CN112410630A - Flexible MnNiTi-based magnetic phase change alloy material and preparation method, regulation and control method and application thereof - Google Patents

Flexible MnNiTi-based magnetic phase change alloy material and preparation method, regulation and control method and application thereof Download PDF

Info

Publication number
CN112410630A
CN112410630A CN202011191275.XA CN202011191275A CN112410630A CN 112410630 A CN112410630 A CN 112410630A CN 202011191275 A CN202011191275 A CN 202011191275A CN 112410630 A CN112410630 A CN 112410630A
Authority
CN
China
Prior art keywords
mnniti
flexible
phase change
alloy material
magnetic phase
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
CN202011191275.XA
Other languages
Chinese (zh)
Other versions
CN112410630B (en
Inventor
赵晓宇
闫亚新
温嘉红
李勇
李领伟
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.)
Hangzhou Dianzi University
Original Assignee
Hangzhou Dianzi 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 Hangzhou Dianzi University filed Critical Hangzhou Dianzi University
Priority to CN202011191275.XA priority Critical patent/CN112410630B/en
Publication of CN112410630A publication Critical patent/CN112410630A/en
Application granted granted Critical
Publication of CN112410630B publication Critical patent/CN112410630B/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
    • C22C22/00—Alloys based on manganese
    • 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
    • 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
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B21/00—Machines, plants or systems, using electric or magnetic effects
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
    • H01F1/015—Metals or alloys
    • 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]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Power Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

The invention relates to the technical field of magnetic phase change alloy materials, and provides a flexible MnNiTi-based magnetic phase change alloy material and a preparation method, a regulation and control method and application thereof, aiming at solving the problems that the change of magnetism is uncontrollable and the practical feasibility is poor in the existing magnetic phase change material element doping regulation and control mode50Ni50‑a‑bCobTiaWherein a is more than or equal to 9 and less than or equal to 12, and b is more than or equal to 8 and less than or equal to 10. The flexible MnNiTi-based magnetic phase change alloy material is prepared by doping Co element into MnNiTi-based HeuslerIn an alloy system, the obtained alloy can show a large magnetic entropy change effect at room temperature; the regulation and control method is based on bending and rotation, effectively regulates and controls the magnetic anisotropy of the flexible MnNiTi-based magnetic phase change alloy material, is beneficial to obtaining larger rotating magnetocaloric effect, enhances the magnetization intensity and the magnetocaloric effect and obtains the strain-controllable rotary clamping effect.

