CN103409660A - Novel Beta/Gamma-TiAl alloy with ultra-fine grain - Google Patents
Novel Beta/Gamma-TiAl alloy with ultra-fine grain Download PDFInfo
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Abstract
The invention discloses an novel beta/gamma-TiAl alloy with the ultra-fine grain. The novel Beta/Gamma-TiAl alloy comprises the following chemical components according to atomic percent: 40-45% of Al, 2-9% of Nb, 0-4% OF Cr, 0-6% of Mo, 0.1-0.3% of B, and the balance of Ti. The preparation method of the alloy comprises the following steps: electromagnetical induction and smelting in suspension by a water-cooling copper crucible, or consumable arc melting by the water-cooling copper crucible. Through the compound addition of different Beta-phase stable elements, the TiAl alloy laminated structure with the uniform structure and the uniform grain of 10 micrometers is obtained in the cast condition, and a large number of Beta-phase stable elements are stabilized to the room temperature and enriched at the grain boundary of the laminated grain.
Description
Technical field
The invention belongs to TiAl alloy technology field, specifically by the appropriate design alloying constituent, invented the novel β/gamma-TiAl alloy of as cast condition superfine crystal particle of preserving a large amount of β phases on a kind of lamella crystal particle crystal boundary.
Background technology
γ-TiAl base alloy has density low and high temperature intensity and Young's modulus is high, creep resistance and the good over-all properties such as the antioxidant anticorrosive ability is strong and be considered to the high-temperature structural material that the industrial circles such as aerospace, automobile, the energy, weapons have development potentiality.But, due to gamma-TiAl alloy, to organize thickly, anisotropy is strong, and grain-size, at 150 ~ 500 μ m, causes the poor temperature-room type plasticity of this alloy and lower heat deformability, has limited its widespread use.At present, by means such as alloying, thermal treatment, jacket isothermal forging, Canned Hot, jacket hot rollings, come refinement homogenizing tissue, can put forward to a certain extent heavy alloyed plasticity and hot workability, but make its whole tooling cost higher, complex process equipment, be unsuitable for the sizable application of TiAl base alloy.
Itself plasticity of TiAl alloy is poor, and fracture toughness property is low is the Main Bottleneck that limits its use.Evenly, tiny equiax crystal anisotropy is little, add the distortion in man-hour evenly, excellent performance, plasticity be good, is beneficial to casting and plastic working subsequently, this is the unique channel that improves TiAl alloy plasticity and heat deformability.The advantage of β/gamma-TiAl alloy is that β solidifies mutually makes alloy form tiny uniform as-cast structure, and has good heat deformability.The content of β/gamma-TiAl alloy β phase is many more than conventional Ti Al alloy, can reach more than 30%, because β phase (being the B2 phase of ordering under room temperature) is at high temperature body-centered cubic structure, has independently slip system, viscous deformation that can the effective coordination alloy.β/gamma-TiAl alloy, due to the existence of a large amount of β phases, makes alloy under as cast condition, just can obtain tiny more uniform microstructure, and adopts traditional heat forged technology and equipment just can be processed into entity component.Chen Yu bravely wait (a kind of beta-gamma TiAl Alloy And Preparation Method. number of patent application: 201210369708.5) by adding a kind of β phase stable element, vacuum induction melting goes out ingot casting, grain-size is in 50 μ m left and right, and the final thin brilliant β/gamma-TiAl alloy of grain size at 5 ~ 10 μ m that obtain of forging.But different beta phase stable element there are differences the impact of β/gamma-TiAl alloy tissue, the compound interpolation of β phase stable element simultaneously more can organize especially grain fineness number to produce a very large impact by alloy.
Summary of the invention
The object of the present invention is to provide the different β phase stable element of a kind of compound interpolation, when the acquisition laminated structure reaches higher β phase amount, make as-cast grain size reach superfine crystal particle β/gamma-TiAl alloy of 10 μ m.
Realize technical scheme of the present invention:
A kind of novel β/gamma-TiAl alloy with superfine crystal particle, described alloy composition by atomic percent: Al:40 ~ 45%, Nb:2 ~ 9%, Cr:0 ~ 4%, Mo:0 ~ 6%, B:0.1 ~ 0.3%, all the other are Ti, in described alloy, the content of Cr and Mo can not be 0 simultaneously; Its tissue signature is: as-cast structure is laminated structure, and lamella grain-size average out to 10 ~ 30 μ m, β stablize to room temperature mutually and are enriched in lamella crystal particle crystal boundary place.
