CN102462862A - Preparation method for porous tantalum serving as medical metal implant material - Google Patents
Preparation method for porous tantalum serving as medical metal implant material Download PDFInfo
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Abstract
The invention discloses a preparation method for porous tantalum serving as a medical metal implant material. The preparation method is characterized by comprising the following steps of: preparing a tantalum powder sizing agent from a solution prepared from ethyl cellulose serving as an organic bonding agent and absolute ethanol serving as a dispersing agent, and mixed powder of starch and metal tantalum powder; casting the tantalum powder sizing agent into an organic foam body; soaking till pores of the organic foam body are filled with the tantalum powder sizing agent; drying to remove the dispersing agent in the organic foam body into which the tantalum sizing agent is cast; performing degreasing treatment in an inert gas protection atmosphere to remove the organic bonding agent and the organic foam body; sintering in vacuum to obtain a porous sintered body, wherein a sintered neck structure is formed among tantalum powder particles on a foam framework constructed by stacking sintered pure tantalum powder; and performing annealing and conventional post-treatment in vacuum to obtain porous tantalum. The medical metal implant material prepared with the method has superior biocompatibility and safety, has high mechanical property and ductility simultaneously, and is particularly suitable to be taken as a medical implant material for light-load positions of a human body.
Description
Technical field
The present invention relates to a kind of method for preparing of porous medical metal embedded material, relate in particular to a kind of porous tantalum as medical embedded material.
Background technology
Porous medical metal embedded material has important and special purposes such as treatment osseous tissue wound and bone formation necrosis, and existing common this type material has porous metals rustless steel, porous metals titanium etc.Porous embedded material as osseous tissue wound and the use of bone formation necrosis therapeutic; Its porosity should reach 30～80%; And hole preferably all is communicated with and uniform distribution, or hole partly is communicated with and uniform distribution as required, makes it that both the osseous tissue growth phase with human body was consistent; Alleviated the weight of material itself again, implanted use to be fit to human body.
And refractory metals tantalum, because it has outstanding biocompatibility and mechanical property, its porous material is expected to as substituting conventional medical metallic biomaterials such as aforementioned, becomes the biomaterial mainly as bone necrosis's treatment.Since metal tantalum to human body harmless, nontoxic, have no side effect; And along with the develop rapidly of domestic and international medical science; As cognitive further the going deep into of body implanting material, the demand that people implant with the porous metals tantalum material human body becomes more and more urgent, and is also increasingly high to its requirement to tantalum.,, then be the heavy connection constituent material that guarantees freshman bone tissue's normal growth wherein if can have very high uniform distribution interconnected pore and the physical and mechanical properties that adapts with human body as the medical embedded metal tantalum of porous.
As medical embedded porous metal material just as the porous metal material that kind be to be main processing method basically with powder sintering, in particular for obtain porosity communication and equally distributed porous metal foam structure adopt the dipping after drying of metal dust slurry on the organic foam body in the powder sintering to reburn to be called for short the foam impregnation method in the majority for knot.About the powder sintered porosity communication that obtains and common its Metal Mechanic Property of equally distributed porous metal material is not fine, and its main cause is how to arrange the support and the problem of eliminating in relation, the metal powder sintered process of subsiding of pore-forming medium on the technology.And all do not have good solution in the known bibliographical information and laissez-faire nature.
The bibliographical information that adopts metal powder sintered manufactured porous tantalum seldom particularly uses the porous tantalum powder sintering bibliographical information as purpose almost not have to obtain medical embedded material.Can reference be that publication number is CN200510032174, title " three-dimensional through hole or part hole are connected with each other porous metal foam and preparation method thereof " and CN200710152394, title " a kind of novel porous foam tungsten and preparation method thereof ".Yet porous metals that it obtained or for filtering material usefulness, or share for Aero-Space and other high-temperature field but not use as the medical metal embedded material, moreover the also non-porous tantalum of the porous metals of being processed.
About porous tantalum, US5282861 discloses a kind of perforate tantalum material and preparation thereof that is applied to spongy bone implant, cell and organizes sensor.This porous tantalum is processed by pure commercial tantalum; It carries out the carbon skeleton that thermal degradation obtains with the polyurethane precursor is support, and this carbon skeleton is multiple dodecahedron, is the mesh-like structure in it; Integral body spreads all over micropore; Porosity can be up to 98%, the method for commercially pure tantalum through chemical vapour deposition, infiltration is attached on the carbon skeleton to form the porous metals micro structure again, abbreviates chemical deposition as.Its surperficial tantalum layer thickness of the porous tantalum material that this method obtained is between 40～60 μ m; In whole porous material, tantalum heavily accounts for 99%, and carbon skeleton weight then accounts for about 1%.Document is further put down in writing, the comprcssive strength 50～70MPa of this porous material, elastic modelling quantity 2.5～3.5GPa, tensile strength 63MPa, amount of plastic deformation 15%.But with its porous tantalum as medical embedded material, the mechanical property of its material such as ductility have obvious weak point, can have influence on the follow-up processing to porous tantalum material itself, for example cutting of profiled member etc.Also all there is such deficiency at the product that aforesaid metal powder sintered method obtained equally.Owing to the limitation of its preparation method, the finished product purity of acquisition is not enough, and the carbon skeleton residue is arranged again, causes biological safety to reduce.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing of medical embedded material porous tantalum; Porous tantalum material bio-compatibility and biological safety that the inventive method makes are good; Also have good mechanical property simultaneously, be specially adapted to medical embedded material as the light position of human bearing.
