CN106756239B - A kind of medical embedded porous titanium alloy and preparation method - Google Patents

A kind of medical embedded porous titanium alloy and preparation method Download PDF

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CN106756239B
CN106756239B CN201710018779.3A CN201710018779A CN106756239B CN 106756239 B CN106756239 B CN 106756239B CN 201710018779 A CN201710018779 A CN 201710018779A CN 106756239 B CN106756239 B CN 106756239B
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titanium alloy
porous titanium
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CN106756239A (en
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陈锋
余新泉
张友法
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process

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Abstract

The present invention relates to a kind of medical embedded porous titanium alloy and preparation methods, and the component of the alloy is with weight percent are as follows: Nb:37~38wt%；Zr:2~4wt%；Ta:1~2wt%, surplus Ti；Preparation step is: in proportion by Ti, Nb, Ta, TiH2And ZrH2Powder is uniformly mixed, and is cold-pressed into green compact, is sintered in the sintering furnace of applying argon gas, after the completion, opens gas bleeder valve, furnace pressure is made to be quickly reduced to 0.15~0.30MPa, close furnace body power supply later, while being filled with argon gas keeps sinter cooling；Solid solution and ageing treatment finally are carried out to sinter, obtain medical embedded porous titanium alloy.TiH in the present invention2And ZrH2Particle is both foamed material and alloy raw material, and the purity is high of POROUS TITANIUM, hole and mechanical property adjustable range are big, and low elastic modulus and high-intensity performance can be obtained when compared with low porosity, is suitble to prepare medical implant, preparation cost is low.

Description

A kind of medical embedded porous titanium alloy and preparation method
Technical field
The present invention relates to a kind of medical embedded porous titanium alloy and preparation methods, belong to titanium alloy material technology of preparing neck Domain.
Background technique
Titanium and its alloy have good biocompatibility and excellent mechanical property and the corrosion resistant in fluid environment Corrosion is the preferred material of the human bodies hard tissue repairs and substitution such as joint prosthesis (hip, knee, ankle, shoulder, elbow joint) and dental implant Material, that be widely used at present is pure titanium and Ti6Al4V(TC4).Existing problem is: the 1. elasticity modulus (100- of two kinds of titanium alloys 115GPa) it is much higher than human Cortex's bone (5-27GPa), so that implant and bone interface is generated " stress shielding " effect, be used for a long time Bone absorption and osteoporosis will occur, lead to the sterile loosening of implant, shorten the working life；It is harmful to the human body 2. TC4 contains V, Al element, there are security risks for long-time service.In recent years, domestic and foreign scholars by addition to Nb, Ta of human body close friend, Zr, The elements such as Mo, Sn and use microstructure control technique (all by the β phase composition of low elastic modulus), make Medical titanium alloy Elasticity modulus be reduced to 55-70GPa, but be significantly higher than the elasticity modulus of human body hard tissue.
The effective ways for further decreasing titanium alloy elastic modulus are to prepare porous titanium alloy, wherein the introducing of hole just like Lower effect: 1. significantly reducing elasticity modulus, matches with the mechanical property for being replaced bone tissue；2. being conducive to osteoblast Interior growth forms mechanical interlock, finally makes to form an entirety between implant and bone；3. being conducive to the biography of body fluid and nutrient solution It is defeated, accelerate agglutination.
The common preparation method of porous titanium alloy is powder metallurgic method, wherein pine dress powder sintering and foam impregnation The intergranular bonded area of titanium of the POROUS TITANIUM of sintering process preparation is small, is also easy to produce crackle, intensity is lower.The most commonly used is pore creating materials Method is cold-pressed after mixing titanium valve and pore creating material (particles such as ammonium hydrogen carbonate and urea), so that pore creating material is volatilized by Low Temperature Heat Treatment, POROUS TITANIUM is obtained through high temperature sintering, the 10 μm of left sides for obtaining 150~500 μm of macropores (pore creating material size) and being distributed on macropore hole wall Right aperture (sizes of titanium valve particulate interspaces).Disadvantage of this law is that pore size distribution is extremely uneven, and due to pore creating material In the presence of different degrees of pollution can be caused to parent metal.Other preparation methods of porous titanium alloy also utilize electron beam and Laser carries out powder sintered speed forming method, obtains periodic cellular lattice structure, but pore-size is single, and bigger than normal (generally higher than 500 μm), Preparation equipment is expensive, and preparation cost is higher.
