CN105169471A - Implant porous niobium-titanium alloy material for medical use and preparation method of alloy material - Google Patents
Implant porous niobium-titanium alloy material for medical use and preparation method of alloy material Download PDFInfo
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Abstract
The invention relates to a porous niobium-titanium alloy material and a preparation method thereof, and in particular relates to an implant porous niobium-titanium alloy material for medical use and a preparation method of the alloy material, belonging to the field of a medical porous alloy material. According to the implant porous niobium-titanium alloy material for medical use disclosed by the invention, the mass ratio of niobium to titanium in the porous niobium-titanium alloy material is (9 to 1)-(1 to 3), compressive strength is 47.6-109.3Mpa, elasticity modulus is 0.21-0.46GPa, aperture is 400-500 microns and porosity is 40-80%. The invention also discloses a preparation method of the porous niobium-titanium alloy material. The implant porous niobium-titanium alloy material for medical use is closer to human bone in elasticity modulus and is excellent in biocompatibility.
Description
Technical field
The invention belongs to medical porous field of alloy material, be specifically related to a kind of porous niobium titanium alloy material and preparation method thereof, particularly relate to a kind of medical embedded porous niobium titanium alloy material and preparation method thereof, belong to medical porous field of alloy material.
Background technology
Biomaterial is also called bio-medical material, be mainly used in alternative impaired or disappearance human tissue structure, reach the object of repair tissue profile and performance.Metal niobium and titanium have the biocompatibility of good mechanical compatibility, strong corrosion resistant and excellence, are widely used in body bone tissue and substitute field.The medical titanium alloy implant elastic modelling quantity of current application and not mating of people's bone, " stress covers " effect is easily caused in clinical practice, in addition, the low wearability of titanium alloy implant in human body complex environment forms restriction to product life, and above factor finally causes graft failure.The exploitation of porous niobium alloy can reduce the elastic modelling quantity of alloy implants, avoid " stress covers " effect, unique cell structure is conducive to osteoblastic adhesion and propagation, and niobium metal has good wearability, and therefore porous niobium alloy has wide medical application prospect.
Several porous alloy preparation methoies that current domestic and international application is maximum comprise casting, metaliding, fibre metallurgy method and powder metallurgic method etc.Infusion process is applied to the preparation of porous ceramics and cellular glass the earliest by SCHWARTZWALDEN etc., this method is used to porous alloy preparation more and more in recent years.Compare with additive method, infusion process is simple to operate, and equipment requirements is low, the porous alloy porosity of preparation is high, and pore size controllable degree is high, has the three-dimensional communication hole of similar people's bone, and the implant that easily preparation is complex-shaped, be conducive to the exploitation of personalized implant.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, the problem that, elastic modelling quantity high for traditional niobium support sintering temperature greatly easily causes stress to cover, and provides a kind of medical embedded porous niobium titanium alloy material and preparation method thereof.
In order to achieve the above object, technical scheme provided by the invention is:
In described medical embedded porous niobium titanium alloy material, the mass ratio of niobium and titanium is (9:1) ~ (1:3).
Preferably, described porous niobium titanium alloy material comprcssive strength is 47.6 ~ 109.3Mpa, and elastic modelling quantity is 0.21 ~ 0.46GPa, and described porous niobium titanium alloy has the pore structure of mutually through through hole, and aperture is 400 ~ 500 μm, and porosity is 40 ~ 80%.
The method preparing above-mentioned porous niobium titanium alloy material comprises the steps:
(1) by above-mentioned mass ratio niobium powder mixed with titanium valve and carry out ball milling 3.5-4h, be preferably 4h, obtain niobium titanium composite powder;
(2) described niobium titanium composite powder and dispersant solution are mixed with uniformly slip; The ratio of the quality of described niobium titanium composite powder quality and described dispersant solution is (5 ~ 9): 1, and in described dispersant solution, the mass percentage content of dispersant is 3 ~ 6%;
(3) be filled in porous foam template by described uniform sizing material, porous foam template is filled full by uniform sizing material, obtain the impregnated sample containing niobium titanium mixed-powder slurry after flooding; In protective gas atmosphere, described impregnated sample is warming up to 400 ~ 600 DEG C and carries out ungrease treatment, obtain the impregnated sample after defat, preferably, in protective gas atmosphere, by described impregnated sample with ramp to 400 ~ 600 DEG C of 1 ~ 5 DEG C/min, insulation 1h ~ 2h;
(4) impregnated sample after described defat is carried out vacuum-sintering and vacuum annealing in vacuum sintering furnace, being annealed to material comprcssive strength is 47.6 ~ 109.3Mpa, elastic modelling quantity is 0.21 ~ 0.46GPa, and material has the pore structure of mutually through through hole, aperture is 400 ~ 500 μm, and porosity is 40 ~ 80%; Be medical embedded porous niobium titanium alloy material.
