CN113737033A - Preparation method and material of Ti-Ni-Co elastic thermal refrigeration plate - Google Patents

Preparation method and material of Ti-Ni-Co elastic thermal refrigeration plate Download PDF

Info

Publication number
CN113737033A
CN113737033A CN202110998566.8A CN202110998566A CN113737033A CN 113737033 A CN113737033 A CN 113737033A CN 202110998566 A CN202110998566 A CN 202110998566A CN 113737033 A CN113737033 A CN 113737033A
Authority
CN
China
Prior art keywords
temperature
cold
elastic
thermal
rolled sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110998566.8A
Other languages
Chinese (zh)
Other versions
CN113737033B (en
Inventor
周玉美
张磊
党鹏飞
薛德祯
丁向东
孙军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN202110998566.8A priority Critical patent/CN113737033B/en
Publication of CN113737033A publication Critical patent/CN113737033A/en
Application granted granted Critical
Publication of CN113737033B publication Critical patent/CN113737033B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
    • B21C37/02—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets
    • 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
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]

Abstract

The invention discloses a preparation method of a Ti-Ni-Co elastic thermal refrigeration plate and a material thereof, wherein the preparation method comprises the following steps: according to the chemical general formula Ti of the elastic thermal refrigerating material49.2Ni50.8‑xCoxMixing high-purity metal Ti, Ni and Co particles according to the atomic ratio of metal elements Ti, Ni and Co, and smelting by adopting a non-consumable vacuum arc smelting method to obtain a polycrystalline ingot; carrying out high-temperature solid solution under a vacuum condition, quenching, mechanically grinding and polishing, and carrying out hot rolling to obtain a coarse-grained plate; water cooling quenching, and rolling for multiple times to obtain a cold-rolled sheet; cutting, sealing and storing the tube, performing medium-temperature aging treatment, and mechanically grinding and polishing; and (5) performing tube sealing storage again, performing low-temperature aging treatment, and mechanically grinding and polishing to obtain the Ti-Ni-Co elastic thermal refrigeration plate. The invention is based on TiNiOn the basis of heat insulation temperature change, the TiNiCo shape memory alloy with a wider elastic-thermal temperature zone and better elastic-thermal cycling stability is obtained by doping Co element and regulating and controlling a processing technology.

