CN1298874C - Super elasticity low modulus titanium alloy and preparing and processing method - Google Patents
Super elasticity low modulus titanium alloy and preparing and processing method Download PDFInfo
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Abstract
The present invention provides Ti-Nb-Zr titanium alloy which is characterized in that the alloy comprises the chemical ingredients of 20 to 35 wt% of Nb, 2 to 15 wt% of Zr, and Ti and inevitable impurity elements as the rest. The titanium alloy offered by the present invention has the advantages of favorable cold-processing properties, low rate of work hardening, low elastic modulus, high intensity, corrosion resistance and high compatibility with human bodies; cold deformation on a large scale can be carried out by the cold-processing technology, such as the cold-processing technology, the cold-drawing wire technology, etc. The alloy has the functions of super elasticity, shape memory and damping; the alloy can prepare nano materials with nano crystals by the cold deformation, and nano materials of ultrahigh strength can be obtained by heat treatment.
Description
Technical field
The present invention relates to the titanium alloy technical field, specifically a kind of super elasticity low modulus titanium alloy and preparation and working method particularly relate to the Ti-Nb-Zr with super-elasticity, low elastic modulus and high human compatibility and the Ti-Nb-Zr-Sn alloy of medical use.
Background technology
Titanium alloy has advantages such as high human compatibility, low density, low elastic modulus, high strength, anti-human body fluid corrosion, substitutes stainless steel and cobalt base alloy gradually and becomes hard tissue substituting materials such as bone and tooth.Be widely used in clinical medical medical titanium alloy at present and be mainly type alpha+beta Ti-6Al-4V and Ti-6Al-7Nb, its Young's modulus only is half of stainless steel and cobalt base alloy, thereby reduced the stress shielding effect that implant and bone modulus difference cause greatly, reduce osseous tissue and be absorbed risk with the implant fracture.Because the titanium alloy that contains Al and V has cytotoxicity and neurovirulent Al and V ion because of wearing and tearing and corrosion discharge behind long-term implant into body, developed country such as the U.S. and Japan is devoted to develop the β type medical titanium alloy with better human compatibility in middle nineteen nineties, as alloys such as Ti-29Nb-13Ta-4.6Zr, the Ti-15Sn-4Nb-2Ta of Ti-13Nb-13Zr, the Ti-15Mo of the U.S. and Ti-35Nb-5Ta-7Zr and Japan and Ti-15Zr-4Nb-4Ta.Above alloy is the high-strength low-modulus medical titanium alloy, its Young's modulus under the solution treatment condition all greater than 60GPa, Young's modulus is mainly used in preparation and bears the implant of big load, as artificial bone, osteoarthrosis, plantation tooth root and hone lamella generally greater than 80GPa during ageing treatment.
For the Ti-Nb-Zr series titanium alloy, existing at present a plurality of patent applications about the low modulus medical alloy are to 10～20wt.%Nb content (U.S. Patent number: 5,545,227; 5,573,401; 5,169,597), (U.S. Patent number: 5,169,597) and less than the Nb of 24wt.% content and Zr (U.S. Patent number: ternary alloy 4,857,269) has carried out patent protection to 35～50wt.%Nb content.Above alloy is the low modulus medical titanium alloy, yet there are no the open report and the patent application of functional capability such as super-elasticity.
The TiNi shape memory alloy has excellent super-elasticity, utilizes medical device widespread use in clinical medicine of its functional performance preparation.Because the Ni element carinogenicity that can produce anaphylaxis and have, develop the bio-medical material that does not contain the Ni element since middle nineteen nineties, as no Ni medical stainless steel to the part crowd.
The shape memory effect of titanium alloy is found (Baker C, Shape memory effect in a Titanium-35wt%niobium alloy, MetalSci J, 1972 by Baker at first in the Ti-35wt.%Nb alloy; 5:92), Duerig also finds shape memory effect (Duerig TW, Richter DF, Albrecht J, Shape memory inTi-10V-2Fe-3Al, Acta Metall, 1982 in the Ti-10V-2Fe-3Al alloy subsequently; 30:2161).Because the shape memory effect of being found only just produces, and do not find that the alloy of being studied has super-elasticity when high temp. salt soaks rapid heating, therefore it is not furtherd investigate.Recent years, 6319340) and Ti-Mo-Al, Ti-Mo-Ga and Ti-Mo-Ge (Application No.: be that superelastic alloy has carried out patent application 20030188810) the Japan scientific research personnel finds that some titanium alloy has super-elasticity, and to Ti-V-Al, Ti-V-Ga and Ti-V-Ge (U.S. Patent number:.
Hao points out that when the metastable beta titanium alloy of research the content that reduces the crystal particle scale of alloy and control the α phase is the effective ways (HaoYL of preparation high-strength low-modulus titanium alloy, Niinomi M, Kuroda D, Fukunaga K, Zhou YL, Yang R, Suzuki A, Aging response of the Young ' smodulus and mechanical properties of Ti-29Nb-13Ta-4.6Zr for biomedicalapplications, Metall.Mater.Trans.A, 2003; 34:1007).Therefore, preparation crystal grain is the key that overcomes the above problems in the bulk nano material of nanoscale.Yet the present effective ways of not inventing the bulk nano metal material that can prepare industrial application have as yet limited the nano metal material Application and Development.The research of more early stage nano metal material mainly concentrates on pure metal or structural alloys such as copper, iron and titanium, and metastable metallic substance may more or less freelyly carry out nanometer and handle in recent studies show that.Because common metastable metallic substance has functional capability such as super-elasticity and damping, such material will have wide practical use.