The objective of the invention is to realize like this:
A kind of method for preparing of medical embedded material porous tantalum; Adopt the foam impregnation method, it is characterized in that: use ethyl cellulose as the solution that organic binder bond and dehydrated alcohol are mixed with as dispersant, process tantalum powder slurry with the mixed powder of starch and ta powder; And be cast in the organic foam body; Dipping is filled with tantalum powder slurry until organic foam body opening crack, and drying is removed the said dispersant in the organic foam body that is cast with tantalum powder slurry then, and ungrease treatment is to remove said organic binder bond and organic foam body under inert gas shielding atmosphere; Sintering makes porous sintered body under the vacuum; Pile up on the foam framework that constitutes through agglomerating pure tantalum powder, the tantalum powder particles has the sintering neck structure each other, and annealing and conventional post processing make porous tantalum under the vacuum again.
The medical embedded material porous tantalum that the present invention makes has the pore structure that three-dimensional communication distributes, and piles up on the foam framework that constitutes through agglomerating tantalum powder, and the tantalum powder particles has the sintering neck structure each other.The pore structure that three-dimensional communication of the present invention distributes does not get rid of seldom that the three-dimensional hole of part is not communicated with, and for example accounting for that hole about 1% is not communicated with is to belong to negligible.Sintering neck of the present invention is meant that at high temperature, powder is heated, and bonds between the granule, is exactly the sintering phenomenon that we often say.Sintering is meant that the bonded process of metallurgical property at high temperature takes place between powder particle granule, carries out, and realize through atomic migration usually under the fusing point of main component constituent element.Observe through microstructure, can find that the sintering neck (or claiming the contact neck) of granule contact is grown up, and therefore cause performance variation.Along with the raising of sintering temperature, the perhaps prolongation of sintering time or to the reasonable control of sintering temperature and sintering time, the sintering neck just can increase gradually, the ratio of sintering neck just can increase, and the intensity of sintered body increases.Also be that the present invention forms the sintering neck structure also can realize the object of the invention between tantalum powder particles partly.
In the method for preparing of the present invention, the employing ethyl cellulose is an organic adhesive, and ethyl cellulose is widely used in pharmaceutical industry, and it has better bio-safety performance; Dehydrated alcohol is a dispersant, and dehydrated alcohol is volatile, can save drying time effectively; Can after having flooded, detect sample interior whether have hollow, thereby can guarantee the dipping sizing agent quality evenly, also can reduce hydrogen, oxygen content in the porous tantalum behind the sintering; Thereby the reduction impurity content, simultaneously, the porous tantalum shape behind the dipping can be fixed up soon; Be not prone to distortion, guaranteed the stable of sample shape behind the sintering, size; The concentration of ethyl cellulose alcoholic solution of the present invention is low, viscosity is also little, and the quality that therefore immerses slurry is few, can improve the porosity of the porous tantalum material that makes, thereby make the porous tantalum material good biocompatibility that makes; The mixed powder that also adopts tantalum powder and starch to form in the method for preparing of the present invention is raw material constituent; Can effectively increase the porosity and the aperture of the porous tantalum that makes; Simultaneously starch is that people food, the safety used always are good; Starch also is prone to decompose, can improve the purity of the porous tantalum material that finally makes, so the present invention can make the porous tantalum material that makes have very superior biocompatibility and safety; But simultaneously, the inventor finds that in research process ethanol and polymer organic foam are prone to slow reaction takes place at normal temperatures, and the internal structure of destructible sample influences the mechanical property of material; Ethanol in porous tantalum is put the heating of stove the inside into without bone dry, because ethanol volume when heating expands rapidly, influences the purity and the mechanical property of material; When also having porosity and aperture excessive, can make that mechanical property can not get guaranteeing, making easily can't practical application as the porous tantalum of medical embedded material purposes.Around this problem; The inventor has launched series of studies; Thereby seek out other compositions in the preparation raw material such as organic bonding agent selection, dispersant selection and with all have more exquisitely above being used of mixed powder, cooperate follow-up treatment process steps, make the porous tantalum material that makes not only have superior biocompatibility and safety; And its shape is consistent, mechanical property is also better, is specially adapted to the medical embedded material at the light position of human bearings such as frontal bone, facial bone.Simultaneously, simple, the easy control of described method for preparing technology; Whole process of preparation is harmless, pollution-free, the nonhazardous dust, and human body is had no side effect.
In order to improve the mechanical property of porous tantalum, above-mentioned ta powder preferably adopt mean diameter less than 10 μ m, oxygen content less than 0.1% tantalum powder.
Above-mentioned organic foam body can adopt similar substances such as polyurethane foam, polyether ester foam, optimization polyurethane foam of the present invention, and its aperture is 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, hardness>=50 °, further being preferably the aperture is 0.56～0.72mm, density 0.025g/cm
3, the polyurethane foam that hardness is 50 ° ~ 80 ° more helps the formation and the processing of product structure of the present invention.So promptly meet efficiency principle and can guarantee enough mechanical properties again.
In order further to improve the mechanical property of above-mentioned porous tantalum, contents of starch is 5～10% in the mixed-powder of starch and ta powder, is preferably 10%, in weight percentage; The weight percent concentration of above-mentioned ethyl cellulose alcoholic solution is 1～5%, is preferably 3%.
The mixed powder that above-mentioned ta powder and starch are formed and the weight part ratio of ethyl cellulose alcoholic solution are 2～5:1, are preferably 3:1.
Specifically, be with above-mentioned ta powder and starch mix homogeneously, wherein the weight percentage of starch is 10%; Ethyl cellulose is dissolved in to be mixed with weight percent concentration in the dehydrated alcohol be 3% ethyl cellulose alcoholic solution; Then said ethyl cellulose alcoholic solution is joined in the said mixed powder and be made into slurry, the weight ratio of said mixed powder and ethyl cellulose alcoholic solution is 3:1.
