CN109847110A - A kind of porous Ti-Nb-Zr composite artificial bone implant material and its preparation method and application - Google Patents

A kind of porous Ti-Nb-Zr composite artificial bone implant material and its preparation method and application Download PDF

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CN109847110A
CN109847110A CN201811559089.XA CN201811559089A CN109847110A CN 109847110 A CN109847110 A CN 109847110A CN 201811559089 A CN201811559089 A CN 201811559089A CN 109847110 A CN109847110 A CN 109847110A
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porous
composite
green compact
bone implant
artificial bone
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张瑾
何远怀
孙韬
陈安然
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Yunnan University YNU
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Abstract

The present invention provides a kind of porous Ti-Nb-Zr composite artificial bone implant material and its preparation method and application, the method operation is as follows: combining converted steel inner tube with mould holder outer tube and is fixed in hard steel mold, first take out the titanium of mould holder outer tube filling quantitative proportioning, niobium, zirconium, pre-molding obtains cyclic annular cylinder green compact after ammonium hydrogen carbonate composite powder, converted steel inner tube is taken out according to same step, insert the titanium of quantitative proportioning, niobium, precompressed obtains cylinder green compact after zirconium composite powder, the cylinder blank of two one-step formings is compacted be placed under axial progress pulse direct current activated sintering in graphite jig again, it finally obtains porous bone and is implanted into material firmly.Using the bone implant material of the method for the present invention preparation not only due to the porous structure of its outer layer has good biological activity and is suitble to the low elastic modulus to match with skeleton, also there is excellent compressive property because of the structure of its core densification, therefore can be used as ideal artifical bone's tissue implanting material.

Description

A kind of porous Ti-Nb-Zr composite artificial bone implant material and its preparation method and application
Technical field
The present invention relates to bone implant material preparation technical fields more particularly to a kind of porous Ti-Nb-Zr composite artificial bone to plant Enter material and its preparation method and application.
Background technique
Biological medical titanium alloy is because of its good mechanical property, resistance to biological corrosion performance, high-fatigue strength and low elasticity mould The advantages that amount and good biocompatibility, is used widely in the replacement of clinical bone and bone renovating material.But titanium closes Gold inertia natural attribute, make its after being implanted into human body can not active reform of nature bone tissue and physiological environment, between the two It is only simple sealed.And the higher elasticity modulus of titanium alloy shows that biomethanics is incompatible to be will cause with naturally primary bone Stress shielding causes the degeneration or absorption of natural bone function of organization.Therefore titanium alloy cannot be formed with bone tissue effective synosteosis, The ability of Integrated implant, and it be easy to cause implant to loosen under long service state, graft failure is even resulted in, to restrict Extensive use of the titanium alloy in medical field.And the introducing of pore structure can reduce the elasticity modulus of biomaterial, make it Meet natural bone organizational requirements, and increase material surface the tissue that implants, osteocyte and tissue body fluid between connecing Contacting surface product, can induce the ingrowing of bone tissue.Such as according to the literature, it is closed by porous Ti prepared by powder metallurgy mode The porous materials such as golden, porous Ti-Mg alloy and porous Ti-HA composite material all achieve preferable in terms of biological property As a result, the elasticity modulus and bending strength of this polyporous materials are all closer to human body compact bone substance.But pore structure in material Introducing will lead to material mechanical property, corrosive nature decline, and with the variation of pore character (porosity increase, Pore-size increases) and drastically reduce.
