CN117535560A - Large-elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy and preparation method thereof - Google Patents
Large-elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy and preparation method thereof Download PDFInfo
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- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 61
- 230000000694 effects Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 85
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 79
- 239000000126 substance Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000008859 change Effects 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000003723 Smelting Methods 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 230000009466 transformation Effects 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910000734 martensite Inorganic materials 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000010891 electric arc Methods 0.000 claims description 5
- 238000002474 experimental method Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 3
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005057 refrigeration Methods 0.000 abstract description 18
- 238000005516 engineering process Methods 0.000 abstract description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
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- 108010053481 Antifreeze Proteins Proteins 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910003286 Ni-Mn Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
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- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/006—Resulting in heat recoverable alloys with a memory effect
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/52—Alloys
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Abstract
The invention belongs to the technical field of solid-state refrigeration of shape memory alloys, and particularly relates to a large elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy and a preparation method thereof. The invention aims to solve the problems that the existing Co-V-Ga-based shape memory alloy elastic heating and refrigerating material has large stress and low heat insulation temperature. The chemical general formula is Co 51.7 V 31.3 Ga 17‑x Ti x ，0X is more than or equal to 3. Adopting an as-cast polycrystalline alloy arc melting and homogenization heat treatment technology to prepare the alloy; the stress hysteresis is only 21MPa, and the large heat insulation temperature change of-10K exists under 400MPa driving stress; the COP (coefficient of performance) reaches 31.7 at maximum, and the method has the advantages of simple process flow, excellent superelastic performance, large elastic heat effect and the like, and has potential application prospect in the field of elastic heat refrigeration.
Description
Technical Field
The invention belongs to the technical field of shape memory alloy solid-state refrigeration, and particularly relates to a polycrystalline Co-V-Ga-Ti memory alloy with a large elastic thermal effect and a preparation method thereof.
Background
The refrigeration technology is continuously updated and developed for thousands of years, and the original ice making technology is changed into the existing air conditioner refrigeration technology, so that the daily life requirements of people are met, the urban construction is greatly promoted, and the following environmental problems are increasingly aggravated. Meanwhile, the elastic heating refrigeration is considered to be the novel refrigeration technology which is most hopeful to replace the traditional vapor compression technology at present due to the characteristics of higher refrigeration efficiency, specific refrigeration power and the like. At present, the elastic heating refrigeration is mainly based on the thermal effect generated when the shape memory alloy is subjected to solid-solid phase transition under the drive of uniaxial stress, and is carried out by loading and unloading heat release and heat absorption.
The magnitude of the elasto-thermal effect is generally determined by isothermal entropy change (Δs tr ) And adiabatic temperature change (DeltaT) ad ) To perform quantization. In practical application, the elastic heating refrigeration material is often required to be simple and easy to prepare, and has good cycle stability, and the two systems Ni-Ti-based and Ni-Mn-based shape memory alloy with wider research range at present has larger delta T ad However, there are respectively the outstanding problems of large stress hysteresis and brittle nature, and complicated processing and preparation processes are required for improvement. The additional Cu-based and Fe-based shape memory alloy elasto-thermal refrigerant materials also limit their large-scale application due to their intrinsically smaller adiabatic temperature change. For this reason, a Co-V-Ga-based shape memory alloy elasto-thermal refrigerating material with a simple preparation method is widely paid attention to.
Therefore, a brand new Co-V-Ga-Ti shape memory alloy and a preparation method thereof are necessary to be researched to make up for the defects of the existing solid-state elasto-thermal refrigeration technology. Under the preparation condition of adopting the massive polycrystalline alloy, the improvement of the cyclic stability of the alloy is particularly important on the basis of ensuring the large elastic thermal effect, and meanwhile, the alloy has stable super elasticity and can have good cyclic stability.
Disclosure of Invention
The invention aims to solve the problems of large stress applied to the existing Co-V-Ga-based shape memory alloy elastic heating and refrigerating material and low alloy elastic heating effect, and provides a large elastic heating effect polycrystalline Co-V-Ga-Ti memory alloy and a preparation method thereof.