With the cast of above-mentioned slurry, impregnated in the above-mentioned organic foam body, dry then remove the dispersant in the organic foam body that is cast with tantalum powder slurry after, the porosity of the porous tantalum of formation is between 49～79%, hole average diameter 200～550 μ m.The said medical porous tantalum embedded material finished product at least 50% that makes preferably forms the sintering neck structure at least between 80% tantalum powder particles.
The present invention's further characteristics on the other hand are: exsiccant vacuum keeps 10
-1~ 1Pa vacuum, under protective atmosphere, for example vacuum 10 then
-4~ 10
-3Pa, the ungrease treatment of removing organic binder bond and organic foam body under 400 ℃～800 ℃ conditions of temperature; Be not higher than 10 in vacuum again
-4~ 10
-3Pa, 2100～2200 ℃ of temperature, 5～8 hours vacuum-sintering of temperature retention time is handled and is made porous sintered body, can the filling with inert gas protection replace vacuum protection during the sintering process insulation; Carry out vacuum annealing at last and handle, wherein vacuum annealing is handled and is meant that process vacuum-sintering continued keeps temperature to be in 1000～1250 ℃, temperature retention time 5～7 hours, and vacuum is not higher than 10
-4~ 10
-3Pa.
Above-mentioned ungrease treatment condition also includes: the speed with 0.5 ℃/min～5 ℃/min progressively is warming up to 400～800 ℃, feeds with argon to constitute protective atmosphere and be incubated 30min～180min;
The vacuum-sintering condition also includes: vacuum is not higher than 10
-3Pa rises to 900 ℃～1500 ℃ with the heating rate that is not higher than 10～20 ℃/min from room temperature, behind insulation 2h～3h; Be warming up to 2100～2200 ℃ with the heating rate that is not higher than 10 ℃/min again, insulation 3h～5h;
Cooling condition after the vacuum-sintering also includes: vacuum is not higher than 10
-4~ 10
-3Pa not to be higher than 18 ℃/min, to be not less than 8 ℃/min and gradually to fall the cooldown rate mode, and sintered porous bodies segmentation cooling is cooled to 800 ℃, and each section temperature retention time 30min～90min cools to room temperature then with the furnace;
The vacuum annealing condition also includes: vacuum 10
-4~ 10
-3Pa rises to 1000～1250 ℃ with the speed that is not higher than 30 ℃/min, insulation 5～7h; Again with after earlier slow soon to be not less than 5 ℃/min but the cooldown rate segmentation that is not higher than 30 ℃/min is cooled to room temperature, the temperature retention time of each section tapers off and is no more than in 1.5 h～3h and selects.
Further characteristics are on this basis: 80～100 ℃ of said vacuum drying baking temperatures, 5～7 hours drying times; Said ungrease treatment condition also includes: feed the formation protective atmosphere with pure argon gas (99.9999%); Speed with 4 ~ 5 ℃/min rises to 400 ℃ from room temperature, and insulation 60 ~ 90min rises to 600～800 ℃ with the speed of 0.5 ~ 0.8 ℃/min from 400 ℃; Insulation 70 ~ 90min; Said vacuum-sintering condition also includes: the speed with 10～15 ℃/min rises to 900 ~ 1250 ℃ from room temperature, insulation 60 ~ 90min, and vacuum is 10
-4Pa～10
-3Pa; Speed with 10 ~ 20 ℃/min rises to 1300～1500 ℃, insulation 60 ~ 90min, and vacuum is 10
-4Pa～10
-3Pa rises to 2100 ~ 2200 ℃ with the speed of 6 ~ 10 ℃/min, insulation 180 ~ 300min, and vacuum is 10
-4Pa～10
-3Pa; Cooling condition after the vacuum-sintering also includes: vacuum is 10
-4Pa～10
-3Pa is cooled to 1500 ~ 1600 ℃ with the speed of 8～10 ℃/min, insulation 30 ~ 60min; Speed with 11 ~ 14 ℃/min is cooled to 1200 ~ 1250 ℃, insulation 60 ~ 90min; Speed with 10 ~ 15 ℃/min is cooled to 600～800 ℃, then furnace cooling; Said vacuum annealing condition also includes: the speed with 15 ~ 30 ℃/min rises to 1000 ~ 1250 ℃, insulation 300 ~ 420min, and vacuum is 10
-4Pa～10
-3Pa, the speed with 5 ~ 10 ℃/min is cooled to 9000 ℃ again, insulation 90 ~ 150min, vacuum is 10
-4Pa～10
-3Pa; Speed with 10 ~ 20 ℃/min is cooled to 600～800 ℃, insulation 60 ~ 100min, and vacuum is 10
-4Pa～10
-3Pa; Speed with 20 ~ 30 ℃/min is cooled to room temperature, and vacuum is 10
-4Pa～10
-3Pa.