Optimum ratio: in described alloy, the atomic percent of Al is: 42 ~ 43%, the atomic percent of Nb is: 4 ~ 8%, the atomic percent of Cr is: 0 ~ 2%, the atomic percent of Mo is: 0 ~ 4%, the atomic percent of B is: 0.1 ~ 0.2%.
In above-mentioned chemical composition, rationally the selection of beta stable element, be the key that obtains desirable β/gamma-TiAl alloy cast structure.
Nb is one of important element of stablizing the β phase, and a large amount of Nb element of the TiA1 alloy of high Nb content can effectively carry outside heavy alloyed mechanical behavior under high temperature, can also significantly improve the high temperature oxidation resistance of alloy.So when the present invention added in β phase elements compounding, retaining more Nb element addition was 2 ~ 9%, so that retain the advantage of high Nb-TiAl.
Cr, Mo are considered to more effective β phase stable element.The addition of 1 ~ 3%Cr will help to improve plasticity and the hot-work ability of TiAl alloy, but the Cr element can't be stable to room temperature mutually by a large amount of β, and the interpolation of excessive Cr will destroy the laminated structure of TiAl alloy, therefore Cr content should be controlled at below 4%; The Mo element can improve plasticity and the intensity of thin peritectic alloy, improves the Alloy Anti oxidisability, and the most outstanding advantage of novel β/gamma-TiAl alloy is exactly crystal grain thinning, and the Mo element is remarkable to the strengthening effect of thin peritectic alloy, so Mo content is comparatively suitable between 0 ~ 6%.
B element solubleness in the TiAl-Nb alloy is extremely low, but the B compound of separating out when solidifying, but the thinning TiAl alloy grain improves intensity and hot workability, improves the castability of alloy.The B constituent content is advisable 0.1 ~ 0.5%.
Al content must guarantee that the alloy graining primary phase is the β phase, the interpolation of considering the high-melting-point β phase stable elements such as Nb can make TiAl alloy β phase region enlarge to the low Al direction of high temperature, so the content of Al element is controlled at below 45%, guarantees that its primary phase is the β phase and has avoided peritectic transformation.
The melting technology of described alloy adopts following two kinds of methods:
Method one: the melting of water jacketed copper crucible electromagnetic induction suspension, concrete steps are as follows:
1) according to the composition proportion designed, first the Al of half weight and other alloy are put into to the water jacketed copper crucible of smelting furnace, be evacuated to 5 * 10
-3Pa; To the high-purity argon gas that is filled with a certain amount of pressure in stove, the argon pressure scope is 0.8 ~ 1.0MPa, is smelted into ingot, then adds second half Al to carry out melting.
2) multi-pass master alloy melting ingot, by all alloying constituents melting together 3 ~ 4 times, the master alloy ingot that obtains mixing.
Method two: water jacketed copper crucible non-consumable arc melting, concrete steps are as follows:
1) will according to the raw material of the composition proportion designed, put into the water jacketed copper crucible of smelting furnace, and cover bell and be evacuated to 2 * 10
-3Pa; To the high-purity argon gas that is filled with a certain amount of pressure in stove, the argon pressure scope is 0.4 ~ 0.6MPa.
2) before founding master alloy ingot, will be for air-breathing Ti ingot melting 2 ~ 3 times.
3) multi-pass master alloy melting ingot, adopt the non-consumable tungsten electrode first the high-melting-point constituent elements such as Ti, Nb, Cr, Mo to be melted 2 ~ 3 times together under function composite by electromagnetic stirring, then by all alloying constituents melting together 3 ~ 4 times.
The present invention compared with prior art, its remarkable advantage is: by the compound interpolation different beta of Composition Design phase stable element, make β/gamma-TiAl alloy as-cast structure grain refining to 10 μ m, for 1/5 of the grain-size about existing β/γ-TiAl cast alloy 50 μ m, be 1/15 ~ 1/50 of traditional γ-TiAl cast alloy grain-size, retained simultaneously laminated structure a large amount of β is stable to room temperature mutually.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
The accompanying drawing explanation
Fig. 1 is the optical microstructure of Ti-43Al-6Nb-1Cr-1Mo-0.2B alloy.
Fig. 2 is the SEM-BSE tissue of Ti-43Al-6Nb-1Cr-1Mo-0.2B alloy.
Fig. 3 is the XRD diffracting spectrum of Ti-43Al-6Nb-1Cr-1Mo-0.2B alloy.
Fig. 4 is the optical microstructure of Ti-43Al-4Nb-4Mo-0.2B alloy.
Fig. 5 is the SEM-BSE tissue of Ti-43Al-4Nb-4Mo-0.2B alloy.