Summary of the invention
The purpose of this invention is to provide a kind of new titanium alloy (Ti-Nb-Zr system) and preparation and working method with super-elasticity, low modulus, shape memory, damping function, high strength, corrosion-resistant and high human compatibility, this system alloy can be widely used in preparation medical treatment, physical culture and industrial apparatus.
To achieve these goals, technical solution of the present invention is as follows:
Super elasticity low modulus titanium alloy, chemical ingredients are 20～35wt%Nb, 2～12wt%Zr, and surplus is Ti and unavoidable impurities element;
Nb and Zr content are 30～45wt.% in the titanium alloy of the present invention, with guarantee this alloy under room temperature and human body temperature condition, have super-elasticity greater than 2%, less than 60GPa Young's modulus and high damping properties;
Can also contain at least a element among Sn or the Al in the titanium alloy of the present invention, its content is 0.1～12wt.%; Wherein Zr and Sn total content be between 3～20wt.%, make this titanium alloy between-80 ℃～+ 100 ℃ in the temperature range super-elasticity greater than 2%, less than 60GPa Young's modulus and high damping properties;
Titanium alloy of the present invention can contain a small amount of nontoxic interstitial element, and as C, N and/or O, its content is less than 0.5wt.%.
The preparation method of described super elasticity low modulus titanium alloy: comprise vacuum melting, heat treatment step, described heat treatment process is in 200 ℃～900 ℃ solution treatment 10 seconds～2 hours, air cooling or air cooling shrend after 2 seconds～60 seconds, to improve alloy super-elasticity, damping capacity and intensity; Wherein, can be after 200 ℃～900 ℃ solution treatment be quenched, 200 ℃～600 ℃ ageing treatment 10 seconds～60 minutes, air cooling quenched after 2 seconds～60 seconds, with raising alloy super-elasticity, damping capacity and intensity; In addition, described thermal treatment can be handled at 2 minutes～48 hours postcooling of 200 ℃～600 ℃ ageing treatment, makes this alloy have high strength under the low elastic modulus condition.
The working method of described super elasticity low modulus titanium alloy: can carry out hot-work, comprise modes such as hot rolling, hot drawing silk, heat rammer; Cold working be can also carry out, cold rolling, hand-drawn wire, cold swaging or mode such as cold-heading comprised.Wherein, the deformation quantity of cold deformation is controlled at less than 20%, can further reduce the Young's modulus of alloy, makes it less than 45GPa; The cold deformation deformation ratio is greater than 50%, and can prepare crystal particle scale is nano level nano material.
Described crystal particle scale is that nano level nano material is quenched after 10 seconds～2 hours 500 ℃～850 ℃ solution treatment, is the plasticity of nanoscale alloy to improve crystal grain; Or, be the intensity of nanoscale alloy to improve crystal grain 300 ℃～550 ℃ ageing treatment 10 minutes～10 hours; Or,, be the plasticity and the intensity of nanoscale alloy to improve crystal grain then 300 ℃～550 ℃ ageing treatment 10 minutes～10 hours 500 ℃～850 ℃ solution treatment 10 seconds～2 hours.
Compared with prior art, the present invention has more following beneficial effect:
1. system alloy of the present invention has good cold-forming property and very low work hardening rate, can carry out the big scale cold deformation by cold machining process such as cold rolling and hand-drawn wires.
2. system alloy of the present invention has super-elasticity, shape memory and damping function and low elastic modulus, high strength, corrosion-resistant and high human compatibility.
3. system alloy of the present invention can prepare the nano material of crystal grain at nanoscale through cold deformation, can obtain the nano material of superstrength by thermal treatment.
4. the present invention can be widely used in preparation medical treatment, physical culture and industrial apparatus.At first, alloy of the present invention has low elastic modulus, super-elasticity, characteristic such as shape memory effect and high human compatibility, can be used as biomaterial and be applied to clinical medicine, be in particular in: 1) system titanium alloy of the present invention is elementary composition by what human body was had no side effect, has high human compatibility, following application is arranged: utilize its high strength and low modulus characteristic aspect implantation instrument, can prepare hard tissue substituting apparatuses such as skeleton, as artificial bone, osteoarthrosis, plantation tooth root and hone lamella etc., slow down the stress shielding phenomenon that the Young's modulus because of embedded material and bone does not match and produces, weaken the side effect of embedded material, improve the work-ing life of implantation instrument human body; 2), can substitute human body is easily produced anaphylactoid TiNi shape memory alloy, extensively in preparation intravascular stent and wire for correcting shape of tooth etc. because the present invention has super-elasticity and shape memory effect; 3) utilize low modulus of the present invention and super-elasticity, can be used to prepare the flexible fastening apparatus that vertebra etc. is repaired; 4) adopt the surface of the nano material of the present invention's preparation to have high chemically reactive, be easy to coating,, improve the bonding force between titanium alloy substrate, activated coating and the tissue as hydroxyapatite and glass biological ceramics at its surface preparation high biological activity.Secondly, alloy of the present invention has characteristics such as shape memory effect and super-elasticity, can be used as industrial functional materials, for example, utilizes its super-elasticity can prepare spectacle-frame, utilizes its shape memory effect to prepare industrial driving silk.Once more, alloy of the present invention has high strength and low modulus characteristic, can also be used to prepare high-strength structure spare, golf club scope of attack material and spring etc. except can be used as substitute material for human hard tissues.