Description

Flexible MnNiTi-based magnetic phase change alloy material and preparation method, regulation and control method and application thereof
Technical Field
The invention relates to the technical field of magnetic phase change alloy materials, in particular to a flexible MnNiTi-based magnetic phase change alloy material and a preparation method, a regulation and control method and application thereof.
Background
The magnetic phase change material is key to achieving effective magnetic refrigeration by exhibiting a large magnetocaloric effect around room temperature. The core of the refrigeration of the magnetocaloric effect material is a magnetic phase change material which depends on various characteristics, can absorb heat from a cold end of a refrigeration object, transmit the heat to a hot end, and then release the heat to the environment under the reciprocating action of external stimuli such as pressure, an electric field or a magnetic field, so as to achieve the refrigeration effect. Unlike the Freon volatile liquid refrigerant used in the refrigerator and air conditioner for refrigeration, the refrigeration cycle based on the magnetocaloric material is an environment-friendly and relatively energy-saving method, and can possibly replace the traditional refrigeration technology in the future. Therefore, how to obtain the huge magnetocaloric effect close to the room temperature is an urgent problem to be solved.
In order to make the magnetocaloric effect practically applied, the magnetic refrigeration material should satisfy the conditions of small hysteresis and thermal hysteresis (high cycle efficiency), stable performance, easy processing, green safety, environmental protection and the like, so that the magnetic refrigeration material has huge potential in the aspect of high-efficiency refrigeration by utilizing the magnetocaloric effect in heusler alloy. Heusler alloys are one of the most important members of magnetic phase change materials with respect to the magnetocaloric effect, and exhibit many functionalities such as magnetoresistance, magnetocaloric effect, elastic thermal effect, and energy conversion. These effects are mostly related to ferromagnetic martensitic phase transformations, which occur from highly symmetrical austenite to less symmetrical martensite, often accompanied by significant magnetic and structural phase transformations, and often both. In recent years, many heusler alloys whose structures and magnetic transition temperatures are near or near room temperature and accompanied by large magnetocaloric effects have been studied extensively and are widely used for magnetic actuators, sensors, magnetic refrigeration, and the like.
One of the major difficulties in the widespread use of these alloys is their brittleness and poor ductility. To overcome this disadvantage of NiMn-based alloys, the conventional approach is to introduce fcc second phase in the brittle heusler matrix by adding a fourth element to the ternary Ni-Mn-X alloy, which effectively improves the toughness of the heusler alloy. Such as recently reported Ni50Mn50-xTixAnd Mn50Ni50-xTix. In 2015, Liu Eng et al reported a novel NiMn-based Heusler alloy system (Ni-Mn-Ti) composed of all d transition group elements for the first time, which indicates that d-d orbital hybridization can also obtain a high-order structure, and the Ni-Mn-Ti (Co, Fe) system becomes a novel ferromagnetic martensite phase change system through doping of Co or Fe and other elements. Then, people obtain the properties of magnetic field induced phase change, magnetocaloric effect, elastic heating effect, magnetic strain and the like in the system, and the range of materials for ferromagnetic martensite phase change is widened.
In the phase-change materials in the forms of blocks, thin strips, thin films and the like, element doping can introduce chemical driving force, so that two-phase energy balance temperature points move, the martensite phase-change temperature is regulated, and the regulation of magnetic performance is completed. However, the method for adjusting and controlling the element doping of the material has uncontrollable change of magnetism, poor practical feasibility and is not beneficial to wide application.
Disclosure of Invention
The invention provides a flexible MnNiTi-based magnetic phase change alloy material with a low-field anisotropy magnetocaloric effect, aiming at overcoming the problems that the change of magnetism is uncontrollable and the practical feasibility is poor in the conventional magnetic phase change material element doping regulation and control mode.
The invention also provides a preparation method of the flexible MnNiTi-based magnetic phase change alloy material, which is simple to operate, has no special requirements on equipment and is easy to industrialize.
The invention also provides a regulation and control method for the magnetic property of the flexible MnNiTi-based magnetic phase change alloy material, which can effectively regulate and control the magnetic anisotropy of the flexible MnNiTi-based magnetic phase change alloy material, is favorable for obtaining larger rotary magnetocaloric effect, enhances the magnetization intensity and magnetocaloric effect and obtains the strain-controllable rotary clamping effect.
The invention also provides application of the flexible MnNiTi-based magnetic phase change alloy material in the fields of magnetic refrigeration and magnetic devices.
In order to achieve the purpose, the invention adopts the following technical scheme:
a flexible MnNiTi-based magnetic phase change alloy material has a chemical formula of Mn50Ni50-a-bCobTiaWherein a is more than or equal to 9 and less than or equal to 12, and b is more than or equal to 8 and less than or equal to 10.
In the invention, Co element is doped into a MnNiTi-based Heusler alloy system, and Ni in the original MnNiTi-based alloy is replaced by Co, so that a new alloy is obtained. The Mn-Ni-Co-Ti alloy material can generate martensite phase transformation under the condition of bending or rotating for a certain angle in a magnetic field, so that the distortion of crystal lattices in the material is caused, the distance between magnetic atoms is changed, and the magnetism of a system is forcibly changed. Larger magnetization intensity difference can be obtained along with the generation of phase change, and parameters such as phase change temperature, magnetization intensity and the like of the alloy can be changed along with the phase change, so that the enhanced magnetic refrigeration effect can be shown; on the basis, the dependence relationship between the magnetization intensity and the magnetic field angle is represented by the rotation angle, and the magnetization intensity in the parallel state is obviously larger than that in the vertical state, which shows that the magnetic anisotropy is stronger.