More particularly, a kind of method for preparing of medical embedded material porous tantalum, carry out as follows:
A. the preparation of tantalum powder slurry: with above-mentioned ta powder and starch mix homogeneously, wherein the weight percentage of starch is 10%; Ethyl cellulose is dissolved in to be mixed with weight percent concentration in the dehydrated alcohol be 3% ethyl cellulose alcoholic solution; Then said ethyl cellulose alcoholic solution is joined in the said mixed powder and be made into slurry, the weight ratio of said mixed powder and ethyl cellulose alcoholic solution is 3:1;
B. the preparation of porous tantalum: it is 0.56～0.72mm that above-mentioned tantalum powder slurry is cast in the aperture, density 0.025g/cm
3In the polyurethane organic foam body that hardness is 50 ° ~ 80 °; Dipping is filled with tantalum powder slurry until polyurethane organic foam body opening crack, and drying is removed the dehydrated alcohol in the organic foam body that is cast with tantalum powder slurry then, and ungrease treatment is to remove ethyl cellulose and organic foam body under inert gas shielding atmosphere; Sintering makes porous sintered body under the vacuum; Pile up on the foam framework that constitutes through agglomerating pure tantalum powder, the tantalum powder particles has the sintering neck structure each other, and annealing and conventional post processing make porous tantalum under the vacuum again; 90 ℃ of said vacuum drying baking temperatures, 6 hours drying times, vacuum is 10
-1Pa; Said ungrease treatment condition is: feed to constitute protective atmosphere with pure argon gas (99.9999%), rise to 400 ℃ with the speed of 4 ℃/min from room temperature, insulation 80min rises to 600 ℃, insulation 85min with the speed of 0.8 ℃/min from 400 ℃; Said vacuum-sintering condition is: the speed with 13.5 ℃/min rises to 1000 ℃ from room temperature, insulation 80min, and vacuum is 10
-4Pa; Speed with 17 ℃/min rises to 1300 ℃, insulation 90min, and vacuum is 10
-4Pa rises to 2200 ℃ with the speed of 8 ℃/min, insulation 250min, and vacuum is 10
-4Pa; Cooling condition after the vacuum-sintering is: vacuum is 10
-4Pa is cooled to 1500 ℃ with the speed of 8 ℃/min, insulation 33min; Speed with 11 ℃/min is cooled to 1200 ℃, insulation 65min; Speed with 13 ℃/min is cooled to 700 ℃, then furnace cooling; Said vacuum annealing condition is: the speed with 16 ℃/min rises to 1100 ℃, insulation 400min, and vacuum is 10
-4Pa, the speed with 6 ℃/min is cooled to 900 ℃ again, insulation 90min, vacuum is 10
-4Pa; Speed with 11 ℃/min is cooled to 700 ℃, insulation 60min, vacuum 10
-4Pa; Speed with 22 ℃/min is cooled to room temperature, and vacuum is 10
-4Pa.
Medical embedded material porous tantalum with said structure characteristics can satisfy the requirement of bio-compatibility and biological safety fully; Particularly its foam framework is to be piled up by agglomerating pure tantalum powder to constitute; The sintering neck structure that the tantalum powder particles has has each other greatly improved mechanical property such as the ductility of this material, anti-folding anti-bending strength, is lower than 0.5% through its impurity content of test simultaneously; This porous tantalum finished product even pore distribution and connection, density 3.5～8.5g/cm
3, porosity 49～79%, pore diameter 200～550 μ m; Elastic modelling quantity 2.5～3.8GPa, yield strength 35～75MPa, comprcssive strength 40～90MPa, hardness 150～270MPa, amount of plastic deformation 7.4%～11.3%, tensile strength 60～70 MPa, the elongation 7.3%～10.7% of having no progeny; Not only do not influence elastic modelling quantity, yield strength of porous material etc., and be to have improved these performance parameters that porous material is stressed.And when carrying out anti-bending test, the fracture rate of the sintering neck that forms between each tantalum powder particles is less than 45%, and the fracture rate of tantalum powder particles inside further illustrates new product reliability of structure of the present invention greater than 55%.
Description of drawings
Fig. 1 is the X-ray diffraction analysis collection of illustrative plates (XRD figure) of the porous tantalum of method for preparing preparation according to the invention;
Fig. 2 is the vertical microscope analysis chart of macrostructure of the porous tantalum of method for preparing according to the invention preparation;
Fig. 3 is the scanning electron microscope analysis figure (SEM figure) of microstructure of the porous tantalum of method for preparing according to the invention preparation
Can be observed from accompanying drawing: porous tantalum three-dimensional communication hole according to the invention, even pore distribution helps that osteoblast adheres to, differentiation and growth, promotes growing into of bone, can strengthen being connected between implant and the bone, is beneficial to the realization biological fixation.The sintering microstructure uniform particles of porous tantalum of the present invention, the sintering neck is obvious, has guaranteed the good mechanical performance, and has good ductility.
The specific embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment 1: take by weighing ethyl cellulose 8g, put into the container that the 240ml dehydrated alcohol is housed; Placing it in heats on the electric furnace and stir makes it to become the ethyl cellulose alcoholic solution.With 200g balance weighing mean diameter less than 10 microns, oxygen content less than 0.1% tantalum powder 60g and 3.2g starch, add the refrigerative ethyl cellulose alcoholic solution of 10ml, mix, make it to become slurry.(average pore size is 0.48mm, density 0.025g/cm to select 10 * 10 * 30mm cellular polyurethane foam for use
3, 50 ° of hardness) and put into wherein cast, fill with slurry until the polyurethane foam hole, the polyurethane foam that goes out to be filled slurry with clip is put into porcelain dish.Dry in vacuum drying oven, 80 ℃ of baking temperatures, drying time 7h, vacuum keeps 1Pa.Ungrease treatment: vacuum 1 * 10
-3Pa, 600 ℃ of temperature, temperature retention time 3h.Vacuum-sintering: sintering in vacuum drying oven, 2100 ℃ of sintering temperatures, insulation 5h, vacuum 1 * 10
-3Pa ~ 1 * 10
-4Pa, the protection of sintering process applying argon gas is removed surface dirt and dirt behind the taking-up product, and the sample that makes carries out conventional post processing again and gets the porous tantalum finished product.
The porous tantalum finished product that adopts said method to make has the foaming structure that the hole three-dimensional communication distributes, and piles up on the foam framework that constitutes through agglomerating pure tantalum powder, and the tantalum powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the tantalum powder particles in this porous tantalum finished product microstructure surpasses 50%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: this porous tantalum 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 5.5g/cm
3, porosity 66.9%, hole average diameter 300 μ m, elastic modelling quantity 3.5GPa, yield strength 65MPa, comprcssive strength 80MPa, hardness 180MPa, amount of plastic deformation 10.3%, tensile strength 65MPa, the elongation 9.7% of having no progeny; When carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 45% in this porous tantalum microstructure, and the fracture rate of granule interior is greater than 55%.
