US20200024693A1 - Mm'x-y metal composite functional material and preparation method thereof - Google Patents

Mm'x-y metal composite functional material and preparation method thereof Download PDF

Info

Publication number
US20200024693A1
US20200024693A1 US16/311,562 US201716311562A US2020024693A1 US 20200024693 A1 US20200024693 A1 US 20200024693A1 US 201716311562 A US201716311562 A US 201716311562A US 2020024693 A1 US2020024693 A1 US 2020024693A1
Authority
US
United States
Prior art keywords
metal composite
functional material
composite functional
preparation
group
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.)
Abandoned
Application number
US16/311,562
Inventor
Hu ZHANG
Kun Tao
Kewen Long
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.)
Foshan Cheng Xian Technology Co Ltd
University of Science and Technology Beijing USTB
Chuandong Magnetic Electronic Co Ltd
Original Assignee
Foshan Cheng Xian Technology Co Ltd
University of Science and Technology Beijing USTB
Chuandong Magnetic Electronic Co Ltd
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 Foshan Cheng Xian Technology Co Ltd, University of Science and Technology Beijing USTB, Chuandong Magnetic Electronic Co Ltd filed Critical Foshan Cheng Xian Technology Co Ltd
Publication of US20200024693A1 publication Critical patent/US20200024693A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • B22F1/0085—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1036—Alloys containing non-metals starting from a melt
    • 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
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/044—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by jet milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/02—Magnetic