Preferably, the phase transition temperature range of the flexible MnNiTi-based magnetic phase transition alloy material is 150-350K.
The MnNiTi-based magnetic phase change alloy often shows a larger magnetic entropy change effect only near the phase change temperature, and because the phase change temperature of the material can be changed through bending to enable the temperature range to be close to the room temperature, the magnetization difference and the improvement of the magnetocaloric effect can be obtained at the room temperature through the material and the method, on the basis, the angle of the material in a magnetic field is changed to show larger magnetic anisotropy, so that the larger rotary magnetocaloric effect can be obtained, the magnetization and the magnetocaloric effect are enhanced, the strain-controllable rotary clamping effect is obtained, and the precondition can enable the alloy material to have wider prospects in the application fields of magnetic refrigeration, magnetic devices and the like.
Preferably, the maximum entropy change value of the flexible MnNiTi-based magnetic phase change alloy material is 11.25Jkg under the change of a 0-5T magnetic field-1K-1。
The flexible MnNiTi-based magnetic phase change alloy material has a high magnetic entropy change value, so that the flexible MnNiTi-based magnetic phase change alloy material has a good magnetocaloric effect and can be effectively applied to a magnetic refrigeration process.
A preparation method of a flexible MnNiTi-based magnetic phase change alloy material comprises the following steps:
(1) weighing the raw materials according to the proportion in the chemical formula;
(2) performing electric arc melting on the raw materials to obtain a MnNiTi-based alloy block;
(3) and performing melt rapid quenching on the MnNiTi-based alloy block under a vacuum condition to obtain the phase-change thin strip material, namely the flexible MnNiTi-based magnetic phase-change alloy material.
Preferably, in the step (3), in the melt rapid quenching process, the rotation speed of the copper wheel is 15-50 m/s, the strip of the phase-change strip material is about 1-15 cm long and about 20-30 μm thick.
The rotating speed of the copper wheel greatly affects the performance of the alloy thin strip, and the average grain size and the unit cell volume of the alloy thin strip are reduced along with the increase of the wheel speed, so that the distance between Mn and Mn is changed, the cooling speed of the thin strip is regulated, and the thin strips with different phase transition temperatures are obtained. The rotation speed of the invention is preferably 15-50 m/s, and the alloy thin strip with the phase transition temperature near room temperature can be prepared.
A method for regulating and controlling the magnetic performance of a flexible MnNiTi-based magnetic phase-change alloy material comprises the steps of transferring the flexible MnNiTi-based magnetic phase-change alloy material to the surface of a high-molecular base material by using a water-soluble polymer, and changing the magnetic anisotropy of the flexible MnNiTi-based magnetic phase-change alloy material by bending or rotating the high-molecular base material to obtain a rotary clamping effect with adjustable strain so as to realize the regulation and control of the magnetic performance of the flexible MnNiTi-based magnetic phase-change alloy material.
"bending" in the present invention means bending it by mechanical external force, thereby changing magnetism, associated magnetic effects and magnetic anisotropy; the method comprises the step of extruding two ends of a polymer substrate loaded with a magnetic MnNiTi-based magnetic phase change alloy material on the surface, so that the middle part of the flexible MnNiTi-based magnetic phase change alloy material is warped, and bending deformation (tensile strain/compressive strain) is generated.
The rotation in the invention refers to the angle of the macromolecule substrate which is directly and integrally rotated through the measuring rod and is loaded with the magnetic MnNiTi-based magnetic phase-change alloy material on the surface in the magnetic field, fixed strain is kept in the process, the difficult and easy axis of the phase-change thin strip material is obtained, the larger magnetic anisotropy of the material is represented, and the rotation magnetocaloric effect is obtained.
Preferably, the polymer substrate is one selected from the group consisting of polyethylene terephthalate (PBT), mica sheet, polybutylene terephthalate (PET), polypropylene, polyethylene naphthalate (PEN), and Polydimethylsiloxane (PDMS).
Preferably, the water-soluble polymer is polyvinyl alcohol (PVA) or polyethylene glycol (PEG).
Preferably, the method for transferring the flexible MnNiTi-based magnetic phase change alloy material to the surface of the high polymer base material comprises the following steps:
(1) mixing a water-soluble polymer and water in a ratio of 1: (7-9), performing magnetic stirring, heating at 50-60 ℃ for 2-3 h to obtain a water-soluble polymer sol;
(2) placing the flexible MnNiTi-based magnetic phase change alloy material on an object carrying sheet, spin-coating water-soluble polymer sol for 80-90 s by a spin coater to enable the flexible MnNiTi-based magnetic phase change alloy material to be completely adhered to the upper surface of the object carrying sheet, heating to 60-70 ℃, and drying for 3-5 min to obtain a composite thin strip; the rotating speed of the spin coater is 800-1000 r/min;
(3) and (3) solidifying the composite thin strip obtained in the step (2) by adopting a high-molecular base material for 2-3 h, and then stripping the composite thin strip from the object carrying sheet to obtain the flexible MnNiTi-based magnetic phase change alloy material/water-soluble polymer/high-molecular base material sandwich structure. The sandwich structure has a good joint surface, the interface does not fall off after multiple bending cycles, the stress conduction is good, and the regulation and control of later-stage magnetic performance are convenient to complete.