The invention provides a large elastic thermal effect polycrystal Co-V-Ga-Ti memory alloy with a chemical formula of Co 51.7 V 31.3 Ga 17-x Ti x ，0≤x≤3。
The preparation method of the large elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy is completed according to the following steps:
1. preparing materials: according to the chemical general formula Co 51.7 V 31.3 Ga 17-x Ti x Preparing materials, wherein x is more than or equal to 0 and less than or equal to 3, respectively weighing a Co metal simple substance, a V metal simple substance, a Ga metal simple substance and a Ti metal simple substance as raw materials, and removing oxide skin on the surface layer of the metal simple substance;
2. arc melting: putting the raw materials into a copper crucible of a non-consumable high-vacuum arc melting furnace, and smelting after gas washing to obtain a smelted alloy cast ingot;
3. homogenizing heat treatment: and after the smelted alloy cast ingot is completely cooled, sealing and placing the cooled alloy cast ingot into a quartz tube filled with argon for homogenizing heat treatment, and then carrying out ice water cold quenching to obtain the large-elastic thermal effect polycrystalline Co-V-Ga-Ti-based memory alloy.
The invention has the beneficial effects that:
1. the invention prepares a brand new Co-V-Ga-Ti block-shaped polycrystalline memory alloy elastic heating material, which is a brand new high-performance elastic heating refrigeration material. After 30 times of mechanical training, the critical stress platform of the curve is obviously reduced, and the super-elastic curve tends to be stable and has good repeatability;
2. the Co-V-Ga-Ti block-shaped polycrystalline elasto-thermal refrigeration memory alloy prepared by the method can obtain-10K large unloading adiabatic temperature change under the uniaxial stress of 400MPa, and is obviously superior to similar alloys prepared by other methods. Meanwhile, the lower driving stress is also beneficial to improving the circulation stability of the elastic heating refrigerating material;
3. according to the invention, through controlling doping elements, components and the like, the prepared Co-V-Ga-Ti alloy has only 21MPa of stress hysteresis, so that the elastic properties and the cyclic stability of the massive polycrystalline Co-V-Ga-Ti memory alloy are obviously improved. The large elastic thermal effect block polycrystalline Co-V-Ga-Ti elastic thermal refrigeration alloy material obtains the adiabatic temperature change of-10K, the stress hysteresis is only 21MPa, the coefficient of performance is 31.7 at maximum, and the breaking strength is more than 1600MPa. Enriches the types of Co-V-Ga-based shape memory alloy in the existing elasto-thermal refrigeration field, and has reference significance for further optimizing design of large elasto-thermal effect alloy materials.
4. The brand new Co-V-Ga-Ti shape memory alloy has a thermal effect different from that of Co-V-Ga-Mn high-elastic thermal effect memory alloy (patent number: CN 116479290A) in that the Co-V-Ga-Ti shape memory alloy has a large thermal effect of-10K at 400MPa, the stress hysteresis is only 21MPa, and the coefficient of performance COP is more up to 31.7; the driving stress of the novel Co-V-Ga-Ti shape memory alloy is reduced by 150MPa, the stress hysteresis is reduced by 87MPa, and the coefficient of performance is improved by 13. The low driving stress and the low stress hysteresis are very beneficial to the improvement of the cycle stability of the alloy material, and the fatigue service life of the alloy material is greatly improved.