Preferably, during step (1) described ball milling, add dehydrated alcohol as ball-milling medium, then the niobium powder after ball milling and titanium valve are carried out vacuum drying, obtain niobium titanium composite powder.
Preferably, step (2) described dispersant is polyvinyl alcohol, and described dispersant solution is the aqueous solution of polyvinyl alcohol.
Preferably, the described porous foam template of step (3) is polyurethane foam, and polyurethane foam particle diameter is 400 ~ 600 μm; Ensure that dipping slip evenly and completely in the middle of dipping process, what impregnated sample quality was prepared by 50 ~ 80%(the application of densified sample quality is porous sample, and forms a kind of contrast between densified sample).
Preferably, the vacuum of step (4) described vacuum-sintering and vacuum annealing is all lower than 10
-2pa, preferably 10
-3~ 10
-4pa.
Preferably, step (4) described vacuum-sintering is divided into three sections, first paragraph: be incubated 1 ~ 2h after being warming up to 600 DEG C and carry out degreasing sintered; Second segment: be incubated 1.5 ~ 2.5h after being warming up to sintering temperature 1650 DEG C; 3rd section: after naturally cooling to 1200 DEG C of insulation 1 ~ 2h, then cool.
Preferably, in step (4) described vacuum-sintering, the heating rate of first paragraph is 1 ~ 5 DEG C/min; The heating rate of second segment is 5 ~ 10 DEG C/min.
The invention will be further described below:
Porous niobium titanium alloy material of the present invention has the pore structure of mutually through through hole, and porosity is 40 ~ 80%.
The pore structure of through through hole not only can ensure growing into of osseous tissue, and contributes to the migration of cell, attachment and differentiation, and the conveying of nutrient substance and evacuation.Porosity is 40 ~ 80%, can reduce elasticity modulus of materials on the basis ensureing suitable intensity and porosity.
The mass ratio of niobium and titanium is preferably (9:1) ~ (1:3).Adopt this mass ratio, sintering temperature and the manufacturing cost of porous niobium titanium alloy can be effectively reduced, ensure its good mechanical property, biocompatibility and corrosion resistance simultaneously.
Preferably, the aperture of through hole is 300 ~ 500 μm.Have the porous niobium titanium alloy in this aperture, pore size is suitable, is conducive to the attachment of osteocyte, propagation, breaks up and grow into.
Above-mentioned porous niobium titanium alloy, there is three-dimensional communication structure, and there is suitable porosity, elasticity modulus of materials can be reduced on the basis ensureing suitable intensity and porosity, make elastic modelling quantity and people's bone close, to improve mechanical compatibility, to alleviate and even avoid stress capture-effect.
The preparation method of porous niobium titanium alloy of the present invention comprises the following steps:
After niobium powder and titanium powder mixing, then add dispersant solution mixing, obtain niobium titanium mixed-powder slurry, by niobium titanium mixed-powder filled therewith in foraminous die plate, obtain the foraminous die plate containing niobium titanium mixed-powder slurry.
After niobium powder and titanium powder mixing, mix after adding dispersant solution, keep niobium powder and titanium powder mix homogeneously, the niobium titanium mixed-powder slurry contributing to follow-up formation is filled in foraminous die plate smoothly.Use water, as solvent, dispersant preparation is become dispersant solution, cooled dispersant solution is added in niobium titanium alloy powder and stirs, form stable suspension, obtain niobium titanium mixed-powder slurry.Foraminous die plate is put into niobium titanium mixed-powder slurry to flood, until niobium titanium mixed-powder slurry is evenly coated on foraminous die plate, hole is filled completely, when flooding, avoiding any field trash to be mixed into and surperficial plug-hole phenomenon occurs.