Embodiment 2: take by weighing ethyl cellulose 5g, put into the container that the 200ml dehydrated alcohol is housed; Placing it in heats on the electric furnace and stir makes it to become the ethyl cellulose alcoholic solution.With 200g balance weighing mean diameter less than 10 μ m, oxygen content less than 0.1% tantalum powder 40g and starch 4.4g, add 8ml ethyl cellulose alcoholic solution, mix, make it to become slurry.(average pore size is 0.56mm, density 0.030g/cm to select 10 * 10 * 25mm cellular polyurethane foam for use
3, hardness 60
0) put into wherein cast, fill with slurry until the polyurethane foam hole, the polyurethane foam that goes out to be filled slurry with clip is put into porcelain dish.Dry in vacuum drying oven, 100 ℃ of baking temperatures, drying time 5h, vacuum keeps 1 * 10
-1Pa.Ungrease treatment: vacuum 1 * 10
-4Pa, 800 ℃ of temperature, temperature retention time 140min.Vacuum-sintering: sintering in vacuum drying oven, 2200 ℃ of sintering temperatures are incubated 6 hours, vacuum 1 * 10
-4Pa, the protection of sintering process applying argon gas is removed surface dirt and dirt behind the taking-up product, and the sample that makes carries out conventional post processing again and gets the porous tantalum finished product.
The porous tantalum finished product that adopts said method to make has the foaming structure that the hole three-dimensional communication distributes, and piles up on the foam framework that constitutes through agglomerating pure tantalum powder, and the tantalum powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the tantalum powder particles in this porous tantalum finished product microstructure surpasses 60%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: this porous tantalum 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 5.8g/cm
3, porosity 65%, hole average diameter 250 μ m, elastic modelling quantity 3.2GPa, yield strength 60MPa, comprcssive strength 70MPa, hardness 150MPa, amount of plastic deformation 10%, tensile strength 62MPa, the elongation 10% of having no progeny; When carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 40% in this porous tantalum microstructure, and the fracture rate of granule interior is greater than 60%.
Embodiment 3: take by weighing ethyl cellulose 6g, put into the container that 220ml ethanol is housed; Placing it in heats on the electric furnace and stir makes it to become the ethyl cellulose alcoholic solution.With 200g balance weighing mean diameter less than 10 μ m, oxygen content less than 0.1% tantalum powder 45g and starch 2.2g, add 10ml ethyl cellulose alcoholic solution, mix, make it to become slurry.(average pore size is 0.70mm, density 0.035g/cm to select 8 * 8 * 25mm cellular polyurethane foam for use
3, 70 ° of hardness) and put into wherein cast, fill with slurry until the polyurethane foam hole, the polyurethane foam that goes out to be filled slurry with clip is put into porcelain dish.Dry in vacuum drying oven, 90 ℃ of baking temperatures, drying time 6h, vacuum keeps 1 * 10
-1Pa.Ungrease treatment: vacuum is lower than 1 * 10
-3Pa, 400 ℃ of temperature, temperature retention time 1.5h.Vacuum-sintering: sintering in vacuum drying oven, 2100 ℃ of sintering temperatures are incubated 8 hours, vacuum 1 * 10
-3Pa, the protection of sintering process applying argon gas, cooling is come out of the stove, and removes product surface dust and dirt, and the sample that makes carries out conventional post processing again and gets the porous tantalum finished product.
The porous tantalum finished product that adopts said method to make has the foaming structure that the hole three-dimensional communication distributes, and piles up on the foam framework that constitutes through agglomerating pure tantalum powder, and the tantalum powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the tantalum powder particles in this porous tantalum finished product microstructure surpasses 55%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: this porous tantalum 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 4.2g/cm
3, porosity 75%, hole average diameter 400 μ m, elastic modelling quantity 2.8GPa, yield strength 45MPa, comprcssive strength 53MPa, hardness 210MPa, amount of plastic deformation 9.2%, tensile strength 60MPa, the elongation 9.5% of having no progeny; When carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 35% in this porous tantalum microstructure, and the fracture rate of granule interior is greater than 65%.
Embodiment 4: take by weighing ethyl cellulose 7g, put into the container that 230ml ethanol is housed; Placing it in heats on the electric furnace and stir makes it to become the ethyl cellulose alcoholic solution.With 200g balance weighing mean diameter less than 10 μ m, oxygen content less than 0.1% tantalum powder 50g and 2.5g starch, add 11ml ethyl cellulose alcoholic solution, mix, make it to become slurry.(aperture is 0.60mm, density 0.027g/cm to select 12 * 12 * 30mm cellular polyurethane foam for use
3, 80 ° of hardness) and put into wherein cast, fill with slurry until the polyurethane foam hole, the polyurethane foam that goes out to be filled slurry with clip is put into porcelain dish.Dry in vacuum drying oven, 85 ℃ of baking temperatures, drying time 6h, vacuum keeps 1Pa.Ungrease treatment: vacuum 1 * 10
-4Pa～1 * 10
-3Pa, 500 ℃ of temperature, temperature retention time 2h.Vacuum-sintering: sintering in vacuum drying oven, 2150 ℃ of sintering temperatures are incubated 6 hours, vacuum 1 * 10
-4Pa, the protection of sintering process applying argon gas, cooling is come out of the stove, and removes product surface dust and dirt, and the sample that makes carries out conventional post processing again and gets the porous tantalum finished product.