Drawings
FIG. 1 is Co prepared in example 1 51.7 V 31.3 Ga 17 DSC profile of the alloy;
FIG. 2 is Co prepared in example 1 51.7 V 31.3 Ga 17 30 "mechanical training" plots of the alloy;
FIG. 3 is Co prepared in example 1 51.7 V 31.3 Ga 17 EBSD orientation profile of the alloy;
FIG. 4 is Co prepared in example 1 51.7 V 31.3 Ga 17 Room temperature stress-strain diagram of the alloy;
FIG. 5 is Co prepared in example 1 51.7 V 31.3 Ga 17 Adiabatic temperature change-time diagram of alloy;
FIG. 6 is Co prepared in example 2 51.7 V 31.3 Ga 16 Ti 1 DSC profile of the alloy;
FIG. 7 is Co prepared in example 2 51.7 V 31.3 Ga 16 Ti 1 EBSD orientation profile of the alloy;
FIG. 8 is Co prepared in example 2 51.7 V 31.3 Ga 16 Ti 1 Room temperature stress-strain diagram of the alloy;
FIG. 9 is Co prepared in example 2 51.7 V 31.3 Ga 16 Ti 1 Adiabatic temperature change-time diagram of alloy;
FIG. 10 is Co prepared in example 2 51.7 V 31.3 Ga 16 Ti 1 Room temperature superelasticity curve graph of alloy;
FIG. 11 is Co prepared in example 3 51.7 V 31.3 Ga 15 Ti 2 DSC profile of the alloy;
FIG. 12 is Co prepared in example 3 51.7 V 31.3 Ga 15 Ti 2 Room temperature stress-strain diagram of the alloy;
FIG. 13 is Co prepared in example 3 51.7 V 31.3 Ga 15 Ti 2 Adiabatic temperature change versus time diagram of an alloy.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
The first embodiment is as follows: the chemical general formula of the large elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy is Co 51.7 V 31.3 Ga 17-x Ti x ，0≤x≤3。
The brand new Co-V-Ga-Ti shape memory alloy has a spring heat effect different from that of a Co-V-Ga-Mn high spring heat effect memory alloy (patent number: CN 116479290A), the intrinsic difference is that the martensitic transformation driving stress of the Co-V-Ga-Mn shape memory alloy is relatively high (550 MPa), the Co-V-Ga-Ti shape memory alloy has a high spring heat effect of-10K at 400MPa, the stress hysteresis is only 21MPa, the coefficient of performance COP is 31.7, and the breaking strength is more than 1600MPa; the martensite phase transformation driving stress of the novel Co-V-Ga-Ti shape memory alloy is reduced by 150MPa, the stress hysteresis is reduced by 87MPa, and the coefficient of performance is improved by 13. The high performance coefficient shows that the stress hysteresis loss (stress-strain curve sealing area) is greatly reduced, and simultaneously, the lower driving stress and the extremely low stress hysteresis are very favorable for improving the cycle stability of the alloy material, so that the fatigue service life of the alloy can be greatly improved.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: when x=0, co 51.7 V 31.3 Ga 17 The alloy can generate adiabatic temperature change of-5.1K under 400MPa uniaxial stress. The other is the same as in the first embodiment.
And a third specific embodiment: the first difference between this embodiment and the specific embodiment is that: when x=1, co 51.7 V 31.3 Ga 16 Ti 1 The alloy can produce an adiabatic temperature change of-10K under 400MPa uniaxial stress. The other is the same as in the first embodiment.
The specific embodiment IV is as follows: the first difference between this embodiment and the specific embodiment is that: when x=2, co 51.7 V 31.3 Ga 17 Ti 2 The alloy can generate adiabatic temperature change of-4.8K under 400MPa uniaxial stress. The other is the same as in the first embodiment.
Fifth embodiment: the preparation method of the large elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy is completed according to the following steps:
1. preparing materials: according to the chemical general formula Co 51.7 V 31.3 Ga 17-x Ti x Preparing materials, wherein x is more than or equal to 0 and less than or equal to 3, respectively weighing a Co metal simple substance, a V metal simple substance, a Ga metal simple substance and a Ti metal simple substance as raw materials, and removing oxide skin on the surface layer of the metal simple substance;
2. arc melting: putting the raw materials into a copper crucible of a non-consumable high-vacuum arc melting furnace, and smelting after gas washing to obtain a smelted alloy cast ingot;
3. homogenizing heat treatment: and after the smelted alloy cast ingot is completely cooled, sealing and placing the cooled alloy cast ingot into a quartz tube filled with argon for homogenizing heat treatment, and then carrying out ice water cold quenching to obtain the large-elastic thermal effect polycrystalline Co-V-Ga-Ti-based memory alloy.
Specific embodiment six: the fifth difference between this embodiment and the third embodiment is that: in the first step, co is expressed as a chemical general formula 51.7 V 31.3 Ga 16 Ti is used for batching. The other is the same as in the fifth embodiment.
Seventh embodiment: the fifth difference between this embodiment and the third embodiment is that: and secondly, placing the Ga metal simple substance on the uppermost layer when the raw material is placed in a copper crucible of a non-consumable high-vacuum arc melting furnace. The other is the same as in the fifth embodiment.
According to the embodiment, the Ga metal simple substance is placed on the uppermost layer, other simple substances can be wrapped when the Ga metal simple substance is melted, and the phenomenon that the Ga metal simple substance is adhered to the crucible wall to cause inaccurate material components is avoided.