Description

Preparation method and material of Ti-Ni-Co elastic thermal refrigeration plate
Technical Field
The invention relates to preparation and application of a novel elastic thermal refrigeration material, in particular to preparation of a TiNiCo shape memory alloy plate with high elastic thermal cycle stability in a wide super elastic temperature range and a material thereof.
Background
After hundreds of years of scientific and technological development, the energy consumption of buildings, industry and transportation is three great factors for the development of national economy in China, wherein the energy consumption of the buildings and the industry is close to about 70 percent of the total energy consumption of the society, and the energy consumption of refrigeration is about 50 percent of the total energy consumption of the society. Also, with the rapid development of industrial technology in recent centuries, the explosive increase in refrigeration demand has brought about not only the problem of huge consumption of energy, but also other problems at the stake of human life. Until now, the most widely used refrigeration technology is still the conventional air refrigeration compressor, and although the conventional air compression refrigerator has the advantages of high coefficient of performance (COP), the used halogenated alkane refrigerant represented by Freon is combined with ozone to react after entering the atmosphere, so that ozone layer holes are formed.
The elastic heating refrigeration technology means that under the action of uniaxial compression or tensile stress on an elastic heating material (shape memory alloy), the material generates stress to induce martensite phase transformation, namely the elastic heating material generates transformation from austenite to martensite, phase transformation latent heat is released in the process, after an external load is removed, the elastic heating material generates a reverse phase transformation process from martensite to austenite, the phase transformation latent heat is absorbed, the temperature of the material is reduced, and the elastic heating refrigeration effect is obtained. The elastic thermal refrigeration effect is essentially the first-order martensite phase transformation of the material, and is regarded as an effective solid refrigeration mode because the elastic thermal refrigeration effect only relates to two-phase solid phase transformation. The TiNi-based shape memory alloy is the most widely applied shape memory alloy which is the most mature shape memory alloy in commercial use at present. The TiNi-based shape memory alloy has larger phase change latent heat due to the strong first-order phase change of the TiNi-based shape memory alloy, so the TiNi-based shape memory alloy has potential in the field of elastic heating refrigeration. However, the method is also limited by first-order martensitic transformation, and the TiNi-based shape memory alloy has the problems of high superelasticity temperature sensitivity, limited elastic-thermal temperature zone, severe elastic-thermal fatigue caused by thermal attenuation due to elastic-thermal effect, and the like, and is measured and indicated by a half-height wide elastic-thermal temperature zone (a temperature zone corresponding to a half value of maximum adiabatic temperature change) and an adiabatic temperature change attenuation value after multiple cycles, and the like. Taking a common TiNi binary system as an example, although the adiabatic temperature change value is as high as 10-25K, the half-height elastic temperature window is only about 50K, the super elastic temperature window is about 70K, the adiabatic temperature change attenuation is serious after multiple elastic thermal cycles, and some materials are even as high as more than 5K, which limits the engineering application of the shape memory alloy in some fields. Therefore, the method has important engineering significance for reducing the super-elastic temperature sensitivity of the elastic thermal material, widening the elastic thermal temperature zone and the half-height wide elastic thermal temperature window and improving the elastic thermal fatigue resistance of the material.
Disclosure of Invention
The invention aims to provide a preparation method of a Ti-Ni-Co elastic thermal refrigeration plate, which effectively widens the elastic thermal temperature zone of the TiNi-based shape memory alloy and improves the elastic thermal fatigue property of the TiNi-based shape memory alloy, reduces the super elastic temperature sensitivity of the elastic thermal material, widens the elastic thermal temperature zone and the half-height wide elastic thermal temperature window, and improves the elastic thermal fatigue resistance and the high cycle stability of the material by combining element doping, processing strengthening and aging strengthening.
The technical scheme adopted by the invention is as follows:
in one aspect of the invention, a preparation method of a Ti-Ni-Co elastic-thermal refrigeration plate is provided, which comprises the following steps:
step 1, according to the chemical general formula of the elastic thermal refrigerating material Ti49.2Ni50.8-xCoxThe atomic ratio of the metal elements Ti, Ni and Co in the formula is that high-purity metal Ti, Ni and Co particles are mixed, wherein x is more than or equal to 1 and less than 6;
step 2, adopting a non-consumable vacuum arc melting method, adopting high-frequency arc striking under the protection atmosphere of argon and under the vacuum condition, controlling the melting current, and melting under magnetic stirring to obtain a polycrystalline ingot;
step 3, carrying out high-temperature solid melting on the polycrystalline ingot under a vacuum condition, then carrying out water-cooling quenching, and mechanically grinding and polishing an oxide layer on the surface of the quenched polycrystalline ingot;
step 4, carrying out hot rolling treatment on the cast ingot after the solid solution grinding and polishing to obtain a coarse-grained plate, and carrying out water cooling quenching;
step 5, rolling the quenched coarse-grained plate at room temperature, repeatedly rolling for multiple times in each pass, and controlling the cold rolling deformation to obtain a cold-rolled plate;
step 6, mechanically grinding and polishing the surface of the cold-rolled sheet, and cutting the cold-rolled sheet into the cold-rolled sheet;
step 7, selecting a quartz tube to seal and store the cold-rolled sheet after cold rolling;
step 8, performing medium-temperature aging treatment on the cold-rolled sheet preserved by the sealed tube, and then performing water-cooling quenching;
step 9, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically polishing the surface oxide skin of the cold-rolled sheet;
step 10, performing tube sealing storage on the cold-rolled sheet subjected to mechanical polishing treatment again, and repeating the step 7;
step 11, performing low-temperature aging treatment on the sample for pipe sealing, and performing water-cooling quenching on the sample after the low-temperature aging treatment;
and step 12, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically polishing the surface oxide skin of the cold-rolled sheet to obtain the Ti-Ni-Co elastic thermal refrigeration sheet.
In step 2, the degree of vacuum of melting is 5X 10-3The method comprises the following steps of (1) adding magnetic stirring for 5A for 1min under the conditions of more than Pa, 0.05MPa of argon protective gas and smelting current of 250-300A; after each round of melting, the sample is melted by turning over for 5 times or more.
In step 3, the high-temperature solid solution vacuum degree is 5 multiplied by 10-2Pa, and keeping the temperature at 1000 ℃ for 1-12 h.
And step 4, carrying out heat preservation on the cast ingot subjected to solid solution grinding and polishing at the temperature of 800-.
In the step 5, the pressing down is 0.05-0.1mm per pass, the cold rolling deformation is 30-60%, and the thickness of the cold-rolled sheet is 1.25-1.75 mm.
In step 7, the vacuum degree in the tube body of the quartz tube is 1 multiplied by 10-3Pa above, introducing 0.05MPa argon into the quartz tubeAnd (4) protective gas is filled, and the pipe body is sealed.
In the step 8, the medium temperature aging temperature is 400-.