Application No. is the Chinese patents of CN201510836735.2 to disclose a kind of Ti-39Nb-6Zr bio-medical porous titanium Alloy and preparation method thereof, the alloy is by niobium, zirconium and titanium composition, and wherein niobium 39w%, zirconium 6w%, surplus are titanium;The hole of titanium alloy Gap rate is 19.4%-42.1%.Ti-39Nb-6Zr alloy cast ingot is prepared using vacuum consumable smelting method, utilizes rotation electrode Atomization obtains spherical powder particle;Select the alloy powder of 100-150 mesh, add binder or ammonium hydrogen carbonate pore creating material and Binder is sufficiently mixed, and is pressed into green compact;Green compact sintering is carried out in logical argon pipe type sintering furnace, thoroughly removes binder, or make Hole agent and binder obtain porous alloy.The alloy elastic modulus is 3.6GPa~12.4GPa, tensile strength 123.8MPa ~347.5MPa, although the standby cylindrical body porous alloy of the patent system has the advantages that elasticity modulus is low, the porous alloy Need to carry out alloy multiple melting and atomization granulating early period in preparation, and in alloy niobium component ratio it is higher, cause cost It greatly increases, limits its popularization and application;Sintering temperature is higher in preparation process, and heating heating speed is slower, and sintering time is longer; Material uses bonding agent polyethylene glycol in preparation process, and low molecular poly has certain toxicity, and sintering temperature is 300 It DEG C can just decompose, increase the risk as body implanting material.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of radial ingredient is consistent, structure change it is outer The porous Ti-Nb-Zr bone of layer is implanted into material and its preparation method and application firmly.Porous bone provided by the invention is implanted into material firmly to be made It uses with good biocompatibility and high-intensitive, high-corrosion resistance Ti-Nb-Zr alloy as basis material, in outer layer Ti- It is suitably introduced into pore characteristic (porosity and pore diameter) in Nb-Zr alloy material, not only reduces the elasticity of bone and implantation piece Modulus difference further promotes the associativity and conformability of the two.And pulse direct current activated sintering technology is used, compared with conventional powders It is metallurgy sintered to have many advantages, such as that heating rate of temperature fall is fast, soaking time is short, preparation process is clean.
First aspect present invention provides a kind of porous Ti-Nb-Zr composite artificial bone implant material preparation method, the system Preparation Method the following steps are included:
Titanium (Ti), niobium (Nb) and zirconium (Zr) mixed metal powder are put into ball grinder by step (1) under an argon atmosphere, will Argon atmosphere ball grinder, which is put on high energy ball mill, carries out the mixed powder of ball milling, obtains compound gold after then drying in a vacuum drying oven Belong to powders A;
Step (2) composite metal powder A and pore creating material ammonium hydrogen carbonate powder are mixed to get composite powder in V-type batch mixer B;
Step (3), which is combined using converted steel inner tube with mould holder outer tube, to be fixed in hard steel mold, using two steps Molding obtains green compact material: pre-molding obtains cyclic annular cylinder pressure after mould holder outer tube is first taken out filling composite powder B Base, then converted steel inner tube is taken out into filling composite metal powder A and carries out precompressed acquisition cylindrical body green compact;
The cylindrical body green compact of step (4) pre-molding is compacted be placed on pulse direct current activated sintering hearthstone under axial In black mold, extracts vacuum and carry out activated sintering, and persistently vacuumize the ammonium hydrogen carbonate so that green compact outer layer during the sintering process The gas discharge generated is decomposed completely;
(5) room temperature is cooled to the furnace after the completion of sintering, demoulding can be obtained that radial ingredient is consistent, and the outer layer of structure change is more Hole Ti-Nb-Zr composite artificial bone implant material.
Further, niobium (Nb) mass percent is 8~15%, zirconium (Zr) in step (1) the composite metal powder A Mass percent is 8~15%, surplus is titanium (Ti).
Further, stainless ball and mixed metal powder mass ratio are 3:1~10:1 in step (1) Mechanical Milling Process, Dehydrated alcohol is added and is used as dispersing agent, carries out ball milling under argon atmosphere protection, revolving speed is 200~700r/min, the time for 2~ 15 hours;The additional amount of dehydrated alcohol floods powder and ball milling ball enough.