Foraminous die plate is as carrier, the even pore distribution of niobium titanium alloy can be made, be interconnected, be preferably polyurethane foam, more excellent is polyurethane foam, and polyurethane foam resilience is good, and hardness is moderate, be conducive to the dipping of niobium titanium mixed-powder slurry, simultaneously polyurethane foam can be decomposed completely and pollution-free to obtained porous niobium titanium alloy after defat, and after sintering, in porous niobium titanium alloy, phosphorus content is few, ensure that biocompatibility, biological safety and mechanical property.
By selecting the polyurethane foam of different pore size size, regulate the porosity of niobium titanium alloy, pore appearance and pore size.Foraminous die plate also plays moulding effect, and the shape of obtained porous niobium titanium alloy is similar to foraminous die plate profile.The size uniformity of the through hole of porous niobium titanium alloy can be controlled preferably, and control porosity preferably.
Preferably, the aperture of polyurethane foam is 0.6 ~ 1.2mm.Select the polyurethane foam of this pore diameter range that the porous tantalum niobium alloy prepared can be made to have suitable aperture.
Dispersant solution plays bonding and pore-creating effect.Dispersant solution should have certain viscosity, adds in niobium titanium alloy powder, makes niobium powder and titanium powder form stable suspension and has certain caking property; And the structure of foraminous die plate can not be destroyed, to ensure that foraminous die plate plays a role; In addition dispersant solution also should decompose completely under middle cryogenic conditions, noresidue, makes niobium titanium alloy powder pore-forming in sintering process, and obtained porous niobium titanium alloy has good biocompatibility, biological safety and mechanical property.Further, the energy consumption preparing porous niobium titanium alloy is lower.
The particle diameter of niobium powder and titanium powder is preferably 10 ~ 40 μm.Adopt niobium powder and the titanium powder of this powder diameter scope, contribute to preparing the niobium titanium mixed-powder slurry with adequate liquidity, thus be beneficial to niobium titanium mixed-powder slurry and evenly apply at porous carrier, ensure being uniformly distributed and being interconnected of porous niobium titanium alloy mesopore, also can ensure the mechanical property of impregnated sample and porous niobium titanium alloy simultaneously.
The purity of niobium powder and titanium powder is high, and wherein oxygen content is less than 0.1%, and carbon content is less than 0.02%, and the porous niobium titanium alloy component that obtains can be made homogeneous, and aperture is less, porous nickel.Control oxygen content and carbon content, the biocompatibility introducing impurity infringement porous niobium titanium alloy can be avoided, reduce its mechanical property.
The ratio of the gross mass of niobium powder and titanium powder and the quality of dispersant solution is (5 ~ 9): 1, and under this mass ratio, obtained porous niobium titanium alloy pore communication is good, good mechanical properties, and even pore distribution, is applicable to the requirement of bone tissue engineering scaffold.
The porosity of the concentration scalable porous niobium titanium alloy of dispersant solution, pore appearance and pore size.Dispersant solution is preferably the aqueous solution that mass percent is the polyvinyl alcohol of 3 ~ 6%, can make the viscosity of the niobium titanium mixed-powder slurry of preparation and mobility moderate, meet dipping requirement.
In protective gas atmosphere, impregnated sample is warming up to 400 ~ 600 DEG C and carries out ungrease treatment, obtain the impregnated sample after defat.
Impregnated sample is placed in tungsten crucible, puts into atmosphere furnace and carry out ungrease treatment.Protective gas 30min is passed into drive atmosphere furnace air away in atmosphere furnace.Temperature in atmosphere furnace is raised to 400 ~ 600 DEG C from room temperature with the speed of 1 ~ 5 DEG C/min, insulation 1 ~ 2h.Powered-down, the impregnated sample furnace cooling after defat, completes ungrease treatment.
Preferably, protective gas is argon, and the purity of protective gas is 99.999%.Argon is noble gas, stable in properties, and in the argon gas atmosphere of 99.999%, oxidation reaction is less likely to occur for niobium powder and titanium powder.