The MnNiTi-based magnetic phase-change alloy thin strip material is transferred to the surface of a flexible high-molecular base material by a spin coating mode through a water-soluble polymer (PVA or PEG) and the like, bending strain is transmitted to the phase-change alloy thin strip by bending the high-molecular base material, the strain and the hard-to-magnetize axis of the phase-change thin strip are regulated and controlled, and the magnetic anisotropy of a thin strip sandwich structure is changed, so that the method is favorable for obtaining a larger rotary magnetocaloric effect, obtains a strain-adjustable rotary clamping effect, and is expected to be used in a magnetic refrigeration process.
Preferably, in step (2), the slide is selected from one of a silicon wafer, a glass slide and a silicon dioxide coating sheet.
An application of a flexible MnNiTi-based magnetic phase change alloy material in the fields of magnetic refrigeration and magnetic devices.
Therefore, the invention has the following beneficial effects:
(1) according to the flexible MnNiTi-based magnetic phase change alloy material, the Co element is doped into a MnNiTi-based Heusler alloy system, so that the obtained alloy can show a large magnetic entropy change effect at room temperature;
(2) the preparation method is simple to operate, has no special requirements on equipment, and is easy to industrialize;
(3) the regulation and control method disclosed by the invention is based on bending and rotation, the magnetic anisotropy of the flexible MnNiTi-based magnetic phase-change alloy material is effectively regulated and controlled, and a larger rotary magnetocaloric effect is favorably obtained, so that the magnetization intensity and the magnetocaloric effect are enhanced, and a strain-controllable rotary clamping effect is obtained;
(4) the magnetic anisotropy of the flexible MnNiTi-based magnetic phase change alloy material can be effectively regulated, and the stronger the magnetic anisotropy is, the better the rotary magnetocaloric effect can be obtained, so that the rotary clamping effect with adjustable strain is realized, and the flexible MnNiTi-based magnetic phase change alloy material has wider application prospect in the fields of magnetic refrigeration and magnetic devices.
Drawings
FIG. 1 shows Mn in example 150Ni31.5Co8.5Ti10XRD pattern of phase-change thin strip material.
FIG. 2 shows Mn in example 150Ni31.5Co8.5Ti10DSC profile of the phase-change thin band material.
FIG. 3 shows Mn in example 150Ni31.5Co8.5Ti10Cross-sectional SEM images of phase-change thin-ribbon materials.
FIG. 4 shows Mn in example 150Ni31.5Co8.5Ti10SEM images at the phase change thin strip material/PVA/PET sandwich interface.
FIG. 5 shows Mn in example 150Ni31.5Co8.5Ti10A phase-change thin strip material/PVA/PET sandwich structure tiling principle state diagram.
FIG. 6 shows Mn in example 150Ni31.5Co8.5Ti10And (3) a phase-change thin strip material/PVA/PET sandwich structure bending (convex and compressive stress) principle state diagram.
FIG. 7 shows Mn in example 150Ni31.5Co8.5Ti10And (3) a bending (concave, tensile stress) principle state diagram of the phase-change thin strip material/PVA/PET sandwich structure.
FIG. 8 shows Mn in example 150Ni31.5Co8.5Ti10MT curve of phase-change thin strip material/PVA/PET sandwich structure under different tensile stress.
FIG. 9 shows Mn in example 150Ni31.5Co8.5Ti10MT curve of phase-change thin strip material/PVA/PET sandwich structure under different compressive stress.
FIG. 10 shows Mn in example 150Ni31.5Co8.5Ti10The phase-change thin-strip material/PVA/PET sandwich structure is tiled and bent to regulate and control a magnetic anisotropy pole figure in two states (the two states are in a 90-degree relation).
FIG. 11 shows Mn in example 150Ni31.5Co8.5Ti10Phase-change thin strip materialThe PVA/PET sandwich structure is tiled and rotated to an isothermal magnetization curve diagram in the direction of 200 degrees (weak magnetic martensite to strong magnetic austenite process).
FIG. 12 shows Mn in example 150Ni31.5Co8.5Ti10The isothermal magnetization curve plot (weak magnetic martensite to strong magnetic austenite process) of the phase-change thin-strip material/PVA/PET sandwich structure bent and rotated to 170 degrees direction.
FIG. 13 shows Mn in example 150Ni31.5Co8.5Ti10The phase-change thin-strip material/PVA/PET sandwich structure is tiled and rotated to a magnetic entropy transformation diagram in the direction of 200 degrees (a weak magnetic martensite to strong magnetic austenite process).
FIG. 14 shows Mn in example 150Ni31.5Co8.5Ti10The phase-change thin strip material/PVA/PET sandwich structure is bent and rotated to the magnetic entropy transformation diagram (weak magnetic martensite to strong magnetic austenite process) of the direction of 170 degrees.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
The magnetic phase change alloy thin strip required to be prepared in the invention is a polycrystalline sample and is prepared by using an electric arc melting and melt rapid quenching method. The raw material of the alloy is a metal simple substance prepared according to a stoichiometric ratio, and the purity of the used transition metal and main group elements is over 99.99 percent.
Example 1
(1) Preparing materials: according to the chemical formula Mn50Ni31.5Co8.5Ti10The high-purity raw materials Ni, Mn, Co and Ti are weighed according to the proportion, and an oxide layer on the surface of the required transition metal element needs to be carefully ground off before the materials are mixed.
Taking Mn as an example, the raw materials are cleaned and smelted before proportioning to ensure the purity of the raw materials, and the method comprises the following specific steps:
1) putting a certain amount of Mn simple substance into a beaker, then pouring a dilute hydrochloric acid solution diluted by water with the volume ratio of about 1:1 to perform chemical reaction, and rapidly stirring by using a glass rod in the reaction process;
2) when the oxide disappears and the Mn surface shows a bright metallic luster, the waste solution after the reaction in the beaker is quickly poured off:
3) washing the reacted metal Mn with deionized water twice and then rinsing with industrial alcohol twice;
4) putting the cleaned Mn into a smelting furnace for smelting for three times, carefully polishing an oxide layer on the surface after each smelting, and carefully scrubbing a copper crucible;
5) and (3) cutting the smelted Mn ingot by using a metal pliers, and if the section shows very uniform metal luster, no obvious oxide impurities are seen, thus proving that the purification of Mn is finished.