Eighth embodiment: the fifth difference between this embodiment and the third embodiment is that: the smelting after the gas washing in the second step specifically comprises the following steps: vacuumizing to 3×10 -3 Pa, then reversely charging protective high-purity argon to 5X 10 4 Pa; adjusting the smelting current to 50-500A, and smelting the raw materials into button ingots by utilizing a high-temperature electric arc. The other is the same as in the fifth embodiment.
Detailed description nine: this embodiment differs from the eighth embodiment in that: the single smelting time lasts for 2min; in order to ensure the components of the alloy to be uniform, after the primary smelting is finished, the ingot casting is repeatedly turned over and remelted for 4 times, and electromagnetic stirring is matched in the 4 smelting processes, wherein the stirring time is longer than 15s; before each smelting process, smelting high-purity Ti ingots to consume oxygen in an arc smelting furnace; and after smelting is completed, the power supply is turned off, and the ingot casting is cooled to room temperature by the water-cooled copper crucible. The other is the same as in the eighth embodiment.
Detailed description ten: this embodiment differs from the ninth embodiment in that: the melted alloy cast ingot obtained in the second step is cut into DSC test samples with the size of phi 3 multiplied by 1mm through linear cuttingA product for testing whether the alloy has a thermoelastic martensitic transformation; cut out 3X 6mm 3 The small cubic column sample is used for testing mechanical property and elasto-thermal property, and the used equipment is MTS E44 electronic universal experiment machine. The other steps are the same as those in the embodiment nine.
Eleventh embodiment: the fifth difference between this embodiment and the third embodiment is that: and polishing and cleaning in the third step, namely polishing the smelted alloy cast ingot with 300-mesh coarse sand paper and cleaning with acetone solution. The other is the same as in the fifth embodiment.
The following examples are used to verify the benefits of the present invention:
embodiment one: the preparation method of the large elastic thermal effect polycrystalline Co-V-Ga-Ti-based memory alloy is completed according to the following steps:
step one, material preparation: according to the chemical general formula Co 51.7 V 31.3 Ga 17 Preparing materials, namely weighing a Co metal simple substance, a V metal simple substance and a Ga metal simple substance as raw materials, wherein the purity of the raw materials is over 99.9;
step two, arc melting: placing the raw materials into a copper crucible of a non-consumable high vacuum arc melting furnace, and vacuumizing to 3×10 -3 Pa, then reversely charging protective high-purity argon to 5X 10 4 Pa; adjusting the smelting current to 50-500A, smelting the raw materials into button ingots by utilizing a high-temperature electric arc, wherein the single smelting time lasts for 2min; in order to ensure the components of the alloy to be uniform, after the primary smelting is finished, the ingot casting is repeatedly turned over and remelted for 4 times, and electromagnetic stirring is matched in the 4 smelting processes, wherein the stirring time is longer than 15s; before each smelting, high-purity Ti ingots are smelted to consume oxygen in an arc smelting furnace. After smelting is completed, turning off a power supply, and cooling the ingot to room temperature by a water-cooled copper crucible to obtain a button-type alloy ingot;
step three, homogenizing heat treatment: after the smelted alloy cast ingot is completely cooled, polishing and cleaning with alcohol, sealing the alloy cast ingot prepared in the second step into a quartz tube filled with argon, placing the quartz tube into a box-type resistance furnace, and carrying out homogenization heat treatment for 20 hours at 1473K to eliminate generation in the solidification processDendrite segregation of (2) and reduction of non-transition second phase content, and then taking out and placing in ice water for cold quenching to obtain Co with large elastic thermal effect 51.7 V 31.3 Ga 17 And (3) casting a shape memory alloy ingot. Co to be obtained 51.7 V 31.3 Ga 17 Cutting a DSC test sample with the size of phi 3 multiplied by 1mm from the shape memory alloy cast ingot through linear cutting, and testing whether the alloy has thermoelastic martensitic transformation or not; cut out 3X 6mm 3 The small cubic column sample is used for testing mechanical property and elasto-thermal property, and the used equipment is MTS E44 electronic universal experiment machine.