Fig. 6 is the XRD diffractogram of Ti-43Al-4Nb-4Mo-0.2B alloy.
Fig. 7 is the optical microstructure of Ti-43Al-4Nb-2Cr-0.2B alloy.
Fig. 8 is the SEM-BSE tissue of Ti-43Al-4Nb-2Cr-0.2B alloy.
Fig. 9 is the XRD diffractogram of Ti-43Al-4Nb-2Cr-0.2B alloy.
Embodiment
The specific embodiment of the invention process is as follows:
(1) design of alloy:
Selecting β is the Ti-Al-Nb-Cr-Mo-B alloy of primary phase mutually, according to the Ti-Al binary phase diagram and select mutually principle, by the proportion relation (interpolation or replacement Nb, Cr, Mo element) of adjusting between β phase stable element, make alloy formation laminated structure and lamella crystal particle crystal boundary place have a large amount of β phases, obtain simultaneously the β/gamma-TiAl alloy of superfine crystal particle.Particularly, Al content need to guarantee that the alloy graining primary phase is the β phase, on the basis that retains most of Nb, adds the Nb of part Cr and Mo replacement same amount, when strengthening β phase stabilizing power, preserves lower laminated structure.Stabilizing element Nb, the Cr of the β phase of compound interpolation, Mo must be stabilized to high temperature β mutually room temperature and form the B2 phase in addition.
(2) mother alloy melting:
According to (1) resulting alloying constituent, adopt the configuration of high pure metal constituent element, purity such as the table 1 of each metal constituent element, under the protection of high-purity Ar gas, adopt water jacketed copper crucible electromagnetic induction suspension melting equipment to found mother alloy.Mother alloy is the master alloy ingot of melting to obtain mixing repeatedly.Or adopt water jacketed copper crucible non-consumable arc-melting furnace repeatedly to carry out induction stirring when melting and buckle ingot with the mother alloy that obtains mixing.
Table 1 prepares master alloy ingot and selects the purity of metal constituent element (%)
| Alloying element | Ti | Al | Nb | Cr | Mo | B |
| Purity/% | 99.999 | 99.999 | 99.999 | 99.99 | 99.9 | 99.9 |
(3) microstructure characterizes
Utilize opticmicroscope, XRD, DSC and SEM to carry out Microstructure characterization to the novel β/gamma-TiAl alloy of preparation, sample is taken from ingot casting (diameter 35mm) apart from 6mm place, center, adopts 5%HF+5%HNO
3+ 90%H
2The O(volume ratio) corrosion treatment.
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
(1) raw-material selecting
The present invention prepares purity such as the table 1 of each metal constituent element that master alloy ingot selects, and alloying constituent is Ti-43Al-6Nb-1Cr-1Mo-0.2B (atomic percent).
(2) preparation of master alloy ingot
Under the high-purity argon gas protective condition, adopt water jacketed copper crucible electromagnetic induction suspension melting equipment to found master alloy ingot, its specific procedure is as follows:
1) after the surperficial mechanical grinding of raw metal is removed to surperficial oxide skin, get the raw materials ready according to the composition proportion designed, the weight of the about 40g of every ingot left and right.Be evacuated to 5 * 10
-3Pa; To the high-purity argon gas (99.999%) that is filled with a certain amount of pressure in stove, the argon pressure scope is 0.8 ~ 1.0MPa.First the Al of half weight is smelted into to ingot together with other alloy, then adds second half Al.
2) multi-pass master alloy melting ingot: by all alloying constituents melting together 3 ~ 4 times, the master alloy ingot that obtains mixing.The power adopted during melting is 20 ~ 25KW.
(3) microstructure characterizes
Fig. 1 is the metallographic by the mentioned component as-cast structure, can find out that the grain-size of this composition As-cast Microstructure is about 10 μ m.Fig. 2,3 is respectively SEM and the XRD figure spectrum of alloy, can find out, a large amount of white β is enriched in the grain boundaries of lamella crystal grain mutually.
The above-mentioned fact shows, compare traditional gamma-TiAl alloy and existing β/gamma-TiAl alloy, the present invention obtain novel β/the gamma-TiAl alloy as-cast structure is even, obtains the superfine crystal particle of average 10 μ m, simultaneously a large amount of β are stablized to room temperature mutually and are evenly distributed on lamella crystal particle crystal boundary place.
Adopt the composition identical with embodiment 1, the master alloy ingot preparation method adopts water jacketed copper crucible non-consumable arc melting, and its specific procedure is as follows:
1) after the surperficial mechanical grinding of raw metal is removed to surperficial oxide skin, get the raw materials ready according to the composition proportion material designed; The material that will prepare according to the weight of every ingot 40g left and right is put into the water jacketed copper crucible of smelting furnace, covers bell and is evacuated to 2 * 10
-3Pa; To the high-purity argon gas (99.999%) that is filled with a certain amount of pressure in stove, the argon pressure scope is 0.4 ~ 0.6MPa.
2) before founding master alloy ingot, will be for air-breathing Ti ingot melting 2 ~ 3 times.
3) multi-pass master alloy melting ingot: adopt the non-consumable tungsten electrode first the high-melting-point constituent elements such as Ti, Nb, Cr, Mo to be melted 2 ~ 3 times together under function composite by electromagnetic stirring, then by all alloying constituents melting together 3 ~ 4 times, the mother alloy button ingot that obtains mixing.The electric current adopted during melting is 500 ~ 650A, and the voltage that induction stirring adopts is 1 ~ 3V.
By microstructure, characterize, find that water jacketed copper crucible non-consumable arc melting prepares alloy prepared by grain size, phase composite and the melting of water jacketed copper crucible electromagnetic induction suspension that novel β/gamma-TiAl alloy characterizes out identical.
Embodiment 3
Adopt the preparation method identical with embodiment 1, alloying constituent is Ti-43Al-4Nb-4Mo-0.2B (atomic percent).As Fig. 4, the alloy grain size average out to 10 μ m of acquisition, stablize a large amount of β to room temperature mutually and be enriched in lamella crystal particle crystal boundary place (Fig. 5,6) simultaneously, but the B compound Ti of black strip in tissue, occurred
2B, can affect the processing characteristics of alloy.
Embodiment 4
Adopt the composition identical with embodiment 3, the preparation method identical with embodiment 2 obtained the alloy of same die size and phase composite.
Embodiment 5
Adopt the preparation method identical with embodiment 1, alloying constituent is Ti-43Al-4Nb-2Cr-0.2B (atomic percent).As Fig. 7, alloy grain size average out to 10 ~ 20 μ m of acquisition, stable less slightly to the β phase content of room temperature, be enriched in lamella crystal particle crystal boundary place (Fig. 8,9).
Embodiment 6
Adopt the composition identical with embodiment 5, the preparation method identical with embodiment 2 obtained the alloy of same die size and phase composite.
Embodiment 7
Adopt the preparation method identical with embodiment 1, alloying constituent is Ti-40Al-8Nb-0.5Cr-0.5Mo-0.2B (atomic percent).As-cast Microstructure is even, obtains the superfine crystal particle of average 10 μ m, and without the B compound, the β phase content is more and stable to room temperature simultaneously, is evenly distributed on lamella crystal particle crystal boundary place.
Embodiment 8
Adopt the composition identical with embodiment 7, the preparation method identical with embodiment 2 obtained the identical alloy of homogeneity of structure, grain size and phase composite.
Embodiment 9
Adopt the preparation method identical with embodiment 1, alloying constituent is Ti-45Al-9Nb-4Cr-0.5Mo-0.1B (atomic percent).Alloy structure is even, and the lamella grain size is about 20 μ m, and the β phase content is less.
Embodiment 10
Adopt the composition identical with embodiment 9, the preparation method identical with embodiment 2 obtained the identical alloy of homogeneity of structure, grain size and phase composite.
Embodiment 11
Adopt the preparation method identical with embodiment 1, alloying constituent is Ti-42Al-2Nb-0.5Cr-6Mo-0.3B (atomic percent).Alloy structure is even, and the lamella grain size is about 10 μ m, and a large amount of β are evenly distributed on around the lamella crystal particle crystal boundary mutually.
Embodiment 12
Adopt the composition identical with embodiment 11, the preparation method identical with embodiment 2 obtained the identical alloy of homogeneity of structure, grain size and phase composite.
Claims (8)
1. novel β/gamma-TiAl alloy with superfine crystal particle, it is characterized in that: described alloy composition by atomic percent: Al:40 ~ 45%, Nb:2 ~ 9%, Cr:0 ~ 4%, Mo:0 ~ 6%, B:0.1 ~ 0.3%, all the other are Ti, in described alloy, the content of Cr and Mo can not be 0 simultaneously; Its tissue signature is: as-cast structure is laminated structure, and lamella grain-size average out to 10 ~ 30 μ m, β stablize to room temperature mutually and are enriched in lamella crystal particle crystal boundary place.
2. the novel β/gamma-TiAl alloy of superfine crystal particle according to claim 1, it is characterized in that: in this alloy, the atomic percent of Al is: 42 ~ 43%.