The prepared metal simple substances are proportioned according to the chemical proportion and uniformly mixed, and for volatile elements such as Mn, the consumption in the smelting process is compensated by considering the appropriate increase of the dosage, so that the components of the sample are ensured.
(2) Smelting: smelting is carried out by adopting a water-cooled copper crucible electric arc furnace, the electric arc furnace is cooled by a circulating water cooling system, the prepared raw materials are respectively placed at the center position of the bottom of the copper crucible, the positions of different samples are recorded, and then a furnace cover is closed. Before smelting, the furnace is vacuumized. The vacuum pumping process is divided into two stages: pumping to below 10 Pa by mechanical pump, and pumping to pressure less than 3x10 by molecular pump-3Pa, and finally, filling high-purity Ar gas of 0.05MPa into the furnace cavity to start smelting.
When a sample is smelted, the tungsten electrode is lowered to a sample block which needs to be smelted by using a knob at the top end of the electric arc furnace, the electrode is close to a sharp corner of the sample block as much as possible, the tip effect is utilized to assist arc striking, the distance between the electrode and the sample needs to be carefully adjusted, the arc striking is difficult, and the electrode is small and is easy to touch the sample. The striking button was pressed and the sample was melted using the high temperature generated by the arc. In the smelting process, in order to ensure that the sample is fully and uniformly melted, attention needs to be paid to stirring the melted liquid alloy by using an electromagnetic stirrer. For the raw material metal containing easy volatilization, the size of smelting current and smelting time must be strictly controlled during smelting. After the smelting is finished, the arc voltage is gradually reduced, then the power supply is turned off, and in order to further obtain a uniform alloy sample, the ingot is turned over and repeatedly smelted for 3-4 times.
(3) Melt rapid quenching: placing the alloy ingot smelted in an electric arc furnace in a water-cooled copper crucible, melting by induction smelting method, tilting the copper crucible, blowing the molten alloy out of the bottom orifice of the quartz tube through Ar gas, rapidly cooling and solidifying on a copper wheel rotating at high speed, wherein the rotation speed of the copper wheel is 20 m/s, the length of the spun thin strip is about 5cm, the thickness is about 25 mu m, and Mn is prepared50Ni31.5Co8.5Ti10And (3) phase-change thin strip material.
Mn prepared in the step (3)50Ni31.5Co8.5Ti10The crystal structure of the phase-change thin strip material is tested by X-ray diffraction (XRD) at 300K, and the test result is shown in figure 1, and the phase-change thin strip material has a 5M and B2 phase structure, which shows that martensite transformation occurs near room temperature, and is consistent with the DSC result of figure 2.
Then adding the Mn50Ni31.5Co8.5Ti10The SEM test of the phase-change thin strip material is shown in fig. 3, and as can be seen from fig. 3, the grain oriented growth is caused by the process of the strip throwing process, and it can be seen that the growth rule of the columnar grains in the cross section perpendicular to the surface of the thin strip is very obvious. It is likely that grain growth on the surface of the ribbon is relatively random due to the absence of heat treatment. The boundary condition changes are relatively sensitive and can be easily adjusted during the martensitic transformation.
(4) Spin coating: mixing PVA with water in a ratio of 1: 9 is fully dissolved in the mass ratio; magnetically stirring the prepared solution, heating the solution at the temperature of 55 ℃ for 2 hours to prepare PVA sol; taking the prepared Mn50Ni31.5Co8.5Ti10Placing the thin strip on a silicon wafer, spin-coating PVA 90s on the thin strip through a spin coater, and spin-coatingIn the process, the rotating speed of the spin coater is 1000 r/min, so that Mn is added50Ni31.5Co8.5Ti10The thin strip is completely adhered to the upper surface of the silicon chip; drying the prepared composite thin strip after spin coating, wherein the heating temperature is 65 ℃, and the drying time is 4min, so as to prepare the composite thin strip; then, the PET substrate is solidified on the prepared composite thin belt, and after 3 hours of solidification, the PET substrate is stripped from the silicon wafer to obtain Mn with good stress conduction50Ni31.5Co8.5Ti10The phase-change thin strip material/PVA/PET sandwich structure. FIG. 4 shows this Mn50Ni31.5Co8.5Ti10SEM images of the interface of the phase-change thin strip material/PVA/PET sandwich structure show that the interface is well bonded, which is beneficial to the transmission of bending stress.
Changing the Mn50Ni31.5Co8.5Ti10The curvature of the phase-change thin-strip material/PVA/PET sandwich structure enables the phase-change thin-strip material/PVA/PET sandwich structure to be subjected to certain strain, the magnetic performance and related magnetic effects are tested, and the strain calculation formula is as follows: epsilon = τ/2R, where τ is the thickness of the thin strip and R is the radius of curvature of the thin strip, the bending strain in this example is the maximum bending strain, and the thin strip is not damaged. Then adding the Mn50Ni31.5Co8.5Ti10MT test under different stresses is carried out on the phase-change thin strip material/PVA/PET sandwich structure, the force application principle state diagrams are respectively shown in figures 5, 6 and 7, the corresponding test results are shown in figures 8 and 9, and the Mn is50Ni31.5Co8.5Ti10The phase-change thin-strip material/PVA/PET sandwich structure can obtain large magnetization intensity difference before and after phase change, and the intensity difference after bending is further increased, so that a large magnetic refrigeration effect can be shown.
Mn with SQUID50Ni31.5Co8.5Ti10The measurement of the relevant magnetism of the phase-change thin strip material/PVA/PET sandwich structure characterizes the influence of the strain of the angle regulation of the bending or rotating magnetic anisotropic material on the magnetization intensity, the anisotropy and the like of the alloy thin strip. FIG. 10 shows Mn in two states of tiling and bending control50Ni31.5Co8.5Ti10Phase-change thin strip material/PVA/PETMagnetic anisotropy pole diagram of Mingmi structure (the two are in 90 degree relation).