In the step 11, the low-temperature aging temperature is 250-300 ℃, and the temperature is kept for 24-72 h.
On the other hand, the invention provides the Ti-Ni-Co elastic thermal refrigeration material prepared by the method, and the chemical general formula of the elastic thermal refrigeration material is Ti49.2Ni50.8-XCox，1≤x＜6。
The Ti-Ni-Co elastic thermal refrigeration material prepared by the method has a nanocrystalline structure, and the grain size is below hundred nanometers.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
by Co element doping, cold rolling processing and medium-temperature and low-temperature two-step aging treatment, the stress field generated by precipitates formed by element doping and aging inhibits the first-order martensitic phase transformation, promotes the martensitic phase transformation from long-range transformation to short-range transformation, promotes the phase transformation dispersion and simultaneously reduces the volume change before and after the phase transformation. The method reduces the probability of dislocation introduction in the phase change process while reducing the temperature sensitivity of the superelasticity, thereby realizing the synchronous promotion of the elastic thermal temperature zone, the half-height wide elastic thermal temperature window and the elastic thermal cycle stability.
The TiNiCo shape memory alloy bomb thermal refrigeration material provided by the invention has a bomb thermal temperature zone of 90K-120K and a full width at half maximum bomb thermal temperature window of 60-120K, has a wide temperature range bomb thermal characteristic, and has a good bomb thermal fatigue resistance characteristic, wherein after 50 times of bomb thermal cycles, the absolute attenuation value of the thermal insulation temperature change of the TiNiCo bomb thermal refrigeration material is within 2.5K, and the relative attenuation value of the thermal insulation temperature change is less than or less than 10%.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:
FIG. 1 is a technical circuit of TiNiCo bomb thermal refrigerating material of the invention.
Fig. 2 is a schematic view of a DSC curve of temperature increase and decrease in the embodiment 1 of the TiNiCo bomb thermal refrigerating material of the present invention.
FIG. 3 is a schematic diagram of the thermal cycle performance of the TiNiCo bomb in example 1 of the invention.
FIG. 4 is a schematic view of the temperature-changing elastic-thermal properties of the TiNiCo elastic thermal refrigeration material of the embodiment 1 of the invention.
Fig. 5 is a schematic view of a DSC curve of temperature increase and decrease in the embodiment 2 of the TiNiCo bomb thermal refrigerating material of the present invention.
FIG. 6 is a schematic diagram of the thermal cycle performance of the TiNiCo bomb refrigeration material of the invention in example 2.
FIG. 7 is a schematic view of the temperature-changing elastic-thermal properties of the TiNiCo elastic thermal refrigeration material of the embodiment 2 of the invention.
Fig. 8 is a schematic view of a DSC curve of temperature increase and decrease in a TiNiCo bomb thermal refrigerating material of example 3 of the present invention.
FIG. 9 is a schematic diagram of the thermal cycle performance of the TiNiCo bomb in example 3 of the thermal refrigeration material of the invention.
FIG. 10 is a schematic view of the temperature-changing elastic-thermal properties of the TiNiCo elastic thermal refrigeration material of the embodiment 3 of the invention.
Fig. 11 is a schematic view of a DSC curve of temperature increase and decrease in a TiNiCo bomb thermal refrigerating material of embodiment 4 of the present invention.
FIG. 12 is a schematic diagram of the thermal cycle performance of the TiNiCo bomb as an example 4 of the thermal refrigeration material of the invention.
Fig. 13 is a schematic view of the temperature-changing elastic-thermal performance of the TiNiCo elastic-thermal refrigeration material of the embodiment 4 of the present invention.
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions of the present invention are provided to explain the present invention without limiting the invention thereto.
As shown in FIG. 1, the invention provides a preparation method of a TiNiCo bomb thermal refrigeration material, which comprises the following steps:
step 1, according to the chemical general formula of the elastic thermal refrigerating material Ti49.2Ni50.8-xCoxThe atomic ratio of metal elements Ti, Ni and Co in the formula is that 99.5 percent of high-purity metal Ti, Ni and Co particles are mixed, wherein x is more than or equal to 1 and less than 6.
Step 2, melting by adopting a non-consumable vacuum arc melting methodSmelting to obtain a polycrystalline ingot: the furnace body is pumped for multiple times by a mechanical pump and a molecular pump until the vacuum degree in the furnace body reaches 5 multiplied by 10-3And introducing argon protective gas of 0.05MPa into the furnace body after the pressure is higher than Pa to achieve an arc striking condition. And then arc striking is carried out at high frequency, the smelting current is controlled to be 250-300A, magnetic stirring is added for 5A, the time is 1min, after each round of smelting, in order to ensure that the components are uniform, the sample needs to be turned over, and the turning-over smelting is carried out for 5 times or more, so that the polycrystalline ingot is finally obtained.
Step 3, carrying out high-temperature solid melting on the polycrystalline ingot under a vacuum condition: putting the polycrystal ingot into a vacuum tube furnace, and extracting the polycrystal ingot with the vacuum degree of 5 multiplied by 10-2And (3) keeping the temperature of Pa and 1000 ℃ for 1-12h, then performing water-cooling quenching, and mechanically polishing an oxide layer on the surface of the quenched polycrystalline ingot.
Step 4, carrying out hot rolling treatment on the cast ingot after the solid solution grinding polishing: and (3) preserving the temperature of the ingot after the solid solution at 800-1100 ℃ for 15min, and carrying out hot rolling treatment after the ingot is completely hot. And during hot rolling, controlling the downward pressing of each pass to be 0.05-0.2mm, finally obtaining a coarse-grained plate with the thickness of about 2.5mm, and carrying out water-cooling quenching treatment on the coarse-grained plate.
And 5, rolling the quenched coarse-grained plate at room temperature: and (3) pressing down by 0.05-0.1mm in each pass, repeatedly rolling for multiple times in each pass, and finally controlling the cold rolling deformation to be 30-60% to obtain the plate with the thickness of 1.25-1.75 mm.
And 6, mechanically grinding and polishing the surface of the cold-rolled sheet, and processing the cold-rolled sheet into a rectangular cold-rolled sheet with the length of 120mm and the width of 9mm through electric spark cutting.
And 7, selecting a quartz tube to seal the cold-rolled sheet after cold rolling for storage: and (4) selecting a quartz tube with the inner diameter of 10mm to seal and store the cold-rolled sample. The method specifically comprises the following steps: the tube body is pumped for multiple times by a mechanical pump and a diffusion pump in a low-high pumping way until the vacuum degree in the tube body reaches 1 multiplied by 10-3And after the pressure is higher than Pa, introducing argon protective gas of 0.05MPa into the quartz tube, and then burning the quartz tube through hydrogen to seal the tube body so as to achieve the inert gas protection condition.
And 8, performing medium-temperature aging treatment on the cold-rolled sheet stored in the sealed tube, wherein the aging temperature is 400-550 ℃, the aging time is 0.2-2h, quenching the sample subjected to medium-temperature aging treatment, and performing mechanical grinding and polishing treatment on the oxide skin on the surface of the cut sample.
And 9, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically polishing the surface oxide skin of the cold-rolled sheet.
Step 10, performing tube sealing storage on the cold-rolled sheet subjected to mechanical polishing treatment again, and repeating the step 7;
step 11, performing low-temperature aging treatment on the sample with the sealed tube, wherein the aging temperature is 250-300 ℃, preserving heat for 24-72h, and performing water-cooling quenching on the sample after low-temperature aging;