Definitions

  • the present invention relates to the technical field of metal materials, and more particularly, to an MM′X—Y (M and M′ are transitional elements, and X is an element of IIIA group or IVA group) metal composite functional material and a preparation method thereof.
  • Martensitic phase transition is an important diffusionless solid-state phase transition of crystal structure, and is a first-order transition. Martensite is formed in carbon steels by the rapid cooling of the austenite form of iron at such a high rate that carbon atoms do not have time to diffuse out of the crystal structure in large enough quantities to form cementite.
  • the martensitic reaction begins during cooling when the austenite reaches the martensite start temperature and the parent austenite becomes mechanically unstable.
  • the face-centered cubic austenite transforms to a highly strained body-centered tetragonal form called martensite that is supersaturated with carbon.
  • the shear deformations that result produce a large number of dislocations, which is a primary strengthening mechanism of steels.
  • Martensitic transition materials are widely used for strengthening steels, toughening materials, reducing quenching deformations, improving shape-memory effect and enhancing super-elasticity. They're ideal functional materials.
  • the martensitic transition process is usually accompanied with a drastic change of crystal structure.
  • the aforesaid effect is also applied for shape-memory alloys. Namely, the material with a certain shape is cooled at a high temperature higher than the martensitic transition temperature (T M ), thereby forming a low-temperature martensitic phase. In this state, the material deforms under load. After being heated to the martensitic reverse transition temperature (T A ), it is restored to the original shape. It's difficult to improve the response frequency and sensitivity of traditional shape-memory alloys because their deformations are controlled by temperature and stress variation.
  • the martensitic transition of some materials can be controlled by a magnetic field other than a temperature field and a stress field.
  • These novel materials with ferromagnetic and thermo-elastic martensitic transition are called ferromagnetic martensitic transition alloys. Due to the coupling effect of the magnetic transition and the structural transition, the structure, the magnetic properties and the electric properties of the crystal are changed violently.
  • the ferromagnetic shape-memory alloys present various functional effects such as shape-memory effect, magnetostriction effect, magneto-resistance effect, Hall effect and magneto-thermal effect, etc. These rich magnetic properties and potential application values make the ferromagnetic martensitic transition alloys become novel functional materials that attract wide attentions.
  • the largest family of the ferromagnetic martensitic transition alloys is the Heusler alloys, including Ni—Mn—Ga, Ni—Mn—Al, Ni—Mn—In and Ni—Mn—Sn. More recently, a novel MM′X (M and M′ are transitional elements, and X is an element of IIIA group or IVA group) ferromagnetic martensitic transition material (e.g., MnCoGe or MnNiGe) has been found by researchers. Through adjusting the compositions and preparing processes, the MM′X alloy also shows a magnetic-field-induced ferromagnetic martensitic transition.
  • the MM′X alloy can be used as a multifunctional material (e.g., shape-memory material, negative expansion material and magnetic refrigeration material, etc.), and is considered as a new generation of ferromagnetic martensitic transition functional materials.
  • the purpose of the present invention is to solve the shortcomings in the prior art by providing an MM′X—Y metal composite functional material and a preparation method thereof.
  • an MM′X—Y metal composite functional material with an excellent mechanical performance and ferromagnetic martensitic transition can be prepared.
  • the prepared material possesses a high magnetic refrigeration performance and a wide application range.
  • the present invention adopts the following technical solution:
  • An MM′X—Y metal composite functional material comprising the following components in percentage by volume:
  • A% of M a M′ b X c and B% of Y wherein each of M and M′ is any one element of a transition group or an alloy of more than one element, X is any one element of IIIA group or IVA group or an alloy of more than one element, and Y is any one element of IB group, IIB group, IIA group or IVA group, or an alloy of more than one element, wherein the value range of a, b and c is 0.8-1.2, and the sum of A% and B% is 100%.
  • A% is 50%-95%, and B% is 5%-50%.
  • A% is 60%-90%, and B% is 10%-40%.
  • a preparation method of the MM′X—Y metal composite functional material comprising the steps of:
  • Mn is excessively added according to the atomic ratio of 1%-10% for compensating its volatile and burning losses during the preparation process, thereby obtaining the single phase.
  • Mn is excessively added according to the atomic ratio of 2%-5%.
  • the pressure in the smelting furnace is controlled to be smaller than or equal to 3 ⁇ 10 ⁇ 3 Pa after being vacuumed.
  • the smelting temperature is higher than 1300° C., and the smelting time is 0.5-10 minutes.
  • the pressure in the smelting furnace is 2 ⁇ 10 ⁇ 3 -10 ⁇ 3 Pa after being vacuumed.
  • the smelting temperature is 1300-1700° C., and the smelting time is 2-3 minutes.
  • the vacuuming and annealing temperature is 600-1100° C., and the time is 1-30 days.
  • the vacuuming and annealing temperature is 700-900° C., and the time is 5-15 days.
  • the crushing method comprises one or any combination of the following methods including grinding, vibration grinding, rolling grinding, ball milling and jet milling, etc.
  • the screen is a standard screen with a mesh size greater than 10 mesh, and the particle size of the powder is smaller than 2 mm.
  • the screen is a standard screen with a mesh size of 100-300 mesh, and the particle size of the powder is 0-0.2 mm.
  • the pressing formation is to press the powder into a required size or shape through a rolling method, a mold pressing method, an extrusion method, a powder injection forming method or a discharge plasma sintering method.
  • the pressure is 300-1500 Mpa
  • the temperature is 0-900° C.
  • the time is 1-240 minutes
  • the intensity of the magnetic field is 0-5 T.
  • the pressure is 600-1000 MPa
  • the temperature is 0-500° C.
  • the time is 5-60 minutes
  • the intensity of the magnetic field is 0-2 T.
  • the curing temperature is 0-900° C. and the curing time is 1-15 days.
  • the curing temperature is 0-500° C. and the curing time is 2-7 days.
  • the present invention has the following advantages:
  • the present invention provides a novel MM′X—Y metal composite functional material;
  • the mechanical performance of the MM′X—Y metal composite functional material prepared according to the present invention is far higher than the traditional MM′X material;
  • the prepared MM′X—Y metal composite functional material has an ideal magnetothermal effect, thus can be used as a magnetic refrigeration material;
  • the preparation method of the present invention can prepare MM′X—Y metal composite functional materials with any size and shape according to actual requirements;
  • the preparation method of the present invention is simple, and can be easily operated and realized in industrial production.
  • FIG. 1 is a topography diagram of the smelted Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 prepared according to embodiment 1 of the present invention
  • FIG. 2 is a topography diagram of the smelted 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In metal composite functional material prepared according to embodiment 1 of the present invention
  • FIG. 3 is a stress-strain curve graph of the 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In metal composite functional material prepared according to embodiment 1 of the present invention
  • FIG. 4 is a diagram showing the temperature dependence of ⁇ S of the 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In metal composite functional material prepared according to embodiment 1 of the present invention in different magnetic fields;
  • FIG. 5 is a stress-strain curve graph of the 75% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +25% In metal composite functional material prepared according to embodiment 2 of the present invention.
  • FIG. 6 is a stress-strain curve graph of the 80% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +20% In metal composite functional material prepared according to embodiment 3 of the present invention.
  • the present invention discloses a 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In metal composite functional material and a preparation method thereof.
  • the preparation method of the 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In metal composite functional material comprising the steps of:
  • FIG. 1 The morphology of the smelted Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 sample prepared in embodiment 1 is shown in FIG. 1 .
  • FIG. 1 After a traditional smelting process, the sample undergoes a martensitic transition when being cooled from a high temperature to a room temperature. The sample is crumbled due to the huge internal stress generated in the transition process, making the forming and mechanical machining become extremely difficult. The application range of the functional material is thus greatly limited.
  • the morphology of the product of embodiment 1 is shown in FIG. 2 . As can be seen, it can be easily formed and processed, effectively solving the prior technical problems.
  • the stress-strain curve test cannot be carried out.
  • the mechanical performance of the product prepared in embodiment 1 is remarkably improved so that the test can be easily performed.
  • the stress-strain curve of the prepared product can be tested by using a WDW200D type microcomputer control universal material tester. As shown in FIG. 3 , after being tested, the compressive strength of the prepared product is 45 MPa, and the corresponding strain is 9.2%.
  • FIG. 4 shows the temperature dependence of ⁇ S of the prepared product in different magnetic fields. As can be seen, when the transition temperature is near 311K, the maximum value of the magnetic entropy change appears.
  • the maximum magnetic entropy change of the sample is respectively 4.5 J/kgK, 9.9 J/kgK, and 15.3 J/kgK.
  • a magnetic field at intensity of 2 T can be obtained by utilizing the permanent magnet NdFeB. Therefore, the magnetic entropy changes of the material when the magnetic intensity varies from 0 to 2 T attracts more attentions.
  • the maximum value of the magnetic entropy change (9.9 J/kgK) of the prepared product is much greater than that (when the magnetic intensity is 2 T, the magnetic entropy change is 5.0 J/kgK) of the traditional room-temperature magnetic refrigeration material Gd. It means that the product of the aforesaid embodiment can be used as a better room-temperature functional material.
  • the present invention discloses a 75% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +25% In metal composite functional material and a preparation method thereof.
  • the preparation method of the 75% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +25% In metal composite functional material comprising the steps of:
  • the stress-strain curve of the 75% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +25% In metal composite material can be tested by using a WDW200D type microcomputer control universal material tester. As shown in FIG. 5 , after being tested, the compressive strength of the prepared product is 48 MPa, and the corresponding strain is 15.6%. Meanwhile, the magnetic test shows that the magnetothermal effect of the prepared product of embodiment 2 is better than that of the traditional room-temperature magnetic refrigeration material Gd.
  • the present invention discloses an 80% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +20% In metal composite functional material and a preparation method thereof.
  • the preparation method of the 80% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +20% In metal composite functional material comprising the steps of:
  • the stress-strain curve of the 80% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +20% In metal composite material can be tested by using a WDW200D type microcomputer control universal material tester. As shown in FIG. 6 , after being tested, the compressive strength of the prepared product is 41 MPa, and the corresponding strain is 14.9%.
  • the present invention discloses a 60% MnCoCu 0.08 Ge 0.92 +40% Sn metal composite functional material and a preparation method thereof.
  • the preparation method of the 60% MnCoCu 0.08 Ge 0.92 +40% Sn metal composite functional material comprising the steps of:
  • the present invention discloses a 75% Mn 0.95 CoGe 0.9 Si 0.1 +25% InSn metal composite functional material and a preparation method thereof.
  • the preparation method of the 75% Mn 0.95 CoGe 0.9 Si 0.1 +25% InSn metal composite functional material comprising the steps of:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