The elasticity modulus of human Cortex's bone is 5~27GPa, and porosity 5.4~14.2%, resists by 5~150 μm of pore-size 130~180MPa of Compressive Strength.Biocompatibility height, free of contamination porous titanium alloy are prepared, its elasticity modulus and hole knot are made Structure is close with human body hard tissue, and mechanical strength is high, this is current human's hard tissue repair and substitution institute's urgent problem to be solved.
Summary of the invention
Technical problem: the purpose of the present invention is to provide a kind of medical embedded porous titanium alloys, and the alloy is compared with low porosity When low elastic modulus and high-intensity performance can be obtained, be suitble to prepare medical implant.
It is a further object to provide a kind of preparation method of medical embedded porous titanium alloy, preparation costs Low, preparation process Pore genesis is adjustable.
Technical solution: the present invention provides a kind of medical embedded porous titanium alloys, and the component of the porous titanium alloy is with weight Percentage calculates are as follows:
Nb:37wt%~38wt%；
Zr:2wt%~4wt%；
Ta:1wt%~2wt%；
Surplus is Ti.
Wherein:
A kind of medical embedded porous titanium alloy as described in claim 1, it is characterised in that: the porous titanium alloy Porosity is 20.3~36.5%, the diameter d size in hole are as follows: the compression strength of 0 < d≤150 μm, the porous titanium alloy is 335~552MPaMPa, elasticity modulus are 9.2~25.4GPa.
The present invention also provides a kind of preparation methods of medical embedded porous titanium alloy, method includes the following steps:
1) Ti powder, Nb powder, Ta powder, TiH, are weighed in proportion2Powder and ZrH2Powder, wherein TiH2The weight ratio of powder and Ti powder is 0.400~0.500；
2), by the weighed powder merging vacuum ball grinder of step 1), mixing is mixed in three-dimensional motion batch mixer Mixed-powder is placed in mold is cold-pressed into green compact later by powder；
3), the green compact for obtaining step 2) are put into vacuum sintering furnace, and cold conditions is filled with argon gas after vacuumizing, and adjust sintering furnace Middle pressure is 0.10~0.15MPa, is warming up to 900~1050 DEG C later, and 1.5~3h of heat preservation is sintered, and obtains sinter；
4) after the completion of, being sintered, the gas bleeder valve for opening vacuum sintering furnace carries out pressure release, takes out sinter after cooling, carries out Solution treatment obtains solid solution.
5), the solid solution for obtaining step 4) carries out ageing treatment, obtains medical embedded porous titanium alloy.
Wherein:
The Ti powder, Nb powder, Ta powder, TiH2Powder and ZrH2The purity of powder is 99.6wt% or more.
The partial size of the Ti powder is 20~70 μm；The partial size of Nb powder is 25~50 μm；The partial size of Ta powder is 10~20 μm； TiH2The partial size of powder is 10~25 μm；ZrH2The partial size of powder is 10~25 μm.
Described in step 2) in three-dimensional motion batch mixer mixing when a length of 6~8h, the pressure for being cold-pressed into green compact Power is 150~200MPa, and the shape of the green compact is cylindrical body.
The purity of the argon gas is 99.990~99.999vol%, and the rate of the heating is 250~300 DEG C/h.
The gas bleeder valve that vacuum sintering furnace is opened described in step 4) carries out pressure release, takes out the specific mistake of sinter after cooling Journey are as follows: after the completion of sintering, by vacuum sintering furnace with the rate of 0.3~1.0MPa/min, pressure release is faced to gas bleeder valve is preset Pressure release 0.15~0.30MPa of value in boundary's is precipitated the supersaturated hydrogen in sinter quickly, closes power supply later, in critical pressure release value Under conditions of constant, it is persistently filled with argon gas into vacuum sintering furnace, is reduced to in-furnace temperature with the rate of 30~50 DEG C/min After 600~700 DEG C, gas bleeder valve is fully opened, continues to be filled with argon gas into furnace, keeps furnace temperature cooling with the rate of 300~400 DEG C/h To room temperature, sinter is taken out.