and step 12, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically polishing the surface oxide skin of the cold-rolled sheet to obtain the Ti-Ni-Co elastic thermal refrigeration sheet.
The invention is further illustrated by the following specific examples.
Example 1:
the TiNiCo elastic thermal refrigeration material alloy component is Ti49.2Ni49.8Co1The preparation process comprises the following steps:
firstly, Ti is mixed according to atom percentage49.2Ni49.8Co1Weighing 99.5 percent of high-purity Ti, Ni and Co metal particle raw materials.
Secondly, uniformly mixing the weighed metal raw materials, placing the metal raw materials in a vacuum arc melting Cu crucible, and preparing an original ingot by adopting a non-consumable vacuum arc melting method;
the specific smelting conditions are as follows: the furnace body is pumped for multiple times by a mechanical pump and a molecular pump until the vacuum degree in the furnace body reaches 5 multiplied by 10-3And introducing argon protective gas of 0.05MPa into the furnace body after the pressure is higher than Pa to achieve an arc striking condition. At the moment, arc striking is carried out at high frequency, the smelting current is controlled to be 250A, magnetic stirring is added for 5A, the time is 1min, after each round of smelting, in order to ensure that the components are uniform, a sample needs to be turned over, and turning-over smelting is carried out for 5 times or more, so that polycrystalline Ti is obtained49.2Ni49.8Co1Casting ingots;
thirdly, solid solution homogenization heat treatment. Mixing Ti49.2Ni49.8Co1Putting the cast ingot into a vacuum tube furnace, and extracting the cast ingot with the vacuum degree of 5 multiplied by 10-2Keeping the temperature of Pa and 1000 ℃ for 5 hours, and then quickly quenching by water coolingAnd mechanically polishing the surface oxide layer.
And fourthly, preserving the temperature of the obtained cast ingot at 1000 ℃ for 15min, and carrying out hot rolling treatment after the cast ingot is completely hot. During hot rolling, the reduction of each pass is controlled to be 0.2mm, and coarse-grained Ti with the thickness of 2.4mm is finally obtained49.2Ni49.8Co1And quenching the plate.
And fifthly, rolling the obtained coarse-grained plate at room temperature, wherein the reduction of each pass is 0.05mm, the rolling is repeated for multiple times, and finally the cold rolling deformation is controlled to be 45% to obtain the plate with the thickness of 1.32 mm.
And sixthly, performing surface mechanical grinding and polishing treatment on the cold-rolled sheet, and processing the cold-rolled sheet into a rectangular cold-rolled sheet with the length of 120mm and the width of 9mm through electric spark cutting.
And seventhly, selecting a quartz tube with the inner diameter of 10mm to seal and store the cold-rolled sample. The method specifically comprises the following steps: the tube body is pumped for multiple times by a mechanical pump and a diffusion pump in a low-high pumping way until the vacuum degree in the tube body reaches 1 multiplied by 10-3And after the pressure is higher than Pa, introducing argon protective gas of 0.05MPa into the quartz tube, and then burning the quartz tube through hydrogen to seal the tube body so as to achieve the inert gas protection condition.
And eighthly, performing medium-temperature aging treatment on the cold-rolled sheet stored in the sealed tube, wherein the aging temperature is 400 ℃, the aging time is 1h, then quenching the sample after medium-temperature aging treatment, and performing mechanical grinding and polishing treatment on oxide skin on the surface of the cut sample.
And ninthly, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically polishing the surface oxide skin of the cold-rolled sheet.
And step ten, sealing and storing the sample after the medium-temperature aging, wherein the operation steps and the operation requirements are the same as those of the step six.
Step ten, performing low-temperature aging treatment on the medium-temperature aging sample after the tube sealing preservation, wherein the aging temperature is 250 ℃, preserving the heat for 48 hours, and performing water-cooling quenching on the sample after the low-temperature aging treatment;
step eleven, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically grinding and polishing the oxide skin on the surface of the cut sample to obtain the final Ti49.2Ni49.8Co1A nanocrystalline sheet.
As shown in FIG. 2, FIG. 2 is Ti49.2Ni49.8Co1The DSC curve diagram of the alloy shows that the test temperature is-150-65 ℃, the temperature rise and fall rate is 10K/min, and the processing technology inhibits the martensite phase transformation, the phase transformation peak is weak, and the first-order phase transformation characteristic is weakened. Example 1 there was a temperature induced martensitic transformation and an R transformation, RfThe value is 39.5 c, and at room temperature, the alloy is completely austenitic.
As shown in FIG. 3, FIG. 3 is Ti49.2Ni49.8Co1The alloy thermal cycle performance diagram of 50 times elasticity is shown, the test temperature is 50 ℃, the sample is slowly loaded to 800MPa and then quickly unloaded, the loading rate is 0.84mm/min, and the unloading rate is 42mm/min so as to simulate the heat insulation environment. Measuring Ti49.2Ni49.8Co1The initial cycle heat insulation temperature change of the alloy reaches 24.01K, after 50 cycles, the heat insulation temperature change of the alloy is attenuated to 21.71K, the absolute attenuation of the heat insulation temperature change is 2.3K, the relative reduction is 9.5%, the heat insulation temperature change is lower than that of TiNi binary alloy, and good elastic thermal cycle stability is shown.
As shown in FIG. 4, FIG. 4 is Ti49.2Ni49.8Co1Schematic diagram of alloy variable-temperature elastic thermal property. As shown in the figure, Ti49.2Ni49.8Co1The alloy shows an elastic thermal temperature zone of 283K to 363K, 60K in total, and the half-height wide elastic thermal temperature window is 61K.
Overall, Ti in example 149.2Ni49.8Co1The alloy shows better wide temperature range and better cycle stable elastic-thermal property.
Example 2:
the TiNiCo elastic thermal refrigeration material alloy component is Ti49.2Ni48.8Co2The preparation process comprises the following steps:
firstly, Ti is mixed according to atom percentage49.2Ni48.8Co2Weighing 99.5 percent of high-purity Ti, Ni and Co metal particle raw materials.
Secondly, uniformly mixing the weighed metal raw materials, placing the metal raw materials in a vacuum arc melting Cu crucible, and preparing an original ingot by adopting a non-consumable vacuum arc melting method;
the specific smelting conditions are as follows: the furnace body is pumped for multiple times by a mechanical pump and a molecular pump until the vacuum degree in the furnace body reaches 5 multiplied by 10-3And introducing argon protective gas of 0.05MPa into the furnace body after the pressure is higher than Pa to achieve an arc striking condition. At the moment, arc striking is carried out at high frequency, the smelting current is controlled to be 280A, magnetic stirring is added for 5A, the time is 1min, after each round of smelting, in order to ensure that the components are uniform, a sample needs to be turned over, and turning-over smelting is carried out for 5 times or more, so that polycrystalline Ti is obtained49.2Ni48.8Co2And (5) ingot casting.
Thirdly, solid solution homogenization heat treatment. Mixing Ti49.2Ni48.8Co2Putting the cast ingot into a vacuum tube furnace, and extracting the cast ingot with the vacuum degree of 5 multiplied by 10-2And (3) after the temperature is kept for 2h at the temperature of 1000 ℃ under Pa, rapidly quenching, and mechanically grinding and polishing the surface oxide layer.
And fourthly, preserving the temperature of the obtained cast ingot at 800 ℃ for 15min, and carrying out hot rolling treatment after the cast ingot is completely hot. During hot rolling, the reduction of each pass is controlled to be 0.1mm, and coarse-grained Ti with the thickness of 2.52mm is finally obtained49.2Ni48.8Co2And quenching the plate.