Further, the average grain diameter of the titanium (Ti), niobium (Nb) and zirconium (Zr) is respectively less than 100 μm, purity >= 99.95%;The pore creating material ammonium hydrogen carbonate powder average particle size is 80~450 μm.
Further, the mass percent of step (2) composite metal powder A in composite powder B is 50~90%, pore-creating The mass percent of agent ammonium hydrogen carbonate powder is 10~50%;
Step (2) mixing process carries out under ar gas environment, batch mixer revolving speed be 50~150r/min, the time be 10~ 40min。
Further, the cyclic annular cylinder green compact diameter of step (3) composite powder B pre-moldingRange is By the core material diameter of composite metal powder A pre-moldingRange isThe diameter of whole cylinder green compact is consistent with cyclic annular cylinder green compact diameter, green compact height H≤50mm.
Further, the axial compaction pressure that step (4) applies cylindrical body green compact is 50~400MPa, in sintering process It persistently vacuumizes so that vacuum degree is maintained at 10Pa hereinafter, the target temperature of pulse direct current activated sintering is 850~1250 in furnace DEG C, sintering time is 5~15min, and the heating rate of target temperature is 50~150 DEG C/min;In temperature-rise period, when temperature rises When to 150 DEG C, heat preservation decomposes pore creating material completely in 1~2 minute, then is heated to being sintered with 60~200 DEG C/min heating rate Target temperature.Preferably, the target temperature of pulse direct current activated sintering is 1000~1150 DEG C.
Further, after step (5) sintering, sintering furnace is cooled to room temperature with the rate of temperature fall of 20~100 DEG C/min.
Second aspect of the present invention provides the porous Ti-Nb-Zr composite artificial bone implant material that the preparation method obtains.
Third aspect present invention provides the application of the porous Ti-Nb-Zr composite artificial bone implant material.The present invention mentions The radial ingredient one that the ingredient of confession is pure, even tissue, elasticity modulus is low, intensity is suitable, biocompatibility and osteogenic activity are good It causes, the porous bone of the outer layer of structure change is implanted into material firmly can be used as good medical embedded or alternate material, be suitable for preparation The materials such as dental implant, joint prosthesis, bone wound product, structure design be that clinical application provides in preparation method Corresponding Research foundation.
The features of the present invention is as follows: the present invention, which combines converted steel inner tube with mould holder outer tube, is fixed on hard punching block In tool, mould holder outer tube is first taken out, Ti, Nb, Zr, NH of quantitative proportioning are inserted4HCO3Pre-molding after composite powder, is obtained Cyclic annular cylinder green compact is obtained, takes out converted steel inner tube according to same step, is inserted after Ti, Nb, Zr composite powder of quantitative proportioning in advance Pressure obtains cylinder green compact, then the cylinder blank of two one-step formings is compacted be placed in graphite jig to carry out under certain axial compressive force Pulse direct current activated sintering, the final radial ingredient of acquisition is consistent, and the porous bone of the outer layer of structure change is implanted into material firmly.Using this hair The bone implant material of bright method preparation is not only due to the porous structure of its outer layer has good biological activity and is suitble to and human body bone The low elastic modulus that bone matches also has excellent compressive property because of the structure of its core densification, therefore can be used as ideal Artifical bone's tissue implanting material, be suitable for preparation dental implant, joint prosthesis, the materials such as bone wound product.It is straight using pulse It flowing activated sintering method and prepares Ti-Nb-Zr composite artificial bone tissue alternate material, sintering time is short, and it is energy-efficient, it does not need to bond Agent, it is environmentally protective.In addition, proportion and sintering condition of the present invention by control tri- kinds of ingredients of Ti, Nb, Zr, so that final The bone material ectonexine faying face arrived is presented metallurgy type and combines without apparent crack defect, and have both excellent mechanical performances and It is suitable for pore structure characteristic (pore-size and porosity).