The porous tantalum finished product that adopts said method to make has the foaming structure that the hole three-dimensional communication distributes, and piles up on the foam framework that constitutes through agglomerating pure tantalum powder, and the tantalum powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the tantalum powder particles in this porous tantalum finished product microstructure surpasses 70%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: this porous tantalum 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 6g/cm
3, porosity 60%, hole average diameter 200 μ m, elastic modelling quantity 3.8GPa, yield strength 60MPa, comprcssive strength 75MPa, hardness 250MPa, amount of plastic deformation 10.3%, tensile strength 70MPa, the elongation 10.6% of having no progeny; When carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 10% in this porous tantalum microstructure, and the fracture rate of granule interior is greater than 57%.
Embodiment 5: a kind of porous tantalum; It is raw material less than 10 μ m, oxygen content less than 0.1% ta powder and starch with particle diameter; The weight percentage of starch is 10% in the mixed-powder of said starch and ta powder; Adopting percentage by weight is that 1～5% ethyl cellulose alcoholic solution is processed tantalum powder slurry, and is cast in the polyurethane foam carrier; Vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make then.
Wherein, the polyurethane foam of selecting for use, its aperture is 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, hardness is greater than 50 °;
Vacuum drying: vacuum keeps 10
-1～1Pa is to remove the ethanol in the polyurethane foam of filling with slurry;
Ungrease treatment: under inert gas shielding atmosphere or vacuum 1 * 10
-4Pa～1 * 10
-3Pa, 400 ℃～800 ℃ of temperature, and temperature retention time 30～180min is to remove ethyl cellulose and polyurethane foam wherein;
Vacuum-sintering: vacuum is not higher than 1 * 10
-4Pa～1 * 10
-3Pa, 2100～2200 ℃ of temperature, temperature retention time 5～8 hours, applying argon gas or other inert gas shielding during the sintering process insulation are to obtain porous material;
Vacuum annealing: keep temperature to be in 1000～1250 ℃ through the vacuum-sintering continued, temperature retention time 5～7 hours, vacuum is not higher than 1 * 10
-4Pa～1 * 10
-3Pa handles to carry out stress relief annealing; The sample that makes carries out conventional post processing again and gets the porous tantalum finished product.
In conjunction with each accompanying drawing, we can find out the porous tantalum finished product that adopts said method to make, and have the foaming structure that the hole three-dimensional communication distributes, and pile up on the foam framework that constitutes through agglomerating pure tantalum powder, and the tantalum powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the tantalum powder particles in this porous tantalum finished product microstructure surpasses 80%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: this porous tantalum is to have the pore structure that three-dimensional communication distributes; Its impurity content is lower than 0.5% finished product; Its even pore distribution and connection; Density 3.5～8.5g/cm3, porosity 49～79%, pore diameter 200～550 μ m; Elastic modelling quantity 2.5～3.8GPa, yield strength 35～75MPa, comprcssive strength 40～90MPa, hardness 150～270MPa, amount of plastic deformation 7.4%～11.3%, tensile strength 60～70 MPa, the elongation 7.3%～10.7% of having no progeny; When carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 45% in this porous tantalum microstructure, and the fracture rate of granule interior is greater than 55%.
Embodiment 6: a kind of porous tantalum; It is raw material less than 10 μ m, oxygen content less than 0.1% ta powder and starch with particle diameter; The weight percentage of starch is 10% in the mixed-powder of starch and ta powder; With the ethyl cellulose ethanol solution is that binder solution is processed slurry, and to be cast in its aperture be 0.56～0.72mm, density 0.025～0.035g/cm
3, in the polyurethane foam carrier that hardness is 50 °～80 °; Vacuum drying, ungrease treatment, vacuum-sintering, vacuum annealing and conventional post processing make then.
Wherein, ethyl cellulose is heated to dissolving with dehydrated alcohol and is mixed with percentage by weight 3% ethyl cellulose alcoholic solution; Then with weight be 2～5 parts metal mixed tantalum powder to add cooled weight be in 1 part the said ethyl cellulose alcoholic solution, stir and process starchiness; Again above-mentioned polyurethane foam is put into and be starchy slurry and flood repeatedly until the polyurethane foam hole and fill with;
Vacuum drying is removing the ethanol in the polyurethane foam of filling with tantalum powder slurry, and vacuum keeps 1Pa, 80～100 ℃ of baking temperatures, drying time 5～7h;
The dried polyurethane foam of against vacuum places the tungsten device to put into the nonoxidizing atmosphere stove and is warming up to 800 ℃ with certain heating rate; Protective atmosphere is that 99.999% argon carries out ungrease treatment; Its before heating up, feed earlier argon at least 0.5h to get rid of furnace air; The temperature control process: the speed with 4 ℃/min rises to 400 ℃ from room temperature, insulation 1h, and argon feeds speed 0.5L/min; Speed with 0.5 ℃/min rises to 800 ℃, insulation 1.5h, argon feeding speed 1L/min from 400 ℃; Powered-down again, the sample furnace cooling after the defat, argon feeds speed 1L/min, when being cooled to room temperature, closes argon;
Place with the tungsten device for the sample after the ungrease treatment to be warming up to 2100 ℃ with certain heating rate in the fine vacuum high temperature sintering furnace and to carry out vacuum-sintering, the vacuum of sintering furnace will reach 1 * 10 at least before heating up
-3Pa rises to 900 ℃ with the speed of 10～15 ℃/min from room temperature, insulation 1h, and vacuum is 1 * 10
-4Pa; Speed with 10 ℃/min rises to 1300 ℃, insulation 1.5h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 6 ℃/min rises to 2100 ℃, insulation 3h, and vacuum is 1 * 10
-3Pa; Sintering finishes, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 14 ℃/min is cooled to 1250 ℃, insulation 1h; Speed with 15 ℃/min is cooled to 800 ℃, insulation 1.5h, furnace cooling then;
The cooled sample of against vacuum sintering places vacuum annealing furnace to be warming up to 1000 ℃ with certain heating rate with the corundum container to carry out stress relief annealing and handle, and the vacuum before heating up in the annealing furnace will reach 1 * 10 at least
-3Pa rises to 1000 ℃ with the speed of 15 ℃/min from room temperature, insulation 5h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 5 ℃/min is cooled to 900 ℃ again, insulation 2.5h, and vacuum is 1 * 10
-4Pa～1 * 10
-3Pa; Speed with 10 ℃/min is cooled to 600 ℃, insulation 1.5h, and vacuum is 1 * 10
-4Pa; Speed with 20 ℃/min is cooled to room temperature, and vacuum is 1 * 10
-4Pa.Carry out conventional post processing at last and make porous tantalum.