And fifthly, rolling the obtained coarse-grained plate at room temperature, pressing down by 0.1mm in each pass, repeatedly rolling for multiple times in each pass, and finally controlling the cold rolling deformation to be 44% to obtain the plate with the thickness of 1.41 mm.
And sixthly, performing surface mechanical grinding and polishing treatment on the cold-rolled sheet, and processing the cold-rolled sheet into a rectangle with the length of 120mm and the width of 9mm through electric spark cutting.
And seventhly, selecting a quartz tube with the inner diameter of 10mm to seal and store the cold-rolled sample. The method specifically comprises the following steps: the vacuum degree in the tube body reaches 1 multiplied by 10 after the low-high tube body is pumped by a mechanical pump and a diffusion pump-3And after the pressure is higher than Pa, introducing argon protective gas of 0.05MPa into the quartz tube, and then burning the quartz tube through hydrogen to seal the tube body so as to achieve the inert gas protection condition.
And eighthly, performing medium-temperature aging treatment on the cold-rolled sheet stored in the sealed tube, wherein the aging temperature is 450 ℃, the aging time is 1.5h, then quenching the sample subjected to medium-temperature aging treatment, and performing mechanical grinding and polishing treatment on oxide skin on the surface of the cut sample.
And ninthly, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically polishing the surface oxide skin of the cold-rolled sheet.
And step ten, sealing and storing the sample after the medium-temperature aging, wherein the operation steps and the operation requirements are the same as those of the step six.
Step ten, performing low-temperature aging treatment on the medium-temperature aging sample after the tube sealing preservation, wherein the aging temperature is 280 ℃, preserving the heat for 72 hours, and performing water-cooling quenching on the sample after the low-temperature aging treatment;
step eleven, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically grinding and polishing the oxide skin on the surface of the cut sample to obtain the final Ti49.2Ni48.8Co2A nanocrystalline sheet.
As shown in FIG. 5, FIG. 5 is Ti49.2Ni48.8Co2The DSC curve diagram of the alloy shows that the test temperature is-150-65 ℃, the temperature rise and fall rate is 10K/min, and the curve shows that the processing technology greatly inhibits the martensite phase transformation, the phase transformation peak is weakly dispersed, and the phase transformation characteristic is weakened. Example 2 there is only a temperature induced R phase transition, RfThe value is 20 ℃, so that at room temperature the alloy is completely austenitic.
As shown in FIG. 6, FIG. 6 is Ti49.2Ni48.8Co2The alloy thermal cycle performance diagram of 50 times elasticity is shown, the test temperature is-10 ℃, the sample is slowly loaded to 700MPa and then quickly unloaded, the loading rate is 0.84mm/min, and the unloading rate is 42mm/min so as to simulate the heat insulation environment. Measuring Ti49.2Ni48.8Co2The initial circulation heat insulation temperature change of the alloy reaches 13.65K, after 50 times of circulation, the heat insulation temperature change of the alloy is attenuated to 12.68K, the absolute attenuation of the heat insulation temperature change is only 0.97K, the relative reduction is 7%, the heat insulation temperature change is lower than that of the TiNi binary alloy, and the elastic thermal fatigue resistance is good; showing better elastic thermal cycling stability.
As shown in FIG. 7, FIG. 7 is Ti49.2Ni48.8Co2Schematic diagram of alloy variable-temperature elastic thermal property. As shown in the figure, Ti49.2Ni48.8Co2The alloy exhibits 233K to 323K, in totalThe half-height wide elastic thermal temperature window of the elastic thermal temperature zone of 90K reaches 62K, which is higher than the level of the TiNi binary alloy.
Overall, Ti in example 249.2Ni48.8Co2The alloy shows better wide temperature range and high cycle stability elastic-thermal characteristics.
Example 3:
the TiNiCo elastic thermal refrigeration material alloy component is Ti49.2Ni46.8Co4The preparation process comprises the following steps:
firstly, Ti is mixed according to atom percentage49.2Ni46.8Co4Weighing 99.5 percent of high-purity Ti, Ni and Co metal particle raw materials.
Secondly, uniformly mixing the weighed metal raw materials, placing the metal raw materials in a vacuum arc melting Cu crucible, and preparing an original ingot by adopting a non-consumable vacuum arc melting method;
the specific smelting conditions are as follows: the furnace body is pumped for multiple times by a mechanical pump and a molecular pump until the vacuum degree in the furnace body reaches 5 multiplied by 10-3And introducing argon protective gas of 0.05MPa into the furnace body after the pressure is higher than Pa to achieve an arc striking condition. At the moment, arc striking is carried out at high frequency, the smelting current is controlled to be 300A, magnetic stirring is added for 5A, the time is 1min, after each round of smelting, in order to ensure that the components are uniform, a sample needs to be turned over, and turning-over smelting is carried out for 5 times or more, so that polycrystalline Ti is obtained49.2Ni46.8Co4Casting ingots;
thirdly, solid solution homogenization heat treatment. Mixing Ti49.2Ni46.8Co4Putting the cast ingot into a vacuum tube furnace, and extracting the cast ingot with the vacuum degree of 5 multiplied by 10-2And (3) after the temperature is kept for 1h at the temperature of 1000 ℃ under Pa, rapidly carrying out water cooling quenching, and carrying out mechanical grinding and polishing treatment on the surface oxide layer.
And fourthly, preserving the temperature of the obtained cast ingot at 1100 ℃ for 15min, and carrying out hot rolling treatment after the cast ingot is completely hot. During hot rolling, the reduction of each pass is controlled to be 0.15mm, and coarse-grained Ti with the thickness of 2.45mm is finally obtained49.2Ni46.8Co4And quenching the plate.
And fifthly, rolling the obtained coarse-grained plate at room temperature, pressing down by 0.08mm in each pass, repeatedly rolling in each pass for multiple times, and finally controlling the cold rolling deformation to be 60% to obtain the plate with the thickness of 1.25 mm.
And sixthly, performing surface mechanical grinding and polishing treatment on the cold-rolled sheet, and processing the cold-rolled sheet into a rectangular cold-rolled sheet with the length of 120mm and the width of 9mm through electric spark cutting.
And seventhly, selecting a quartz tube with the inner diameter of 10mm to seal and store the cold-rolled sample. The method specifically comprises the following steps: the tube body is pumped for multiple times by a mechanical pump and a diffusion pump in a low-high pumping way until the vacuum degree in the tube body reaches 1 multiplied by 10-3And after the pressure is higher than Pa, introducing argon protective gas of 0.05MPa into the quartz tube, and then burning the quartz tube through hydrogen to seal the tube body so as to achieve the inert gas protection condition.
And eighthly, performing medium-temperature aging treatment on the cold-rolled sheet stored in the sealed tube, wherein the aging temperature is 500 ℃, the aging time is 2 hours, then quenching the sample subjected to medium-temperature aging treatment, and performing mechanical grinding and polishing treatment on oxide skin on the surface of the cut sample.
And ninthly, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically polishing the surface oxide skin of the cold-rolled sheet.
And step ten, sealing and storing the sample after the medium-temperature aging, wherein the operation steps and the operation requirements are the same as those of the step six.
Step ten, performing low-temperature aging treatment on the medium-temperature aging sample after the tube sealing preservation, wherein the aging temperature is 300 ℃, preserving the heat for 24 hours, and performing water-cooling quenching on the sample after the low-temperature aging treatment;
step eleven, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically grinding and polishing the oxide skin on the surface of the cut sample to obtain the final Ti49.2Ni46.8Co4A nanocrystalline sheet.