Solution treatment described in step 4) is to be placed in sinter in quartz ampoule to vacuumize sealing, later by the vacuum sealing Quartz ampoule be placed in resistance furnace and be heated to 850~1000 DEG C, 0.5~2h is kept the temperature, then by quartz ampoule together with sinter It quenches in water, makes the matrix beta phase structure of sinter.
Ageing treatment described in step 5) is that solid solution is placed in quartz ampoule to vacuumize sealing, later by the vacuum sealing Quartz ampoule be heated to 350~400 DEG C in resistance furnace, keep the temperature 1~2h, then quartz ampoule quenched together with sinter into water In.
The utility model has the advantages that compared with prior art, the present invention have it is following a little:
1、TiH2Powder and ZrH2Powder is both foamed material, is also alloy raw material after decomposing.Since titanium valve and zirconium powder are By to brittle TiH2Powder and ZrH2Powder carries out ball mill grinding and dehydrogenation and obtains, and directlys adopt TiH2Powder and ZrH2Powder End is used as raw material, can significantly save the cost of raw material of titanium, zirconium.
2, on the one hand the hole of POROUS TITANIUM is formed by " leaving " after the gap sintering of the powder such as Ti, on the one hand by the quick of hydrogen It is precipitated and is formed, the rate (liberation of hydrogen speed) that can be reduced by air pressure in sintering temperature (solubility for determining hydrogen in titanium alloy), furnace It is adjusted with technological parameters such as gas bleeder valve pressure settings (adjust hydrogen partial pressure), it is the wider distribution of pore-size, more uniform, it is full The hole requirement of foot implantation material.
3, the matrix using Ti-Nb base beta-titanium alloy as porous titanium alloy, elasticity modulus only have traditional α or alpha+beta titanium The 50~60% of alloy, namely low elastic modulus can be obtained using lower porosity, meet the low elasticity mould of implantation material Amount and high-intensitive requirement.
4, using TiH2And ZrH2It is pollution-free to POROUS TITANIUM as foamed material.Due to the reduction of hydrogen, POROUS TITANIUM Carbon, oxygen etc. are mingled with that content is low, and sintering temperature is 100~200 DEG C lower than the sintering temperature of prior powder metallurgy.
5, using low-temperature short-time ageing treatment, micro ω phase is precipitated on β phase matrix, is basically unchanged elasticity modulus In the case of significantly improve intensity.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is the optics metallograph of porous titanium alloy.
Specific embodiment
The present invention is based on following thinkings to prepare low elastic modulus, high-intensitive medical embedded porous titanium alloy:
①TiH2Powder and ZrH2Powder starts to decompose and be precipitated H at 450 DEG C or more, these H facilitate reduction and close powder grain The oxide on surface promotes the elements diffusion for respectively closing powder intergranular in green compact and alloying, forms sintering neck.At the same time, TiH2And ZrH2It is gradually reduced into Ti and Zr, and participates in alloying.
2. the part H being precipitated is merged into hydrogen (H2), furnace body is entered by powder gap, partially diffuses into alloyed powder End.High pressure (pressure that high temperature argon and hydrogen are formed, about 0.8~0.9MPa) under high temperature in sealed furnace makes to protect in beta-titanium alloy Hold the solubility (theoretical calculation up to 9200ppm or more, much higher than the solubility of hydrogen in the alpha titanium alloys such as pure titanium) of higher hydrogen.
3. opening gas bleeder valve decompression after the completion of 900~1050 DEG C of sintering, the supersaturated hydrogen in alloy passes through vacancy and crystalline substance Rapid diffusional precipitation at the defects of boundary forms the long and narrow interconnected pore to differ in size in the titanium alloy of " softening ".Subsequent fills Argon can cool down rapidly pore structure, prevent hole from occurring to develop in high temperature and be closed.
