CN111210959B - Material capable of regulating magnetism and related magnetic effect through bending or twisting and preparation method and application thereof - Google Patents

Material capable of regulating magnetism and related magnetic effect through bending or twisting and preparation method and application thereof Download PDF

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CN111210959B
CN111210959B CN201911023357.0A CN201911023357A CN111210959B CN 111210959 B CN111210959 B CN 111210959B CN 201911023357 A CN201911023357 A CN 201911023357A CN 111210959 B CN111210959 B CN 111210959B
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赵晓宇
李勇
温嘉红
李领伟
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Hangzhou Dianzi University
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • 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
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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Abstract

The invention relates to the field of magnetic materials, in particular to a material capable of regulating magnetism and related magnetic effect through bending or twisting, wherein the chemical formula of the material is Ni50‑aCoaMn35‑bFebXcWherein a is more than or equal to 12 and less than or equal to 17, b is more than or equal to 0 and less than or equal to 10, c is more than or equal to 5 and less than or equal to 20, and X comprises Sn, Ga, In, Si, Ge, Ti, Zr, Hf, V, Nb and Ta. The preparation method of the material comprises the following steps: and (3) arc melting the high-purity raw materials to obtain a NiMi-based alloy block, and performing melt rapid quenching on the block in vacuum to obtain the phase-change thin strip material. The method overcomes the defects that the method for regulating the magnetism by applying isostatic pressure in the prior art is single in effect, poor in controllability, complex in pressure application mode and limited in application, the obtained phase-change alloy thin strip can show larger magnetism regulation and large magnetocaloric effect near room temperature, can be effectively applied to the magnetic refrigeration process, and can realize strain output through bending or twisting, so that the magnetism and related magnetic effect of the phase-change alloy thin strip are regulated, and the application prospect is effectively expanded.

Description

Material capable of regulating magnetism and related magnetic effect through bending or twisting and preparation method and application thereof
Technical Field
The invention relates to the field of magnetic materials, in particular to a material capable of regulating and controlling magnetism and related magnetic effects through bending or twisting, and a preparation method and application thereof.
Background
The inducing factors of the martensitic transformation include magnetic field, temperature and strain. In some magnetic material systems, the parent phase and the martensite phase have different magnetic behaviors. When martensitic transformation occurs, the magnetic atomic distance changes due to the distortion of the crystal lattice, and the magnetism of the material is changed, so that the martensitic transformation occurs while the magnetism changes. In the magnetic martensitic transformation process, if the material undergoes martensitic transformation accompanied by magnetic transformation such as antiferromagnetic transformation, ferromagnetic transformation, paramagnetic transformation, etc., a large difference in magnetization is easily obtained before and after the transformation. When an external magnetic field or strain is introduced to enable the material to have ferromagnetic martensite phase transformation, abundant physical effects such as magnetic drive large strain, magnetic drive shape memory, large magnetic entropy change, superelasticity, large magnetoresistance, Hall effect, exchange bias and the like can be obtained. Therefore, the ferromagnetic martensitic phase change material becomes one of hot spots of current magnetic functional material research.
The common point of the commonly researched ferromagnetic martensite phase transformation systems comprises Heusler alloy, MM' X alloy and the like, and the common point is that transition group elements and main group elements can form p-d orbital hybridization, have high ordered atomic occupation and form a high-stability structure. Thereby realizing the stabilization of the parent phase, the adjustment of the phase transition temperature, the adjustment and control of each atom to display different magnetic behaviors and the like.
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 form of blocks, thin strips, thin films and the like, the application of isostatic pressure can introduce a mechanical driving force, so that two-phase energy balance temperature points move, further martensite phase transformation is regulated and controlled, and the regulation and control of magnetic properties are completed, for example, the Chinese patent with the application number of 201811479048X is based on the principle.
However, the regulation and control method for applying isostatic pressure to the material has the disadvantages of single mechanical effect, poor controllability, complex pressing method, limited application and no contribution to practical application.
Disclosure of Invention
The invention provides a method for realizing tensile or compressive strain output through bending or twisting, so as to realize regulation and control of material magnetism and related magnetic effect, and a preparation method and application thereof, aiming at overcoming the defects that the method for regulating and controlling magnetism through applying static pressure in the prior art is single in effect, poor in controllability, complex in pressure application mode and limited in application.