Description of drawings
Figure 1A is a Ti-20Nb-2Zr/Ti-35Nb-2Zr diffusion couple stereoscan photograph of the present invention;
Figure 1B is a Ti-20Nb-2Zr/Ti-35Nb-2Zr diffusion couple EDAX results;
Fig. 1 C is the variation of Ti-20Nb-2Zr/Ti-35Nb-2Zr diffusion couple component gradient district Young's modulus;
Fig. 2 is the Young's modulus of Ti-Nb-Zr alloy;
Fig. 3 is the Young's modulus of Ti-Nb-Zr-Sn alloy;
Fig. 4 A is a Ti-28Nb-2Zr-8Sn alloy X-ray diffraction spectrum;
Fig. 4 B is a Ti-32Nb-8Zr-8Sn alloy X-ray diffraction spectrum;
Fig. 5 is Ti-30Nb-10Zr alloy loading-unloading stress strain curve figure;
Fig. 6 is Ti-28Nb-15Zr alloy loading-unloading stress strain curve figure;
Fig. 7 is Ti-28Nb-8Zr-2Sn alloy loading-unloading stress strain curve figure;
Fig. 8 is Ti-24Nb-4Zr-7.9Sn alloy loading-unloading stress strain curve figure;
Fig. 9 is Ti-20Nb-4Zr-12Sn alloy loading-unloading stress strain curve figure;
Figure 10 is Ti-28Nb-2Zr-6Sn-2Al alloy loading-unloading stress strain curve figure;
Figure 11 is the average Young's modulus of Ti-24Nb-4Zr-7.9Sn alloy;
Figure 12 is Ti-Nb-Zr-Sn alloy cold rolled sheet and foil figure;
Figure 13 is a Ti-Nb-Zr-Sn alloy hand-drawn wire material;
Figure 14 A is a Ti-24Nb-4Zr-7.9Sn alloy cold rolled plate material transmission electron microscope light field image pattern;
Figure 14 B is a Ti-24Nb-4Zr-7.9Sn alloy cold rolled plate material electron-diffraction diagram;
Figure 15 is that 1.5 millimeters cold-reduced sheets of Ti-24Nb-4Zr-7.9Sn alloy are at 500 ℃ of transmission electron microscope electron diffraction patterns of handling 1 hour.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1
Get the described composition of table 1, adopt the melting of magnetic stirring vacuum non-consumable arc furnace to prepare required alloy, weight 60 gram samples.For guaranteeing that alloying constituent is even, upset button ingot, melt back three times.The button ingot forges into 10mm * 10mm stub at 950 ℃, and line cuts into 20 * 6 * 4mm sample.Sample is pressed the described diffusion couple of table 1 through sand papering and polished finish, and the diffusion welding connection was carried out in 1000 ℃ of insulations in 4 hours under vacuum condition respectively.The sample that connects places the vacuum high-temperature heat treatment furnace, and insulation was prepared the diffusion couple that thickness of diffusion layer surpasses 1mm greater than 50 hours under 1300 ℃ of conditions.Wherein: stereoscan photograph and EDAX results by Ti-20Nb-5Zr and Ti-35Nb-5Zr alloy composition diffusion couple are seen Figure 1A, 1B.
Table 1 Ti-Nb-Zr/Ti-Nb-Zr and Ti-Nb-Zr-Sn/Ti-Nb-Zr-Sn diffusion couple composition
| Ti-20Nb-2Zr/Ti-35Nb-2Zr | Ti-20Nb-5Zr/Ti-35Nb-5Zr | Ti-20Nb-8Zr/Ti-35Nb-8Zr |
| Ti-20Nb-4Zr-2Sn/Ti-35Nb-4Zr-2Sn | Ti-20Nb-4Zr-5Sn/Ti-35Nb-4Zr-5Sn | Ti-20Nb-4Zr-8Sn/Ti-35Nb-4Zr-8Sn |
| Ti-20Nb-8Zr-2Sn/Ti-35Nb-8Zr-2Sn | Ti-20Nb-8Zr-5Sn/Ti-35Nb-8Zr-5Sn | Ti-20Nb-8Zr-8Sn/Ti-35Nb-8Zr-8Sn |
| Ti-20Nb-12Zr-2Sn/Ti-35Nb-12Zr-2Sn | Ti-20Nb-12Zr-5Sn/Ti-35Nb-12Zr-5Sn | Ti-20Nb-12Zr-8Sn/Ti-35Nb-12Zr-8Sn |
After the diffusion couple sand papering and electropolishing with preparation, utilize recovery of elasticity, Young's modulus and hardness in the impression instrument research loading-unloading process, determine the relation of alloying constituent and Young's modulus and hardness.Fig. 1 C is seen in the variation of Ti-20Nb-2Zr/Ti-35Nb-2Zr diffusion couple component gradient district Young's modulus.