An MM′X—Y metal composite functional material and a preparation method thereof; an MM′X—Y metal composite functional material, comprising the following components in percentage by volume: A% of MaM′bXc and B% of Y, wherein each of M and M′ is any one element of a transition group or an alloy of more than one element, X is any one element of IIIA group or IVA group or an alloy of more than one element, and Y is any one element of IB group, IIB group, IIA group or IVA group, or an alloy of more than one element, wherein the value range of a, b and c is 0.8-1.2, and the sum of A% and B% is 100%; the material is prepared through smelting, annealing, crushing, mixing, pressing and curing, etc.; the mechanical performance of the MM′X—Y metal composite functional material prepared according to the present invention is far higher than the traditional MM′X material; the prepared MM′X—Y metal composite functional material has an ideal magnetothermal effect, thus can be used as a magnetic refrigeration material; the method can prepare MM′X—Y metal composite functional materials with any size and shape according to actual requirements; the method is simple, and can be easily operated and realized.

Description

    TECHNICAL FIELD OF THE INVENTION
  • The present invention relates to the technical field of metal materials, and more particularly, to an MM′X—Y (M and M′ are transitional elements, and X is an element of IIIA group or IVA group) metal composite functional material and a preparation method thereof.
    • BACKGROUND OF THE INVENTION
  • Martensitic phase transition is an important diffusionless solid-state phase transition of crystal structure, and is a first-order transition. Martensite is formed in carbon steels by the rapid cooling of the austenite form of iron at such a high rate that carbon atoms do not have time to diffuse out of the crystal structure in large enough quantities to form cementite. The martensitic reaction begins during cooling when the austenite reaches the martensite start temperature and the parent austenite becomes mechanically unstable. As a result of the cooling, the face-centered cubic austenite transforms to a highly strained body-centered tetragonal form called martensite that is supersaturated with carbon. The shear deformations that result produce a large number of dislocations, which is a primary strengthening mechanism of steels. During this process, an increasingly large percentage of the austenite transforms to martensite until the lower phase transition temperature is reached, at which time the transition is completed. Martensitic transition materials are widely used for strengthening steels, toughening materials, reducing quenching deformations, improving shape-memory effect and enhancing super-elasticity. They're ideal functional materials.
  • For the huge structural difference between the martensitic phase and the parent phase, the martensitic transition process is usually accompanied with a drastic change of crystal structure. The aforesaid effect is also applied for shape-memory alloys. Namely, the material with a certain shape is cooled at a high temperature higher than the martensitic transition temperature (TM), thereby forming a low-temperature martensitic phase. In this state, the material deforms under load. After being heated to the martensitic reverse transition temperature (TA), it is restored to the original shape. It's difficult to improve the response frequency and sensitivity of traditional shape-memory alloys because their deformations are controlled by temperature and stress variation.
  • In recent years, researches have shown that the martensitic transition of some materials can be controlled by a magnetic field other than a temperature field and a stress field. These novel materials with ferromagnetic and thermo-elastic martensitic transition are called ferromagnetic martensitic transition alloys. Due to the coupling effect of the magnetic transition and the structural transition, the structure, the magnetic properties and the electric properties of the crystal are changed violently. As a result, the ferromagnetic shape-memory alloys present various functional effects such as shape-memory effect, magnetostriction effect, magneto-resistance effect, Hall effect and magneto-thermal effect, etc. These rich magnetic properties and potential application values make the ferromagnetic martensitic transition alloys become novel functional materials that attract wide attentions.
  • Presently, the largest family of the ferromagnetic martensitic transition alloys is the Heusler alloys, including Ni—Mn—Ga, Ni—Mn—Al, Ni—Mn—In and Ni—Mn—Sn. More recently, a novel MM′X (M and M′ are transitional elements, and X is an element of IIIA group or IVA group) ferromagnetic martensitic transition material (e.g., MnCoGe or MnNiGe) has been found by researchers. Through adjusting the compositions and preparing processes, the MM′X alloy also shows a magnetic-field-induced ferromagnetic martensitic transition. During the transition, a huge deformation of crystal structure and a magneto-thermal effect are achieved, and the phase transition temperature can be adjusted within a wide range. Thus, the MM′X alloy can be used as a multifunctional material (e.g., shape-memory material, negative expansion material and magnetic refrigeration material, etc.), and is considered as a new generation of ferromagnetic martensitic transition functional materials.
  • However, the huge deformation of crystal structure of the MM′X functional material during the martensitic transition process generates a large internal stress, making the MM′X functional material broken after the transition. Thus, the difficulty of forming and mechanical machining is sharply increased, and the application range of the material is greatly limited. Moreover, the research on how to improve the mechanical performance of the MM′X functional material has not been reported until now.
  • In conclusion, it's urgent for those skilled in this field to develop a novel MM′Y functional material with good mechanical properties.
    • SUMMARY OF THE INVENTION
  • The purpose of the present invention is to solve the shortcomings in the prior art by providing an MM′X—Y metal composite functional material and a preparation method thereof. According to the method of the present invention, an MM′X—Y metal composite functional material with an excellent mechanical performance and ferromagnetic martensitic transition can be prepared. The prepared material possesses a high magnetic refrigeration performance and a wide application range.
  • To achieve the above purpose, the present invention adopts the following technical solution:
  • An MM′X—Y metal composite functional material, comprising the following components in percentage by volume:
  • A% of MaM′bXc and B% of Y, wherein each of M and M′ is any one element of a transition group or an alloy of more than one element, X is any one element of IIIA group or IVA group or an alloy of more than one element, and Y is any one element of IB group, IIB group, IIA group or IVA group, or an alloy of more than one element, wherein the value range of a, b and c is 0.8-1.2, and the sum of A% and B% is 100%.