In order to realize the purpose of the invention, the invention is realized by the following technical scheme:
a material with magnetic property and related magnetic effect controllable by bending or twisting, the material has a chemical formula of Ni50- aCoaMn35-bFebXcWherein a is more than or equal to 12 and less than or equal to 17, b is more than or equal to 0 and less than or equal to 10, c is more than or equal to 5 and less than or equal to 20, and X comprises Sn, Ga, In, Si, Ge, Ti, Zr, Hf, V, Nb and Ta.
Co and Fe elements are doped into a Ni-Mn-based Heusler alloy system, Ni in the original Ni-Mn-based Heusler alloy is replaced by Co, and Mn is replaced by Fe, so that the novel alloy is obtained. The alloy material can generate martensite phase transformation under the condition of bending or torsion, so that the crystal lattice in the material is distorted, the magnetic atom distance is changed, and the magnetism of the system is forcibly changed. A larger difference of magnetization intensity 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 difference, so that an enhanced magnetic refrigeration effect can be shown.
Preferably, the phase transition temperature range of the material is-100-200 ℃, and the Curie temperature is 10-100 ℃.
According to the invention, the phase transition temperature of the material can be respectively adjusted by the replacement amount of Ni and Mn through Co and Fe, so that the phase transition temperature range of the material can be changed within-100-200 ℃, and meanwhile, the Curie temperature of the material can also be changed within the range of 10-100 ℃.
The NiMn-based ferromagnetic shape memory alloy usually shows a large magnetic entropy change effect only near the phase transition temperature, and the material can change the phase transition temperature and the Curie temperature through bending or torsion, and the two temperature ranges are close to room temperature, so that the material and the method can obtain large magnetization difference at room temperature, thereby showing a large magnetic refrigeration effect at the condition of being close to the room temperature, and the alloy material has a wider prospect in the application fields of magnetic refrigeration, magnetic devices and the like.
Preferably, the maximum entropy change value of the material is 15Jkg under the change of a 0-2T magnetic field-1K-1(ii) a Under the change of a 0-5T magnetic field, the maximum entropy change value is 40Jkg-1K-1。
The material has a high magnetic entropy change value, so that the material has a good magnetocaloric effect and can be effectively applied to a magnetic refrigeration process.
A method for preparing a material capable of regulating magnetism and related magnetic effects through bending or twisting comprises the following steps:
(1) weighing high-purity raw materials according to the proportion in the chemical formula;
(2) arc melting the raw materials to obtain a NiMi-based alloy block;
(3) And performing melt rapid quenching on the block body under vacuum to obtain the phase-change thin strip material, namely the thin strip material with magnetism and related magnetic effect regulated and controlled by bending or twisting.
Preferably, the vacuum degree of arc melting is less than 3X 10-3Pa。
Preferably, the rotation speed of the copper wheel in the preparation process is 10-45 m/s, the length of the thrown thin strip is about 2-15 cm, and the thickness of the thin strip is about 20-30 mu m.
According to the invention, the cooling speed of the thin strip can be different by changing the rotating speed of the copper wheel, so that the alloy thin strip prepared by different rotating speeds of the copper wheel has different phase transition temperatures.
Preferably, the degree of vacuum during annealing is less than 1X 10-3Pa, the annealing temperature is 600-900 ℃, the annealing time is 1-7 days, and the annealing temperature is cooled to room temperature along with the furnace after the annealing is finished.
The thin strip prepared by the rapid quenching method is subjected to rapid cooling from a liquid phase directly to a solid phase, atoms in the alloy thin strip are not in an equilibrium state with lower energy but in a metastable state, and the thin strip has larger internal stress. Therefore, the phase transition temperature can be regulated and controlled by carrying out post annealing on the strip in the fast quenching state. In the post-annealing process of the alloy thin strip, a structure and stress relaxation process is carried out, so that the positions of atoms are changed, the distance between atoms in the material is adjusted, and the phase transition temperature of the alloy thin strip is influenced.
The method for regulating and controlling the magnetism and the related magnetic effect of the phase-change thin strip obtained by the preparation method through bending or twisting utilizes mechanical external force to buckle or twist the phase-change thin strip, so that the magnetism and the related magnetic effect of the phase-change thin strip material are changed.