According to above result of study, determine to have the composition range of low elastic modulus alloy, select Ti-Nb-Zr and Ti-Nb-Zr-Sn alloying constituent among Fig. 2 and Fig. 3, adopt magnetic stirring vacuum non-consumable arc furnace melting 60 gram samples.For guaranteeing that alloying constituent is even, upset button ingot, melt back three times.The button ingot forges into 10mm * 10mm stub at 950 ℃, be encapsulated in the vitreosil pipe, 850 ℃ through solution treatment in 30 minutes, silica tube taken out to smash behind the air cooling 20s drops in the water.To the alloy of described solution treatment, being processed into working zone is the Elongation test sample of φ 3mm * 15mm, 1 * 10
-3s
-1Strain rate under carry out stretching experiment.Be the accuracy that guarantees that young's modulus in tension is measured, adopt strain gage record stress-strain curve, from the linear elasticity deformation section calculating Young's modulus of curve, the result is referring to Fig. 2 and Fig. 3.The result shows: control the content of alloy element Nb, Zr, Sn, can effectively reduce the Young's modulus of alloy.
Embodiment 2
Difference from Example 1 is: present embodiment research alloying constituent is to α " influence of martensite transformation temperature, determine that alloy has the composition range of superelastic properties.
Option table 2 interalloy compositions adopt magnetic stirring vacuum non-consumable arc furnace melting 60 gram samples.For guaranteeing that alloying constituent is even, upset button ingot, melt back three times.The button ingot forges into 10mm * 10mm stub at 950 ℃, be encapsulated in the vitreosil pipe, 850 ℃ through solution treatment in 30 minutes, silica tube taken out to smash behind the air cooling 20s drops in the water.Utilize differential thermal analysis,, in ± 150 ℃ of scopes, measure the martensite and the austenite transformation temperature of alloy with 10 ℃/minute heating and cooling speed.The analysis to measure result draws 1wt.%Nb, Zr and Sn and reduces about 17.6 ℃, 41.2 ℃ of martensite transformation temperatures and 40.9 ℃ (seeing Table 3) respectively.
The composition of table 2 Ti-Nb-Zr-Sn alloy
| 20Nb | 22Nb | 24Nb | 26Nb | 28Nb | 32Nb | |
| 2Zr-8Sn 4Zr-4Sn 4Zr-8Sn 4Zr-12Sn 6Zr-2Sn 8Zr-2Sn 8Zr-8Sn | √ √ √ √ × × √ | √ √ √ √ × √ √ | √ √ √ √ × √ × | √ √ √ × √ √ × | √ √ × × √ × × | √ √ √ × √ × √ |
Table 3 alloying element is to alloy α " influence of martensitic phase transition temperature
| 1wt.％Nb | 1wt.％Zr | 1wt.％Sn | |
| Phase transition temperature | -17.6℃ | -41.2℃ | -40.9℃ |
For alloy described in the table 2, through sand papering with after rotten quarter, corrosion was removed stressor layers, utilize the X-ray diffraction analysis instrument, adopt 2 θ/θ interlocking method, in ℃ scope of 2 θ=30～90, sweep velocity is to measure the diffraction spectra of alloy under 1 ℃ of/minute condition, analyzes phase composite and each lattice parameter mutually in the alloy.Wherein: the X-ray diffraction spectrum of Ti-28Nb-2Zr-8Sn and Ti-32Nb-8Zr-8Sn alloy is seen Fig. 4 A, 4B respectively.
According to above alloying constituent to α " experimental result of martensitic phase transition temperature influence, select α " Ti-Nb-Zr and the Ti-Nb-Zr-Sn alloying constituent of low 0 ℃ of martensitic phase transition temperature (be specially: Ti-30Nb-10Zr; Ti-28Nb-15Zr; Ti-28Nb-8Zr-2Sn; Ti-24Nb-4Zr-7.9Sn; Ti-20Nb-4Zr-12Sn), adopt magnetic stirring vacuum non-consumable arc furnace melting 60 gram samples.For guaranteeing that alloying constituent is even, upset button ingot, melt back three times.The button ingot forges into 10mm * 10mm stub at 950 ℃, be encapsulated in the vitreosil pipe, 850 ℃ through solution treatment in 30 minutes, silica tube taken out to smash behind the air cooling 20s drops in the water.To the alloy of described solution treatment, being processed into working zone is the Elongation test sample of φ 3mm * 15mm, 1 * 10
-3s
-1Strain rate under carry out CYCLIC LOADING test.For guaranteeing the accuracy of super-elasticity test, adopt strain gage record stress-strain curve, therefrom determine the super-elasticity of alloy.As legend, show that Ti-Nb-Zr and Ti-Nb-Zr-Sn alloy have good hyperelastic alloy loading-unloading test curve and see Fig. 5～Fig. 9.In addition, calculating to resilient deformation section slope in Fig. 5～Fig. 9 loading-unloading test curve shows, Ti-Nb-Zr and Ti-Nb-Zr-Sn are that alloy has low-down Young's modulus, being about 40～50 GPa, only is 35%～45% of medical titanium alloys such as Ti-6Al-4V, Ti-6Al-7Nb, Ti-5Al-2.5Fe.
Embodiment 3
For the Ti-28Nb-2Zr-6Sn-2Al alloy that adds alloy element Al, adopt magnetic stirring vacuum non-consumable arc furnace melting 60 gram samples.For guaranteeing that alloying constituent is even, upset button ingot, melt back three times.The button ingot forges into 10mm * 10mm stub at 950 ℃, be encapsulated in the vitreosil pipe, 850 ℃ through solution treatment in 30 minutes, silica tube taken out to smash behind the air cooling 20s drops in the water.Figure 10 is this alloy loading-unloading stress strain curve figure, shows that adding alloy element Al still can obtain high super-elasticity and low elastic modulus.
