CN102312129A - Method for preparing titanium niobium zirconium tin biomedical titanium alloys by discharge plasma sintering - Google Patents
Method for preparing titanium niobium zirconium tin biomedical titanium alloys by discharge plasma sintering Download PDFInfo
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- 238000005245 sintering Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 30
- IEANPTLKZVMHNW-UHFFFAOYSA-N [Sn].[Nb].[Zr].[Ti] Chemical compound [Sn].[Nb].[Zr].[Ti] IEANPTLKZVMHNW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 47
- 239000000956 alloy Substances 0.000 claims abstract description 36
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000010439 graphite Substances 0.000 claims abstract description 15
- 239000010955 niobium Substances 0.000 claims abstract description 15
- 238000005303 weighing Methods 0.000 claims abstract description 15
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- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
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- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910001040 Beta-titanium Inorganic materials 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
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- 238000009413 insulation Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 9
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- 238000002490 spark plasma sintering Methods 0.000 description 3
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
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- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 1
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- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a method for preparing titanium niobium zirconium tin biomedical titanium alloys by discharge plasma sintering, and belongs to the technical field of biomedical material preparation. The method provided by the invention comprises the following steps of: weighing Ti, Nb, Zr and Sn metal powders according to a chemical composition ratio, mixing the powders by a ball mill, putting into a graphite die, then placing into a discharge plasma sintering furnace, applying axial pressure of 10-40MPa, sintering in vacuum with the vacuum degree being 2-6 Pa while the heating rate is 50-100 DEG C/min and the sintering temperature is 950-1100 DEG C, keeping warm for 5-10 min after reaching the sintering temperature, and cooling in furnace to room temperature to obtain the titanium niobium zirconium tin biomedical titanium alloy material. The titanium niobium zirconium tin biomedical titanium alloys prepared by the method has uniform components and microstructure, high density (more than 98%), low elastic modulus (41-50GPa) and the like. In the mean while, the method provided by the invention has advantages of simple process, convenient operation and low cost, and is easy to realize industrial production.
Description
Technical field
The present invention relates to a kind of method for preparing titanium niobium zirconium tin biological medical titanium alloy, particularly a kind of method of utilizing discharge plasma sintering to prepare titanium niobium zirconium tin biological medical titanium alloy belongs to the bio-medical material preparing technical field.
Background technology
In artificial implantable bioartificial medical metal material; Titanium alloy relies on its excellent biological compatibility, mechanical characteristic (high specific strength, low elastic modulus etc.) and wear-corrosion resistance; Become the medical ideal materials that are implanted into product such as joint prosthesis (hip, knee, shoulder, ankle, elbow, wrist, articulations digitorum manus etc.), bone wound product (intramedullary nail, steel plate, screw etc.), backbone correcting internal fixation system, tooth implant, prosthetic valves, intervention property angiocarpy bracket, obtained in above-mentioned field using widely.
For the implantation that is implemented in people intravital long-term and no rejection and alternative; Continuous development and improvement course have been experienced in the research of biomedical beta-titanium alloy material, from traditional pure titanium, titanium aluminum vanadium alloy (Ti-6Al-4V), titanium aluminium niobium alloy (Ti-6Al-7Nb) up to present new type beta type medical titanium alloy.The main means that current domestic and international researchist obtains β type medical titanium alloy are that adding niobium (Nb), tantalum (Ta), zirconium (Zr), tin β such as (Sn) stablize and strengthening element in pure titanium (Ti); The adding of above-mentioned element can not only significantly reduce the Young's modulus of material, the intensity and the wear and corrosion behavior of raising alloy; And because to add element nontoxic and in implanting to human body, can not produce anaphylaxis; Thereby have excellent biological compatibility, become the current new bio medical titanium alloy human body that has application prospect most and substitute and repair with one of critical material.