Impregnated sample after defat is carried out vacuum-sintering, obtains porous niobium titanium alloy, porous niobium titanium alloy has the pore structure of mutually through through hole, and porosity is 40 ~ 80%.
Impregnated sample after defat is placed in tungsten crucible, puts into vacuum drying oven and sinter, the vacuum of vacuum drying oven is extracted into 10
-4~ 10
-3pa.Then the temperature in vacuum drying oven is raised to 1600 ~ 1700 DEG C from room temperature with the speed of 10 ~ 20 DEG C/min, insulation 1.5 ~ 2.5h; Finally be cooled to 1100 ~ 1200 DEG C with the speed of 10 ~ 15 DEG C/min again, after insulation 1 ~ 2h, sintering terminates, furnace cooling.
Multistage heating rate is adopted in sintering process, the heating rate that leading portion is higher can promote temperature faster, impel niobium powder and titanium powder to be sintered together as early as possible, prevent the impregnated sample after defat because intensity is not enough and cave in, also can improve sintering efficiency simultaneously; The heating rate that back segment is lower, can make the impurity such as carbon, oxygen get rid of comparatively thorough, promote the abundant sintering of porous niobium titanium alloy.Cooling procedure adopts interim rate of temperature fall, is conducive to the homogenization of crystal grain and reduces the internal stress of porous niobium titanium alloy.
The preparation method of above-mentioned porous niobium titanium alloy, combine template infusion process and powder metallurgy process, preparation technology is simple, equipment is simple, cost is low, the pore property of scalable porous niobium titanium alloy, the high and porous nickel of the preparation method porosity of obtained porous niobium titanium alloy, has three-dimensional communication structure.
Further, the preparation method of above-mentioned porous niobium titanium alloy, low for equipment requirements, easily realize difform goods requirement, harmless, pollution-free, nonhazardous dust, has no side effect to human body.
Bio-medical porous niobium titanium alloy prepared by the preparation method of above-mentioned porous niobium titanium alloy, porosity is 40 ~ 80%, and pore diameter is 300 ~ 500 μm, and elastic modelling quantity is 0.21 ~ 0.46Gpa, and comprcssive strength is 27.6 ~ 59.3Mpa.Bio-medical porous niobium titanium alloy is conducive to osteoblastic adhesion, reproduction restraint, promotes biological fixation; Also meet the relevant mechanical property needed for osseous tissue substitution material simultaneously.While guarantee higher porosity, by the component content of adjustment niobium titanium alloy, the elastic modelling quantity of material can also be regulated further, the generation reducing or avoid stress to cover.
The present invention selects niobium as matrix material, and appropriate titanium, as the second constituent element, adopts infusion process and powder metallurgic method to prepare niobium titanium alloy.The discoveries such as ELIAS etc., Ma Xiumei etc. and LONG, compared with titanium, niobium has the advantages such as high strength, low elastic modulus, good wearability, avirulence, is more suitable for medical material exploitation.The research of joint Yun Feng etc. shows, the high temperature refractory of pure niobium limits its sintering process, and pure niobium sintered article granule bond strength is not high, lower compressive strength.The present invention utilizes the low melting point of titanium and high temperature active to promote the sintering of niobium powder particles, solves the problem that prior powder metallurgy sintering process is difficult to prepare niobium alloy.
Porous niobium titanium alloy of the present invention, there is three-dimensional communication structure, and there is suitable porosity, elasticity modulus of materials can be reduced on the basis ensureing suitable intensity and porosity, make elastic modelling quantity and people's bone close, to improve mechanical compatibility, to alleviate and even avoid stress capture-effect.
The preparation method of porous niobium titanium alloy of the present invention, preparation technology is simple, and equipment is simple, and energy consumption is lower, reduces cost of material, and the pore property of porous niobium titanium alloy is easy to regulate.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of the porous niobium titanium alloy material of niobium powder and embodiment 1 and embodiment 2 preparation;
Fig. 2 is the pore appearance scanning electron microscope (SEM) photograph of porous niobium titanium alloy material prepared by embodiment 2.