As shown in FIG. 8, FIG. 8 is Ti49.2Ni46.8Co4The DSC curve diagram of the alloy shows that the test temperature is-150-65 ℃, the temperature rise and fall rate is 10K/min, and the curve shows that the processing technology greatly inhibits the martensite phase transformation, the phase transformation peak is weak, the first-order phase transformation characteristic is weakened, and the phase transformation enthalpy can not be counted. Example 3 there is only a temperature induced R phase transition, RfThe value is 7 c, so at room temperature the alloy is completely austenitic.
As shown in FIG. 9, FIG. 9 is Ti49.2Ni46.8Co4The alloy thermal cycle performance diagram of 50 times elasticity is shown, the test temperature is-60 ℃, the sample is slowly loaded to 700MPa and then quickly unloaded, the loading rate is 0.84mm/min, and the unloading rate is 42mm/min so as to simulate the heat insulation environment. Measuring Ti49.2Ni46.8Co4The initial cycle heat insulation temperature change of the alloy reaches 8.75K, after 50 cycles, the heat insulation temperature change of the alloy is attenuated to 8.71K, the absolute attenuation of the heat insulation temperature change is only 0.04K, the relative reduction is 0.4%, the absolute attenuation is far lower than the level of the TiNi binary alloy, the elastic thermal fatigue resistance is good, and the elastic thermal cycle stability is excellent.
As shown in FIG. 10, FIG. 10 is Ti49.2Ni46.8Co4Schematic diagram of alloy variable-temperature elastic thermal property. As shown in the figure, Ti49.2Ni46.8Co4The alloy shows 173K to 273K, and the total 100K elastic thermal temperature range, the half-height wide elastic thermal temperature window of the alloy reaches 80K, which is far higher than the 70K elastic thermal temperature range of the TiNi binary alloy and the level of 50K half-height wide elastic thermal temperature window.
Overall, Ti in example 349.2Ni46.8Co4The alloy shows excellent wide temperature range and high cycle stability elastic-thermal characteristics.
Example 4:
the TiNiCo elastic thermal refrigeration material alloy component is Ti49.2Ni44.8Co6The preparation process comprises the following steps:
firstly, Ti is mixed according to atom percentage49.2Ni44.8Co6Weighing 99.5 percent of high-purity Ti, Ni and Co metal particle raw materials.
Secondly, uniformly mixing the weighed metal raw materials, placing the metal raw materials in a vacuum arc melting Cu crucible, and preparing an original ingot by adopting a non-consumable vacuum arc melting method;
the specific smelting conditions are as follows: the furnace body is pumped for multiple times by a mechanical pump and a molecular pump until the vacuum degree in the furnace body reaches 5 multiplied by 10-3And introducing argon protective gas of 0.05MPa into the furnace body after the pressure is higher than Pa to achieve an arc striking condition. At the moment, arc striking is carried out at high frequency, the smelting current is controlled to be 270A, magnetic stirring is added for 5A, the duration is 1min, and each round of smelting is carried outThen, in order to ensure the components to be uniform, the sample needs to be turned over, and the sample is turned over and smelted for 5 times or more to obtain the polycrystalline Ti49.2Ni44.8Co6And (5) ingot casting.
Thirdly, solid solution homogenization heat treatment. Mixing Ti49.2Ni44.8Co6Putting the cast ingot into a vacuum tube furnace, and extracting the cast ingot with the vacuum degree of 5 multiplied by 10-2And (3) after the temperature is kept for 12h at the temperature of 1000 ℃ under Pa, rapidly quenching, and mechanically grinding and polishing the surface oxide layer.
And fourthly, preserving the temperature of the obtained cast ingot at 950 ℃ for 15min, and carrying out hot rolling treatment after the cast ingot is completely hot. During hot rolling, the reduction of each pass is controlled to be 0.05mm, and coarse-grained Ti with the thickness of 2.48mm is finally obtained49.2Ni44.8Co6And quenching the plate.
And fifthly, rolling the obtained coarse-grained plate at room temperature, pressing down by 0.06mm in each pass, repeatedly rolling for multiple times in each pass, and finally controlling the cold rolling deformation to be 30% to obtain the plate with the thickness of 1.75 mm.
And sixthly, performing surface mechanical grinding and polishing treatment on the cold-rolled sheet, and processing the cold-rolled sheet into a rectangle with the length of 120mm and the width of 9mm through electric spark cutting.
And seventhly, selecting a quartz tube with the inner diameter of 10mm to seal and store the cold-rolled sample. The method specifically comprises the following steps: the vacuum degree in the tube body reaches 1 multiplied by 10 after the low-high tube body is pumped by a mechanical pump and a diffusion pump-3And after the pressure is higher than Pa, introducing argon protective gas of 0.05MPa into the quartz tube, and then burning the quartz tube through hydrogen to seal the tube body so as to achieve the inert gas protection condition.
And eighthly, performing medium-temperature aging treatment on the cold-rolled sheet stored in the sealed tube, wherein the aging temperature is 550 ℃, the aging time is 0.2h, then quenching the sample subjected to medium-temperature aging treatment, and performing mechanical grinding and polishing treatment on oxide skin on the surface of the cut sample.
And ninthly, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically polishing the surface oxide skin of the cold-rolled sheet.
And step ten, sealing and storing the sample after the medium-temperature aging, wherein the operation steps and the operation requirements are the same as those of the step six.
Step ten, performing low-temperature aging treatment on the medium-temperature aging sample after the tube sealing preservation, wherein the aging temperature is 270 ℃, preserving the heat for 36 hours, and performing water-cooling quenching on the sample after the low-temperature aging treatment;
step eleven, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically grinding and polishing the oxide skin on the surface of the cut sample to obtain the final Ti49.2Ni44.8Co6A nanocrystalline sheet.
As shown in FIG. 11, FIG. 11 is Ti49.2Ni44.8Co6The DSC curve diagram of the alloy shows that the test temperature is-150-50 ℃, the temperature rise and fall rate is 10K/min, and the curve shows that the processing technology greatly inhibits the martensite phase transformation, the phase transformation peak is weakly dispersed, the phase transformation characteristic disappears, and the phase transformation enthalpy and the phase transformation temperature can not be effectively counted.
As shown in FIG. 12, FIG. 12 is Ti49.2Ni44.8Co6The alloy thermal cycle performance diagram of 50 times elasticity is shown, the testing temperature is-90 ℃, the sample is slowly loaded to 820MPa and then quickly unloaded, the loading rate is 0.84mm/min, and the unloading rate is 42mm/min so as to simulate the heat insulation environment. Measuring Ti49.2Ni44.8Co6The initial cycle heat insulation temperature change of the alloy reaches 6.72K, after 50 cycles, the heat insulation temperature change of the alloy is attenuated to 6.53K, the absolute attenuation of the heat insulation temperature change is only 0.19K, the relative reduction is 2.8%, the heat insulation temperature change is far lower than that of a TiNi binary alloy, and the heat insulation temperature change has good elasticity and thermal fatigue resistance; exhibit excellent elastic thermal cycle stability.
As shown in fig. 13, fig. 13 is Ti49.2Ni44.8Co6Schematic diagram of alloy variable-temperature elastic thermal property. As shown in the figure, Ti49.2Ni44.8Co6The alloy exhibits an elastic thermal temperature range of 173K to 273K, up to 100K, and a full width at half maximum elastic thermal window of up to 71K.
Overall, Ti in example 449.2Ni44.8Co6The alloy shows better wide temperature range and high cycle stability elastic-thermal characteristics.
The present invention is not limited to the above-mentioned embodiments, and based on the technical solutions disclosed in the present invention, those skilled in the art can make some substitutions and modifications to some technical features without creative efforts according to the disclosed technical contents, and these substitutions and modifications are all within the protection scope of the present invention.