The phase-change thin strip can be bent or twisted through mechanical external force, so that the magnetism of the phase-change thin strip and related magnetic effects are changed. The mechanical external force comprises extruding two ends of the thin strip to enable the middle of the thin strip to be warped so as to generate buckling (tensile or compressive strain), or enabling two ends of the thin strip to rotate in different directions respectively so as to form torsion, or enabling the thin strip to be adhered to the surface of other base materials, and enabling the tensile or compressive strain generated by the base materials to be transmitted to the phase-change thin strip through changing the shape of the base materials through the mechanical external force.
Meanwhile, the buckling or torsion controllability of the phase-change thin strip is strong through mechanical external force, the pressing mode is simple, and the application range is wide, so that the magnetism of the thin strip and related magnetic effects can be effectively regulated and controlled, and the application range of the material is widened.
Preferably, the method transfers the phase-change thin strip to the surface of the polymer substrate, changes the curvature of the deformation of the phase-change thin strip by bending the polymer substrate, and introduces tensile or compressive strain to the phase-change thin strip, thereby changing the magnetic properties and associated magnetic effects of the phase-change thin strip material.
Therefore, the invention has the following beneficial effects:
(1) co and Fe elements are doped into a Ni-Mn based Heusler alloy system, and the obtained alloy can show a large magnetic entropy change effect at room temperature.
(2) The magnetic refrigeration method has the advantages of high magnetic entropy change value and good magnetic thermal effect, and can be effectively applied to the magnetic refrigeration process.
(3) The strain output can be realized through bending or twisting, so that the magnetism and related magnetic effects are regulated and controlled, and the application prospect is effectively expanded.
Drawings
FIG. 1 shows Ni35Co15Mn33Fe2Ti15XRD pattern of thin bands.
FIG. 2 shows Ni35Co15Mn33Fe2Ti15DSC profile of thin band.
FIG. 3 shows Ni35Co15Mn33Fe2Ti15M-T plot of thin strip.
FIG. 4 shows Ni35Co15Mn33Fe2Ti15Isothermal magnetization profile of thin strip (weak magnetic martensite to strong magnetic austenite process).
FIG. 5 shows Ni35Co15Mn33Fe2Ti15Magnetic entropy transformation diagram (weak magnetic martensite to strong magnetic austenite process) of thin strip.
FIG. 6 shows Ni for buckling control35Co15Mn33Fe2Ti15M-T plot of thin strip.
FIG. 7 shows Ni buckling-regulated at 280K35Co15Mn33Fe2Ti15M-H diagram of thin strip.
FIG. 8 shows Ni35Co15Mn33Fe2Ti15Magnetic entropy transformation of thin strip (strong magnetic austenite to weak magnetic martensite process).
FIG. 9 shows Ni buckling control35Co15Mn33Fe2Ti15Magnetic entropy transformation of thin strip (strong magnetic austenite to weak magnetic martensite process).
FIG. 10 is a diagram showing the state of the examples 6 and 7.
Detailed Description
The invention is further described with reference to the drawings and the specific embodiments. The following description of the embodiments is provided to enable any person skilled in the art to make and use the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the following embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
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
A material with controllable magnetic property and related magnetic effect by bending or twisting has a chemical formula of Ni35Co15Mn33Fe2Ti15The preparation method of the material comprises the following steps:
(1) preparing materials: high-purity raw materials of Ni, Mn, Fe, Co and Ti are weighed according to the proportion in the chemical formula, and an oxide layer on the surface of a required transition metal element is carefully ground off before proportioning.
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 dosage is also properly increased to compensate the loss in the smelting process and ensure the components of the sample.
(2) Smelting: smelting is carried out by adopting a water-cooled copper crucible electric arc furnace, and the electric arc furnace is cooled by a circulating water cooling system and is to be subjected toThe prepared raw materials are respectively placed at the center of the bottom of the copper crucible, the positions of different samples are recorded, and then the 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: the alloy ingot which is melted in the electric arc furnace is put in a water-cooling copper crucible and melted by an induction melting method, then the copper crucible is inclined, the melted alloy is blown out of a narrow opening at the bottom of a quartz tube through Ar gas, and the alloy ingot is rapidly cooled and solidified on a copper wheel which rotates at high speed to prepare a thin strip.