Detailed description of the invention
embodiment 1
1, weighing polyvinyl alcohol 6g, puts into the beaker that 100ml deionized water is housed, and adds appropriate distilled water to graduation mark, beaker is put into water bath heating in water bath and stir, make it the aqueous solution becoming polyvinyl alcohol.According to the ratio of niobium powder and titanium powder weight ratio 9:1,45g niobium powder and 5g titanium powder is weighed respectively with balance, oxygen content is less than 0.1%, carbon content is less than 0.02%, niobium titanium composite powder is obtained by after niobium powder and titanium powder ball milling, niobium titanium composite powder is added the aqueous solution of 7g polyvinyl alcohol, be uniformly mixed, obtain niobium titanium mixed-powder slurry.Select
φthe polyurethane foam of the porous of 10 × 25mm is put into and is wherein flooded, and till filling niobium titanium mixed-powder slurry, with clip, the polyurethane foam being filled niobium titanium mixed-powder slurry is put into porcelain dish in polyurethane foam hole.
2, the porcelain dish of the polyurethane foam be equipped with containing niobium titanium mixed-powder slurry is placed in vacuum drying oven drying, baking temperature is 40 DEG C, drying time 4h, vacuum keep 1Pa, obtain impregnated sample.The porosity of impregnated sample is 65%, and pore mean diameters is 300 ~ 400 μm.
3, impregnated sample is placed in tungsten crucible, puts into atmosphere furnace and carry out ungrease treatment, in atmosphere furnace, pass into argon.Temperature in atmosphere furnace is raised to 600 DEG C from room temperature with the speed of 5 DEG C/min, insulation 1h.Powered-down, the impregnated sample furnace cooling after defat, close gas when temperature cool to room temperature, defat completes.
4, by the cooled tungsten crucible that impregnated sample after defat is housed, put into vacuum drying oven and sinter, the vacuum of vacuum drying oven is extracted into 10
-3pa.Then the temperature in vacuum drying oven is raised to 1600 DEG C from room temperature with the speed of 20 DEG C/min, insulation 1h; Be increased to 1950 DEG C with the speed of 5 DEG C/min again, insulation 3.5h, then be cooled to 1700 DEG C with the speed of 5 DEG C/min, insulation 1h, is finally cooled to 1200 DEG C with the speed of 10 DEG C/min again, and after insulation 1h, sintering terminates, and furnace cooling, obtains porous niobium titanium alloy.
5, take out porous niobium titanium alloy and be placed in dehydrated alcohol, adopt the cleaning of 40KHz ultrasonic vibration, remove surface dirt and dirt, adopt omnipotent test machine for mechanism detection perform.
Adopt the porous niobium titanium alloy that said method is obtained, have three-dimensional communication pore structure, even pore distribution, impurity content is lower than 0.4%.Have between niobium titanium powder granule and significantly sinter neck structure.The density of porous niobium titanium alloy is 4.57g/cm
3, porosity 60%, pore diameter 400 ~ 600 μm, elastic modelling quantity 2.41Gpa, comprcssive strength 83Mpa.
embodiment 2
1, weighing polyvinyl alcohol 5g, puts into the beaker that 100ml deionized water is housed, and adds appropriate distilled water to graduation mark, beaker is put into water bath heating in water bath and stir, make it the aqueous solution becoming polyvinyl alcohol.According to the ratio of niobium powder and titanium powder weight ratio 3:1,60g niobium powder and 20g titanium powder is weighed respectively with balance, oxygen content is less than 0.1%, carbon content is less than 0.02%, after niobium powder and titanium powder ball milling, obtain niobium titanium composite powder, niobium titanium composite powder is added the aqueous solution of 10g polyvinyl alcohol, be uniformly mixed, obtain niobium titanium mixed-powder slurry.Select the polyurethane foam of the porous of 10 × 10 × 30mm to put into wherein to flood, fill niobium titanium mixed-powder slurry in polyurethane foam hole till, with clip, the polyurethane foam being filled niobium titanium mixed-powder slurry is put into porcelain dish.