FIG. 1 is Co prepared in example one 51.7 V 31.3 Ga 17 DSC profile of the alloy. The thermal hysteresis of the alloy is 30K after the scanning speed of 40K/min is adopted, the phase transformation enthalpy is 8.1J/g, and the phase transformation entropy is 27J/kg.k. FIG. 2 is Co prepared in example one 51.7 V 31.3 Ga 17 The critical stress platform and the residual strain of the alloy after mechanical training are obviously reduced after 30 times of mechanical training stress strain curves of the alloy. FIG. 3 is Co prepared in example 1 51.7 V 31.3 Ga 17 The EBSD orientation profile of the alloy is seen to be that of<001> A Orientation, uneven distribution of internal grain size and large internal friction loss. FIG. 4 is Co prepared in example 1 51.7 V 31.3 Ga 17 Room temperature stress-strain curve of the alloy at loading and unloading rates of 0.3 and 3mm/s, the residual strain of the alloy is greater, resulting in Co as shown in FIG. 5 51.7 V 31.3 Ga 17 The room temperature unloading adiabatic temperature change of the alloy is only-5.1K.
Embodiment two: the preparation method of the large elastic thermal effect polycrystalline Co-V-Ga-Ti-based memory alloy prepared by the embodiment is completed according to the following steps:
step one, material preparation: according to the chemical formula Co 51.7 V 31.3 Ga 16 Ti 1 Preparing materials, namely weighing a Co metal simple substance, a V metal simple substance, a Ga metal simple substance and a Ti metal simple substance as raw materials;
step two, the high-purity metal simple substance C with the atomic percentage of 99.9 percent and more than 51.7:31.3:16:1 is preparedo, V, ga, ti placing into a water-cooled copper crucible of an arc melting furnace chamber, and placing Ga metal simple substance into the uppermost layer; vacuumizing to 3×10 -3 Pa, then reversely charging protective high-purity argon to 5X 10 4 Pa; adjusting the smelting current to 50-500A, smelting the raw materials into button ingots by utilizing a high-temperature electric arc, wherein the single smelting time lasts for 2min; in order to ensure the components of the alloy to be uniform, after the primary smelting is finished, the ingot casting is repeatedly turned over and remelted for 4 times, and electromagnetic stirring is matched in the 4 smelting processes, wherein the stirring time is longer than 15s; before each smelting, high-purity Ti ingots are smelted to consume oxygen in an arc smelting furnace. After smelting is completed, turning off a power supply, and cooling the ingot to room temperature by a water-cooled copper crucible to obtain a button-type alloy ingot;
step three, homogenizing heat treatment: after the smelted alloy cast ingot is completely cooled, polishing and cleaning with alcohol, sealing the alloy cast ingot prepared in the second step into a quartz tube filled with argon, placing the quartz tube into a box-type resistance furnace, performing homogenization heat treatment for 20 hours at 1473K to eliminate dendrite segregation generated in the solidification process and reduce the content of non-transition second phases, taking out, placing into ice water, and performing cold quenching to obtain Co with large elastic heating effect 51.7 V 31.3 Ga 16 Ti 1 And (3) casting a shape memory alloy ingot.
Co to be obtained 51.7 V 31.3 Ga 16 Ti 1 Cutting a DSC test sample with the size of phi 3 multiplied by 1mm from the shape memory alloy cast ingot through linear cutting, and testing whether the alloy has thermoelastic martensitic transformation or not; cut out 3X 6mm 3 The small cubic column sample is used for testing mechanical property and elasto-thermal property, and the used equipment is MTS E44 electronic universal experiment machine.
FIG. 6 is Co prepared in example 2 51.7 V 31.3 Ga 16 Ti 1 DSC curve graph of alloy shows that after Ti doping, its martensitic transformation characteristic temperature is lower than room temperature, thermal hysteresis is reduced to 23.5K, and transformation enthalpy is 7.8J/g. FIG. 7 is Co prepared in example 2 51.7 V 31.3 Ga 16 Ti 1 EBSD orientation profile of an alloy in which<001>The grain size distribution of the A orientation is uniform, which is beneficial toThe alloy has obviously improved elasto-thermal effect. FIG. 8 is Co prepared in example 2 51.7 V 31.3 Ga 16 Ti 1 The residual strain is further reduced by the room temperature stress-strain curve of the alloy. The change in room temperature adiabatic temperature at 0.3 and 3mm/s loading and unloading rates as shown in FIG. 9 was directly to-10K. For this purpose, the present invention further studied Co as shown in FIG. 10 51.7 V 31.3 Ga 16 Ti 1 Room temperature superelasticity graph of the alloy. The alloy stress hysteresis of the component is only 21MPa, and the coefficient of performance COP of the component reaches 31.7.