The Ti-Nb-Zr-Sn alloy is a kind of new type beta type medical titanium alloy by domestic independent development, compare with other kind medical titanium alloy, its have Young's modulus lower (33～73GPa), advantage such as HS, super-elasticity.According to document Y.L. Hao; S.J. Li; S.Y. Sun, R. Yang. Effect of Zr and Sn on Young's modulus and superelasticity of Ti-Nb-based alloys. Materials Science and Engineering A, 2006; Vol. 441 (1-2), pp 112-118; Y.L. Hao, S.J. Li, S.Y. Sun; C.Y. Zheng, R. Yang. Elastic deformation behaviour of Ti-24Nb-4Zr-7.9Sn for biomedical applications. Acta Biomaterialia, 2007; Vol. 3 (2), pp 277-286; G.L. Zhao; G. Wen, Y. Song, K. Wu. Near surface martensitic transformation and recrystallization in a Ti-24Nb-4Zr-7.9Sn alloy substrate after application of a HA coating by plasma spraying. Materials Science and Engineering C; 2011; Vol. 31 (1-2), pp 106-113. report, the Ti-Nb-Zr-Sn alloy preparation method adopts vacuum melting method; Alloy has excellent super-elasticity and low-down Young's modulus; Very near the Young's modulus of the natural bone of human body, the four kinds of elements of the titanium that contains, niobium, zirconium, tin in the while alloy are nontoxic and have excellent biological compatibility, and over-all properties is superior at present at the maximum Ti-6Al-4V medical titanium alloy of clinical use.
At present preparation titanium niobium zirconium tin biological medical titanium alloy mainly adopts vacuum melting method (to see above-mentioned document and Chinese patent: ZL200410092858.1); Owing in alloy, added niobium, zirconium refractory metal element, its fusing point, density is all greater than titanium elements, and has characteristics such as bad plasticity, deformation; Because vacuum melting method self inherent shortcoming; Can't avoid component segregation in the alloy process fully in preparation, tissue odds is even and defective such as loose, shrinkage cavity, for component segregation and the casting flaw of improving material, often need carry out repeatedly remelting to material; Not only increase cost, and can bring the material contamination problem.Therefore; Adopt the titanium niobium zircalloy manufacturing cost of vacuum melting method method preparation will be higher than traditional T i-6Al-4V medical titanium alloy; And the defective that occurs may cause mechanics and the wear and corrosion behavior of material etc. the decline phenomenon to occur and the requirement that do not reach the clinical application coideal, and is particularly even more serious during large-scale production.
Sintered powder technique provides new approach for solving and improving the problems referred to above.Discharge plasma sintering (Spark Plasma Sintering; Be called for short SPS) be a kind of novel advanced special powder thermal sintering technology; Compare with traditional vacuum powder sintering method, discharge plasma sintering method has advantages such as warming and cooling rate fast (100 ℃/more than the min), sintering time short (finishing generally about 15min from being warmed up to insulation), density high (reaching as high as 99%), the cleaning of preparation process.Utilize this method to prepare titanium niobium zirconium tin biological medical titanium alloy and can overcome the deficiency that vacuum melting method exists, can not only improve the even phenomenon of component segregation and tissue odds of material, and the high density that alloy is obtained, and then have the excellent comprehensive performance.Up to the present, for the research that utilizes SPS technology preparation titanium niobium zirconium tin biomedical beta-titanium alloy material, do not find relevant report as yet both at home and abroad.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing discharge plasma sintering to prepare titanium niobium zirconium tin biological medical titanium alloy; Obtain the titanium niobium zirconium tin biological medical titanium alloy composition that homogeneous microstructure, density are high, Young's modulus is low, can be used as human body and implant and equivalent material.