Embodiment 4
According to the result of study of embodiment 1 and 2, determine to have the composition range of low elastic modulus and superelastic alloy.Be example with the Ti-24Nb-4Zr-7.9Sn alloy below, provide processing, thermal treatment process and performance thereof.
Adopt vacuum consumable electrode arc furnace, 30 kilograms of Ti-24Nb-4Zr-7.9Sn alloy cast ingots of melting.In 850 ℃ of coggings and forging, 20 millimeters bars of preparation φ roll into 10 millimeters thin rods of φ at 800 ℃ then.
The temperature and time that 10 millimeters thin excellent employing tables 4 of φ provide is heat-treated air cooling shrend after 20 seconds then.Sample is processed into the tension specimen that working zone is φ 3mm * 15mm after the thermal treatment, 1 * 10
-3s
-1Strain rate under carry out 3% loading-unloading test.For guaranteeing the accuracy of Young's modulus and super-elasticity test, adopt strain gage record stress-strain curve, therefrom determine the Young's modulus and the super-elasticity of alloy.As can be seen from Table 4: alloy has low elastic modulus and super-elasticity at thermal treatment (the being solution treatment) temperature and the heat treatment time of broad.
Table 4 Ti-24Nb-4Zr-7.9Sn alloy Young's modulus and super-elasticity
| Heat treating regime | Young's modulus (Gpa) | Super-elasticity (%) |
| The hot rolling attitude | 42 | 2.8 |
| 900 ℃ * 60 minutes | 44 | 2.7 |
| 850 ℃ * 30 minutes | 44 | 2.9 |
| 850 ℃ * 60 minutes | 42 | 2.8 |
| 850 ℃ * 90 minutes | 45 | 2.8 |
| 700 ℃ * 30 minutes | 41 | 2.9 |
| 700 ℃ * 60 minutes | 43 | 2.8 |
| 650 ℃ * 30 minutes | 46 | 2.6 |
| 650 ℃ * 60 minutes | 47 | 2.5 |
| 600 ℃ * 60 minutes | 54 | 2.2 |
| 500 ℃ * 10 minutes | 48 | 2.9 |
| 500 ℃ * 20 minutes | 54 | 2.2 |
| 500 ℃ * 30 minutes | 58 | 1.9 |
| 450 ℃ * 10 minutes | 50 | 2.9 |
| 450 ℃ * 30 minutes | 54 | 2.5 |
| 400 ℃ * 10 minutes | 46 | 2.9 |
| 300 ℃ * 10 minutes | 44 | 2.9 |
| 850 ℃ * 30 minutes+500 ℃ * 10 minutes | 45 | 2.8 |
| 850 ℃ * 30 minutes+450 ℃ * 10 minutes | 50 | 2.8 |
Annotate: latter two carries out ageing treatment after being treated to solution treatment and air cooling shrend in 20 seconds table 4, and described ageing treatment is respectively 500 ℃ * 10 minutes, air cooling shrend after 20 seconds; 450 ℃ * 10 minutes, air cooling shrend after 20 seconds.
10 millimeters thin rods of φ are heat-treated (being solution treatment, no shrend), air cooling then at the temperature and time that table 5 provides.Sample is processed into the tension specimen that working zone is φ 3mm * 15mm after the thermal treatment, 1 * 10
-3s
-1Strain rate under carry out 3% loading-unloading test.For guaranteeing the accuracy of Young's modulus and super-elasticity test, adopt strain gage record stress-strain curve, therefrom determine the Young's modulus and the super-elasticity of alloy.As can be seen from Table 5: alloy adopts the air cooling mode also can obtain low elastic modulus and super-elasticity after thermal treatment, but super-elasticity is lower than in the table 4 air cooling shrend mode after 20 seconds.
Table 5 Ti-24Nb-4Zr-7.9Sn alloy Young's modulus and super-elasticity
| Heat treating regime | Young's modulus (GPa) | Super-elasticity (%) |
| The hot rolling attitude | 42 | 2.8 |
| 850 ℃ * 30 minutes | 48 | 2.5 |
| 850 ℃ * 60 minutes | 50 | 2.5 |
| 850 ℃ * 90 minutes | 47 | 2.6 |
| 500 ℃ * 10 minutes | 48 | 2.7 |
What table 4 and table 5 provided is the initial Young's modulus of alloy, and its average Young's modulus is lower.Figure 11 provides the average Young's modulus under several typical heat treatment condition of Ti-24Nb-4Zr-7.9Sn alloy, shows that the average Young's modulus minimum value of alloy is about 20GPa.
The thin rod of 10 millimeters of φ is heat-treated in the conditions that table 5 provides, air cooling then, and being processed into working zone is the Elongation test sample of φ 3mm * 15mm, 1 * 10
-3s
-1Strain rate under Elongation test.For guaranteeing the accuracy of Young's modulus test, adopt strain gage record stress-strain curve, therefrom determine the Young's modulus of alloy.As can be seen from Table 6: for the invention alloy, tensile strength greater than the 1000MPa condition under, Young's modulus can be less than 70GPa; Tensile strength less than the 1000MPa condition under, Young's modulus is between 40～50GPa.