Compared with prior art, the invention has the following advantages:
(1) the method for the invention prepares biomaterial even tissue, radial outer porous part elasticity modulus Low, radial core tight section intensity is suitable for, biocompatibility is good;The pore character of radial porous part be cell adherence, Proliferation and differentiation provide space, and material is promoted to form good biological bone combination and Integrated implant ability in implantation process;And And the pore creating material in preparation process is nontoxic ammonium hydrogen carbonate, can decompose completely at a lower temperature, pass through sintering The vacuum system of furnace is volatilized completely, and thus obtained porous part is remained without any impurity, provides guarantor for the cleanliness of material Barrier;And preparation method of the present invention is easy to operate, low in cost, industrialization easy to accomplish.
(2) orthopaedics that the present invention prepares is implanted into material mechanical performance and elasticity modulus and natural primary bone tissue firmly With spend it is higher, compression strength up to 180~490MPa, elasticity modulus be 18~48GPa, with bone (elasticity modulus≤30GPa, 100~230MPa of compression strength) matching degree is higher, and it is mitigated or eliminated because of the incompatible stress shielding to caused by of biomethanics, draws Rise natural bone function of organization degeneration or absorption, so as to avoid in long service state implant loosen, be even implanted into The risk of failure.
(3) orthopaedics that the present invention prepares is implanted into element of the material using Ti-Nb-Zr as basis material, in material firmly Zr has better biocompatibility and adaptability relative to Cr, Ni, Mn, Al and V in conventional medical alloy;And Nb and Zr is easy to form one layer of fine and close rutile structure passivating film on the surface of the material in human body environment, is conducive to improve the resistance to of material Corrosive nature.
Detailed description of the invention
Fig. 1 is preform blank flow chart in the embodiment of the present invention 1;(a) cyclic annular cylinder base is suppressed, (b) suppresses core, (c) Cylinder base is suppressed, (d) is demoulded;
Fig. 2 is the X ray diffracting spectrum of composite material after pulse direct current activated sintering in the embodiment of the present invention 1;
Fig. 3 is that radial ingredient prepared by the embodiment of the present invention 1 is consistent, and the porous bone of the outer layer of structure change is implanted into Ti-Nb- firmly Zr composite material SEM figure.
Specific embodiment
Technical solution of the present invention is further described below with reference to embodiment, specific descriptions are only used for explaining this hair The bright rather than restriction present invention.
Embodiment 1
The present embodiment provides a kind of radial ingredient is consistent, the porous Ti-15Nb-15Zr bone of the outer layer of structure change is implanted into material firmly The preparation method of material, specifically includes the following steps:
(1) by average grain diameter is 30 μm, purity is 99.95% titanium, niobium and zirconium metal powder according to nominal mass percentage Weigh than titanium 70%, niobium 15% and zirconium 15% and be put into ball grinder body, dehydrated alcohol is added and ball material mass ratio is 5:1 Stainless steel ball and sealed shell of tank, which operates in glove box;Mechanical ball mill revolving speed is 280r/min, time 8 Hour;60 DEG C of drying obtain composite metal powder A in a vacuum drying oven after the completion of ball milling.