Claims (10)

1. A preparation method of a Ti-Ni-Co elastic heat refrigeration plate is characterized by comprising the following steps:
step 1, according to the chemical general formula of the elastic thermal refrigerating material Ti49.2Ni50.8-xCoxThe atomic ratio of the metal elements Ti, Ni and Co in the formula is that high-purity metal Ti, Ni and Co particles are mixed, wherein x is more than or equal to 1 and less than 6;
step 2, adopting a non-consumable vacuum arc melting method, adopting high-frequency arc striking under the protection atmosphere of argon and under the vacuum condition, controlling the melting current, and melting under magnetic stirring to obtain a polycrystalline ingot;
step 3, carrying out high-temperature solid melting on the polycrystalline ingot under a vacuum condition, then carrying out water-cooling quenching, and mechanically grinding and polishing an oxide layer on the surface of the quenched polycrystalline ingot;
step 4, carrying out hot rolling treatment on the cast ingot after the solid solution grinding and polishing to obtain a coarse-grained plate, and carrying out water cooling quenching;
step 5, rolling the quenched coarse-grained plate at room temperature, repeatedly rolling for multiple times in each pass, and controlling the cold rolling deformation to obtain a cold-rolled plate;
step 6, mechanically grinding and polishing the surface of the cold-rolled sheet, and cutting the cold-rolled sheet into the cold-rolled sheet;
step 7, selecting a quartz tube to seal and store the cold-rolled sheet after cold rolling;
step 8, performing medium-temperature aging treatment on the cold-rolled sheet preserved by the sealed tube, and then performing water-cooling quenching;
step 9, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically polishing the surface oxide skin of the cold-rolled sheet;
step 10, performing tube sealing storage on the cold-rolled sheet subjected to mechanical polishing treatment again, and repeating the step 7;
step 11, performing low-temperature aging treatment on the sample for pipe sealing, and performing water-cooling quenching on the sample after the low-temperature aging treatment;
and step 12, crushing the quartz tube, taking out the cold-rolled sheet, and mechanically polishing the surface oxide skin of the cold-rolled sheet to obtain the Ti-Ni-Co elastic thermal refrigeration sheet.
2. The method for preparing a Ti-Ni-Co elasto-thermal refrigerating plate as claimed in claim 1, wherein in the step 2, the smelting vacuum degree is 5 x 10-3The method comprises the following steps of (1) adding magnetic stirring for 5A for 1min under the conditions of more than Pa, 0.05MPa of argon protective gas and smelting current of 250-300A; after each round of melting, the sample is melted by turning over for 5 times or more.
3. The method for preparing a Ti-Ni-Co elastic-thermal refrigerating plate as claimed in claim 1, wherein in the step 3, the high-temperature solid solution vacuum degree is 5 x 10-2Pa, and keeping the temperature at 1000 ℃ for 1-12 h.
4. The method for preparing a Ti-Ni-Co elastic thermal refrigeration plate as claimed in claim 1, wherein in step 4, the ingot after solution treatment and polishing is hot-rolled at 800-1100 ℃ for 15-40min, and the pressing of each pass is controlled to be 0.05-0.2mm, and the thickness of the coarse-crystalline plate is 1.8-3.0 mm.
5. The method for preparing a Ti-Ni-Co elastic thermal refrigeration plate as claimed in claim 1, wherein in the step 5, the reduction is 0.05-0.1mm per pass, the cold rolling deformation is 30-60%, and the thickness of the cold rolled plate is 1.25-1.75 mm.
6. The method for preparing a Ti-Ni-Co elasto-thermal refrigerating plate as claimed in claim 1, wherein in step 7, the vacuum degree in the tube body of the quartz tube is 1 x 10-3And (4) introducing argon protective gas of 0.05MPa into the quartz tube above Pa, and sealing the tube body.
7. The method for preparing a Ti-Ni-Co elastic thermal refrigeration plate as claimed in claim 1, wherein the step 8, the medium temperature aging temperature is 400-550 ℃, and the aging time is 0.2-2 h.
8. The method for preparing a Ti-Ni-Co elastic thermal refrigeration plate as claimed in claim 1, wherein the step 11, the low temperature aging temperature is 250 ℃ and 300 ℃, and the heat preservation time is 24-72 h.
9. The Ti-Ni-Co elastic thermal refrigeration material prepared by the method of any one of claims 1 to 8, wherein the chemical general formula of the elastic thermal refrigeration sheet material is Ti49.2Ni50.8-XCox，1≤x＜6。
10. The Ti-Ni-Co elasto-thermal refrigerating material according to claim 9, wherein the elasto-thermal refrigerating material has a nanocrystalline structure with a grain size below hundred nanometers.
CN202110998566.8A 2021-08-27 2021-08-27 Preparation method and material of Ti-Ni-Co elastic thermal refrigeration plate Active CN113737033B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110998566.8A CN113737033B (en) 2021-08-27 2021-08-27 Preparation method and material of Ti-Ni-Co elastic thermal refrigeration plate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110998566.8A CN113737033B (en) 2021-08-27 2021-08-27 Preparation method and material of Ti-Ni-Co elastic thermal refrigeration plate