4. on the one hand the hole of POROUS TITANIUM is formed by " leaving " after the gap sintering of the powder such as Ti, on the one hand by the quick of hydrogen It is precipitated and is formed, the rate (liberation of hydrogen speed) that can be reduced by air pressure in sintering temperature (solubility for determining hydrogen in titanium alloy), furnace It is adjusted with techniques such as gas bleeder valve pressure settings (adjusting hydrogen partial pressure).
5. the elasticity modulus of conventional titanium alloy is high, low elastic modulus can only be obtained by high porosity, but lead to its intensity Sharply decline.The present invention uses Ti-Nb based alloy, and elasticity modulus only has the 50~60% of conventional titanium alloy, namely using compared with Low elastic modulus can be obtained in low porosity, while keeping higher intensity.
To further understand the present invention, the present invention program is described combined with specific embodiments below, but should managed Solution, these descriptions are only further explanation the features and advantages of the present invention, rather than limiting to the claimed invention.
Embodiment 1
With Ti, Nb, Ta, TiH of high-purity2And ZrH2Powder is raw material alloyage, each component weight and granularity are as follows: Ti Powder 40.467g, wherein 20 μm and 50 μm of Ti powder weight equalizations；Nb powder 38.000g, 25 μm；Ta powder 2.000g, wherein 10 μm and The powder weight of 20 μm of Ta is impartial；TiH2Powder 16.187g, 10 μm；ZrH2Powder 4.088g, 10 μm.Each alloying element weight percent Are as follows: Nb:38wt%；Zr:4wt%；Ta:2wt% surplus is Ti.Powder is placed in vacuum ball grinder, in three-dimensional motion mixing 6h is mixed in machine, and powder is cold-pressed into cylindrical body green compact, pressure 200MPa in a mold later；Cylindrical body green compact are put into very In empty sintering furnace, cold conditions is filled with the argon gas that purity is 99.990vol%, pressure 0.10MPa after vacuumizing.Later with 300 DEG C/ The heating rate of h is heated to 900 DEG C, keeps the temperature 3h.After the completion of sintering, pressure regulation gas bleeder valve is opened, makes in furnace air pressure with 0.3MPa/ The rate of min is reduced to 0.30MPa, and the supersaturated hydrogen in sinter is precipitated quickly, forms porous body.Furnace body electricity is closed later Source, while argon gas is filled in furnace, so that furnace gas is released (popping pressure is set in 0.30MPa) from gas bleeder valve, makes furnace temperature 700 DEG C are reduced to the rate of 30 DEG C/min.Hereafter gas bleeder valve (communicating with atmosphere) is fully opened, continues to be filled with argon in furnace Gas makes furnace temperature be cooled to room temperature with the rate of 400 DEG C/h.Cylindrical body is taken out, is placed it in quartz ampoule later and vacuumizes sealing, It carries out solution treatment: being heated to 850 DEG C in resistance furnace, keep the temperature 2h, in water that then quartz ampoule is quenched together with sinter.Finally It carries out ageing treatment: cylindrical body being placed in quartz ampoule and vacuumizes sealing, 350 DEG C are heated in resistance furnace, keep the temperature 2h, then It quenches in water.Porous titanium alloy is by β phase and micro ω phase composition, porosity 20.3%, the distribution of bore dia d size are as follows: and 0 < d≤ 50 μm, 53%；50 < d≤100 μm, 43%；100 < d≤150 μm, 4%；Mechanical property are as follows: compression strength 587MPa, springform Measure 24.6GPa.