Wherein the rotation speed of the copper wheel is 15 m/s in the preparation process, the length of the spun thin strip is about 2 cm, the thickness is about 20 mu m, and then the thin strip is annealed, and the vacuum degree is less than 1 multiplied by 10 during annealing-3Pa, the annealing temperature is 600 ℃, the annealing time is 1 day, and furnace cooling treatment is carried out after the annealing is finished.
Example 2
A material with controllable magnetic property and related magnetic effect by bending or twisting has a chemical formula of Ni38Co12Mn35Sn5The preparation method of the material comprises the following steps:
(1) preparing materials: high-purity raw materials Ni, Mn, Co and Sn are weighed according to the proportion in the chemical formula, and an oxide layer on the surface of a required transition metal element is carefully ground off before batching.
(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 carefully placed at the center position of the bottom of the copper crucible together, the positions of different samples are recorded, and then a furnace cover is lowered. Before smelting, the furnace is firstly vacuumized. The vacuum pumping process is divided into two stages: firstly, pumping to about 5 Pa by a mechanical pump, and then pumping the air pressure to less than 3x10 by a diffusion pump -3High vacuum of about Pa, and finally filling high-purity Ar gas with 0.6 atmospheric pressure into the furnace cavity to start smelting.
When carrying out the sample smelting, utilize the knob on electric arc furnace top to descend the tungsten electrode to more to press close to the sample piece that needs the smelting, let the electrode be close to the closed angle department of sample piece as far as possible, utilize the tip effect to assist the arcing, the distance of electrode and sample will carefully be transferred, has big difficult arcing, has little the electrode and touches the sample easily. 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, an electromagnetic stirrer is used for stirring the molten liquid alloy. 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 to further obtain a uniform alloy sample, and the ingot is turned over and repeatedly smelted for 3-4 times.
(3) Melt rapid quenching: if a sample of the alloy is desired to be rapidly phase formed, the alloy may be prepared by melt rapid quenching into a polycrystalline or amorphous sample in the form of a ribbon by pouring the molten alloy onto a high speed rotating copper roll and rapidly cooling and solidifying the molten alloy to form a thin ribbon. The alloy ingot which is smelted in an electric arc furnace is placed in a water-cooled copper crucible and is smelted by an induction smelting heating method, then the copper crucible is inclined, and the smelted alloy is poured on the edge of a copper wheel which rotates at a high speed to be rapidly cooled and solidified to form a strip.
Wherein the rotation speed of the copper wheel is 20 m/s in the preparation process, the length of the spun thin strip is about 5 cm, the thickness is about 25 mu m, and then the thin strip is annealed, and the vacuum degree is less than 1 multiplied by 10 during annealing-3Pa, the annealing temperature is 750 ℃, the annealing time is 2 days, and furnace cooling treatment is carried out after the annealing is finished.
Example 3
A material with controllable magnetic property and related magnetic effect by bending or twisting has a chemical formula of Ni34CoaMn30Fe5Ge 10The preparation method of the material comprises the following steps:
(1) preparing materials: high-purity raw materials of Ni, Mn, Fe, Co and Ge are weighed according to the proportion in the chemical formula, and an oxide layer on the surface of a required transition metal element is carefully ground off before proportioning.
(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 carefully placed at the center position of the bottom of the copper crucible, the positions of different samples are recorded, and then the furnace is vacuumized before a furnace cover is lowered to start smelting. The vacuum pumping process is divided into two stages: firstly, pumping to about 5 Pa by a mechanical pump, and then pumping the air pressure to less than 3x10 by a diffusion pump-3Pa or so, and finally filling high-purity Ar gas with 0.6 atmospheric pressure into the furnace cavity to start smelting.
When carrying out the sample smelting, utilize the knob on electric arc furnace top to descend the tungsten electrode to more to press close to the sample piece that needs the smelting, let the electrode be close to the closed angle department of sample piece as far as possible, utilize the tip effect to assist the arcing, the distance of electrode and sample will carefully be transferred, has big difficult arcing, has little the electrode and touches the sample easily. 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, an electromagnetic stirrer is used for stirring the molten liquid alloy. 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 to further obtain a uniform alloy sample, and the ingot is turned over and repeatedly smelted for 3-4 times.