The present invention realizes through following technical scheme: utilize discharge plasma sintering to prepare the method for titanium niobium zirconium tin biological medical titanium alloy, pass through following process steps:
(1) presses the mass percent (wt.%) of Ti64～73%, Nb22～24%, Zr3～4%, Sn2～8%, take by weighing purity respectively and be 99.9%, mean particle size is Ti, Nb, Zr, the Sn metal-powder of 1～45 μ m;
(2) metal-powder that step (1) is taken by weighing is put into the ball mill ball grinder, is evacuated to 6-10Pa, carries out ball milling then and mixes powder 6～24 hours, obtains mixed metal powder;
(3) mixed metal-powder is packed in the cylindricality graphite jig, insert again in the discharge plasma sintering stove, and apply the axle pressure of 10～40 MPa through the drift at graphite jig two ends; System carries out sintering after being evacuated to 2～6 Pa; With the speed of 50～100 ℃/min, be warming up to 950～1100 ℃ sintering temperature, insulation 5～10 min; Naturally cool to room temperature with stove then, move back mould and promptly obtain titanium niobium zirconium tin biomedical beta-titanium alloy material.
The invention has the advantages that: overcome defectives such as the component segregation, the tissue odds that occur in the traditional vacuum smelting method for preparing titanium niobium zirconium tin biological medical titanium alloy process are even and loose, shrinkage cavity; And the higher shortcoming of manufacturing cost; Make full use of advantages such as the discharge plasma sintering warming and cooling rate is fast, sintering time is short, density is high, the cleaning of preparation process; Improve the even phenomenon of component segregation and tissue odds of alloy, reduce the alloy manufacturing cost.Utilize the titanium niobium zirconium tin biological medical titanium alloy of the inventive method preparation to have composition and homogeneous microstructure, density height (more than 98%), the low advantages such as (41～50 GPa) of Young's modulus; The inventive method technology is simple, easy to operate, with low cost simultaneously, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 mixes the Ti-24Nb-4Zr-8Sn mixed metal powder SEM shape appearance figure of powder after 6 hours for ball milling of the present invention;
Ti-24Nb-4Zr-8Sn alloy XRD diffracting spectrum under the different sintering temperatures of Fig. 2 the present invention;
Ti-24Nb-4Zr-8Sn alloy metallographic structure shape appearance figure under 950 ℃ of sintering temperatures of Fig. 3 the present invention;
Ti-24Nb-4Zr-8Sn alloy metallographic structure shape appearance figure under 1100 ℃ of sintering temperatures of Fig. 4 the present invention.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described.
Embodiment 1:This process step that utilizes discharge plasma sintering to prepare titanium niobium zirconium tin biological medical titanium alloy method is:
(1) press the mass percent (wt.%) of Ti64%, Nb24%, Zr4%, Sn8%, the Ti that take by weighing purity and be 99.9%, mean particle size is 45 μ m, Nb, Zr, Sn metal-powder be totally 25 grams;
(2) metal-powder that step (1) is taken by weighing is put into the ball mill ball grinder, is evacuated to 6 Pa, carries out ball milling then and mixes powder 6 hours, obtains mixed metal powder;
(3) be in the cylindricality graphite jig of 20mm with the mixed metal-powder internal diameter of packing into; Insert in the discharge plasma sintering stove again, and apply the axle pressure of 40 MPa through the drift at graphite jig two ends, system carries out sintering after being evacuated to 2 Pa; Speed with 100 ℃/min; Be warming up to 1100 ℃ sintering temperature, be incubated 5min, remain the axle pressure of 40 MPa in the sintering process; Naturally cool to room temperature with stove then, move back mould and promptly obtain titanium niobium zirconium tin (Ti-24Nb-4Zr-8Sn) biomedical beta-titanium alloy material.
Utilize ESEM (SEM), the SEM shape appearance figure of observing the mixed powder of powder after 6 hours of ball milling in this example is as shown in Figure 1.As can be seen from the figure, the particulate granularity has certain reduction after ball milling mixes powder, and particle mixes.By identical processing condition in this example; With mixed metal-powder; Carry out sintering at 950 ℃, 1000 ℃, 1050 ℃; Together with the Ti-24Nb-4Zr-8Sn biomedical beta-titanium alloy material that this example obtains at 1100 ℃ of sintering, to measure, also pass through to calculate the relative density that obtains respective alloy with Archimedes (Archimedes) method, the Young's modulus that obtains respective alloy through the mechanics compression testing is as shown in table 1.