Embodiment 2:
With Ti, Nb, Ta, TiH of high-purity2And ZrH2Powder is raw material alloyage, each component weight and granularity are as follows: Ti Powder 40.987g, wherein 20 μm, 50 μm and 70 μm of Ti powder weight is impartial；Nb powder 37.300g, wherein 25 μm and 50 μm of Nb powder Weight is impartial；Ta powder 1.300g, 15 μm；TiH2Powder 17.625g, 20 μm；ZrH2Powder 3.577g, 15 μm.Each alloying element weight hundred Divide ratio are as follows: Nb:37.3wt%；Zr:3.5wt%；Ta:1.3wt% surplus is Ti.Powder is placed in vacuum ball grinder, three Maintenance and operation is moved in batch mixer and mixes 6.5h, and powder is cold-pressed into cylindrical body green compact, pressure 180MPa in a mold later；By cylinder Body green compact are put into vacuum sintering furnace, cold conditions be filled with after vacuumizing purity be 99.999vol% argon gas, pressure 0.12MPa, 950 DEG C are heated to the heating rate of 285 DEG C/h later, keeps the temperature 2.5h.After the completion of sintering, pressure regulation gas bleeder valve is opened, furnace is made Interior air pressure is reduced to 0.25MPa with the rate of 0.5MPa/min, and the supersaturated hydrogen in sinter is precipitated quickly, is formed porous Body.Furnace body power supply is closed later, while being filled with argon gas in furnace, and furnace gas is made to release (popping pressure setting from gas bleeder valve In 0.25MPa), so that furnace temperature is reduced to 675 DEG C with the rate of 35 DEG C/min.Hereafter gas bleeder valve (communicating with atmosphere) is fully opened, Continue to be filled with argon gas in furnace, furnace temperature is made to be cooled to room temperature with the rate of 375 DEG C/h.Cylindrical body is taken out, places it in stone later Ying Guanzhong vacuumizes sealing, carries out solution treatment: being heated to 900 DEG C in resistance furnace, keeps the temperature 1.5h, then by quartz ampoule and sintering Object is quenched together in water.It finally carries out ageing treatment: cylindrical body being placed in quartz ampoule and vacuumizes sealing, is heated in resistance furnace To 370 DEG C, 1.5h is kept the temperature, in water of then quenching.Porous titanium alloy is by β phase and micro ω phase composition, porosity 25.5%, hole The distribution of diameter d size are as follows: 0 < d≤50 μm, 47%；50 < d≤100 μm, 42%；100 < d≤150 μm, 11%；Mechanical property are as follows: Compression strength 490MPa, elasticity modulus 19.2GPa.
Embodiment 3:
With Ti, Nb, Ta, TiH of high-purity2And ZrH2Powder is raw material alloyage, each component weight and granularity are as follows: Ti Powder 40.546g, wherein 50 μm and 70 μm of Ti powder weight is impartial；Nb powder 37.000g, 50 μm；Ta powder 1.000g, 20 μm；TiH2 Powder 20.273g, wherein 15 μm and 25 μm of TiH2Powder weight is impartial；ZrH2Powder 2.044g, 25 μm.Each alloying element weight percent Than are as follows: Nb:37wt%；Zr:2wt%；Ta:1wt%, surplus Ti.Powder is placed in vacuum ball grinder, it is mixed in three-dimensional motion 8h is mixed in material machine, and powder is cold-pressed into cylindrical body green compact, pressure 150MPa in a mold later；Cylindrical body green compact are put into In vacuum sintering furnace, cold conditions is filled with the argon gas that purity is 99.999vol%, pressure 0.15MPa, later with 250 after vacuumizing DEG C/heating rate of h is heated to 1050 DEG C, keep the temperature 1.5h.After the completion of sintering, open pressure regulation gas bleeder valve, make in furnace air pressure with The rate of 1.0MPa/min is reduced to 0.15MPa, and the supersaturated hydrogen in sinter is precipitated quickly, forms porous body.It closes later Closed furnace body power supply, while argon gas is filled in furnace, releasing furnace gas from gas bleeder valve, (popping pressure is set in 0.15MPa), furnace temperature is made to be reduced to 600 DEG C with the rate of 50 DEG C/min.Hereafter gas bleeder valve (communicating with atmosphere) is fully opened, after Continue and be filled with argon gas in furnace, furnace temperature is made to be cooled to room temperature with the rate of 300 DEG C/h.Cylindrical body is taken out, places it in quartz later Sealing is vacuumized in pipe, carries out solution treatment: being heated to 1000 DEG C in resistance furnace, keeps the temperature 0.5h, then by quartz ampoule and sintering Object is quenched together in water.It finally carries out ageing treatment: cylindrical body being placed in quartz ampoule and vacuumizes sealing, is heated in resistance furnace To 400 DEG C, 1h is kept the temperature, in water of then quenching.Porous titanium alloy is by β phase and micro ω phase composition, porosity 36.5%, Kong Zhi The distribution of diameter d size are as follows: 0 < d≤50 μm, 29%；50 < d≤100 μm, 50%；100 < d≤150 μm, 21%；Mechanical property are as follows: anti- Compressive Strength 335MPa, elasticity modulus 9.2GPa.