The porous tantalum finished product that adopts said method to make has the foaming structure that the hole three-dimensional communication distributes, and piles up on the foam framework that constitutes through agglomerating pure tantalum powder, and the tantalum powder particles has the sintering neck structure each other.And the sintering neck structure that forms between the tantalum powder particles in this porous tantalum finished product microstructure surpasses 80%.
The inventor detects by porous material density, porosity, aperture and the various mechanical property of standards such as GB/T5163-2006, GB/T5249-1985, GB/T6886-2001 to above-mentioned porous tantalum finished product: this porous tantalum 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 7.45g/cm
3, porosity 55%, hole average diameter 250 μ m, elastic modelling quantity 3.5GPa, yield strength 55MPa, comprcssive strength 70MPa, hardness 230MPa, amount of plastic deformation 10.4%, tensile strength 70MPa, the elongation 9.7% of having no progeny; When carrying out anti-bending test by the method for metal bending strength measurement, the fracture rate of sintering neck is less than 40% in this porous tantalum microstructure, and the fracture rate of granule interior is greater than 60%.
In the method that the foregoing description 6 provides, we can also do other selection to wherein each kind of condition can obtain porous tantalum of the present invention equally.In following embodiment, if do not specify that the parameters condition is all identical with previous embodiment 6 in the table.
Gained porous tantalum finished product is pressed preceding method and is detected:
| Embodiment | 7 | 8 | 9 | 10 | 11 | 12 |
| Density (g/cm 3） | 7.8 | 6.2 | 5.5 | 6.0 | 3.6 | 3.3 |
| Porosity (%) | 53 | 63 | 67 | 75 | 78 | 80 |
| Aperture (μ m) | 200 | 210 | 250 | 280 | 330 | 410 |
| Elastic modelling quantity (GPa) | 2.9 | 3.5 | 3.3 | 3.8 | 2.6 | 2.4 |
| Yield strength (MPa) | 65 | 72 | 70 | 75 | 65 | 60 |
| Comprcssive strength (MPa) | 75 | 80 | 80 | 90 | 70 | 70 |
| Hardness (MPa) | 200 | 230 | 210 | 260 | 180 | 190 |
| Amount of plastic deformation (%) | 10.30 | 9.20 | 10.25 | 11.22 | 9.28 | 9.29 |
| Tensile strength (MPa) | 63 | 66 | 64 | 70 | 63 | 60 |
| The elongation (%) of having no progeny | 8.35 | 8.60 | 8.50 | 9.70 | 8.80 | 8.7 |
| Sintering neck fracture rate (%) | 41 | 43 | 45 | 43 | 40 | 52 |
| Granule interior fracture rate (%) | 59 | 60 | 55 | 50 | 57 | 48 |
Claims (9)
1. the method for preparing of a medical embedded material porous tantalum; It is characterized in that: the solution that uses ethyl cellulose to be mixed with as dispersant as organic binder bond and dehydrated alcohol; Process tantalum powder slurry with the mixed powder of starch and ta powder, and be cast in the organic foam body, dipping is filled with tantalum powder slurry until organic foam body opening crack; Drying is removed the said dispersant in the organic foam body that is cast with tantalum powder slurry then; Ungrease treatment is to remove said organic binder bond and organic foam body under inert gas shielding atmosphere, and sintering makes porous sintered body under the vacuum, piles up on the foam framework that constitutes through agglomerating pure tantalum powder; The tantalum powder particles has the sintering neck structure each other, and annealing and conventional post processing make porous tantalum under the vacuum again.
2. the method for claim 1 is characterized in that: said organic foam body adopts polyurethane foam, and its aperture is 0.48～0.89mm, density 0.015 g/cm
3～0.035g/cm
3, hardness>=50 °; Said ta powder adopt mean diameter less than 10 μ m, oxygen content less than 0.1% tantalum powder.
3. method for preparing as claimed in claim 2 is characterized in that: the aperture of said polyurethane foam is 0.56～0.72mm, density 0.025g/cm
3, 50 ° ~ 80 ° of hardness.
4. like claim 1,2 or 3 described methods, it is characterized in that: contents of starch is 5～10% in the mixed-powder of said starch and ta powder, in weight percentage; The weight percent concentration of said ethyl cellulose alcoholic solution is 1～5%.
5. method for preparing as claimed in claim 4 is characterized in that: the mixed powder that said ta powder and starch are formed and the weight part ratio of ethyl cellulose alcoholic solution are 2～5:1.
6. method for preparing as claimed in claim 1 is with said ta powder and starch mix homogeneously, and wherein the weight percentage of starch is 10%; Ethyl cellulose is dissolved in to be mixed with weight percent concentration in the dehydrated alcohol be 3% ethyl cellulose alcoholic solution; Then said ethyl cellulose alcoholic solution is joined in the said mixed powder and be made into slurry, the weight ratio of said mixed powder and ethyl cellulose alcoholic solution is 3:1.