(3) Melt rapid quenching: if a sample of the alloy is desired to be rapidly phase formed, the alloy may be prepared by melt rapid quenching into a polycrystalline or amorphous sample in the form of a ribbon by pouring the molten alloy onto a high speed rotating copper roll and rapidly cooling and solidifying the molten alloy to form a thin ribbon. The alloy ingot which is smelted in an electric arc furnace is placed in a water-cooled copper crucible and is smelted by an induction smelting heating method, then the copper crucible is inclined, and the smelted alloy is poured on the edge of a copper wheel which rotates at a high speed to be rapidly cooled and solidified to form a strip.
Wherein the rotation speed of the copper wheel is 30 m/s in the preparation process, the length of the cast thin strip is about 10 cm, the thickness is about 28 mu m, and then the thin strip is annealed, and the vacuum degree is less than 1 multiplied by 10 during annealing-3Pa, annealing temperature of 800 ℃, annealing time of 2 days, and furnace cooling treatment after the annealing is finished.
Example 4
A material with controllable magnetic property and related magnetic effect by bending or twisting has a chemical formula of Ni33Co17Mn25Fe10 Zr 20The preparation method of the material comprises the following steps:
(1) preparing materials: high-purity raw materials of Ni, Mn, Fe, Co, Ti and Zr are weighed according to the proportion in the chemical formula, and an oxide layer on the surface of a required transition metal element is carefully ground off before proportioning.
(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 carefully placed at the center position of the bottom of the copper crucible, the positions of different samples are recorded, and then the furnace is vacuumized before a furnace cover is lowered to start smelting. The vacuum pumping process is divided into two stages: firstly, pumping to about 5 Pa by a mechanical pump, and then pumping the air pressure to less than 3x10 by a diffusion pump-3Pa or so, and finally filling high-purity Ar gas with 0.6 atmospheric pressure 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 to further obtain a uniform alloy sample, and the ingot is turned over and repeatedly smelted for 3-4 times.
(3) Melt rapid quenching: if a sample of the alloy is desired to be rapidly phase formed, the alloy may be prepared into a polycrystalline or amorphous sample in the form of a ribbon by melt quenching, in which the molten alloy is poured onto a high speed rotating copper roll and rapidly cooled and solidified to form a thin ribbon. The alloy ingot which is smelted in the electric arc furnace is placed in a water-cooling copper crucible, and is smelted by an induction smelting heating method, then the copper crucible is inclined, and the smelted alloy is poured on the edge of a copper wheel rotating at high speed to be rapidly cooled and solidified, so that a strip is manufactured.
Wherein the rotation speed of the copper wheel is 45 m/s in the preparation process, the length of the thrown thin strip is about 15 cm, the thickness of the thin strip is about 30 mu m, then the thin strip is annealed, and the vacuum degree in annealing is less than 1 multiplied by 10-3Pa, annealing temperature of 900 ℃, annealing time of 3 days, and furnace cooling treatment after the annealing is finished.
Example 5
A material with controllable magnetic property and related magnetic effect by bending or twisting has a chemical formula of Ni33Co17Mn25Fe10 W 20The preparation method of the material comprises the following steps:
(1) preparing materials: high-purity raw materials of Ni, Mn, Fe, Co, Ti and W are weighed according to the proportion in the chemical formula, and an oxide layer on the surface of a required transition metal element is carefully ground off before the materials are mixed.
(2) Smelting: smelting is carried out by adopting a water-cooled copper crucible electric arc furnace, and the electric arc furnace is cooled by a circulating water cooling systemCarefully placing the prepared raw materials together at the center of the bottom of a copper crucible, recording the positions of different samples, and vacuumizing the furnace before lowering a furnace cover to start smelting. The vacuum pumping process is divided into two stages: firstly, pumping to about 5 Pa by a mechanical pump, and then pumping the air pressure to less than 3x10 by a diffusion pump-3Pa or so, and finally filling high-purity Ar gas with 0.6 atmospheric pressure into the furnace cavity, starting smelting, and repeatedly smelting for 3-4 times.