  • In another aspect of the present invention, A% is 50%-95%, and B% is 5%-50%.
  • In another aspect of the present invention, A% is 60%-90%, and B% is 10%-40%.
  • A preparation method of the MM′X—Y metal composite functional material, comprising the steps of:
      • 1) Preparing raw materials according to the chemical formula of MaM′bXc;
      • 2) Feeding the prepared raw materials into a smelting furnace, vacuuming the furnace and cleansing the furnace by argon; subsequently, smelting the prepared raw materials under the protection of argon, thereby obtaining the MaM′bXc alloy;
      • 3) Vacuuming and annealing the MaM′bXc alloy;
      • 4) Respectively crushing and grinding the vacuumed and annealed MaM′bXc alloy and Y material; after screening, obtaining powders;
      • 5) Respectively measuring out the powder of MaM′bXc alloy with a volume percentage of A%, and the powder of Y material with a volume percentage of B%; subsequently, mixing them uniformly;
      • 6) Adopting a pressing formation method to press the uniformly mixed powder under magnetic field, thereby obtaining the formed material;
      • 7) Curing the formed material, thereby obtaining the MM′X metal composite functional material.
  • In another aspect of the present invention, when M or M′ is Mn, Mn is excessively added according to the atomic ratio of 1%-10% for compensating its volatile and burning losses during the preparation process, thereby obtaining the single phase.
  • In another aspect of the present invention, when M or M′ is Mn, Mn is excessively added according to the atomic ratio of 2%-5%.
  • In another aspect of the present invention, the pressure in the smelting furnace is controlled to be smaller than or equal to 3×10−3 Pa after being vacuumed. The smelting temperature is higher than 1300° C., and the smelting time is 0.5-10 minutes.
  • In another aspect of the present invention, the pressure in the smelting furnace is 2×10−3-10−3 Pa after being vacuumed. The smelting temperature is 1300-1700° C., and the smelting time is 2-3 minutes.
  • In another aspect of the present invention, the vacuuming and annealing temperature is 600-1100° C., and the time is 1-30 days.
  • In another aspect of the present invention, the vacuuming and annealing temperature is 700-900° C., and the time is 5-15 days.
  • In another aspect of the present invention, the crushing method comprises one or any combination of the following methods including grinding, vibration grinding, rolling grinding, ball milling and jet milling, etc. The screen is a standard screen with a mesh size greater than 10 mesh, and the particle size of the powder is smaller than 2 mm.
  • In another aspect of the present invention, the screen is a standard screen with a mesh size of 100-300 mesh, and the particle size of the powder is 0-0.2 mm.
  • In another aspect of the present invention, the pressing formation is to press the powder into a required size or shape through a rolling method, a mold pressing method, an extrusion method, a powder injection forming method or a discharge plasma sintering method. During the process of the pressing formation, the pressure is 300-1500 Mpa, the temperature is 0-900° C., the time is 1-240 minutes and the intensity of the magnetic field is 0-5 T.
  • In another aspect of the present invention, during the process of the pressing formation, the pressure is 600-1000 MPa, the temperature is 0-500° C., the time is 5-60 minutes and the intensity of the magnetic field is 0-2 T.
  • In another aspect of the present invention, the curing temperature is 0-900° C. and the curing time is 1-15 days.
  • In another aspect of the present invention, the curing temperature is 0-500° C. and the curing time is 2-7 days.
  • Compared with the prior art, the present invention has the following advantages:
  • First, the present invention provides a novel MM′X—Y metal composite functional material; second, the mechanical performance of the MM′X—Y metal composite functional material prepared according to the present invention is far higher than the traditional MM′X material; third, the prepared MM′X—Y metal composite functional material has an ideal magnetothermal effect, thus can be used as a magnetic refrigeration material; fourth, the preparation method of the present invention can prepare MM′X—Y metal composite functional materials with any size and shape according to actual requirements; fifth, the preparation method of the present invention is simple, and can be easily operated and realized in industrial production.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • To clearly expound the technical solution of the present invention, the drawings and embodiments are hereinafter combined to illustrate the present invention. Obviously, the drawings are merely some embodiments of the present invention and those skilled in the art can associate themselves with other drawings without paying creative labor.
  • FIG. 1 is a topography diagram of the smelted Mn0.6Fe0.4NiSi0.5Ge0.5 prepared according to embodiment 1 of the present invention;
  • FIG. 2 is a topography diagram of the smelted 70% Mn0.6Fe0.4NiSi0.5Ge0.5+30% In metal composite functional material prepared according to embodiment 1 of the present invention;
  • FIG. 3 is a stress-strain curve graph of the 70% Mn0.6Fe0.4NiSi0.5Ge0.5+30% In metal composite functional material prepared according to embodiment 1 of the present invention;
  • FIG. 4 is a diagram showing the temperature dependence of ΔS of the 70% Mn0.6Fe0.4NiSi0.5Ge0.5+30% In metal composite functional material prepared according to embodiment 1 of the present invention in different magnetic fields;
  • FIG. 5 is a stress-strain curve graph of the 75% Mn0.6Fe0.4NiSi0.5Ge0.5+25% In metal composite functional material prepared according to embodiment 2 of the present invention;
  • FIG. 6 is a stress-strain curve graph of the 80% Mn0.6Fe0.4NiSi0.5Ge0.5+20% In metal composite functional material prepared according to embodiment 3 of the present invention.
    •  DETAILED DESCRIPTION OF THE INVENTION
  • Drawings and detailed embodiments are combined hereinafter to elaborate the technical principles of the present invention.
    • Embodiment 1
  • As shown in FIGS. 1-4, the present invention discloses a 70% Mn0.6Fe0.4NiSi0.5Ge0.5+30% In metal composite functional material and a preparation method thereof.
  • The preparation method of the 70% Mn0.6Fe0.4NiSi0.5Ge0.5+30% In metal composite functional material, comprising the steps of:
      • 1) Preparing raw materials according to the chemical formula of Mn0.6Fe0.4NiSi0.5Ge0.5, wherein the raw materials are commercially available metals including Mn, Fe, Ni, Si and Ge with a purity higher than 99.9 wt. %, and Mn is excessively added according to the atomic ratio of 5% for compensating its volatile and burning losses during the preparation process;