3. the novel β/gamma-TiAl alloy of superfine crystal particle according to claim 1, it is characterized in that: in this alloy, the atomic percent of Nb is: 4 ~ 8%.
4. the novel β/gamma-TiAl alloy of superfine crystal particle according to claim 1, it is characterized in that: in this alloy, the atomic percent of Cr is: 0 ~ 2%.
5. the novel β/gamma-TiAl alloy of superfine crystal particle according to claim 1, it is characterized in that: in this alloy, the atomic percent of Mo is: 0 ~ 4%.
6. the novel β/gamma-TiAl alloy of superfine crystal particle according to claim 1, it is characterized in that: in this alloy, the atomic percent of B is: 0.1 ~ 0.2%.
7. the novel β/gamma-TiAl alloy of superfine crystal particle according to claim 1, it is characterized in that: the melting technology of described alloy is the melting of water jacketed copper crucible electromagnetic induction suspension, and concrete steps are as follows:
1) according to the composition proportion designed, first the Al of half weight and other alloy are put into to the water jacketed copper crucible of smelting furnace, be evacuated to 5 * 10
-3Pa; To the high-purity argon gas that is filled with a certain amount of pressure in stove, the argon pressure scope is 0.8 ~ 1.0MPa, is smelted into ingot, then adds second half Al to carry out melting;
2) multi-pass master alloy melting ingot, by all alloying constituents melting together 3 ~ 4 times, the master alloy ingot that obtains mixing.
8. the novel β/gamma-TiAl alloy of superfine crystal particle according to claim 1, it is characterized in that: the melting technology of described alloy is water jacketed copper crucible non-consumable arc melting, and concrete steps are as follows:
1) will according to the raw material of the composition proportion designed, put into the water jacketed copper crucible of smelting furnace, and cover bell and be evacuated to 2 * 10
-3Pa; To the high-purity argon gas that is filled with a certain amount of pressure in stove, the argon pressure scope is 0.4 ~ 0.6MPa;
2) before founding master alloy ingot, will be for air-breathing Ti ingot melting 2 ~ 3 times;
3) multi-pass master alloy melting ingot, adopt the non-consumable tungsten electrode first the high-melting-point constituent elements such as Ti, Nb, Cr, Mo to be melted 2 ~ 3 times together under function composite by electromagnetic stirring, then by all alloying constituents melting together 3 ~ 4 times.
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| CN103820677A (en) * | 2014-03-12 | 2014-05-28 | 北京工业大学 | Novel Mn-contained beta-gamma TiAl intermetallic compound material with high Nb content and preparation method thereof |
| CN105803257A (en) * | 2016-04-14 | 2016-07-27 | 南京理工大学 | Method for improving liquid-state fluidity of TiAl-Nb alloy |
| CN105821470A (en) * | 2016-04-14 | 2016-08-03 | 南京理工大学 | Dual-structure titanium aluminum (TiAl) alloy and preparation method thereof |
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| CN103820677B (en) * | 2014-03-12 | 2016-03-02 | 北京工业大学 | A kind of containing the novel β of Mn height Nb-γ TiAl intermetallic compound material and preparation method thereof |
| CN105803257A (en) * | 2016-04-14 | 2016-07-27 | 南京理工大学 | Method for improving liquid-state fluidity of TiAl-Nb alloy |
| CN105821470A (en) * | 2016-04-14 | 2016-08-03 | 南京理工大学 | Dual-structure titanium aluminum (TiAl) alloy and preparation method thereof |
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| CN107653397A (en) * | 2017-09-27 | 2018-02-02 | 北京科技大学 | A kind of high Nb TiAl alloys of β γ with excellent high deformability |
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| CN112071375B (en) * | 2020-06-01 | 2024-03-05 | 南京工业大学 | Design method of TiAl-based superalloy material |
| CN112626373A (en) * | 2020-11-20 | 2021-04-09 | 重庆理工大学 | High-temperature titanium-aluminum alloy and preparation method thereof |
| CN116607048A (en) * | 2022-02-09 | 2023-08-18 | 中国科学院金属研究所 | Gamma-TiAl alloy for precision casting and preparation method thereof |
| CN114959361A (en) * | 2022-06-17 | 2022-08-30 | 芜湖天科航空科技有限公司 | TiAl alloy capable of precipitating large amount of ordered omega phase and preparation method thereof |
| CN114959361B (en) * | 2022-06-17 | 2023-11-28 | 芜湖天科航空科技有限公司 | TiAl alloy capable of precipitating a large amount of ordered omega phases and preparation method thereof |
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