Table 1
| Sintering temperature (℃) | Density (%) | Young's modulus (GPa) |
| 950 | 98.26 | 48 |
| 1000 | 98.33 | 47 |
| 1050 | 98.45 | 42 |
| 1100 | 98.52 | 41 |
Can know that from measuring result under 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃ four kinds of sintering temperatures, the Ti-24Nb-4Zr-8Sn alloy has all obtained the high-compactness more than 98%.Along with the rising of sintering temperature, the density of sample increases, but the increase amplitude is less.Used X x ray diffractometer x (XRD) check and analysis the structure of alloy (as shown in Figure 2), the result shows that alloy all belongs to β type medical titanium alloy under four kinds of sintering temperatures, by β-Ti mutually and a small amount of unfused Nb, the phase composite of Zr element.Through observation by light microscope alloy organizing pattern (like Fig. 3, shown in Figure 4); The Ti powder melts and is bound up in sintering process; The Ti matrix has been advanced in the high melting point alloy element part solid solution of adding; A small amount of unfused Nb, Zr element are embedded on the β phase Ti matrix, it can also be seen that simultaneously grain edges melts, and demonstrate tangible metallurgical binding between the particle.On the mechanical test machine, carried out the compressive modulus of elasticity test, the result is as shown in table 1, and the elastic mould value that can find out alloy has lower Young's modulus at 41～48GPa.
Above-mentioned experimental result shows; Utilize the Ti-24Nb-4Zr-8Sn medical titanium alloy of the inventive method preparation to have the low (advantages such as 41～48GPa) of composition and homogeneous microstructure, density height (more than 98%), Young's modulus; And technology is simple, easy to operate, and is suitable to body implanting material.
Embodiment 2:This process step that utilizes discharge plasma sintering to prepare titanium niobium zirconium tin biological medical titanium alloy method is:
(1) press the mass percent (wt.%) of Ti73%, Nb22%, Zr4%, Sn2%, the Ti that take by weighing purity and be 99.9%, mean particle size is 40 μ m, Nb, Zr, Sn metal-powder be totally 25 grams;
(2) metal-powder that step (1) is taken by weighing is put into the ball mill ball grinder, is evacuated to 10Pa, carries out ball milling then and mixes powder 6 hours, obtains mixed metal powder;
(3) be in the cylindricality graphite jig of 20mm with the mixed metal-powder internal diameter of packing into; Insert in the discharge plasma sintering stove again, and apply the axle pressure of 40 MPa through the drift at graphite jig two ends, system carries out sintering after being evacuated to 2 Pa; Speed with 100 ℃/min; Be warming up to 1100 ℃ sintering temperature, be incubated 5min, remain the axle pressure of 40 MPa in the sintering process; Naturally cool to room temperature with stove then, move back mould and promptly obtain titanium niobium zirconium tin (Ti-22Nb-4Zr-2Sn) biomedical beta-titanium alloy material.
Identical with embodiment 1; By identical processing condition in this example; With mixed metal-powder, carry out sintering at 950 ℃, 1000 ℃, 1050 ℃, the Ti-22Nb-4Zr-2Sn biomedical beta-titanium alloy material that obtains at 1100 ℃ of sintering together with this example; Measure, also pass through to calculate the relative density that obtains the Ti-22Nb-4Zr-2Sn alloy with Archimedes (Archimedes) method, the Young's modulus that obtains respective alloy through the mechanics compression testing is as shown in table 2.Also all more than 98%, elastic mould value is at 43～50GPa for the density of alloy.