2, the porcelain dish of the polyurethane foam be equipped with containing niobium titanium mixed-powder slurry is placed in vacuum drying oven drying, baking temperature is 60 DEG C, drying time 6h, vacuum keep 1 × 10
-1pa, obtains impregnated sample.The porosity of impregnated sample is 73%, and pore mean diameters is 400 μm ~ 600 μm.
3, impregnated sample is placed in tungsten crucible, puts into atmosphere furnace and carry out ungrease treatment, in atmosphere furnace, pass into argon.Temperature in atmosphere furnace is raised to 500 DEG C from room temperature with the speed of 3 DEG C/min, insulation 2h.Powered-down, the impregnated sample furnace cooling after defat, close gas when temperature cool to room temperature, defat completes.
4, by the cooled tungsten crucible that impregnated sample after defat is housed, put into vacuum drying oven and sinter, the vacuum of vacuum drying oven is extracted into 10
-3pa.Then the temperature in vacuum drying oven is raised to 1520 DEG C from room temperature with the speed of 15 DEG C/min, insulation 0.8h; Be increased to 1870 DEG C with the speed of 8 DEG C/min again, insulation 2h, then be cooled to 1600 DEG C with the speed of 7 DEG C/min, insulation 0.5h, and then be cooled to 1150 DEG C with the speed of 12 DEG C/min, after insulation 2h, sintering terminates, and furnace cooling, obtains porous niobium titanium alloy.
5, take out porous niobium titanium alloy and be placed in dehydrated alcohol, adopt the cleaning of 40KHz ultrasonic vibration, remove surface dirt and dirt, adopt omnipotent test machine for mechanism detection perform.
Adopt the porous niobium titanium alloy that said method is obtained, have three-dimensional communication pore structure, even pore distribution, impurity content is lower than 0.4%.Have between niobium titanium powder granule and significantly sinter neck structure.The density of porous niobium titanium alloy is 4.31g/cm
3, porosity 68%, pore diameter 400 ~ 600 μm, elastic modelling quantity 2.06Gpa, comprcssive strength 93Mpa.
embodiment 3
1, weighing polyvinyl alcohol 3g, puts into the beaker that 100ml deionized water is housed, and adds appropriate distilled water to graduation mark, beaker is put into water bath heating in water bath and stir, make it the aqueous solution becoming polyvinyl alcohol.According to the ratio of niobium powder and titanium powder weight ratio 1:1,50g niobium powder and 50g titanium powder is weighed respectively with balance, oxygen content is less than 0.1%, carbon content is less than 0.02%, after niobium powder and titanium powder ball milling, obtain niobium titanium composite powder, niobium titanium composite powder is added the aqueous solution of 14g polyvinyl alcohol, be uniformly mixed, obtain niobium titanium mixed-powder slurry.Select
φthe polyurethane foam of the porous of 10 × 25mm is put into and is wherein flooded, and till filling niobium titanium mixed-powder slurry, with clip, the polyurethane foam being filled niobium titanium mixed-powder slurry is put into porcelain dish in polyurethane foam hole.
2, the porcelain dish of the polyurethane foam be equipped with containing niobium titanium mixed-powder slurry is placed in vacuum drying oven drying, baking temperature is 80 DEG C, drying time 8h, vacuum keep 1 × 10
-1pa, obtains impregnated sample.The porosity of impregnated sample is 80%, and pore mean diameters is 300 μm ~ 500 μm.
3, impregnated sample is placed in tungsten crucible, puts into atmosphere furnace and carry out ungrease treatment, in atmosphere furnace, pass into argon.Temperature in atmosphere furnace is raised to 400 DEG C from room temperature with the speed of 1 DEG C/min, insulation 2h.Powered-down, the impregnated sample furnace cooling after defat, close gas when temperature cool to room temperature, defat completes.
4, by the cooled tungsten crucible that impregnated sample after defat is housed, put into vacuum drying oven and sinter, the vacuum of vacuum drying oven is extracted into 10
-4pa.Then the temperature in vacuum drying oven is raised to 1300 DEG C from room temperature with the speed of 10 DEG C/min, insulation 1h; Be increased to 1650 DEG C with the speed of 5 DEG C/min again, insulation 2h, then be cooled to 1400 DEG C with the speed of 5 DEG C/min, insulation 0.5h, and then be cooled to 1100 DEG C with the speed of 10 DEG C/min, after insulation 1h, sintering terminates, and furnace cooling, obtains porous niobium titanium alloy.