(3) Melt rapid quenching: the molten alloy is poured onto a copper roll rotating at a high speed to be rapidly cooled and solidified, and a thin strip is produced. The alloy ingot which is smelted in an electric arc furnace is placed in a water-cooled copper crucible and is smelted by an induction smelting heating method, then the copper crucible is inclined, and the smelted alloy is poured on the edge of a copper wheel which rotates at a high speed to be rapidly cooled and solidified to form a strip.
Wherein the rotation speed of the copper wheel is 45 m/s in the preparation process, the length of the thrown thin strip is about 15 cm, the thickness of the thin strip is about 30 mu m, then the thin strip is annealed, and the vacuum degree in annealing is less than 1 multiplied by 10-3Pa, annealing temperature of 900 ℃, annealing time of 7 days, and furnace cooling treatment after the annealing is finished.
Example 6
Ni prepared in example 135Co15Mn33Fe2Ti15The ribbon is transferred to the surface of a polymer substrate (the polymer substrate can be PET, polydimethylsiloxane, PBT or polypropylene, etc.) as shown in fig. 10, bending strain is introduced to the phase-change ribbon by bending the polymer substrate, so that the deformation curvature of the phase-change ribbon is changed to be subjected to certain strain, and magnetic properties and related magnetic effects are tested, wherein the strain calculation formula is as follows: epsilon = τ/2R, where τ is the thickness of the ribbon and R is the radius of curvature of the ribbon, the bending strain in this example is the maximum bending strain, and the test results are shown as bend 1 in fig. 6, 7 and 9.
Example 7
Ni prepared in example 135Co15Mn33Fe2Ti15The thin strip is transferred to the surface of the polymer substrate (the polymer substrate may bePET, polydimethylsiloxane, PBT or polypropylene, etc.), bending strain is introduced to the phase-change thin strip by bending the polymer substrate, so as to change the curvature of the deformation of the phase-change thin strip to have a certain strain, and magnetic properties and related magnetic effects are tested, wherein the strain calculation formula is as follows: ε = 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 less than that in example 6, and the test results are shown as bend 2 in FIG. 6.
And (3) data analysis:
ni prepared in example 135Co15Mn33Fe2Ti15The crystal structure of the thin strip is tested by X-ray diffraction (XRD) at 300K, the test result is shown in figure 1, and the thin strip sample is found to have no other impurity phase and present a single-phase B2 phase structure.
Then adding the Ni35Co15Mn33Fe2Ti15As shown in fig. 2 and 3, the DSC and M-T tests of the ribbon showed that the ribbon had a phase transition temperature in the range of-50 to 20 ℃ and a curie temperature of about 80 ℃, indicating that the ribbon could exhibit a large difference in magnetization before and after the phase transition (fig. 3) and a large magnetic refrigeration effect, as shown in fig. 2.
FIG. 4 is Ni35Co15Mn33Fe2Ti15According to an isothermal magnetization curve diagram (from weak magnetic martensite to strong magnetic austenite) of the thin strip in a phase transformation temperature range (237K-267K), the magnetic structure phase transformation driven by a magnetic field can be obviously observed in the phase transformation temperature range.
FIG. 5 is Ni35Co15Mn33Fe2Ti15The magnetic entropy change diagram (from weak magnetic martensite to strong magnetic austenite) of the thin strip shows that the magnetic entropy change value is as high as 7.5 Jkg in a 2T magnetic field change in a phase transition temperature region-1K-1(ii) a Under the change of a 5T magnetic field, the magnetic entropy change value is as high as 19 Jkg-1K-1(ii) a There are great potential applications for refrigeration technology.
NiMn with MPMSBased on measurement of relevant magnetism of the ferromagnetic shape memory alloy thin film, the influence of strain regulated by bending or torsion on parameters such as phase transition temperature, magnetization intensity and the like of the alloy thin strip and a magnetocaloric effect is represented. Wherein the free curve of FIG. 6 is Ni in the unstrained condition35Co15Mn33Fe2Ti15M-T diagram of thin strip with maximum magnetization of 72emu g-1FIG. 6 shows that the bending 1 and the bending 2 are Ni controlled by buckling in examples 6 and 7, respectively35Co15Mn33Fe2Ti15M-T diagram of the strip, as can be seen from the figure, for Ni35Co15Mn33Fe2Ti15The magnetization of the thin strip after stress increases with the increase of bending strain, wherein the maximum magnetization of the bend 1 in example 6 reaches 108 emu g -1Whereas in example 6 the maximum magnetization of bend 2 reached 92 emu g-1When the bending stress is removed, the maximum magnetic field strength returns to the initial 72emu g-1Left and right, indicating that the process of magnetization increase induced by bending is reversible.