(2) be by composite metal powder A and average grain diameter 80~450 μm of purity assays pore creating material ammonium hydrogen carbonate (NH4HCO3) powder obtains composite powder B in V-type batch mixer with revolving speed 150r/min mixing 30min;In composite powder B, The mass percent of composite metal powder A is 80%, the mass percent of pore creating material ammonium hydrogen carbonate powder is 20%;
(3) it is combined and is fixed in hard steel mold with mould holder outer tube using converted steel inner tube, then consolidate mold Determine device outer tube and take out filling composite powder B, is taken out after compacting outside mould holder be in control cyclic annular cylinder green compact by hand, then will be hard Matter steel inner tube is taken out after filling powders A is compacted by hand and obtains cylindrical body green compact, integrally applies to the cylindrical body green compact of pre-molding (as shown in Figure 1) is demoulded after the axial compressive force of 50MPa;
(4) the cylindrical body green compact after demoulding is placed in the graphite jig of pulse direct current activated sintering furnace, then in furnace It extracts vacuum and reaches 10Pa, sintered target temperature is set as 1050 DEG C, soaking time 6min;Target temperature temperature-rise period with 50 DEG C/ When min heating rate is heated to 150 DEG C, 1 minute is kept the temperature, then sintered target temperature is heated to 100 DEG C/min heating rate 1050℃.It is cooled to room temperature after sintering with the rate of temperature fall of 50 DEG C/min.Guarantor is persistently vacuumized during activated sintering Vacuum degree is held in 10Pa or so, consistent, the structure that can be obtained radial ingredient of demoulding after being rapidly cooled to room temperature with furnace is completed in sintering The porous Ti-15Nb-15Zr bone implant material of the outer layer of variation.
Fig. 2 is that the X-ray diffraction (XRD) of 1 material prepared of embodiment is analyzed.By detection: preparing material phase group At single, there is not pore creating material and pollutant miscellaneous phase, it is ensured that its biological safety as bone implant material.Utilize GB/ T7314-2017 " metal material room temperature compression test method " detects the mechanical property for preparing material.The result shows that: its Compression strength is 368MPa, elasticity modulus 29GPa, with natural bone (elasticity modulus≤30GPa, compression strength 100~ 230MPa) matching degree is higher.Fig. 3 is the transversal cross-section scanning electron microscope shape appearance figure (SEM) of 1 material prepared of embodiment And chemical component EDS energy spectrum diagram.Fig. 3's (a) the result shows that: the consistency of Ti-15Nb-15Zr alloy material core is up to 93.8%, the hole of outer layer uniform perforation since the decomposition of pore creating material ammonium hydrogen carbonate produces, foring porosity is 32% Porous structure Ti-15Nb-15Zr alloy outer, and smelting is presented without apparent crack defect in composite material ectonexine faying face Golden formula combines, and provides guarantee for the mechanics synergisticing performance of the material.The EDS of Fig. 3 (b-d) analysis shows: titanium in composite material, Niobium, zr element are evenly distributed, and without apparent component segregation, ensure that materials microstructure uniformity.ISO- is used to the material 2738 standard detections it is found that its porous layer pore mean diameters be 320 μm, be conducive to osteocyte adherency, growth and increment, and And the connected biological reticular structure of outer perforation is presented between hole, osteocyte ingrowing and the formation of capillary can not only be facilitated, More energy can also be absorbed by cooperative transformation when material bears external force.
Embodiment 2
The present embodiment provides a kind of radial ingredient is consistent, the porous Ti-18Nb-15Zr bone of the outer layer of structure change is implanted into material firmly The preparation method of material, specifically includes the following steps:
(1) by average grain diameter is 30 μm, purity is 99.95% titanium, niobium and zirconium metal powder according to nominal mass percentage Weigh than titanium 67%, niobium 18% and zirconium 15% and be put into ball grinder body, dehydrated alcohol is added and ball material mass ratio is 5:1 Stainless steel ball and sealed shell of tank, which operates in glove box;Mechanical ball mill revolving speed is 400r/min, and the time 7 is small When;60 DEG C of drying obtain composite metal powder A in a vacuum drying oven after the completion of ball milling.