      • 2) Adopting an electric arc smelting method; feeding the prepared raw materials into a smelting furnace, vacuuming the smelting furnace until the pressure intensity reaches 2×10−3 Pa, and cleansing the furnace by argon; subsequently, smelting the prepared raw materials at a temperature of 1500° C. for 3 minutes under the protection of argon, thereby obtaining the cast ingot Mn0.6Fe0.4NiSi0.5Ge0.5;
      • 3) Placing the Mn0.6Fe0.4NiSi0.5Ge0.5 into a quartz tube with a vacuum degree of 5×10−3 Pa, and annealing at a temperature of 850° C. for 7 days;
      • 4) Respectively crushing and grinding the vacuumed and annealed Mn0.6Fe0.4NiSi0.5Ge0.5 and metal In by using an agate mortar, and screening out the irregular powder with a size smaller than 0.1 mm according to the screening standard of 150-mesh;
      • 5) Respectively measuring out the Mn0.6Fe0.4NiSi0.5Ge0.5 powder with a volume percentage of 70%, and the In powder with a volume percentage of 30%; subsequently, mixing them uniformly;
      • 6) Pressing the uniformly mixed powder at the condition of 150° C. and 900 MPa for 5 minutes under zero magnetic field, thereby obtaining a cylindrical 70% Mn0.6Fe0.4NiSi0.5Ge0.5+30% In metal composite functional material with a diameter of 10 mm;
      • 7) Curing at a temperature of 150° C. for 7 days, thereby obtaining the 70% Mn0.6Fe0.4NiSi0.5Ge0.5+30% In metal composite functional material, namely, the product of this embodiment.
  • The morphology of the smelted Mn0.6Fe0.4NiSi0.5Ge0.5 sample prepared in embodiment 1 is shown in FIG. 1. As can be seen from FIG. 1, after a traditional smelting process, the sample undergoes a martensitic transition when being cooled from a high temperature to a room temperature. The sample is crumbled due to the huge internal stress generated in the transition process, making the forming and mechanical machining become extremely difficult. The application range of the functional material is thus greatly limited. The morphology of the product of embodiment 1 is shown in FIG. 2. As can be seen, it can be easily formed and processed, effectively solving the prior technical problems.
  • For the mechanical performance of the traditional crumbled MM′X alloy is extremely poor, the stress-strain curve test cannot be carried out. In contrast, the mechanical performance of the product prepared in embodiment 1 is remarkably improved so that the test can be easily performed. The stress-strain curve of the prepared product can be tested by using a WDW200D type microcomputer control universal material tester. As shown in FIG. 3, after being tested, the compressive strength of the prepared product is 45 MPa, and the corresponding strain is 9.2%.
  • After measuring the isothermal magnetization curve (M-H curve) of the prepared product by using a magnetic measurement system (Versalab Free Measurement System developed by Quantum Design, Inc.), the magnetic entropy change ΔS can be calculated from the isothermal magnetization curve according to Maxwell's relation ΔS=∫0 H(∂M/∂T)HdH . FIG. 4 shows the temperature dependence of ΔS of the prepared product in different magnetic fields. As can be seen, when the transition temperature is near 311K, the maximum value of the magnetic entropy change appears. When the intensity of the magnetic field respectively varies from 0 to 1 T, 0 to 2 T, and 0 to 3 T, the maximum magnetic entropy change of the sample is respectively 4.5 J/kgK, 9.9 J/kgK, and 15.3 J/kgK. Presently, a magnetic field at intensity of 2 T can be obtained by utilizing the permanent magnet NdFeB. Therefore, the magnetic entropy changes of the material when the magnetic intensity varies from 0 to 2 T attracts more attentions. Under such a circumstance, the maximum value of the magnetic entropy change (9.9 J/kgK) of the prepared product is much greater than that (when the magnetic intensity is 2 T, the magnetic entropy change is 5.0 J/kgK) of the traditional room-temperature magnetic refrigeration material Gd. It means that the product of the aforesaid embodiment can be used as a better room-temperature functional material.
    • Embodiment 2
  • As shown in FIG. 5, the present invention discloses a 75% Mn0.6Fe0.4NiSi0.5Ge0.5+25% In metal composite functional material and a preparation method thereof. The preparation method of the 75% Mn0.6Fe0.4NiSi0.5Ge0.5+25% In metal composite functional material, comprising the steps of:
      • 1) Preparing raw materials according to the chemical formula of Mn0.6Fe0.4NiSi0.5Ge0.5, wherein the raw materials are commercially available metals including Mn, Fe, Ni, Si and Ge with a purity higher than 99.9 wt. %, and Mn is excessively added according to the atomic ratio of 5% for compensating its volatile and burning losses during the preparation process;
      • 2) Adopting an electric arc smelting method; feeding the prepared raw materials into a smelting furnace, vacuuming the smelting furnace until the pressure intensity reaches 2.5×10−3 Pa, and cleansing the furnace by argon; subsequently, smelting the prepared raw materials at a temperature of 1700° C. for 2 minutes under the protection of argon, thereby obtaining the cast ingot Mn0.6Fe0.4NiSi0.5Ge0.5;
      • 3) Placing the Mn0.6Fe0.4NiSi0.5Ge0.5 into a quartz tube with a vacuum degree of 5×10−3 Pa, and annealing at a temperature of 850° C. for 8 days;
      • 4) Respectively crushing and grinding the vacuumed and annealed Mn0.6Fe0.4NiSi0.5Ge0.5 and metal In by using an agate mortar, and screening out the irregular powder with a size smaller than 0.07 mm according to the screening standard of 200-mesh;
      • 5) Respectively measuring out the Mn0.6Fe0.4NiSi0.5Ge0.5 powder with a volume percentage of 75%, and the In powder with a volume percentage of 25%; subsequently, mixing them uniformly;
      • 6) Pressing the uniformly mixed powder at the condition of 140° C. and 900 MPa for 10 minutes under zero magnetic field, thereby obtaining a cylindrical 75% Mn0.6Fe0.4NiSi0.5Ge0.5+25% In metal composite functional material with a diameter of 10 mm;
      • 7) Curing at a temperature of 500° C. for 7 days, thereby obtaining the 75% Mn0.6Fe0.4NiSi0.5Ge0.5+25% In metal composite functional material.
  • The stress-strain curve of the 75% Mn0.6Fe0.4NiSi0.5Ge0.5+25% In metal composite material can be tested by using a WDW200D type microcomputer control universal material tester. As shown in FIG. 5, after being tested, the compressive strength of the prepared product is 48 MPa, and the corresponding strain is 15.6%. Meanwhile, the magnetic test shows that the magnetothermal effect of the prepared product of embodiment 2 is better than that of the traditional room-temperature magnetic refrigeration material Gd.
    • Embodiment 3
  • As shown in FIG. 6, the present invention discloses an 80% Mn0.6Fe0.4NiSi0.5Ge0.5+20% In metal composite functional material and a preparation method thereof. The preparation method of the 80% Mn0.6Fe0.4NiSi0.5Ge0.5+20% In metal composite functional material, comprising the steps of:
      • 1) Preparing raw materials according to the chemical formula of Mn0.6Fe0.4NiSi0.5Ge0.5, wherein the raw materials are commercially available metals including Mn, Fe, Ni, Si and Ge with a purity higher than 99.9 wt. %, and Mn is excessively added according to the atomic ratio of 3% for compensating its volatile and burning losses during the preparation process;
      • 2) Adopting an electric arc smelting method; feeding the prepared raw materials into a smelting furnace, vacuuming the smelting furnace until the pressure intensity reaches 3×10−3 Pa, and cleansing the furnace by argon; subsequently, smelting the prepared raw materials at a temperature of 1700° C. for 2 minutes under the protection of argon, thereby obtaining the cast ingot Mn0.6Fe0.4NiSi0.5Ge0.5;
      • 3) Placing the Mn0.6Fe0.4NiSi0.5Ge0.5 into a quartz tube with a vacuum degree of 5×10−3 Pa, and annealing at a temperature of 750° C. for 15 days;
      • 4) Respectively crushing and grinding the vacuumed and annealed Mn0.6Fe0.4NiSi0.5Ge0.5 and metal In by using an agate mortar, and screening out the irregular powder with a size smaller than 0.1 mm according to the screening standard of 150-mesh;
      • 5) Respectively measuring out the Mn0.6Fe0.4NiSi0.5Ge0. 5 powder with a volume percentage of 80%, and the In powder with a volume percentage of 20%; subsequently, mixing them uniformly;
      • 6) Pressing the uniformly mixed powder at the condition of 140° C. and 900 MPa for 6 minutes in zero magnetic field, thereby obtaining a cylindrical 80% Mn0.6Fe0.4NiSi0.5Ge0.5+20% In metal composite functional material with a diameter of 10 mm;
      • 7) Curing at a temperature of 500° C. for 7 days, thereby obtaining the 80% Mn0.6Fe0.4NiSi0.5Ge0.5+20% In metal composite functional material.
  • The stress-strain curve of the 80% Mn0.6Fe0.4NiSi0.5Ge0.5+20% In metal composite material can be tested by using a WDW200D type microcomputer control universal material tester. As shown in FIG. 6, after being tested, the compressive strength of the prepared product is 41 MPa, and the corresponding strain is 14.9%.
    • Embodiment 4
  • The present invention discloses a 60% MnCoCu0.08Ge0.92+40% Sn metal composite functional material and a preparation method thereof. The preparation method of the 60% MnCoCu0.08Ge0.92+40% Sn metal composite functional material, comprising the steps of:
      • 1) Preparing raw materials according to the chemical formula of MnCoCu0.08Ge0.92, wherein the raw materials are commercially available metals including Mn, Co, Cu and Ge with a purity higher than 99.9 wt. %, and Mn is excessively added according to the atomic ratio of 3% for compensating its volatile and burning losses during the preparation process;
      • 2) Adopting an electric arc smelting method; feeding the prepared raw materials into a smelting furnace, vacuuming the smelting furnace until the pressure intensity reaches 2×10−3 Pa, and cleansing the furnace by argon; subsequently, smelting the prepared raw materials at a temperature of 1600° C. for 3 minutes under the protection of argon, thereby obtaining the cast ingot MnCoCu0.8Ge0.92;
      • 3) Placing the MnCoCu0.08Ge0.92 into a quartz tube with a vacuum degree of 5×10−3 Pa, and annealing at a temperature of 800° C. for 15 days;
      • 4) Respectively crushing and grinding the vacuumed and annealed MnCoCu0.08Ge0.92 and metal Sn by using a jet mill, and screening out the irregular powder with a size smaller than 0.05 mm according to the screening standard of 300-mesh;
      • 5) Respectively measuring out the MnCoCu0.08Ge0.92 powder with a volume percentage of 60%, and the Sn powder with a volume percentage of 40%; subsequently, mixing them uniformly;
      • 6) Pressing the uniformly mixed powder at the condition of room temperature and 960 MPa for 15 minutes in a magnetic field at intensity of 1.5 T, thereby obtaining a cylindrical 60% MnCoCu0.08Ge0.92+40% Sn metal composite functional material with a diameter of 10 mm;
      • 7) Curing at a temperature of 500° C. for 7 days, thereby obtaining the 60% MnCoCu0.08Ge0.92+40% Sn metal composite functional material, namely, the product of this embodiment.
    Embodiment 5
  • The present invention discloses a 75% Mn0.95CoGe0.9Si0.1+25% InSn metal composite functional material and a preparation method thereof. The preparation method of the 75% Mn0.95CoGe0.9Si0.1+25% InSn metal composite functional material, comprising the steps of:
      • 1) Preparing raw materials according to the chemical formula of Mn0.95CoGe0.9Si0.1, wherein the raw materials are commercially available metals including Mn, Go, Ge and Si with a purity higher than 99.9 wt. %, and Mn is excessively added according to the atomic ratio of 4% for compensating its volatile and burning losses during the preparation process;
      • 2) Adopting an electric arc smelting method; feeding the prepared raw materials into a smelting furnace, vacuuming the smelting furnace until the pressure intensity reaches 3×10−3 Pa, and cleansing the furnace by argon; subsequently, smelting the prepared raw materials at a temperature of 1400° C. for 3 minutes under the protection of argon, thereby obtaining the cast ingot Mn0.95COGe0.9Si0.1;
      • 3) Placing the Mn0.95CoGe0.9Si0.1 into a quartz tube with a vacuum degree of 5×10−3 Pa, and annealing at a temperature of 900° C. for 5 days;
      • 4) Respectively crushing and grinding the vacuumed and annealed Mn0.95CoGe0.9Si0.1 and metal InSn by using a high energy ball mill, and screening out the irregular powder with a size smaller than 0.06 mm according to the screening standard of 250-mesh;
      • 5) Respectively measuring out the Mn0.95CoGe0.9Si0.1 powder with a volume percentage of 75%, and the InSn powder with a volume percentage of 25%; subsequently, mixing them uniformly;
      • 6) Pressing the uniformly mixed powder at the condition of 800° C. and 600 MPa for 15 minutes in zero magnetic field, thereby obtaining a cylindrical 75% Mn0.95CoGe0.9Si0.1+25% InSn metal composite functional material with a diameter of 10 mm;
      • 7) Curing at a temperature of 500° C. for 7 days, thereby obtaining the 75% Mn0.95CoGe0.9Si0.1+25% InSn metal composite functional material, namely, the product of this embodiment.
  • The description of above embodiments allows those skilled in the art to realize or use the present invention. Without departing from the spirit and essence of the present invention, those skilled in the art can combine, change or modify correspondingly according to the present invention. Therefore, the protective range of the present invention should not be limited to the embodiments above but conform to the widest protective range which is consistent with the principles and innovative characteristics of the present invention. Although some special terms are used in the description of the present invention, the scope of the invention should not necessarily be limited by this description. The scope of the present invention is defined by the claims.