FIG. 7 shows Ni buckling-regulated at 280K35Co15Mn33Fe2Ti15M-H diagram of thin strip. As can be seen from the figure, the thin strip has a large difference in magnetization before and after bending. The control on the magnetism of the thin strip can be realized, and larger magnetic entropy change is predicted.
FIG. 8 and FIG. 9 are Ni, respectively35Co15Mn33Fe2Ti15The magnetic entropy transformation diagram before and after the strip is bent (strong magnetic austenite to weak magnetic martensite process). As can be seen from the figure, the magnetic entropy change of the thin strip can be enhanced by introducing the strain, and the expansion of the refrigeration temperature zone and the improvement of the refrigeration capacity are realized by regulating and controlling the magnetic phase change temperature and the magnetocaloric effect.

Claims (7)

1. A method for regulating and controlling magnetism and related magnetic effect of phase-change thin band with chemical formula of Ni50-aCoaMn35- bFebXcWherein a is more than or equal to 12 and less than or equal to 17, b is more than 0 and less than or equal to 10, c is more than or equal to 5 and less than or equal to 20, and X comprises SnGa, In, Si, Ge, Ti, Zr, Hf, V, Nb, Ta, characterized In that buckling or twisting is performed by a mechanical external force to apply tensile stress or compressive stress to the phase-change ribbon, thereby changing the magnetic properties and associated magnetic effects of the phase-change ribbon material;
Wherein the buckling by mechanical external force means: extruding two ends of the phase-change thin strip to enable the middle of the thin strip to be warped, and accordingly buckling is generated; or transferring the phase-change thin strip to the surface of the high-molecular base material, extruding two ends of the high-molecular base material to bend the high-molecular base material, and introducing bending strain to the phase-change thin strip;
the torsion by the mechanical external force is as follows: rotating two ends of the phase-change thin strip in different directions respectively to form torsion; or the phase-change thin strip is transferred to the surface of the polymer substrate, and the two ends of the polymer substrate are respectively rotated in different directions to form torsion, so that the bending strain is introduced to the phase-change thin strip.
2. The method for regulating and controlling the magnetism and the related magnetic effect of the phase-change thin strip according to claim 1, wherein the phase-change temperature of the phase-change thin strip ranges from-100 ℃ to 200 ℃, and the Curie temperature ranges from 10 ℃ to 100 ℃.
3. The method for regulating and controlling magnetism and related magnetic effects of the phase-change thin strip according to claim 1, wherein the maximum entropy change value of the phase-change thin strip is 15Jkg under the change of 0-2T magnetic field-1K-1(ii) a Under the change of a 0-5T magnetic field, the maximum entropy change value is 40Jkg-1K-1。
4. The method for regulating and controlling the magnetism and the related magnetic effect of the phase-change thin strip according to claim 1, wherein the method for preparing the phase-change thin strip comprises the following steps:
(1) Weighing high-purity raw materials according to the proportion in the chemical formula;
(2) arc melting the raw materials to obtain a NiMi-based alloy block;
(3) and performing melt rapid quenching on the block body under vacuum to obtain the phase-change thin strip material, namely the thin strip material with magnetism and related magnetic effect regulated and controlled by bending or twisting.
5. The method for controlling magnetism and related magnetic effects of the phase-change thin strip of claim 4, wherein the arc melting vacuum is less than 3 x 10-3Pa。
6. The method for regulating and controlling the magnetism and the related magnetic effect of the phase-change thin strip according to claim 4, wherein the rotation speed of a copper wheel in the preparation process is 10-45 m/s, the length of the thin strip which is thrown out is 2-15 cm, and the thickness of the thin strip is 20-30 μm.
7. The method as claimed in claim 4, wherein the degree of vacuum during annealing is less than 1 x 10-3Pa, annealing temperature is 600-900 ℃, annealing time is 1-7 days, and furnace cooling treatment is carried out after annealing is finished.
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