Table 6 Ti-24Nb-4Zr-7.9Sn alloy room temperature tensile performance
| Heat treating regime | Young's modulus (Gpa) | Intensity (Mpa) | Plasticity (%) |
| The hot rolling attitude | 42 | 850 | 24 |
| 850 ℃ * 30 minutes | 44 | 750 | 29 |
| 850 ℃ * 60 minutes | 42 | 740 | 28 |
| 700 ℃ * 30 minutes | 41 | 750 | 29 |
| 650 ℃ * 30 minutes | 46 | 820 | 25 |
| 650 ℃ * 60 minutes | 47 | 830 | 25 |
| 500 ℃ * 10 minutes | 48 | 950 | 20 |
| 500 ℃ * 30 minutes | 58 | 1040 | 16 |
| 500 ℃ * 60 minutes | 60 | 1140 | 15 |
| 450 ℃ * 240 | 70 | 1250 | 14 |
| 450 ℃ * 480 | 70 | 1200 | 14 |
Annotate: table 6 back two is handled and is adopted 450 ℃ * 240 minutes, 450 ℃ * 480 minutes direct aging to handle in the example, and the type of cooling is air cooling.
Embodiment 5
According to the result of study of embodiment 1 and 2, determine to have the composition range of low elastic modulus and superelastic alloy.Be example with the Ti-24Nb-4Zr-7.6Sn alloy below, provide processing, thermal treatment process and performance thereof.
Adopt vacuum consumable electrode arc furnace, 30 kilograms of Ti-24Nb-4Zr-7.6Sn alloy cast ingots of melting.In 850 ℃ of coggings and forging, 20 millimeters bars of preparation φ roll into 10 millimeters thin rods of φ at 800 ℃ then.
10 millimeters thin rods of φ are heat-treated air cooling shrend after 20 seconds then at the temperature and time that table 7 provides.Sample is processed into the tension specimen that working zone is φ 3mm * 15mm after the thermal treatment, 1 * 10
-3s
-1Strain rate under carry out 3% loading-unloading test.For guaranteeing the accuracy of Young's modulus and super-elasticity test, adopt strain gage record stress-strain curve, therefrom determine the Young's modulus and the super-elasticity of alloy.
Table 7 Ti-24Nb-4Zr-7.6Sn alloy Young's modulus and super-elasticity
| Heat treating regime | Young's modulus (Gpa) | Super-elasticity (%) |
| The hot rolling attitude | 44 | 2.8 |
| 900 ℃ * 60 minutes | 44 | 2.6 |
| 850 ℃ * 30 minutes | 44 | 2.8 |
| 850 ℃ * 60 minutes | 46 | 2.8 |
| 850 ℃ * 90 minutes | 45 | 2.8 |
| 750 ℃ * 60 minutes | 44 | 2.8 |
| 700 ℃ * 30 minutes | 44 | 2.8 |
| 700 ℃ * 60 minutes | 41 | 2.9 |
| 600 ℃ * 60 minutes | 48 | 2.6 |
| 600 ℃ * 30 minutes | 50 | 2.2 |
| 550 ℃ * 30 minutes | 60 | 1.8 |
| 500 ℃ * 10 minutes | 50 | 2.9 |
| 500 ℃ * 30 minutes | 60 | 2.0 |
| 850 ℃ * 30 minutes+500 ℃ * 10 minutes | 47 | 2.8 |
| 850 ℃ * 30 minutes+450 ℃ * 10 minutes | 51 | 2.7 |
Annotate: latter two processing example of table 7 is to carry out ageing treatment after solution treatment and the air cooling shrend in 20 seconds, and the type of cooling is respectively air cooling shrend after 20 seconds.
10 millimeters thin rods of φ are heat-treated at the temperature and time that table 8 provides, then air cooling.Sample is processed into the tension specimen that working zone is φ 3mm * 15mm after the thermal treatment, 1 * 10
-3s
-1Strain rate under carry out 3% loading-unloading test.For guaranteeing the accuracy of Young's modulus and super-elasticity test, adopt strain gage record stress-strain curve, therefrom determine the Young's modulus and the super-elasticity of alloy.
Table 8 Ti-24Nb-4Zr-7.6Sn alloy Young's modulus and super-elasticity
| Heat treating regime | Young's modulus (Gpa) | Super-elasticity (%) |
| The hot rolling attitude | 44 | 2.8 |
| 850 ℃ * 30 minutes | 48 | 2.5 |
| 850 ℃ * 60 minutes | 50 | 2.5 |
| 850 ℃ * 90 minutes | 47 | 2.6 |
| 500 ℃ * 10 minutes | 48 | 2.7 |
10 millimeters thin rods of φ are heat-treated in the condition that table 9 provides, then air cooling.Being processed into working zone is the Elongation test sample of φ 3mm * 15mm, 1 * 10
-3s
-1Strain rate under Elongation test.For guaranteeing the accuracy of Young's modulus test, adopt strain gage record stress-strain curve, therefrom determine the Young's modulus of alloy.