For the constructed Mn in the two states of flat laying and bending50Ni31.5Co8.5Ti10The phase-change thin strip material/PVA/PET sandwich structure is used for carrying out magnetic measurement of a rotating angle, a rotating magnetocaloric effect is introduced through the angle of a rotating anisotropic material in a magnetic field, a polar diagram of the dependence relationship between magnetization intensity and the angle of the magnetic field is obtained, the distribution condition of magnetic anisotropy in two states is shown, an easy magnetization axis and a hard magnetization axis are obtained, the angle relationship (vertical) of the magnetic anisotropy in a bending state and a flat state is obtained, the stress is applied to the easy magnetization axis/the hard magnetization axis of the thin strip, the magnetic anisotropy of the thin strip can be changed, the magnetic anisotropy deflects, and the stronger the magnetic anisotropy is more beneficial to obtaining a larger rotating magnetocaloric effect, so that the magnetization intensity and the magnetocaloric effect are both enhanced, and the strain-controllable rotary clamping effect is obtained.
FIG. 11 shows Mn flatly laid and rotated to 200 degree orientation50Ni31.5Co8.5Ti10Isothermal magnetization curve diagram (from weak magnetic martensite to strong magnetic austenite) of the phase-change thin-strip material/PVA/PET sandwich structure; FIG. 12 shows Mn adjusted in the direction of bending and rotating to 170 °50Ni31.5Co8.5Ti10Isothermal magnetization curve diagram (from weak magnetic martensite to strong magnetic austenite) of the phase-change thin-strip material/PVA/PET sandwich structure; FIG. 13 shows Mn tiled and rotated to 200 degree orientation50Ni31.5Co8.5Ti10The magnetic entropy transformation diagram of the phase-change thin strip material/PVA/PET sandwich structure (from weak magnetic martensite to strong magnetic austenite); FIG. 14 shows Mn adjusted in the direction of bending and rotating to 170 °50Ni31.5Co8.5Ti10Magnetic entropy transformation diagram (weak magnetic martensite to strong magnetic austenite process) of phase-change thin strip material/PVA/PET sandwich structure. It can be seen from the figure that the magnetic structure phase change driven by the magnetic field can be obviously observed in the phase change temperature range, the saturation magnetization is increased in the bending state, and stronger magnetic anisotropy is indicated. The stronger the magnetic anisotropy is, the more beneficial to obtain the larger rotating magnetocaloric effect, so that the magnetization intensity and the magnetocaloric effect are bothThe strain-adjustable rotary clamping effect is obtained, and the application prospect is effectively expanded.
Example 2
Embodiment 2 is different from embodiment 1 in that the chemical formula of the flexible MnNiTi-based magnetic phase change alloy material (phase change thin strip material) is: mn50Ni28Co10Ti12And (4) different steps and completely the same other processes.
And (4): polyethylene glycol (PEG) was mixed with water at a ratio of 1: 7 is fully dissolved in the mass ratio; magnetically stirring the prepared solution, heating the solution at 50 ℃ for 3 hours to prepare PEG sol; taking the prepared Mn50Ni28Co10Ti12Placing the thin strip on a glass slide, spin-coating PVA (polyvinyl alcohol) 90s by a spin coater, wherein the rotation speed of the spin coater is 1000 r/min in the spin coating process, so that Mn (manganese) is obtained50Ni28Co10Ti12The thin strip is completely adhered to the upper surface of the glass slide; drying the composite thin strip prepared after spin coating, wherein the heating temperature is 60 ℃, and the drying time is 5min, so as to prepare the composite thin strip; then, a Polydimethylsiloxane (PDMS) substrate is solidified on the prepared composite thin belt, and after the solidification time is 2.5 hours, the PDMS substrate is stripped from the glass slide to obtain Mn with good stress conduction50Ni28Co10Ti12The phase-change thin-band material/PEG/PDMS sandwich structure is changed50Ni28Co10Ti12The curvature of the phase-change thin-band material/PEG/PDMS sandwich structure enables the phase-change thin-band material/PEG/PDMS sandwich structure to be subjected to certain strain, and magnetic performance and related magnetic effects are tested, wherein a strain calculation formula is as follows: epsilon = τ/2R, where τ is the thickness of the thin strip and R is the radius of curvature of the thin strip, the bending strain in this embodiment is the maximum bending strain, the thin strip is not damaged, and the test result is equivalent to that in embodiment 1, and will not be described herein again.
Example 3
Example 3 differs from example 1 in that the chemical formula of the flexible MnNiTi-based magnetic phase change alloy material is: mn50Ni33Co8Ti9And (4) different steps and completely the same other processes.
And (4): mixing polyethylene glycol (A), (B), (C) and (C)PEG) with water at a ratio of 1: 8 is fully dissolved; magnetically stirring the prepared solution, heating the solution at the temperature of 60 ℃ for 2.5 hours to prepare PEG sol; taking the prepared Mn50Ni33Co8Ti9Placing the thin strip on a glass slide, spin-coating PVA (polyvinyl alcohol) 90s by a spin coater, wherein the rotation speed of the spin coater is 1000 r/min in the spin coating process, so that Mn (manganese) is obtained50Ni33Co8Ti9The thin strip is completely adhered to the upper surface of the glass slide; drying the composite thin strip obtained after spin coating at the heating temperature of 70 ℃ for 3min to obtain a composite thin strip; then solidifying a polyethylene naphthalate (PEN) substrate on the prepared composite thin belt, and stripping from a glass slide after 2 hours of solidification time to obtain Mn with good stress conduction50Ni33Co8Ti9The phase change thin strip material/PEG/PEN sandwich structure is changed50Ni33Co8Ti9The curvature of the phase change thin strip material/PEG/PEN sandwich structure enables the sandwich structure to be subjected to certain strain, magnetic performance and related magnetic effects are tested, and a strain calculation formula is as follows: epsilon = τ/2R, where τ is the thickness of the thin strip and R is the radius of curvature of the thin strip, the bending strain in this embodiment is the maximum bending strain, the thin strip is not damaged, and the test result is equivalent to that in embodiment 1, and will not be described herein again.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (10)