5, take out porous niobium titanium alloy and be placed in dehydrated alcohol, adopt the cleaning of 40KHz ultrasonic vibration, remove surface dirt and dirt, adopt omnipotent test machine for mechanism detection perform.
Adopt the porous niobium titanium alloy that said method is obtained, have three-dimensional communication pore structure, even pore distribution, impurity content is lower than 0.4%.Have between niobium titanium powder granule and significantly sinter neck structure.Density of material 3.39g/cm
3, porosity 70%, pore diameter 400 ~ 600 μm, elastic modelling quantity 1.86Gpa, comprcssive strength 87Mpa.
embodiment 4
1, weighing polyvinyl alcohol 3g, puts into the beaker that 100ml deionized water is housed, and adds appropriate distilled water to graduation mark, beaker is put into water bath heating in water bath and stir, make it the aqueous solution becoming polyvinyl alcohol.According to the ratio of niobium powder and titanium powder weight ratio 1:3,20g niobium powder and 60g titanium powder is weighed respectively with balance, oxygen content is less than 0.1%, carbon content is less than 0.02%, after niobium powder and titanium powder ball milling, obtain niobium titanium composite powder, niobium titanium composite powder is added the aqueous solution of 10g polyvinyl alcohol, be uniformly mixed, obtain niobium titanium mixed-powder slurry.Select
φthe polyurethane foam of the porous of 10 × 25mm is put into and is wherein flooded, and till filling niobium titanium mixed-powder slurry, with clip, the polyurethane foam being filled niobium titanium mixed-powder slurry is put into porcelain dish in polyurethane foam hole.
2, the porcelain dish of the polyurethane foam be equipped with containing niobium titanium mixed-powder slurry is placed in vacuum drying oven drying, baking temperature is 80 DEG C, drying time 6h, vacuum keep 1 × 10
-1pa, obtains impregnated sample.The porosity of impregnated sample is 70%, and pore mean diameters is 300 ~ 600 μm.
3, impregnated sample is placed in tungsten crucible, puts into atmosphere furnace and carry out ungrease treatment, in atmosphere furnace, pass into argon.Temperature in atmosphere furnace is raised to 400 DEG C from room temperature with the speed of 1 DEG C/min, insulation 1.5h.Powered-down, the impregnated sample furnace cooling after defat, close gas when temperature cool to room temperature, defat completes.
4, by the cooled tungsten crucible that impregnated sample after defat is housed, put into vacuum drying oven and sinter, the vacuum of vacuum drying oven is extracted into 10
-4pa.Then the temperature in vacuum drying oven is raised to 1300 DEG C from room temperature with the speed of 10 DEG C/min, insulation 1h; Be increased to 1650 DEG C with the speed of 5 DEG C/min again, insulation 2.5h, then be cooled to 1400 DEG C with the speed of 10 DEG C/min, insulation 0.5h, and then be cooled to 1100 DEG C with the speed of 15 DEG C/min, after insulation 2.5h, sintering terminates, and furnace cooling, obtains porous niobium titanium alloy.
5, take out porous niobium titanium alloy and be placed in dehydrated alcohol, adopt the cleaning of 40KHz ultrasonic vibration, remove surface dirt and dirt, adopt omnipotent test machine for mechanism detection perform.
Adopt the porous niobium titanium alloy that said method is obtained, have three-dimensional communication pore structure, even pore distribution, impurity content is lower than 0.3%.Have between niobium titanium powder granule and significantly sinter neck structure.The density of porous niobium titanium alloy is 3.15g/cm
3, porosity 65%, pore diameter 400 ~ 600 μm, elastic modelling quantity 1.89Gpa, comprcssive strength 88Mpa.
data test
Porous niobium titanium alloy material prepared by Example 1 and embodiment 2, and niobium powder carries out X-ray diffraction test, result is as shown in Figure 1.As can be seen from Figure 1, the X ray diffracting spectrum of porous niobium titanium alloy does not change along with the change of content of niobium, and does not finally introduce the impurity such as carbide, oxide and intermetallic compound.