Table 9 Ti-24Nb-4Zr-7.6Sn alloy room temperature tensile performance
| Heat treating regime | Young's modulus (Gpa) | Intensity (Mpa) | Plasticity (%) |
| The hot rolling attitude | 44 | 850 | 28 |
| 850 ℃ * 30 minutes | 44 | 720 | 33 |
| 850 ℃ * 60 minutes | 46 | 740 | 35 |
| 700 ℃ * 30 minutes | 41 | 750 | 29 |
| 650 ℃ * 30 minutes | 44 | 790 | 31 |
| 500 ℃ * 10 minutes | 50 | 980 | 24 |
| 500 ℃ * 30 minutes | 57 | 1120 | 20 |
| 500 ℃ * 60 minutes | 62 | 1240 | 19 |
| 450 ℃ * 240 minutes | 72 | 1320 | 17 |
| 450 ℃ * 480 minutes | 74 | 1260 | 18 |
Annotate: latter two handles example for directly carrying out ageing treatment table 9, and the type of cooling is air cooling.
Embodiment 6
Adopt and add TiO
2Method, the research oxygen level is to Ti-24Nb-4Zr-7.9Sn alloy Young's modulus and hyperelastic influence.Adopt magnetic stirring vacuum non-consumable arc furnace melting 60 gram samples, for guaranteeing that alloying constituent is even, upset button ingot, melt back three times.The button ingot forges into 10mm * 10mm stub at 950 ℃.Sample is processed into the tension specimen that working zone is φ 3mm * 15mm, 1 * 10
-3s
-1Strain rate under carry out 3% loading-unloading test.For guaranteeing the accuracy of Young's modulus and super-elasticity test, adopt strain gage record stress-strain curve, therefrom determine the Young's modulus and the super-elasticity of alloy.Measuring result sees Table 10.
Table 10 oxygen level is to Ti-24Nb-4Zr-7.9Sn alloy Young's modulus and super-elasticity influence
| Oxygen level (wt.%) | Young's modulus (Gpa) | Super-elasticity (%) |
| 0.11 | 42 | 2.8 |
| 0.24 | 48 | 2.5 |
| 0.42 | 56 | 2.0 |
Embodiment 7
Hot rolling system Ti-24Nb-4Zr-7.9Sn alloy bar material among the embodiment 4 unloads after 2% tensile deformation at ambient temperature, and stress-strain curve forms the ring of complete closed, and this encircles pairing absorption can be 0.42MJ m
-3, suitable 6% energy is absorbed.This S. E. A. is 25% of high damping material polypropylene and a nylon, is a kind of good damping metallic substance.Because the intensity of 2% tensile deformation reaches 565MPa, can use under high-strength damping environment.
Hot rolling system Ti-24Nb-4Zr-7.6Sn alloy bar material among the embodiment 5 unloads after 2% tensile deformation at ambient temperature, and stress-strain curve forms the ring of complete closed, and this encircles pairing absorption can be 0.48MJ m
-3, suitable 6.5% energy is absorbed.
For Ti-24Nb-4Zr-7.9Sn in embodiment 4 and 5 and Ti-24Nb-4Zr-7.6Sn alloy, at 850 ℃ of slabs after forging 15 millimeters, cold rolling without carrying out under the process annealing treatment condition, cold rolling deformation ratio is respectively 80%, 90% and 98%, obtaining average grain size is the nano level alloy of 120 nanometers, 50 nanometers and 20 nanometers, is rolled into sheet material and the foil (seeing Figure 12) of 3mm, 1mm and 0.3mm.For 90% cold rolling deformation ratio foil, its intensity only increases about 60MPa than slab, shows that the invention alloy has low-down work hardening rate.
For the thin rod of 10 millimeters of φ in embodiment 4 and 5, at 700 ℃ through hot drawing silk repeatedly, 5 millimeters hot drawing silks of preparation φ material.5 millimeters silk materials of φ are handled without process annealing, and through repeatedly cold-drawn, the accumulation deformation ratio is about 60% and 75%, and cold-drawn becomes φ 3.0mm and φ 2.5mm silk material (seeing Figure 13).
Embodiment 9
Fig. 5-Figure 10 in embodiment 2 and 3 is indicated alloy, and by CYCLIC LOADING-unloading distortion, the research deformation ratio the results are shown in Table 11 to the influence of alloy Young's modulus.
Table 11 deformation ratio influences the alloy Young's modulus
| Alloying constituent | Deformation ratio (%) | |||
| 0 | 3 | 5 | 12 | |
| Ti-30Nb-10Zr | 45GPa | 35GPa | 24GPa | 28GPa |
| Ti-28Nb-15Zr | 46GPa | 34GPa | 23GPa | 31GPa |
| Ti-30Nb-8Zr-2Sn | 44GPa | 32GPa | 24GPa | 34GPa |
| Ti-24Nb-4Zr-7.9Sn | 42GPa | 31GPa | 21GPa | 35GPa |
| Ti-20Nb-4Zr-12Sn | 46GPa | 34GPa | 26GPa | 34GPa |
| Ti-28Nb-2Zr-6Sn-2Al | 45GPa | 30GPa | 21GPa | 33GPa |
For the Ti-24Nb-4Zr-7.9Sn among the embodiment 8 and Ti-24Nb-4Zr-7.6Sn alloy cold rolled sheet and foil, grain-size by transmission electron microscope research material and foil, the result shows that when cold rolling deformation ratio is respectively 80%, 90% and 98% average grain size is respectively 120 nanometers, 50 nanometers and 20 nanometers.As legend, Figure 14 A, 14B provide the transmission electron microscope bright field image and the electron diffraction pattern of 1.5 millimeters cold-reduced sheets of Ti-24Nb-4Zr-7.9Sn alloy (cold rolling processing deformation ratio is 90%), show that crystal particle scale is less than 50 nanometers.