7. like each described method for preparing of claim 1～6, it is characterized in that: said exsiccant vacuum is 10
-1~ 1Pa; Then under protective atmosphere, vacuum 10
-4~ 10
-3Pa, the ungrease treatment of removing organic binder bond and organic foam body under 400 ℃～800 ℃ conditions of temperature; Be not higher than 10 in vacuum again
-4~ 10
-3Pa, 2100～2200 ℃ of temperature, 5～8 hours vacuum-sintering of temperature retention time is handled and is made porous sintered body, filling with inert gas protection during the sintering process insulation; Carry out vacuum annealing at last and handle, wherein vacuum annealing is handled and is meant that process vacuum-sintering continued keeps temperature to be in 1000～1250 ℃, temperature retention time 5～7 hours, and vacuum is not higher than 10
-4~ 10
-3Pa.
8. method for preparing as claimed in claim 7 is characterized in that: said ungrease treatment condition also includes: the speed with 0.5 ℃/min～5 ℃/min progressively is warming up to 400～800 ℃, feeds with argon to constitute protective atmosphere and be incubated 30min～180min;
The vacuum-sintering condition also includes: vacuum is not higher than 10
-3Pa rises to 900 ℃～1500 ℃ with the heating rate that is not higher than 10～20 ℃/min from room temperature, behind insulation 2h～3h; Be warming up to 2100～2200 ℃ with the heating rate that is not higher than 10 ℃/min again, insulation 3h～5h;
Cooling condition after the vacuum-sintering also includes: vacuum is not higher than 10
-4~ 10
-3Pa not to be higher than 18 ℃/min, to be not less than 8 ℃/min and gradually to fall the cooldown rate mode, and sintered porous bodies segmentation cooling is cooled to 800 ℃, and each section temperature retention time 30min～90min cools to room temperature then with the furnace;
The vacuum annealing condition also includes: vacuum 10
-4~ 10
-3Pa rises to 1000～1250 ℃ with the speed that is not higher than 30 ℃/min, insulation 5～7h; Again with after earlier slow soon to be not less than 5 ℃/min but the cooldown rate segmentation that is not higher than 30 ℃/min is cooled to room temperature, the temperature retention time of each section tapers off and is no more than in 1.5 h～3h and selects.
9. method for preparing as claimed in claim 8 is characterized in that: 80～100 ℃ of said vacuum drying baking temperatures, drying time 5～7; Said ungrease treatment condition also includes: the pure argon gas with 99.9999% feeds and constitutes protective atmosphere; Speed with 4 ~ 5 ℃/min rises to 400 ℃ from room temperature; Insulation 60 ~ 90min rises to 600～800 ℃, insulation 70 ~ 90min with the speed of 0.5 ~ 0.8 ℃/min from 400 ℃; Said vacuum-sintering condition also includes: the speed with 10～15 ℃/min rises to 900 ~ 1250 ℃ from room temperature, insulation 60 ~ 90min, and, vacuum is 10
-4Pa～10
-3Pa; Speed with 10 ~ 20 ℃/min rises to 1300～1500 ℃, insulation 60 ~ 90min, and, vacuum is 10
-4Pa～10
-3Pa rises to 2100 ~ 2200 ℃ with the speed of 6 ~ 10 ℃/min, insulation 180 ~ 300min, and vacuum is 10
-4Pa～10
-3Pa; Cooling condition after the vacuum-sintering also includes: vacuum is 10
-4Pa～10
-3Pa is cooled to 1500 ~ 1600 ℃ with the speed of 8～10 ℃/min, insulation 30 ~ 60min; Speed with 11 ~ 14 ℃/min is cooled to 1200 ~ 1250 ℃, insulation 60 ~ 90min; Speed with 10 ~ 15 ℃/min is cooled to 600～800 ℃, then furnace cooling; Said vacuum annealing condition also includes: the speed with 15 ~ 30 ℃/min rises to 1000 ~ 1250 ℃, insulation 300 ~ 420min, and vacuum is 10
-4Pa～10
-3Pa, the speed with 5 ~ 10 ℃/min is cooled to 9000 ℃ again, insulation 90 ~ 150min, vacuum is 10
-4Pa～10
-3Pa; Speed with 10 ~ 20 ℃/min is cooled to 600～800 ℃, insulation 60 ~ 100min, and vacuum is 10
-4Pa～10
-3Pa; Speed with 20 ~ 30 ℃/min is cooled to room temperature, and vacuum is 10
-4Pa～10
-3Pa.
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| US20050048193A1 (en) * | 2001-02-19 | 2005-03-03 | Isotis N.V. | Porous metals and metal coatings for implants |
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| CN101448534A (en) * | 2006-05-17 | 2009-06-03 | 生物技术公司 | Anisotropic nanoporous coatings for medical implants |
| CN101660076A (en) * | 2009-10-14 | 2010-03-03 | 北京师范大学 | Macro mesh structural porous tantalum prepared by dipping and sintering organic foams |
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2010
- 2010-11-17 CN CN 201010547676 patent/CN102462862B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997031738A1 (en) * | 1996-02-27 | 1997-09-04 | Astro Met, Inc. | Porous materials and method for producing |
| US20050048193A1 (en) * | 2001-02-19 | 2005-03-03 | Isotis N.V. | Porous metals and metal coatings for implants |
| CN101448534A (en) * | 2006-05-17 | 2009-06-03 | 生物技术公司 | Anisotropic nanoporous coatings for medical implants |
| CN101195048A (en) * | 2006-12-08 | 2008-06-11 | 许才德 | Compound medicament washing bracket and method for preparing the same |
| CN101660076A (en) * | 2009-10-14 | 2010-03-03 | 北京师范大学 | Macro mesh structural porous tantalum prepared by dipping and sintering organic foams |
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