It (2) is 80~450 μm by composite metal powder A and average grain diameter, the pore creating material ammonium hydrogen carbonate of purity assay (NH4HCO3) powder obtains composite powder B in V-type batch mixer with revolving speed 50r/min mixing 20min;In composite powder B, The mass percent of composite metal powder A is 80%, the mass percent of pore creating material ammonium hydrogen carbonate powder is 10%;
(3) it is combined and is fixed in hard steel mold with mould holder outer tube using converted steel inner tube, then consolidate mold Determine device outer tube and take out filling composite powder B, is taken out after compacting outside mould holder be in control cyclic annular cylinder green compact by hand, then will be hard Matter steel inner tube is taken out after filling powders A is compacted by hand and obtains cylindrical body green compact, integrally applies to the cylindrical body green compact of pre-molding It is demoulded after the axial compressive force of 100MPa;
(4) the cylindrical body green compact after demoulding is placed in the graphite jig of pulse direct current activated sintering furnace, then in furnace It extracts vacuum and reaches 10Pa, sintered target temperature is respectively set as 850 DEG C, 900 DEG C, 950 DEG C and 1000 DEG C, soaking time 10min; When target temperature temperature-rise period is heated to 150 DEG C with 100 DEG C/min heating rate, 2 minutes are kept the temperature, then with 100 DEG C/min heating Rate is heated to sintered target temperature.It is cooled to room temperature after sintering with the rate of temperature fall of 50 DEG C/min.In activated sintering Persistently vacuumizing in journey keeps vacuum degree in 10Pa or so, and demoulding after being rapidly cooled to room temperature with furnace is completed in sintering can be obtained diameter It is consistent to ingredient, the porous Ti-18Nb-15Zr bone implant material of the outer layer of structure change.
Sample prepared by sintered target temperature different in this example is subjected to GB/T7314-2017 " metal material room temperature pressure Contracting test method " mechanics properties testing, the results are shown in Table 1.
Influence of the different sintering temperatures of table 1 to composite materials property
Sintering temperature (DEG C) Elasticity modulus (GPa) Compression strength (MPa)
850 20.4 212.5
900 18.6 267.9
950 19.7 329.2
1000 22.3 341.7
As test result it is found that material compression strength prepared by the present embodiment be 212~342MPa, elasticity modulus 19 ~22GPa is higher with natural bone (elasticity modulus≤30GPa, 100~230MPa of compression strength) matching degree.Wherein, the power of material Learn performance and sintering temperature close relation: with the raising of sintering temperature, the elasticity modulus presentation of composite material is first reduced Raised trend afterwards, and compression strength is improved with the raising of sintering temperature.

Claims (10)

1. a kind of porous Ti-Nb-Zr composite artificial bone implant material preparation method, which is characterized in that the preparation method includes Following steps:
Titanium (Ti), niobium (Nb) and zirconium (Zr) mixed metal powder are put into ball grinder by step (1) under an argon atmosphere, by argon gas Atmosphere ball grinder, which is put on high energy ball mill, carries out the mixed powder of ball milling, obtains composite metal powder after then drying in a vacuum drying oven Last A;
Step (2) composite metal powder A and pore creating material ammonium hydrogen carbonate powder are mixed to get composite powder B in V-type batch mixer;
Step (3), which is combined using converted steel inner tube with mould holder outer tube, to be fixed in hard steel mold, using two one-step formings Obtain green compact material: pre-molding obtains cyclic annular cylinder green compact after mould holder outer tube is first taken out filling composite powder B, then Converted steel inner tube is taken out into filling composite metal powder A and carries out precompressed acquisition cylindrical body green compact;
The cylindrical body green compact of step (4) pre-molding is compacted be placed on pulse direct current activated sintering furnace graphite mo(u)ld under axial In tool, extracts vacuum and carry out activated sintering, and persistently vacuumized during the sintering process so that the ammonium hydrogen carbonate of green compact outer layer is complete Decompose the gas discharge generated;
(5) room temperature is cooled to the furnace after the completion of sintering, demoulding can be obtained that radial ingredient is consistent, and the outer layer of structure change is porous Ti-Nb-Zr composite artificial bone implant material.
2. porous Ti-Nb-Zr composite artificial bone implant material preparation method according to claim 1, which is characterized in that step Niobium (Nb) mass percent is 8~20% in (1) described composite metal powder A suddenly, zirconium (Zr) mass percent is 8~15%, Surplus is titanium (Ti).