Table 2
| Sintering temperature (℃) | Density (%) | Young's modulus (GPa) |
| 950 | 98.31 | 50 |
| 1000 | 98.38 | 46 |
| 1050 | 98.49 | 41 |
| 1100 | 98.56 | 43 |
Embodiment 3:This process step that utilizes discharge plasma sintering to prepare titanium niobium zirconium tin biological medical titanium alloy method is:
(1) press the mass percent (wt.%) of Ti69%, Nb23%, Zr3%, Sn5%, the Ti that take by weighing purity and be 99.9%, mean particle size is 10 μ m, Nb, Zr, Sn metal-powder be totally 25 grams;
(2) metal-powder that step (1) is taken by weighing is put into the ball mill ball grinder, is evacuated to 8 Pa, carries out ball milling then and mixes powder 12 hours, obtains mixed metal powder;
(3) be in the cylindricality graphite jig of 20mm with the mixed metal-powder internal diameter of packing into; Insert in the discharge plasma sintering stove again, and apply the axle pressure of 30 MPa through the drift at graphite jig two ends, system carries out sintering after being evacuated to 4 Pa; Speed with 80 ℃/min; Be warming up to 1000 ℃ sintering temperature, be incubated 8min, remain the axle pressure of 30 MPa in the sintering process; Naturally cool to room temperature with stove then, move back mould and promptly obtain titanium niobium zirconium tin (Ti-23Nb-3Zr-5Sn) biomedical beta-titanium alloy material.
Embodiment 4:This process step that utilizes discharge plasma sintering to prepare titanium niobium zirconium tin biological medical titanium alloy method is:
(1) press the mass percent (wt.%) of Ti67%, Nb24%, Zr3%, Sn6%, the Ti that take by weighing purity and be 99.9%, mean particle size is 1 μ m, Nb, Zr, Sn metal-powder be totally 25 grams;
(2) metal-powder that step (1) is taken by weighing is put into the ball mill ball grinder, is evacuated to 9 Pa, carries out ball milling then and mixes powder 8 hours, obtains mixed metal powder;
(3) be in the cylindricality graphite jig of 20mm with the mixed metal-powder internal diameter of packing into; Insert in the discharge plasma sintering stove again, and apply the axle pressure of 20 MPa through the drift at graphite jig two ends, system carries out sintering after being evacuated to 6Pa; Speed with 50 ℃/min; Be warming up to 950 ℃ sintering temperature, be incubated 10min, remain the axle pressure of 20 MPa in the sintering process; Naturally cool to room temperature with stove then, move back mould and promptly obtain titanium niobium zirconium tin (Ti-24Nb-3Zr-6Sn) biomedical beta-titanium alloy material.
Embodiment 5:This process step that utilizes discharge plasma sintering to prepare titanium niobium zirconium tin biological medical titanium alloy method is:
(1) press the mass percent (wt.%) of Ti67%, Nb24%, Zr3%, Sn6%, the Ti that take by weighing purity and be 99.9%, mean particle size is 35 μ m, Nb, Zr, Sn metal-powder be totally 25 grams;
(2) metal-powder that step (1) is taken by weighing is put into the ball mill ball grinder, is evacuated to 7 Pa, carries out ball milling then and mixes powder 24 hours, obtains mixed metal powder;
(3) be in the cylindricality graphite jig of 20mm with the mixed metal-powder internal diameter of packing into; Insert in the discharge plasma sintering stove again, and apply the axle pressure of 35 MPa through the drift at graphite jig two ends, system carries out sintering after being evacuated to 5Pa; Speed with 60 ℃/min; Be warming up to 1050 ℃ sintering temperature, be incubated 6min, remain the axle pressure of 35MPa in the sintering process; Naturally cool to room temperature with stove then, move back mould and promptly obtain titanium niobium zirconium tin (Ti-24Nb-3Zr-6Sn) biomedical beta-titanium alloy material.