Publications (2)

Publication Number Publication Date
CN113737033A true CN113737033A (en) 2021-12-03
CN113737033B CN113737033B (en) 2022-08-09

Family

ID=78733580

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110998566.8A Active CN113737033B (en) 2021-08-27 2021-08-27 Preparation method and material of Ti-Ni-Co elastic thermal refrigeration plate

Country Status (1)

Country Link
CN (1) CN113737033B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004107777A (en) * 2002-09-20 2004-04-08 Toshiba Corp Austenitic heat resistant alloy, production method therefor and steam turbine parts
CN112981151A (en) * 2021-02-07 2021-06-18 西安交通大学 High-elastic thermal effect block Ti-Ni-based material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004107777A (en) * 2002-09-20 2004-04-08 Toshiba Corp Austenitic heat resistant alloy, production method therefor and steam turbine parts
CN112981151A (en) * 2021-02-07 2021-06-18 西安交通大学 High-elastic thermal effect block Ti-Ni-based material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUMEI ZHOU ET AL: ""Strain glass in doped Ti50(Ni50-xDx) (D = Co, Cr, Mn) alloys:Implication for the generality of strain glass in defect-containing ferroelastic systems"", 《ACTA MATERIALIA》 *

Also Published As

Publication number Publication date
CN113737033B (en) 2022-08-09

Similar Documents

Publication Publication Date Title
Yang et al. Enhanced cyclability of elastocaloric effect in boron-microalloyed Ni-Mn-In magnetic shape memory alloys
US8109100B2 (en) Magnetocaloric refrigerant
US20130200293A1 (en) La(fe,si)13-based multi-interstitial atom hydride magnetic refrigeration material with high temperature stability and large magnetic entropy change and preparation method thereof
CN104694813A (en) LaFeSi-based magnetic refrigeration material as well as preparation method and application thereof
CN109524190A (en) A kind of rare earth-iron-silicon substrate magnetic refrigeration composite material and preparation method thereof
Imran et al. Elastocaloric effects in polycrystalline Ni-Fe-Ga foams with hierarchical pore architecture
Guan et al. Extraordinary mechanical properties and successive caloric effects with ultrahigh cyclic stability in directionally solidified Ni36. 6Co12. 8Mn34. 7Ti15. 9 alloy
Tong et al. Achieving enhanced mechanical, pseudoelastic and elastocaloric properties in Ni-Mn-Ga alloys via Dy micro-alloying and isothermal mechanical cyclic training
Zhang et al. Enhanced cyclability of superelasticity and elastocaloric effect in Cu and B co-doped Co-Ni-Ga shape memory alloys
CN109680200B (en) Mn-based magnetic phase change alloy and preparation method and application thereof
Huang et al. Enhanced cyclic stability and enlarged working temperature window of NiFeGa elastocaloric refrigerant via introducing strong texture and ductile interfacial precipitate
Guan et al. Ultrahigh cyclic stability and giant elastocaloric effect in directionally solidified (Ni50Mn28Fe2. 5Ti19. 5) 99.4 B0. 6 alloy
Xuan et al. Mechanical and elastocaloric effect of Fe and Co co-doped Ni–Mn–Al ferromagnetic shape memory alloys
CN107574347B (en) A kind of praseodymium cobalt-base alloys magnetic refrigerating material and its preparation method and application
CN113737033B (en) Preparation method and material of Ti-Ni-Co elastic thermal refrigeration plate
CN111394614A (en) Ti-Ni-Cu-Nb elastic thermal refrigeration material and preparation method thereof
CN109112344B (en) Preparation method of Pd-In-Fe elastic-thermal refrigeration material with linear superelasticity
CN104357727A (en) Mn-Fe-P-Si magnetic refrigeration material and preparation method thereof
CN106636843A (en) MnNiSi-based magnetic alloy capable of serving as magnetic refrigeration material
Feng et al. Improvement of mechanical properties and elastocaloric effect in Ag doped Ni-Mn-In magnetic shape memory alloys
CN106148765B (en) Ni2FeGa class stress refrigerating materials and preparation method and application
Xu et al. Enhanced elastocaloric effect and mechanical properties of Gd-doped Ni-Co-Mn-Ti-Gd metamagnetic shape memory alloys
Su et al. Large Elastocaloric Effect in Fe‐Doped Co–Fe–V–Ga Shape Memory Alloys
CN105671396A (en) Terbium-germanium-antimony material for room temperature magnetic refrigeration and preparing method of material
CN115261674A (en) High-phase-change latent heat titanium-nickel-based shape memory alloy and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant