa～1Pa vacuum, be dried and remove the dispersant in the Organic Foam Material that is cast with niobium powder slurry, under inert gas shielding atmosphere, low vacuum is in 1 * 10
-3pa, under 400 ℃～800 ℃ conditions of temperature, ungrease treatment, to remove organic binder bond and Organic Foam Material, then is 1 * 10 in vacuum
-4pa～1 * 10
-3pa, 1700～1800 ℃ of temperature, under the temperature retention time condition of 3～5 hours, vacuum-sintering makes porous sintered body, during sintering process insulation, can also filling with inert gas protection replace vacuum protection; Pure niobium powder through sintering is piled up on the foam framework forming, and niobium powder particles has sintering neck structure each other, then vacuum annealing and conventional post processing make porous niobium finished product; Wherein vacuum annealing is processed and to be referred to and after vacuum-sintering, continue to keep temperature in 900～1100 ℃, temperature retention time 1～3 hour, and vacuum is not for higher than 1 * 10
-3pa; The mass percentage concentration of described amidin is 2～6%.
2. preparation method as claimed in claim 1, is characterized in that: described Organic Foam Material is polyurethane foam; The porosity of described porous niobium finished product is between 51.0～77.7%, and hole average diameter 200～500 μ m, form sintering neck structure between at least 50% niobium powder particles in described porous niobium finished product.
3. preparation method as claimed in claim 1 or 2, it is characterized in that: described slurry is that starch is heated to dissolve with distilled water, adopt amidin and the described metal niobium powder of percentage by weight 5% to make niobium powder slurry, wherein, it is, in the described amidin of 1 part, to stir and make starchiness that the metal niobium powder that is 3～5 parts by weight adds weight; And to be cast in aperture be 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, hardness is more than or equal in the polyurethane foam of 50 °.
4. preparation method as claimed in claim 3, is characterized in that: the weight part ratio of described metal niobium powder and amidin is 4:1; The aperture of described polyurethane foam is 0.56～0.72mm, density 0.025g/cm
3, 50 °～80 ° of hardness.
5. preparation method as claimed in claim 4, is characterized in that: described ungrease treatment condition also includes: the speed with 0.5 ℃/min～3 ℃/min is progressively warming up to 400～800 ℃, with noble gas, passes into and forms protective atmosphere and be incubated 1.5～3h;
Vacuum-sintering condition also includes: vacuum is 1 * 10
-4pa～1 * 10
-3pa, rises to 900 ℃～1400 ℃ with the heating rate of 10 ~ 20 ℃/min from room temperature, after insulation 1h～2h; With the heating rate lower than 20 ℃/min, be warming up to 1700～1800 ℃ again, be at least incubated 2h;
After vacuum-sintering, also carry out coolingly, described cooling condition includes: vacuum is 1 * 10
-4pa～1 * 10
-3pa, with not higher than 25 ℃/min, is not less than 15 ℃/min and gradually falls cooldown rate mode, and to sintered porous bodies segmentation cooling down to 600～800 ℃, 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 ℃ with the speed higher than 30 ℃/min not, insulation 4h～6h; To be not less than 10 ℃/min but not to be cooled to room temperature higher than the cooldown rate segmentation of 30 ℃/min soon after first slow, the temperature retention time of each section tapers off and is no more than 1.5 h again.
6. method as claimed in claim 5, is characterized in that: 70～80 ℃ of described vacuum drying baking temperatures, 6～8 hours drying times; Described ungrease treatment condition also includes: be progressively warming up to 400～800 ℃, the purity of take passes into formation protective atmosphere as 99.9999% argon, speed with 1～3 ℃/min rises to 400 ℃ from room temperature, insulation 0.5～1h, speed with 0.5～1.5 ℃/min rises to 600～800 ℃, insulation 1～2h from 400 ℃; Described vacuum-sintering condition also includes: the speed with 10～15 ℃/min rises to 900～1100 ℃ from room temperature, insulation 0.5～1h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 10～20 ℃/min rises to 1300～1400 ℃, insulation 0.5～1h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa, rises to 1700～1800 ℃ with the speed of 6～20 ℃/min, insulation 2～3h, and vacuum is 1 * 10
-4pa～1 * 10
-3pa; Cooling condition after vacuum-sintering also includes: vacuum is 1 * 10
-4pa～1 * 10
-3pa; Speed with 15～20 ℃/min is cooled to 1200～1300 ℃, insulation 0.5～1h; Speed with 18～25 ℃/min is cooled to 600～1000 ℃, insulation 1～1.5h, then furnace cooling; Described vacuum annealing condition also includes: the speed with 22～30 ℃/min rises to 900～1100 ℃, insulation 4～6h, and vacuum is not higher than 1 * 10
-3pa, then be cooled to 800 ℃ with the speed of 10～15 ℃/min, insulation 0.5～1.5h, vacuum is not higher than 1 * 10
-3pa; Speed with 16～20 ℃/min is cooled to 600 ℃, insulation 0.5～1.5h, and vacuum is not higher than 1 * 10
-3pa; Speed with 20～30 ℃/min is cooled to room temperature, and vacuum is not higher than 1 * 10
-3pa.
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| CN113118455B (en) * | 2021-04-23 | 2022-11-11 | 吉林大学重庆研究院 | 3D printing method for preparing metal artificial bone based on slurry direct writing |
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| EP1891988A1 (en) * | 2006-08-07 | 2008-02-27 | Debiotech S.A. | Anisotropic nanoporous coatings for medical implants |
| CN101250638A (en) * | 2007-02-21 | 2008-08-27 | 德普伊产品公司 | Porous metal foam structures and methods |
| CN101695586A (en) * | 2009-10-30 | 2010-04-21 | 河北工业大学 | High-intensity porous bone repair material and method for preparing same |
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| CN101250638A (en) * | 2007-02-21 | 2008-08-27 | 德普伊产品公司 | Porous metal foam structures and methods |
| CN101695586A (en) * | 2009-10-30 | 2010-04-21 | 河北工业大学 | High-intensity porous bone repair material and method for preparing same |
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