Embodiment III:
the preparation method of the large elastic thermal effect polycrystalline Co-V-Ga-Ti-based memory alloy prepared by the embodiment is completed according to the following steps:
step one, material preparation: according to the chemical formula Co 51.7 V 31.3 Ga 15 Ti 2 Preparing materials, namely weighing a Co metal simple substance, a V metal simple substance, a Ga metal simple substance and a Ti metal simple substance as raw materials;
step two, placing a high-purity metal simple substance Co, V, ga, ti with the atomic percentage of 99.9% or more of 51.7:31.3:15:2 into a water-cooled copper crucible of an arc melting furnace cavity, and placing a Ga metal simple substance at the uppermost layer; vacuumizing to 3×10 -3 Pa, then reversely charging protective high-purity argon to 5X 10 4 Pa; adjusting the smelting current to 50-500A, smelting the raw materials into button ingots by utilizing a high-temperature electric arc, wherein the single smelting time lasts for 2min; in order to ensure the components of the alloy to be uniform, after the primary smelting is finished, the ingot casting is repeatedly turned over and remelted for 4 times, and electromagnetic stirring is matched in the 4 smelting processes, wherein the stirring time is longer than 15s; before each smelting, high-purity Ti ingots are smelted to consume oxygen in an arc smelting furnace. After smelting is completed, turning off a power supply, and cooling the ingot to room temperature by a water-cooled copper crucible to obtain a button-type alloy ingot;
step three, homogenizing heat treatment: after the smelted alloy cast ingot is completely cooled, polishing and cleaning with alcohol, sealing the alloy cast ingot prepared in the second step into a quartz tube filled with argon, placing the quartz tube into a box-type resistance furnace, and carrying out homogenization heat treatment for 20 hours at 1473KRemoving dendrite segregation generated in the solidification process, reducing the content of non-transition second phase, taking out, and cold quenching in ice water to obtain Co with large elastic heat effect 51.7 V 31.3 Ga 15 Ti 2 And (3) casting a shape memory alloy ingot.
Co to be obtained 51.7 V 31.3 Ga 15 Ti 2 Cutting a DSC test sample with the size of phi 3 multiplied by 1mm from the shape memory alloy cast ingot through linear cutting, and testing whether the alloy has thermoelastic martensitic transformation or not; cut out 3X 6mm 3 The small cubic column sample is used for testing mechanical property and elasto-thermal property, and the used equipment is MTS E44 electronic universal experiment machine.
FIG. 11 shows example 3, co produced 51.7 V 31.3 Ga 15 Ti 2 DSC profile of the alloy. The phase transition enthalpy is 5.9J/g, and the phase transition entropy is 20J/kg.k. FIG. 12 shows Co prepared in example 3 51.7 V 31.3 Ga 15 Ti 2 Room temperature stress-strain curves for the alloys at 0.3 and 3mm/s loading and unloading rates. The component alloy can be fully recovered after stress relief, and the residual strain is almost 0. FIG. 13 is Co prepared in example 3 51.7 V 31.3 Ga 15 Ti 2 The adiabatic temperature change-time diagram of the alloy directly causes the unloading adiabatic temperature change of the alloy to be only-4.8K due to the lower phase change entropy change of the alloy.
The results of comparing the stress hysteresis, the driving stress and the coefficient of performance COP of the Co-V-Ga-Ti shape memory alloy and the Co-V-Ga-Mn shape memory alloy are shown in Table 1, and it is easy to see that the novel Co-V-Ga-Ti shape memory alloy of the invention has excellent elastic performance, greatly reduced driving stress and stress hysteresis, greatly improved coefficient of performance COP, very beneficial to the remarkable improvement of the circulation stability performance, and obvious technical advantages compared with the previous generation Co-V-Ga-Mn shape memory alloy.
The Co-V-Ga-Ti shape memory alloy with the large elastic thermal effect and the preparation method thereof provided by the embodiment of the application are described in detail. Compared with the existing solid-state stress refrigeration alloy material, the elastic heat refrigeration material provided by the invention has a larger and completely reversible elastic heat effect. Meanwhile, the material also has the characteristics of high toughness, low stress hysteresis, high coefficient of performance (COP) and the like, and the martensitic transformation temperature is slightly lower than the room temperature, so that the material is a good material for developing room temperature stress refrigerating working media.