Porous niobium titanium alloy prepared by Example 2 carries out electron-microscope scanning, and as shown in Figure 2, as can be seen from Figure 2, porous niobium titanium alloy porosity prepared by embodiment 2 is high, and even pore distribution, three-dimensional communication is good for scanning result.
Claims (9)
1. a medical embedded porous niobium titanium alloy material, is characterized in that, in described porous niobium titanium alloy material, the mass ratio of niobium and titanium is (9:1) ~ (1:3).
2. porous niobium titanium alloy material as claimed in claim 1, it is characterized in that, described porous niobium titanium alloy material comprcssive strength is 47.6 ~ 109.3Mpa, elastic modelling quantity is 0.21 ~ 0.46GPa, described porous niobium titanium alloy has the pore structure of mutually through through hole, aperture is 400 ~ 500 μm, and porosity is 40 ~ 80%.
3. prepare the method for porous niobium titanium alloy material as claimed in claim 1 or 2, it is characterized in that, described method comprises the steps:
(1) by mass ratio according to claim 1 niobium powder mixed with titanium valve and carry out ball milling 3.5-4h, obtain niobium titanium composite powder;
(2) described niobium titanium composite powder and dispersant solution are mixed with uniformly slip; The ratio of the quality of described niobium titanium composite powder quality and described dispersant solution is (5 ~ 9): 1, and in described dispersant solution, the mass percentage content of dispersant is 3 ~ 6%;
(3) be filled in porous foam template by described uniform sizing material, porous foam template is filled full by uniform sizing material, obtain the impregnated sample containing niobium titanium mixed-powder slurry after flooding; In protective gas atmosphere, described impregnated sample is warming up to 400 ~ 600 DEG C and carries out ungrease treatment, obtain the impregnated sample after defat;
(4) impregnated sample after described defat is carried out vacuum-sintering and vacuum annealing in vacuum sintering furnace, being annealed to material comprcssive strength is 47.6 ~ 109.3Mpa, elastic modelling quantity is 0.21 ~ 0.46GPa, and material has the pore structure of mutually through through hole, aperture is 400 ~ 500 μm, porosity is 40 ~ 80%, is medical embedded porous niobium titanium alloy material.
4. preparation method as claimed in claim 3, is characterized in that, during step (1) described ball milling, add dehydrated alcohol as ball-milling medium, then the niobium powder after ball milling and titanium valve are carried out vacuum drying, obtain niobium titanium composite powder.
5. preparation method according to claim 7, is characterized in that, step (2) described dispersant is polyvinyl alcohol, and described dispersant solution is the aqueous solution of polyvinyl alcohol.
6. preparation method as claimed in claim 3, it is characterized in that, the described porous foam template of step (3) is polyurethane foam, and polyurethane foam particle diameter is 400 ~ 600 μm.
7. preparation method as claimed in claim 3, it is characterized in that, the vacuum of step (4) described vacuum-sintering and vacuum annealing is all lower than 10
-2pa.
8. preparation method as claimed in claim 3, it is characterized in that, step (4) described vacuum-sintering is divided into three sections, first paragraph: be incubated 1 ~ 2h after being warming up to 600 DEG C and carry out degreasing sintered; Second segment: be incubated 1.5 ~ 2.5h after being warming up to sintering temperature 1650 DEG C; 3rd section: after naturally cooling to 1200 DEG C of insulation 1 ~ 2h, then cool.
9. preparation method as claimed in claim 8, it is characterized in that, in step (4) described vacuum-sintering, the heating rate of first paragraph is 1 ~ 5 DEG C/min; The heating rate of second segment is 5 ~ 10 DEG C/min.
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| CN107837417A (en) * | 2016-09-20 | 2018-03-27 | 重庆润泽医药有限公司 | A kind of porous niobium |
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| CN106735241A (en) * | 2016-12-29 | 2017-05-31 | 西安铂力特激光成形技术有限公司 | A kind of reinforced resin optical soliton interaction method |
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| CN108380890A (en) * | 2018-01-30 | 2018-08-10 | 中南大学 | A kind of low-elasticity-modulus titanium zirconium dentistry implant material and preparation method thereof |
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