Claims (1)
1. method of utilizing discharge plasma sintering to prepare titanium niobium zirconium tin biological medical titanium alloy is characterized in that process step is following:
(1) presses the mass percent of Ti64～73%, Nb22～24%, Zr3～4%, Sn2～8%, take by weighing purity respectively and be 99.9%, mean particle size is Ti, Nb, Zr, the Sn metal-powder of 1～45 μ m;
(2) metal-powder that step (1) is taken by weighing is put into the ball mill ball grinder, is evacuated to 6-10Pa, carries out ball milling then and mixes powder 6～24 hours, obtains mixed metal powder;
(3) mixed metal-powder is packed in the cylindricality graphite jig, insert again in the discharge plasma sintering stove, and apply the axle pressure of 10～40 MPa through the drift at graphite jig two ends; System carries out sintering after being evacuated to 2～6 Pa; With the heat-up rate of 50～100 ℃/min, be heated to 950～1100 ℃ sintering temperature, insulation 5～10 min; Naturally cool to room temperature with stove then, move back mould and promptly obtain titanium niobium zirconium tin biomedical beta-titanium alloy material.
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| CN104857566A (en) * | 2015-04-21 | 2015-08-26 | 昆明理工大学 | Preparation method of titanium-niobium-zirconium-based hydroxyapatite biological composite material |
| CN105463249A (en) * | 2015-12-03 | 2016-04-06 | 华南理工大学 | High-strength low-modulus medical beta-Ti alloy material and preparing method thereof |
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| CN108251695A (en) * | 2018-03-22 | 2018-07-06 | 昆明理工大学 | A kind of preparation method of titanium aluminium niobium zirconium molybdenum alloy |
| 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 |
| CN109136600A (en) * | 2018-07-18 | 2019-01-04 | 昆明理工大学 | A kind of preparation method of antibacterial titanium niobium zirconium copper biomaterial |
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| CN104611611A (en) * | 2015-01-22 | 2015-05-13 | 北京科技大学 | Preparation method for ultralow-elastic-modulus high-strength titanium alloy material |
| CN104857566A (en) * | 2015-04-21 | 2015-08-26 | 昆明理工大学 | Preparation method of titanium-niobium-zirconium-based hydroxyapatite biological composite material |
| CN105463249A (en) * | 2015-12-03 | 2016-04-06 | 华南理工大学 | High-strength low-modulus medical beta-Ti alloy material and preparing method thereof |
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| CN107475564B (en) * | 2017-08-22 | 2019-05-28 | 东北大学 | A kind of preparation method of high-strength compact titanium alloy-ceramics Biocomposite material |
| CN107475564A (en) * | 2017-08-22 | 2017-12-15 | 东北大学 | A kind of preparation method of high-strength compact titanium alloy ceramics Biocomposite material |
| CN107739886A (en) * | 2017-10-11 | 2018-02-27 | 白希壮 | A kind of titanium silver alloy for orthopaedics implant and preparation method thereof |
| CN108034846A (en) * | 2018-01-05 | 2018-05-15 | 中南大学 | A kind of high intensity low elastic modulus zirconium niobium titanium dentistry implant material and preparation method thereof |
| 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 |
| CN108251695A (en) * | 2018-03-22 | 2018-07-06 | 昆明理工大学 | A kind of preparation method of titanium aluminium niobium zirconium molybdenum alloy |
| CN108251695B (en) * | 2018-03-22 | 2020-04-07 | 昆明理工大学 | Preparation method of titanium-aluminum-niobium-zirconium-molybdenum alloy |
| CN109136600A (en) * | 2018-07-18 | 2019-01-04 | 昆明理工大学 | A kind of preparation method of antibacterial titanium niobium zirconium copper biomaterial |
| CN115044803A (en) * | 2022-07-11 | 2022-09-13 | 成都大学 | Titanium alloy with three-phase structure and preparation method thereof |
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