Claims (16)

1. An MM′X—Y metal composite functional material, comprising the following components in percentage by volume:
A% of MaM′bXc and B% of Y, wherein
each of M and M′ is any one element of a transition group or an alloy of more than one element, X is any one element of IIIA group or IVA group or an alloy of more than one element, and Y is any one element of IB group, IIB group, IIA group or IVA group, or an alloy of more than one element, wherein the value range of a, b and c is 0.8-1.2, and the sum of A% and B% is 100%.
2. The MM′X—Y metal composite functional material of claim 1, wherein A% is 50%-95%, and B% is 5%-50%.
3. The MM′X—Y metal composite functional material of claim 1, wherein A% is 60%-90%, and B% is 10%-40%.
4. A preparation method of the MM′X—Y metal composite functional material, comprising the steps of:
1) Preparing raw materials according to the chemical formula of MaM′bXc;
2) Feeding the prepared raw materials into a smelting furnace, vacuuming the furnace and cleansing the furnace by argon; subsequently, smelting the prepared raw materials under the protection of argon, thereby obtaining the MaM′bXc alloy;
3) Vacuuming and annealing the MaM′bXc alloy;
4) Respectively crushing and grinding the vacuumed and annealed MaM′bXc alloy and Y material; after screening, obtaining powders;
5) Respectively measuring out the powder of MaM′bXc alloy with a volume percentage of A%, and the powder of Y material with a volume percentage of B%; subsequently, mixing them uniformly;
6) Adopting a pressing formation method to press the uniformly mixed powder under magnetic field, thereby obtaining the formed material;
7) Curing the formed material, thereby obtaining the MM′X metal composite functional material.
5. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein when M or M′ is Mn, Mn is excessively added according to the atomic ratio of 1%-10% for compensating its volatile and burning losses during the preparation process, thereby obtaining the single phase.
6. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein when M or M′ is Mn, Mn is excessively added according to the atomic ratio of 2%-5%.
7. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein the pressure in the smelting furnace is controlled to be smaller than or equal to 3×10−3 Pa after being vacuumed, wherein the smelting temperature is higher than 1300° C., and the smelting time is 0.5-10 minutes.
8. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein the pressure in the smelting furnace is 2×10−3-3×10−3 Pa after being vacuumed, wherein the smelting temperature is 1300-1700° C., and the smelting time is 2-3 minutes.
9. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein the vacuuming and annealing temperature is 600-1100° C., and the time is 1-30 days.
10. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein the vacuuming and annealing temperature is 700-900° C., and the time is 5-15 days.
11. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein the crushing method comprises one or any combination of the following methods including grinding, vibration grinding, rolling grinding, ball milling and jet milling, etc., wherein the screen is a standard screen with a mesh size greater than 10 mesh, and the particle size of the powder is smaller than 2 mm.
12. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein the screen is a standard screen with a mesh size of 100-300 mesh, and the particle size of the powder is 0-0.2 mm.
13. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein the pressing formation is to press the powder into a required size or shape through a rolling method, a mold pressing method, an extrusion method, a powder injection forming method or a discharge plasma sintering method, wherein during the process of the pressing formation, the pressure is 300-1500 Mpa, the temperature is 0-900° C., the time is 1-240 minutes and the intensity of the magnetic field is 0-5 T.
14. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein during the process of the pressing formation, the pressure is 600-1000 MPa, the temperature is 0-500° C., the time is 5-60 minutes and the intensity of the magnetic field is 0-2 T.
15. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein the curing temperature is 0-900° C. and the curing time is 1-15 days.
16. The preparation method of the MM′X—Y metal composite functional material of claim 4, wherein the curing temperature is 0-500° C. and the curing time is 2-7 days.
US16/311,562 2017-04-13 2017-06-01 Mm'x-y metal composite functional material and preparation method thereof Abandoned US20200024693A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN201710238382.5A CN106917029B (en) 2017-04-13 2017-04-13 A kind of ferromagnetic martensitic traoformation MM ' X-Y metal composite functional materials and preparation method thereof
CN201710238382.5 2017-04-13
PCT/CN2017/086889 WO2018188178A1 (en) 2017-04-13 2017-06-01 Functional mm'x-y metal composite material and preparation method therefor