1. The flexible MnNiTi-based magnetic phase change alloy material is characterized in that the chemical formula of the flexible MnNiTi-based magnetic phase change alloy material is Mn50Ni50-a-bCobTiaWherein a is more than or equal to 9 and less than or equal to 12, and b is more than or equal to 8 and less than or equal to 10.
2. The flexible MnNiTi-based magnetic phase change alloy material as claimed in claim 1, wherein the phase change temperature of the flexible MnNiTi-based magnetic phase change alloy material is in the range of 150-350K.
3. The flexible MnNiTi-based magnetic phase change alloy material as claimed in claim 1, wherein the maximum entropy change value of the flexible MnNiTi-based magnetic phase change alloy material is 11.25Jkg under the change of 0-5T magnetic field-1K-1。
4. A method for preparing a flexible MnNiTi-based magnetic phase change alloy material according to any of claims 1 to 3, comprising the steps of:
(1) weighing the raw materials according to the proportion in the chemical formula;
(2) performing electric arc melting on the raw materials to obtain a MnNiTi-based alloy block;
(3) and performing melt rapid quenching on the MnNiTi-based alloy block under a vacuum condition to obtain the phase-change thin strip material, namely the flexible MnNiTi-based magnetic phase-change alloy material.
5. The production method according to claim 4, wherein in the step (2), the degree of vacuum of arc melting is less than 3x10-3Pa。
6. The method according to claim 4, wherein in the step (3), the rotation speed of the copper wheel during the melt quenching process is 15-50 m/s, the strip of the phase-change strip material has a length of about 1-15 cm and a thickness of about 20-30 μm.
7. A method for regulating and controlling the magnetic property of the flexible MnNiTi-based magnetic phase change alloy material according to any one of claims 1 to 3, wherein the flexible MnNiTi-based magnetic phase change alloy material is transferred to the surface of a polymer substrate by using a water-soluble polymer, and the magnetic anisotropy of the flexible MnNiTi-based magnetic phase change alloy material is changed by bending or rotating the polymer substrate to obtain a spin chuck effect with adjustable strain, thereby realizing the regulation and control of the magnetic property of the flexible MnNiTi-based magnetic phase change alloy material.
8. The control method according to claim 7, wherein the polymer substrate is one selected from polyethylene terephthalate, mica sheet, polybutylene terephthalate, polypropylene, polyethylene naphthalate, and polydimethylsiloxane; the water-soluble polymer is polyvinyl alcohol or polyethylene glycol.
9. A control method according to claim 7, wherein transferring the flexible MnNiTi-based magnetic phase change alloy material to the surface of the polymer substrate comprises the steps of:
(1) mixing a water-soluble polymer and water in a ratio of 1: (7-9), performing magnetic stirring, heating at 50-60 ℃ for 2-3 h to obtain a water-soluble polymer sol;
(2) placing the flexible MnNiTi-based magnetic phase change alloy material on an object carrying sheet, spin-coating water-soluble polymer sol for 80-90 s by a spin coater to enable the flexible MnNiTi-based magnetic phase change alloy material to be completely adhered to the upper surface of the object carrying sheet, heating to 60-70 ℃, and drying for 3-5 min to obtain a composite thin strip; the rotating speed of the spin coater is 800-1000 r/min; the object carrying sheet is selected from one of a silicon wafer, a glass slide and a silicon dioxide coating sheet;
(3) and (3) solidifying the composite thin strip obtained in the step (2) by adopting a high-molecular base material for 2-3 h, and then stripping the composite thin strip from the object carrying sheet to obtain the flexible MnNiTi-based magnetic phase change alloy material/water-soluble polymer/high-molecular base material sandwich structure.
10. Use of a flexible MnNiTi-based magnetic phase change alloy material according to any of claims 1-3 in the field of magnetic refrigeration and magnetic devices.
CN202011191275.XA 2020-10-30 2020-10-30 Flexible MnNiTi-based magnetic phase change alloy material and preparation method, regulation and control method and application thereof Active CN112410630B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011191275.XA CN112410630B (en) 2020-10-30 2020-10-30 Flexible MnNiTi-based magnetic phase change alloy material and preparation method, regulation and control method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011191275.XA CN112410630B (en) 2020-10-30 2020-10-30 Flexible MnNiTi-based magnetic phase change alloy material and preparation method, regulation and control method and application thereof