Embodiment 4:
With Ti, Nb, Ta, TiH of high-purity2And ZrH2Powder is raw material alloyage, each component weight and granularity are as follows: Ti Powder 40.307g, wherein 25 μm and 40 μm of Ti powder weight equalizations；Nb powder 37.600g, 30 μm；Ta powder 1.700g, wherein 15 μm and 25 μm of Ta powder weight is impartial；TiH2Powder 18.541g, 15 μm；ZrH2Powder 2.657g, wherein 10 μm and 25 μm of ZrH2Powder weight It is impartial；Each alloying element weight percent are as follows: Nb:37.6wt%；Zr:2.6wt%；Ta:1.7wt%, surplus Ti.By powder It is placed in vacuum ball grinder, 7.5h is mixed in three-dimensional motion batch mixer, it is raw that powder is cold-pressed into cylindrical body in a mold later Base, pressure 165MPa；Cylindrical body green compact are put into vacuum sintering furnace, cold conditions is filled with purity after vacuumizing and is The argon gas of 99.990vol%, pressure 0.13MPa are heated to 1000 DEG C later with the heating rate of 260 DEG C/h, keep the temperature 2h.? After the completion of sintering, pressure regulation gas bleeder valve is opened, so that air pressure is reduced to 0.20MPa with the rate of 0.75MPa/min, makes sinter In supersaturated hydrogen be quickly precipitated, formed porous body.Furnace body power supply is closed later, while being filled with argon gas in furnace, makes gas in furnace Body releases (popping pressure is set in 0.20MPa) from gas bleeder valve, and furnace temperature is made to be reduced to 650 DEG C with the rate of 40 DEG C/min.This After fully open gas bleeder valve (communicating with atmosphere), continue to be filled with argon gas in furnace, furnace temperature made to be cooled to room with the rate of 350 DEG C/h Temperature.Cylindrical body is taken out, is placed it in quartz ampoule later and vacuumizes sealing, solution treatment is carried out: being heated to 950 in resistance furnace DEG C, 1h is kept the temperature, in water that then quartz ampoule is quenched together with sinter.It finally carries out ageing treatment: cylindrical body is placed in quartz Sealing is vacuumized in pipe, is heated to 380 DEG C in resistance furnace, keeps the temperature 1.7h, in water of then quenching.Porous titanium alloy by β phase and Micro ω phase composition, porosity 31.4%, the distribution of bore dia d size are as follows: 0 < d≤50 μm, 41%；50 < d≤100 μm, 47%；100 < d≤150 μm, 13%；Mechanical property are as follows: compression strength 372MPa, elasticity modulus 13.9GPa.