3. porous Ti-Nb-Zr composite artificial bone implant material preparation method according to claim 1, it is characterised in that: step Suddenly stainless ball and mixed metal powder mass ratio are 3:1~10:1 in (1) Mechanical Milling Process, and dehydrated alcohol is added as dispersion Agent carries out ball milling under argon atmosphere protection, and revolving speed is 200~700r/min, and the time is 2~15 hours.
4. porous Ti-Nb-Zr composite artificial bone implant material preparation method according to claim 1, which is characterized in that institute The average grain diameter for stating titanium (Ti), niobium (Nb) and zirconium (Zr) is respectively less than 100 μm, and purity is >=99.95%;The pore creating material bicarbonate Ammonium powder average particle size is 80~450 μm.
5. porous Ti-Nb-Zr composite artificial bone implant material preparation method according to claim 1, which is characterized in that step Suddenly (2) mass percent of composite metal powder A in composite powder B is the matter of 50~90%, pore creating material ammonium hydrogen carbonate powder Measuring percentage is 10~50%;
Step (2) mixing process carries out under ar gas environment, and batch mixer revolving speed is 50~150r/min, and the time is 10~40min.
6. porous Ti-Nb-Zr composite artificial bone implant material preparation method according to claim 1, which is characterized in that step Suddenly the cyclic annular cylinder green compact diameter of (3) composite powder B pre-moldingRange is By composition metal The core material diameter of powders A pre-moldingRange is The diameter and ring-type of whole cylinder green compact Cylinder green compact diameter is consistent, green compact height H≤50mm.
7. porous Ti-Nb-Zr composite artificial bone implant material preparation method according to claim 1, which is characterized in that step Suddenly (4) are 50~400MPa to the axial compaction pressure that cylindrical body green compact applies, and are persistently vacuumized in sintering process so that in furnace Vacuum degree be maintained at 10Pa hereinafter, pulse direct current activated sintering target temperature be 850~1250 DEG C, sintering time be 5~ 15min, the heating rate of target temperature are 50~150 DEG C/min;In temperature-rise period, when temperature rises to 150 DEG C, heat preservation 1 Pore creating material was decomposed in~2 minutes completely, then sintered target temperature is heated to 60~200 DEG C/min heating rate.
8. porous Ti-Nb-Zr composite artificial bone implant material preparation method according to claim 1, which is characterized in that step Suddenly after (5) sintering, sintering furnace is cooled to room temperature with the rate of temperature fall of 20~100 DEG C/min.
9. a kind of porous Ti-Nb-Zr composite artificial bone implant that the preparation method any according to claim 1~8 obtains Material.
10. a kind of application of porous Ti-Nb-Zr composite artificial bone implant material according to claim 9.
CN201811559089.XA 2018-12-19 2018-12-19 A kind of porous Ti-Nb-Zr composite artificial bone implant material and its preparation method and application Withdrawn CN109847110A (en)

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CN110408815A (en) * 2019-08-21 2019-11-05 湘潭大学 A kind of low elastic modulus, high-intensitive spinodal decomposition type Zr-Nb-Ti alloy material and preparation method thereof
CN110408815B (en) * 2019-08-21 2020-11-06 湘潭大学 Low-elasticity-modulus and high-strength spinodal decomposition type Zr-Nb-Ti alloy material and preparation method thereof
CN111876699A (en) * 2020-06-05 2020-11-03 华南理工大学 SiC fiber reinforced high-porosity Ti-based memory alloy composite material and preparation
CN112642003A (en) * 2020-12-15 2021-04-13 云南省第一人民医院 Preparation method of magnesium/hydroxyapatite porous composite material
RU2765044C1 (en) * 2021-03-29 2022-01-25 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Method for obtaining porous and permeable ring-shaped blanks from a superelastic titanium-zirconium-niobium system alloy

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