The nanometer cold-reduced sheet can obtain when thermal treatment by the β phase of nanoscale and the nano material of α phase composite.It is the transmission electron microscope electron diffraction pattern of the Ti-24Nb-4Zr-7.9Sn alloy of 90% cold-reduced sheet at 1 hour sample of 500 ℃ of ageing treatment that Figure 15 provides deformation ratio, shows that the crystal grain of β matrix phase and α precipitated phase is nanoscale; The X ray methods analyst shows: the crystal particle scale of β matrix phase and α precipitated phase all is about 10 nanometers.
For Ti-24Nb-4Zr-7.9Sn and Ti-24Nb-4Zr-7.6Sn alloy 1.5 mm thick nano-plates, respectively at 350 ℃, 450 ℃ and 4 hours air coolings of 500 ℃ of ageing treatment.Its intensity is higher than 1600MPa, and Young's modulus is less than 90GPa.
For Ti-24Nb-4Zr-7.9Sn and Ti-24Nb-4Zr-7.6Sn alloy 1.5 mm thick nano-plates, respectively 550 ℃, 650 ℃ and 750 ℃ of solution treatment 10 minutes and 90 minutes, back air cooling, its room temperature tensile plasticity is greater than 10%.
At 60 minutes air coolings of 650 ℃ of solution treatment, grain-size only is 400 nanometers for Ti-24Nb-4Zr-7.9Sn and Ti-24Nb-4Zr-7.6Sn alloy 0.45 mm thick nano-plate; At 60 minutes air coolings of 500 ℃ of ageing treatment.Grain-size only is 15 nanometers.Show that this nano material is stable in hot conditions undertissue, has high high temperature microstructure stability than common copper and ferrum nano material.
For Ti-24Nb-4Zr-7.9Sn and Ti-24Nb-4Zr-7.6Sn alloy 1.5 mm thick nano-plates, at 1 minute air cooling of 600 ℃ of solution treatment, at 4 hours air coolings of 450 ℃ of ageing treatment, its room temperature strength is respectively 1540MPa and 1520MPa, and temperature-room type plasticity is higher than 3%.
Claims (13)
1, a kind of super elasticity low modulus titanium alloy is characterized in that: the chemical ingredients of described alloy is 20～35wt%Nb, 2～12wt%Zr, and surplus is Ti and unavoidable impurities element.
2, according to the described super elasticity low modulus titanium alloy of claim 1, it is characterized in that: the total content of described alloy Nb and Zr is at 30～45wt%.
3, according to the described super elasticity low modulus titanium alloy of claim 1, it is characterized in that: also contain at least a element among Sn, the Al in the described alloy, its content is 0.1～12wt%.
4, according to the described super elasticity low modulus titanium alloy of claim 3, it is characterized in that: Zr and Sn total content are between 3～20wt% in the described alloy.
5, according to claim 1,2,3, one of 4 described super elasticity low modulus titanium alloys, it is characterized in that: can contain at least a C, N, the nontoxic interstitial element of O in the described alloy, its content is less than 0.5wt%.
6, a kind of preparation method according to claim 1 or 3 described super elasticity low modulus titanium alloys, comprise vacuum melting, heat treatment step, it is characterized in that: described heat treatment process is 200 ℃～900 ℃ following solution treatment 10 seconds～2 hours, and the type of cooling is that air cooling or air cooling quench after 2 seconds～60 seconds.
7, according to the preparation method of the described super elasticity low modulus titanium alloy of claim 6, it is characterized in that: after described solution treatment and the quenching, quench after 2 seconds～60 seconds at 200 ℃～600 ℃ following ageing treatment 10 seconds～60 minutes, air cooling.
8, a kind of preparation method according to claim 1 or 3 described super elasticity low modulus titanium alloys comprises vacuum melting, heat treatment step, it is characterized in that: described thermal treatment was 200 ℃～600 ℃ ageing treatment 2 minutes～48 hours, and the type of cooling is an air cooling.
9, a kind of working method according to claim 1 or 3 described super elasticity low modulus titanium alloys comprises hot-work and cold working, it is characterized in that: cold working is cold rolling, hand-drawn wire, cold swaging or the cold-heading cold deformation, and the deformation ratio of cold deformation is less than 20%.
10, a kind of working method according to claim 1 or 3 described super elasticity low modulus titanium alloys, comprise hot-work and cold working, it is characterized in that: cold working is cold rolling, hand-drawn wire, cold swaging or the cold-heading cold deformation, the cold deformation deformation ratio is greater than 50%, and obtaining crystal particle scale is nano level Nanoalloy material.
11, according to the working method of the described super elasticity low modulus titanium alloy of claim 10, it is characterized in that: crystal particle scale is that nano level Nanoalloy material quenches after 10 seconds～2 hours 500～850 ℃ of solution treatment.
12, according to the working method of the described super elasticity low modulus titanium alloy of claim 10, it is characterized in that: crystal particle scale is nano level nano material 300～550 ℃ of ageing treatment 10 minutes～10 hours, obtains the strong Nanoalloy material of superelevation.
13, according to the working method of the described super elasticity low modulus titanium alloy of claim 10, it is characterized in that: crystal particle scale is that nano level nano material is 500～850 ℃ of solution treatment 10 seconds～2 hours, then 300～550 ℃ of ageing treatment 10 minutes～10 hours.
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