Claims (7)

1. a kind of preparation method of medical embedded porous titanium alloy, it is characterised in that: the component of the porous titanium alloy is with weight Percentage calculates are as follows:
Nb:37wt% ~ 38wt%；
Zr:2wt% ~ 4wt%；
Ta:1wt% ~ 2wt%；
Surplus is Ti；
The porosity of the porous titanium alloy is 20.3 ~ 36.5%, the diameter d size in hole are as follows: 0 < d≤150 μm, it is described porous The compression strength of titanium alloy is 335 ~ 552MPa, and elasticity modulus is 9.2 ~ 25.4GP a,
Method includes the following steps:
1) Ti powder, Nb powder, Ta powder, TiH, are weighed in proportion2Powder and ZrH2Powder, wherein TiH2The weight ratio of powder and Ti powder is 0.400 ~0.500；
2), by the weighed powder merging vacuum ball grinder of step 1), mixing obtains mixed-powder in three-dimensional motion batch mixer, Mixed-powder is placed in mold later and is cold-pressed into green compact；
3), the green compact for obtaining step 2 are put into vacuum sintering furnace, and cold conditions is filled with argon gas after vacuumizing, and are adjusted and are pressed in sintering furnace Power is 0.10 ~ 0.15 MPa, is warming up to 900 ~ 1050 DEG C later, and 1.5 ~ 3h of heat preservation is sintered, and obtains sinter；
4) after the completion of, being sintered, the gas bleeder valve for opening vacuum sintering furnace carries out pressure release, takes out sinter after cooling, is dissolved Processing, obtains solid solution；
5), the solid solution for obtaining step 4) carries out ageing treatment, obtains medical embedded porous titanium alloy；
Wherein: the gas bleeder valve that vacuum sintering furnace is opened described in step 4) carries out pressure release, takes out the specific of sinter after cooling Process are as follows: after the completion of sintering, by vacuum sintering furnace with the rate of 0.3 ~ 1.0MPa/min, pressure release is faced to gas bleeder valve is preset Pressure release 0.15 ~ 0.30MPa of value in boundary's is precipitated the supersaturated hydrogen in sinter, closes power supply later, is worth in critical pressure release constant Under the conditions of, it is persistently filled with argon gas into vacuum sintering furnace, is reduced to 600 ~ 700 to in-furnace temperature with the rate of 30 ~ 50 DEG C/min After DEG C, gas bleeder valve is fully opened, continues to be filled with argon gas into furnace, so that furnace temperature is cooled to room temperature with the rate of 300 ~ 400 DEG C/h, takes Sinter out.
2. a kind of preparation method of medical embedded porous titanium alloy as described in claim 1, it is characterised in that: the Ti Powder, Nb powder, Ta powder, TiH2Powder and ZrH2The purity of powder is 99.6wt% or more.
3. a kind of preparation method of medical embedded porous titanium alloy as described in claim 1, it is characterised in that: the Ti powder Partial size be 20 ~ 70 μm；The partial size of Nb powder is 25 ~ 50 μm；The partial size of Ta powder is 10 ~ 20 μm；TiH2The partial size of powder is 10 ~ 25 μ m；ZrH2The partial size of powder is 10 ~ 25 μm.
4. a kind of preparation method of medical embedded porous titanium alloy as described in claim 1, it is characterised in that: described in step 2 When a length of 6 ~ 8h of mixing in three-dimensional motion batch mixer, the pressure for being cold-pressed into green compact is 150 ~ 200MPa, described Green compact shape be cylindrical body.
5. a kind of preparation method of medical embedded porous titanium alloy as described in claim 1, it is characterised in that: described in step 3) The purity of argon gas be 99.990 ~ 99.999 vol%, the rate of the heating is 250 ~ 300 DEG C/h.
6. a kind of preparation method of medical embedded porous titanium alloy as described in claim 1, it is characterised in that: described in step 4) Solution treatment be to be placed in sinter in quartz ampoule to vacuumize sealing, the vacuum-packed quartz ampoule is placed in resistance later It is heated to 850 ~ 1000 DEG C in furnace, keeps the temperature 0.5 ~ 2h, then quartz ampoule is quenched in water together with sinter, make the base of sinter Body tissue is beta phase structure.
7. a kind of preparation method of medical embedded porous titanium alloy as described in claim 1, it is characterised in that: described in step 5) Ageing treatment be solid solution is placed in quartz ampoule to vacuumize sealing, later by the vacuum-packed quartz ampoule in resistance furnace It is heated to 350 ~ 400 DEG C, keeps the temperature 1 ~ 2h, in water that then quartz ampoule is quenched together with sinter.
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CN108285990A (en) * 2018-01-30 2018-07-17 宝鸡文理学院 A kind of new type bone implantation titanium alloy and preparation method thereof
CN111804917A (en) * 2020-05-29 2020-10-23 武汉理工大学 Method for improving pore-forming efficiency of metal sublimation pore-forming method based on element reaction/diffusion principle
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