Publications (2)

Publication Number Publication Date
CN112410630A true CN112410630A (en) 2021-02-26
CN112410630B CN112410630B (en) 2022-03-01

Family

ID=74827016

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011191275.XA Active CN112410630B (en) 2020-10-30 2020-10-30 Flexible MnNiTi-based magnetic phase change alloy material and preparation method, regulation and control method and application thereof

Country Status (1)

Country Link
CN (1) CN112410630B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113235055A (en) * 2021-05-07 2021-08-10 杭州电子科技大学 Ni-Mn-Ti-based multi-element alloy target material and preparation method and film thereof
CN116478540A (en) * 2023-04-24 2023-07-25 北京科技大学 Composite material with flexibility and magnetostriction performance as well as preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09143643A (en) * 1995-11-27 1997-06-03 Fujitsu Ltd Alloy for magneto resistance effect element and its production
US20160256923A1 (en) * 2015-03-03 2016-09-08 Institute Of Physics, Chinese Academy Of Sciences Magnetic phase-transformation material
CN109680200A (en) * 2019-03-18 2019-04-26 江西理工大学 A kind of novel Mn base magnetic phase transition alloy and its preparation method and application
CN111210959A (en) * 2019-10-25 2020-05-29 杭州电子科技大学 Material capable of regulating magnetism and related magnetic effect through bending or twisting and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09143643A (en) * 1995-11-27 1997-06-03 Fujitsu Ltd Alloy for magneto resistance effect element and its production
US20160256923A1 (en) * 2015-03-03 2016-09-08 Institute Of Physics, Chinese Academy Of Sciences Magnetic phase-transformation material
CN109680200A (en) * 2019-03-18 2019-04-26 江西理工大学 A kind of novel Mn base magnetic phase transition alloy and its preparation method and application
CN111210959A (en) * 2019-10-25 2020-05-29 杭州电子科技大学 Material capable of regulating magnetism and related magnetic effect through bending or twisting and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHICHENG MA ET AL: "Martensitic transformation and magnetocaloric effect in melt-spun", 《JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113235055A (en) * 2021-05-07 2021-08-10 杭州电子科技大学 Ni-Mn-Ti-based multi-element alloy target material and preparation method and film thereof
CN116478540A (en) * 2023-04-24 2023-07-25 北京科技大学 Composite material with flexibility and magnetostriction performance as well as preparation method and application thereof

Also Published As

Publication number Publication date
CN112410630B (en) 2022-03-01

Similar Documents

Publication Publication Date Title
US20200335246A1 (en) Fe-Co BASED AMORPHOUS SOFT MAGNETIC ALLOY AND PREPARATION METHOD THEREOF
CN112410630B (en) Flexible MnNiTi-based magnetic phase change alloy material and preparation method, regulation and control method and application thereof
CN102851545B (en) Ni-Mn-Ge magnetic shape memory alloy and preparation method thereof
CN105986322B (en) A kind of magnetic phase transition material
CN103611896B (en) A kind of method being prepared MnCoGe base and MnNiGe base alloy thin band by electric arc melting and fast melt-quenching
CN110541116B (en) Crystallization-controllable iron-based nanocrystalline magnetically soft alloy
CN101826385A (en) Magnetic material with exchange bias effect and preparation method thereof
CN111210959B (en) Material capable of regulating magnetism and related magnetic effect through bending or twisting and preparation method and application thereof
CN104772361A (en) Preparation method of amorphous alloy fiber and device for implementing the preparation method
CN109680200B (en) Mn-based magnetic phase change alloy and preparation method and application thereof
CN102610346A (en) Novel rare-earth-free nanometer composite permanent magnet material and preparation method thereof
CN105400998B (en) A kind of Ni Mn Ga alloy thin bands and preparation method thereof
CN108300881B (en) Method for realizing wide-temperature-zone giant negative thermal expansion in MnCoGe-based alloy
CN101734730A (en) Inter-metallic compound material with near-zero thermal expansion character and anti-perovskite structure
Liu et al. Fabrication of SmCo5 alloy via cobalt-induced calciothermic reduction and magnetic properties of its ribbon
Łaszcz et al. Effects of Ti and Gd for Ga substitution on microstructure, magnetic and mechanical properties of polycrystalline Ni-Mn-Ga magnetic shape memory alloy
CN102234746B (en) Zinc-based massive amorphous alloy and preparation method thereof
CN109576530B (en) Giant exchange bias Mn-based alloy and preparation method and application thereof
Xu et al. Enhanced elastocaloric effect and mechanical properties of Gd-doped Ni-Co-Mn-Ti-Gd metamagnetic shape memory alloys
CN109778082B (en) High-low temperature annealing toughness iron-based amorphous alloy and preparation method and application thereof
CN103785827B (en) Ferrocobalt-base alloy magnetic powder material for paint and preparation method
CN113235055A (en) Ni-Mn-Ti-based multi-element alloy target material and preparation method and film thereof
CN105861861A (en) Memory alloy driven by magnetic field to deform and preparing method of memory alloy
CN101509111B (en) Method of producing bulk amorphous alloy material with excellent mechanical performances and high-magnetostriction
CN101509108B (en) Bulk amorphous alloy magnetostriction material and method of producing the same

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