TABLE 1 stress hysteresis, drive stress and coefficient of performance comparison results for Co-V-Ga-Ti and Co-V-Ga-Mn shape memory alloys
Claims (10)
1. A large elastic thermal effect polycrystal Co-V-Ga-Ti memory alloy is characterized in that the chemical formula of the large elastic thermal effect polycrystal Co-V-Ga-Ti memory alloy is Co 51.7 V 31.3 Ga 17-x Ti x ，0≤x≤3。
2. A large elasto-thermal effect polycrystalline Co-V-Ga-Ti memory alloy according to claim 1, characterized in that Co when x=0 51.7 V 31.3 Ga 17 The alloy can generate adiabatic temperature change of-5.1K under 400MPa uniaxial stress.
3. A large elasto-thermal effect polycrystalline Co-V-Ga-Ti memory alloy according to claim 1, characterized in that Co when x = 1 51.7 V 31.3 Ga 16 Ti 1 The alloy can produce an adiabatic temperature change of-10K under 400MPa uniaxial stress.
4. A large elasto-thermal effect polycrystalline Co-V-Ga-Ti memory alloy according to claim 1, characterized in that Co when x = 2 51.7 V 31.3 Ga 17 Ti 2 The alloy can generate adiabatic temperature change of-4.8K under 400MPa uniaxial stress.
5. The method for preparing the large elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy according to claim 1, wherein the method for preparing the large elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy is completed by the following steps:
1. preparing materials: according to the chemical general formula Co 51.7 V 31.3 Ga 17-x Ti x Preparing materials, wherein x is more than or equal to 0 and less than or equal to 3, respectively weighing a Co metal simple substance, a V metal simple substance, a Ga metal simple substance and a Ti metal simple substance as raw materials, and removing oxide skin on the surface layer of the metal simple substance;
2. arc melting: putting the raw materials into a copper crucible of a non-consumable high-vacuum arc melting furnace, and smelting after gas washing to obtain a smelted alloy cast ingot;
3. homogenizing heat treatment: and after the smelted alloy cast ingot is completely cooled, sealing and placing the cooled alloy cast ingot into a quartz tube filled with argon for homogenizing heat treatment, and then carrying out ice water cold quenching to obtain the large-elastic thermal effect polycrystalline Co-V-Ga-Ti-based memory alloy.
6. The method of preparing a polycrystalline Co-V-Ga-Ti memory alloy with a large elastic thermal effect according to claim 5, wherein Co is represented by the chemical formula in the first step 51.7 V 31.3 Ga 16 Ti is used for batching.
7. The method for preparing a large elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy according to claim 5, wherein the gas washing and smelting in the second step is specifically as follows: vacuumizing to 3×10 -3 Pa, then reversely charging protective high-purity argon to 5X 10 4 Pa; adjusting the smelting current to 50-500A, and smelting the raw materials into button ingots by utilizing a high-temperature electric arc.
8. The method for preparing the large elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy according to claim 7, wherein the single melting time lasts for 2min; in order to ensure the components of the alloy to be uniform, after the primary smelting is finished, the ingot casting is repeatedly turned over and remelted for 4 times, and electromagnetic stirring is matched in the 4 smelting processes, wherein the stirring time is longer than 15s; before each smelting process, smelting high-purity Ti ingots to consume oxygen in an arc smelting furnace; and after smelting is completed, the power supply is turned off, and the ingot casting is cooled to room temperature by the water-cooled copper crucible.
9. The method for producing a polycrystalline Co-V-Ga-Ti memory alloy having a large elastic thermal effect according to claim 5, wherein the molten alloy ingot obtained in the second step is cut to have a size of Φ3X1 mm by wire cutting 3 For testing whether the alloy has a thermoelastic martensitic transformation; cut out 3X 6mm 3 The small cubic column sample is used for testing mechanical property and elasto-thermal property, and the used equipment is MTS E44 electronic universal experiment machine.
10. The method for preparing a large elastic thermal effect polycrystalline Co-V-Ga-Ti memory alloy according to claim 5, wherein polishing and cleaning in the third step is to polish a melted alloy ingot with 300-mesh coarse sand paper and clean with acetone solution.
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