Publications (1)

Publication Number Publication Date
US20200024693A1 true US20200024693A1 (en) 2020-01-23

Family

ID=59568323

Family Applications (1)

Application Number Title Priority Date Filing Date
US16/311,562 Abandoned US20200024693A1 (en) 2017-04-13 2017-06-01 Mm'x-y metal composite functional material and preparation method thereof

Country Status (3)

Country Link
US (1) US20200024693A1 (en)
CN (1) CN106917029B (en)
WO (1) WO2018188178A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200168301A1 (en) * 2017-07-12 2020-05-28 United Kingdom Research And Innovation Efficiently populating a phase diagram for multiple substances

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111115588B (en) * 2019-12-27 2023-04-07 天津大学 Spinning zero-energy-gap semiconductor material with zero energy gap protected by lattice symmetry and preparation method thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1237143C (en) * 2002-07-15 2006-01-18 南京大学 Composite room temperature magnetic refrigerating material and its prepn.
CN1304615C (en) * 2004-06-09 2007-03-14 北京科技大学 Compounds with large magnetic entropy changes and their preparation
CN103422014B (en) * 2012-05-22 2015-11-25 中国科学院物理研究所 Thermoplastic shaping bonding magnetic refrigerating working material and its production and use
CN105568108B (en) * 2014-10-09 2017-11-14 中国科学院物理研究所 Keep method and the application of the co-structured phase transformation of strong magnetic of MnNiGe sills
CN105624514B (en) * 2014-10-29 2017-08-01 中国科学院物理研究所 A kind of negative expansion material and its production and use
WO2016104739A1 (en) * 2014-12-26 2016-06-30 大電株式会社 Production method for magnetic refrigeration material
CN105448443A (en) * 2015-11-26 2016-03-30 北京科技大学 Preparation method of bonding martensitic phase change material
CN105714173B (en) * 2016-04-27 2017-08-25 上海电力学院 A kind of manganese cobalt germanium-base alloy magnetic refrigerating material and its preparation

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200168301A1 (en) * 2017-07-12 2020-05-28 United Kingdom Research And Innovation Efficiently populating a phase diagram for multiple substances
US11923050B2 (en) * 2017-07-12 2024-03-05 United Kingdom Research And Innovation Efficiently populating a phase diagram for multiple substances

Also Published As

Publication number Publication date
WO2018188178A1 (en) 2018-10-18
CN106917029B (en) 2018-08-21
CN106917029A (en) 2017-07-04

Similar Documents

Publication Publication Date Title
JP6109843B2 (en) Adhesive La (Fe, Si) 13-based magnetocaloric material and its production method and application
Yu et al. The microstructure and magnetic characteristics of Sm (CobalFe0. 1Cu0. 09Zr0. 03) 7.24 high temperature permanent magnets
CN101919010B (en) Fe-Si-La alloy having excellent magneto-caloric properties
CN109108227B (en) High-flux preparation method of LaFeSi-based magnetic refrigeration material
JPH0421744A (en) Rare earth magnetic alloy excellent in hot workability
WO2018188675A1 (en) High-temperature-stability permanent magnet material and application thereof
TW202125544A (en) R-t-b series permanent magnetic material and preparation method and application thereof
CN101487106B (en) High magnetic striction iron based metallic glass magnetic material and preparation thereof
US20200024693A1 (en) Mm'x-y metal composite functional material and preparation method thereof
Kuang et al. Simultaneously achieved good mechanical properties and large magnetocaloric effect in spark plasma sintered Ni-Mn-In alloys
Jayaraman et al. Near room-temperature magnetocaloric properties of Gd–Ga alloys
Zheng et al. Microstructure and magnetocaloric effects of Mn1. 2Fe0. 8P0. 6Si0. 4B0. 05 alloys prepared by ball milling and spinning methods
Xu et al. Enhanced elastocaloric effect and mechanical properties of Gd-doped Ni-Co-Mn-Ti-Gd metamagnetic shape memory alloys
Jayaraman et al. Near room temperature magnetic entropy changes in as-cast Gd100− xMnx (x= 0, 5, 10, 15, and 20 at.%) alloys
CN109402454B (en) CoVGa-based Heusler alloy for realizing magnetic field driven metamagnetic reverse martensitic phase transformation
RU2675417C2 (en) Manganese antimonide doped with boron as a useful material of a permanent magnet
Wu et al. Martensitic and magnetic transformation behaviours in Mn50Ni42− xSn8Cox polycrystalline alloys
CN109175370B (en) Preparation method of composite material with magnetic field regulation and control of martensite phase transformation
CN105834407B (en) With NaZn13The preparation method of the rare-earth iron-based alloy cpd of type structure
Bureš et al. FeSiBAlNiMo high entropy alloy prepared by mechanical alloying
CN114395718B (en) Preparation method of NiCoMnIn magnetic shape memory alloy micron-sized particles
CN108620582A (en) A kind of composite material and preparation method of magnetic memorial alloy and copper
CN109482880A (en) Preparation method that is a kind of while promoting Ni-Mn-In alloy mechanical property and magnetic heating performance
Zhong et al. Transient liquid phase bonding assisted spark plasma sintering of La-Fe-Si magnetocaloric bulk materials
CN111254338B (en) Magnetostrictive material and preparation method thereof

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE AFTER FINAL ACTION FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: ADVISORY ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION