WO2018188178A1 - Functional mm'x-y metal composite material and preparation method therefor - Google Patents

Functional mm'x-y metal composite material and preparation method therefor Download PDF

Info

Publication number
WO2018188178A1
WO2018188178A1 PCT/CN2017/086889 CN2017086889W WO2018188178A1 WO 2018188178 A1 WO2018188178 A1 WO 2018188178A1 CN 2017086889 W CN2017086889 W CN 2017086889W WO 2018188178 A1 WO2018188178 A1 WO 2018188178A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal composite
functional material
composite functional
material according
preparing
Prior art date
Application number
PCT/CN2017/086889
Other languages
French (fr)
Chinese (zh)
Inventor
张虎
陶坤
龙克文
Original Assignee
佛山市程显科技有限公司
佛山市川东磁电股份有限公司
北京科技大学
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 佛山市程显科技有限公司, 佛山市川东磁电股份有限公司, 北京科技大学 filed Critical 佛山市程显科技有限公司
Priority to US16/311,562 priority Critical patent/US20200024693A1/en
Publication of WO2018188178A1 publication Critical patent/WO2018188178A1/en

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
    • 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 invention relates to the technical field of metal materials, in particular to a metal composite functional material of MM'X-Y (M and M' are transition group elements, X is a group IIIA or IVA element) and a preparation method thereof.
  • Martensitic transformation is a very important non-diffusion crystal structure phase transition in solid phase transition, and the phase transition property is one stage.
  • the high-temperature mother phase lattice point has no diffusion-displacement shear at the atomic scale, so it is also called displacement phase transition.
  • the chemical composition of the two phases remains unchanged before and after the phase change, but the crystal structure of the material changes significantly.
  • the high temperature parent phase is austenite and the low temperature product is martensite.
  • Martensitic transformation materials have many applications in steel reinforcement, material toughening, reduction of quenching deformation, shape memory effect, superelasticity and pseudoelasticity, and are good functional materials.
  • the martensitic transformation process is often accompanied by dramatic crystal structure changes.
  • This effect is applied to the shape memory alloy, that is, it has a certain shape.
  • the material is cooled from a high temperature higher than the martensitic transformation temperature (T M ) to form a low temperature martensite phase, in which state the deformation is applied, and then the material is heated to the martensitic reverse transformation temperature (T A Above, the material returns to its original shape.
  • Conventional shape memory alloys mainly control their deformation by temperature and stress changes, which results in low response frequency and difficulty in sensitivity improvement.
  • ferromagnetic martensitic transition alloys Due to the magnetic phase transition and structural phase transition coupling, the crystal structure, magnetic properties and electrical properties change at the same time, so that the ferromagnetic shape memory alloy exhibits abundant magnetic functional properties, such as shape memory effect, magnetostriction, magnetoresistance effect, Hall effect, magnetocaloric effect, etc. Rich magnetic properties and potential application value make ferromagnetic horse
  • the austenitic phase change alloy has become a new type of functional material that has received much attention.
  • ferromagnetic martensitic transformation alloys include Ni-Mn-Ga, Ni-Mn-Al, Ni-Mn-In, Ni-Mn-Sn and the like.
  • MM'X ferromagnetic martensitic transformation material
  • M and M' are transition group elements, X is a group IIIA or IVA element
  • the MM'X alloy also exhibits a magnetic field-induced ferromagnetic martensitic transformation through composition and process adjustment, accompanied by large crystal structure changes and magnetocaloric effects during the phase transition, and its phase transition temperature can be very wide. Adjustment in the temperature zone. Therefore, it can be regarded as a multi-functional material such as a shape memory effect material, a negative expansion material, and a magnetic refrigeration material, and is considered as a new-generation ferromagnetic martensitic transformation functional material.
  • the object of the present invention is to provide a MM'XY metal composite functional material and a preparation method thereof, which can prepare a MM'XY metal composite functional material which has good mechanical properties and ferromagnetic martensitic transformation, and exhibits good performance. Magnetic refrigeration performance can greatly advance the application of this functional material.
  • a MM'XY metal composite functional material comprising the following components and their volume percentages: A% of M a M' b X c and B% of Y, wherein:
  • M, M' is any one of transition elements or an alloy of more than one element
  • X is any one of the elements of group IIIA or IVA or an alloy of more than one element
  • Y is any one of Group IB, Group IIB, Group IIIA, Group IVA or an alloy of more than one element;
  • a, b, and c are in the range of 0.8 to 1.2;
  • the A% is 50% to 95%
  • the B% is 5% to 50%.
  • the A% is 60% to 90%, and the B% is 10% to 40%.
  • a preparation method of MM'X-Y metal composite functional material comprises the following steps:
  • the molding material is cured to obtain a product MM'X metal composite functional material.
  • Mn is added in an excess of 1% to 10% by atomic ratio to compensate for volatilization and burning during the preparation, thereby obtaining a single phase.
  • Mn when the M or M' is a Mn element, Mn is added in an excess of 2% to 5% by atomic ratio.
  • the pressure after the vacuuming of the melting furnace is controlled to be less than or equal to 3 ⁇ 10 -3 Pa, the melting temperature is 1300 ° C or higher, and the melting time is 0.5 to 10 min.
  • the pressure after the vacuuming of the melting furnace is 2 ⁇ 10 -3 to 3 ⁇ 10 -3 Pa
  • the melting temperature is 1300 to 1700 ° C
  • the melting time is 2 to 3 min.
  • the vacuum annealing temperature is 600 to 1100 ° C and the time is 1 to 30 days.
  • the vacuum annealing temperature is 700 to 900 ° C and the time is 5 to 15 days.
  • the crushing is performed by any one or a combination of grinding, vibration grinding, rolling mill, ball milling, jet milling, etc.
  • the screening is a standard sieve exceeding 10 mesh
  • the powder of the powder The diameter is less than 2mm.
  • the sieving is a standard sieve of 100 to 300 mesh, and the powder has a particle diameter of 0 to 0.2 mm.
  • the press molding is to press the powder into a desired size and shape by a calendering method, a molding method, an extrusion method, a powder injection molding method, or a discharge plasma sintering method, and the press molding pressure is 300. ⁇ 1500 MPa, temperature is 0-900 ° C, time is 1-240 min, and the strength of the magnetic field is 0-5T.
  • the pressure of the press molding is 600 to 1000 MPa
  • the temperature is 0 to 500 ° C
  • the time is 5 to 60 min
  • the strength of the magnetic field is 0 to 2 T.
  • the curing temperature is 0 to 900 ° C and the time is 1 to 15 days.
  • the curing temperature is 0 to 500 ° C and the time is 2 to 7 days.
  • the present invention provides a novel MM'XY metal composite functional material; 2) The MM'XY metal composite functional material prepared by the present invention has higher mechanical properties than the conventional MM'X material; 3) The preparation of the present invention MM'XY metal composite functional material has good magnetocaloric effect and can be applied to the manufacture of magnetic refrigeration materials. 4) The preparation method of the present invention can be fabricated into MM'XY metal composite functional materials of any shape and size according to actual needs. 5) The preparation method of the invention is simple in process, easy to operate and realizes industrial production, and has important significance for practical application.
  • Example 1 is a topographical view of smelted Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 obtained in Example 1 of the present invention
  • Example 2 is a topographical view of a 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In metal composite functional material prepared in Example 1 of the present invention
  • Example 3 is a graph showing a stress-strain curve of a 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In metal composite functional material prepared in Example 1 of the present invention
  • Example 4 is a graph showing dependence of ⁇ S on temperature of a 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In composite metal functional material prepared in Example 1 of the present invention under different magnetic fields;
  • Example 5 is a graph showing a stress-strain curve of a 75% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +25% In metal composite functional material prepared in Example 2 of the present invention
  • Fig. 6 is a graph showing the stress-strain curve of an 80% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 + 20% In metal composite functional material obtained in Example 3 of the present invention.
  • Embodiment 1 see Figures 1 to 4:
  • the invention provides 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, comprising the following steps:
  • the raw material is prepared according to the chemical formula of Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 , and the raw material is commercially available metal Mn, Fe, Ni, Si, Ge with a purity higher than 99.9 wt.%, wherein Mn is added in excess of 5% atomic ratio. Used to compensate for its volatilization and burning during the preparation process;
  • the prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed to 2 ⁇ 10 -3 Pa, and then washed with argon gas, and then the prepared raw materials are protected at 1500 ° C under argon gas protection. After smelting for 3 min, the ingot Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 was obtained ;
  • Fig. 1 The morphology of the smelted Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 sample prepared in this example is shown in Fig. 1. It can be seen from the figure that after the conventional smelting, the sample undergoes martensite transformation due to cooling from high temperature to room temperature. The large internal stress generated during the phase change causes the sample to be fragmented and cannot be formed and machined, which limits the application of such functional materials.
  • the appearance of the product of this embodiment is shown in Fig. 2, and the product has good molding and processing properties, and the above problems are well solved.
  • MM'X alloys have poor mechanical properties due to sample fragmentation and are not capable of stress-strain curve testing.
  • the mechanical properties of the product of this embodiment are significantly improved, and the mechanical property test can be completely performed.
  • the stress-strain curve of the product of this example was measured on a WDW200D type microcomputer-controlled universal material testing machine. As shown in Fig. 3, the compressive strength of the product of this example was 45 MPa, and the corresponding strain was 9.2%.
  • the isothermal magnetization curve (MH curve) of the product of this example was measured on a magnetic measurement system (Versalab Free measurement system designed by Quantum Design, USA), and then according to Maxwell's relationship:
  • the magnetic entropy change ⁇ S can be calculated from the isothermal magnetization curve.
  • Fig. 4 shows the dependence of ⁇ S on the temperature of the product in the present embodiment under different magnetic fields. It can be seen that the maximum value of the magnetic entropy change occurs in the sample near the phase transition temperature 311K, and the magnetic field changes are 0-1T, 0, respectively. At -2T and 0-3T, the maximum magnetic entropy change of the samples was 4.5 J/kg K, 9.9 J/kg K, and 15.3 J/kg K, respectively.
  • the invention provides 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, comprising the following steps:
  • the raw material is prepared according to the chemical formula of Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 , and the raw material is commercially available metal Mn, Fe, Ni, Si, Ge with a purity higher than 99.9 wt.%, wherein Mn is added in excess of 5% atomic ratio. Used to compensate for its volatilization and burning during the preparation process;
  • the prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed to 2.5 ⁇ 10 -3 Pa, and then washed with argon gas, and then the prepared raw materials are protected at 1700 ° C under argon gas protection. After smelting for 2 min, the ingot Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 was obtained ;
  • the stress-strain curve of the 75% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +25% In metal composite of the product of this example was measured on a WDW200D type microcomputer-controlled universal material testing machine. As shown in FIG. 5, the compression resistance of the product of this example was as shown in FIG. The strength is 48 MPa and the corresponding strain is 15.6%. At the same time, the magnetothermal effect of the product of this embodiment is higher than that of the conventional room temperature magnetic refrigeration material Gd.
  • the invention provides 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, comprising the following steps:
  • the raw material is prepared according to the chemical formula of Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 , and the raw material is a commercially available metal Mn, Fe, Ni, Si, Ge having a purity higher than 99.9 wt.%, wherein Mn is excessively added in an atomic ratio of 3%. Used to compensate for its volatilization and burning during the preparation process;
  • the prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed to 3 ⁇ 10 -3 Pa, and then washed with argon gas, and then the prepared raw materials are protected at 1700 ° C under argon gas protection. After smelting for 2 min, the ingot Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 was obtained ;
  • the stress-strain curve of the 80% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +20% In metal composite of the product of this example was measured on a WDW200D type microcomputer-controlled universal material testing machine. As shown in Fig. 6, the compression resistance of the product of this example was as shown in Fig. 6. The strength is 41 MPa and the corresponding strain is 14.9%.
  • the invention provides a 60% MnCoCu 0.08 Ge 0.92 +40%Sn metal composite functional material and a preparation method thereof, comprising the following steps:
  • the raw material is prepared according to the chemical formula of MnCoCu 0.08 Ge 0.92 , and the raw material is commercially available metal Mn, Co, Cu, Ge having a purity higher than 99.9 wt.%, wherein Mn is excessively added in an atomic ratio of 3% to compensate for Volatilization and burning during preparation;
  • the prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed to 2 ⁇ 10 -3 Pa, and then washed with argon gas, and then the prepared raw materials are protected at 1600 ° C under argon gas protection. After smelting for 3 min, the ingot MnCoCu 0.08 Ge 0.92 was obtained .
  • the invention provides a 75% Mn 0.95 CoCe 0.9 Si 0.1 +25% InSn metal composite functional material and a preparation method thereof, comprising the following steps:
  • the raw material is prepared according to the chemical formula of Mn 0.95 CoCe 0.9 Si 0.1 , and the raw material is commercially available metal Mn, Co, Ge, Si with a purity higher than 99.9 wt.%, wherein Mn is added in excess of 4% atomic ratio for compensation Its volatilization and burning during the preparation process;
  • the prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed to 3 ⁇ 10 -3 Pa, and then washed with argon gas, and then the prepared raw materials are protected at 1400 ° C under argon gas protection. After smelting for 3 min, the ingot Mn 0.95 CoCe 0.9 Si 0.1 was obtained .

Abstract

Disclosed is a functional MM'X-Y metal composite material and a preparation method therefor, with the components in percentage by volume thereof being: A% of MaM'bXc and B% of Y, wherein M and M' are transition group elements; X is an IIIA or IVA group element; Y is one of or an alloy of more than one of the elements of the IB group, IIB group, IIIA group and IVA group; the value ranges of a, b, and c are 0.8-1.2; and the sum of A% and B% is 100%. Same is prepared by means of the steps of smelting, annealing, crushing, mixing, pressing, solidification, etc. Same has higher mechanical properties and a good thermomagnetic effect.

Description

一种MM′X-Y金属复合功能材料及其制备方法MM′X-Y metal composite functional material and preparation method thereof 技术领域Technical field
本发明涉及金属材料技术领域，具体涉及一种MM′X-Y(M和M′为过渡族元素，X为IIIA或IVA族元素)金属复合功能材料及其制备方法。The invention relates to the technical field of metal materials, in particular to a metal composite functional material of MM'X-Y (M and M' are transition group elements, X is a group IIIA or IVA element) and a preparation method thereof.
背景技术Background technique
马氏体相变是固态相变中一种非常重要的非扩散型晶体结构相变，相变性质为一级。相变时，高温母相格点在原子尺度内发生无扩散位移型切变，因此又被称为位移型相变。值得注意的是，在相变过程中，相变前后两相化学成分保持不变，但材料的晶体结构发生显著的改变。通常，人们称高温母相为奥氏体，低温产物为马氏体。马氏体相变材料在钢的强化、材料韧化、减小淬火变形、形状记忆效应、超弹性及伪弹性等方面都有诸多应用，是良好的功能材料。Martensitic transformation is a very important non-diffusion crystal structure phase transition in solid phase transition, and the phase transition property is one stage. In the phase transition, the high-temperature mother phase lattice point has no diffusion-displacement shear at the atomic scale, so it is also called displacement phase transition. It is worth noting that in the phase transition process, the chemical composition of the two phases remains unchanged before and after the phase change, but the crystal structure of the material changes significantly. Generally, it is said that the high temperature parent phase is austenite and the low temperature product is martensite. Martensitic transformation materials have many applications in steel reinforcement, material toughening, reduction of quenching deformation, shape memory effect, superelasticity and pseudoelasticity, and are good functional materials.
由于马氏体相和母相的结构存在很大差异，在马氏体相变过程中往往伴随着剧烈的晶体结构变化，这一效应被应用在形状记忆合金中，即把具有某种形状的材料从高于马氏体相变温度(TM)的高温冷却，使之形成低温马氏体相，在此状态下加载变形，然后，将材料升温至马氏体逆相变温度(TA)以上，材料又恢复到原来的形状。而传统的形状记忆合金主要由温度和应力变化来控制其形变，这导致其响应频率低，且灵敏度提升困难。Due to the large difference in the structure of the martensite phase and the parent phase, the martensitic transformation process is often accompanied by dramatic crystal structure changes. This effect is applied to the shape memory alloy, that is, it has a certain shape. The material is cooled from a high temperature higher than the martensitic transformation temperature (T M ) to form a low temperature martensite phase, in which state the deformation is applied, and then the material is heated to the martensitic reverse transformation temperature (T A Above, the material returns to its original shape. Conventional shape memory alloys mainly control their deformation by temperature and stress changes, which results in low response frequency and difficulty in sensitivity improvement.
近年来，研究发现，除了温度场和应力场外，一些材料的马氏体相变还能够被磁场调控，这种兼有铁磁性和热弹性马氏体相变的新型材料被称为铁磁马氏体相变合金(Ferromagnetic martensitic transition alloys)。由于磁相变和结构相变耦合导致晶体结构、磁性、电性同时发生剧烈变化，从而使铁磁形状记忆合金表现出丰富的磁性功能特性，如形状记忆效应、磁致伸缩、磁电阻效应、霍尔效应、磁热效应等。丰富的磁性能和潜在的应用价值使得铁磁马 氏体相变合金成为广受关注的新型功能材料。In recent years, studies have found that in addition to temperature and stress fields, martensitic transformation of some materials can be controlled by magnetic fields. This new type of material with ferromagnetic and thermoelastic martensitic transformation is called ferromagnetic. Ferromagnetic martensitic transition alloys. Due to the magnetic phase transition and structural phase transition coupling, the crystal structure, magnetic properties and electrical properties change at the same time, so that the ferromagnetic shape memory alloy exhibits abundant magnetic functional properties, such as shape memory effect, magnetostriction, magnetoresistance effect, Hall effect, magnetocaloric effect, etc. Rich magnetic properties and potential application value make ferromagnetic horse The austenitic phase change alloy has become a new type of functional material that has received much attention.
目前，铁磁马氏体相变合金中最大的一类是Heusler合金，包括Ni-Mn-Ga，Ni-Mn-Al，Ni-Mn-In，Ni-Mn-Sn等。最近，研究人员发现了一种新型铁磁马氏体相变材料MM′X(M和M′为过渡族元素，X为IIIA或IVA族元素)合金，如MnCoGe、MnNiGe等。该MM′X合金通过成分和工艺的调节也表现出磁场诱导的铁磁马氏体相变，在相变过程中伴随着巨大的晶体结构变化和磁热效应，并且其相变温度能够在很宽的温区内调节。因此，可以作为形状记忆效应材料、负膨胀材料、磁制冷材料等多功能材料，被认为是新一代铁磁马氏体相变功能材料。At present, the largest class of ferromagnetic martensitic transformation alloys is Heusler alloys, including Ni-Mn-Ga, Ni-Mn-Al, Ni-Mn-In, Ni-Mn-Sn and the like. Recently, researchers have discovered a new type of ferromagnetic martensitic transformation material MM'X (M and M' are transition group elements, X is a group IIIA or IVA element) alloys, such as MnCoGe, MnNiGe, and the like. The MM'X alloy also exhibits a magnetic field-induced ferromagnetic martensitic transformation through composition and process adjustment, accompanied by large crystal structure changes and magnetocaloric effects during the phase transition, and its phase transition temperature can be very wide. Adjustment in the temperature zone. Therefore, it can be regarded as a multi-functional material such as a shape memory effect material, a negative expansion material, and a magnetic refrigeration material, and is considered as a new-generation ferromagnetic martensitic transformation functional material.
然而，MM′X功能材料由于在马氏体相变过程中出现巨大的晶体结构畸变，产生巨大的内应力，导致该类材料相变后碎化，无法进行成型和机械加工，极大地限制了这类马氏体相变材料的应用。而目前对改善MM′X功能材料力学性能的研究还鲜有报道。However, due to the large crystal structure distortion in the martensitic transformation process, the MM'X functional material generates huge internal stress, which causes the material to be broken after phase transformation, and cannot be formed and machined, which greatly limits the material. The application of such martensitic phase change materials. At present, there are few reports on improving the mechanical properties of MM'X functional materials.
鉴于以上研究背景及MM′X功能材料亟待解决的关键问题，如何制备机械性能良好的MM′X功能材料已成为当下研究的重点。In view of the above research background and the key issues to be solved by MM'X functional materials, how to prepare MM'X functional materials with good mechanical properties has become the focus of current research.
发明内容Summary of the invention
本发明的目的是提供一种MM′X-Y金属复合功能材料及其制备方法，能够制备出兼具良好机械性能和铁磁马氏体相变的MM′X-Y金属复合功能材料，并表现出良好的磁制冷性能，能极大地推进该功能材料的应用。The object of the present invention is to provide a MM'XY metal composite functional material and a preparation method thereof, which can prepare a MM'XY metal composite functional material which has good mechanical properties and ferromagnetic martensitic transformation, and exhibits good performance. Magnetic refrigeration performance can greatly advance the application of this functional material.
为了实现上述目的，本发明采用的技术方案如下：In order to achieve the above object, the technical solution adopted by the present invention is as follows:
一种MM′X-Y金属复合功能材料，包括如下组分及其体积百分比：A％的MaM′bXc和B％的Y，其中：A MM'XY metal composite functional material comprising the following components and their volume percentages: A% of M a M' b X c and B% of Y, wherein:
M、M′为过渡族元素中的任意一种元素或一种以上元素的合金；M, M' is any one of transition elements or an alloy of more than one element;
X为IIIA或IVA族元素中的任意一种元素或一种以上元素的合金； X is any one of the elements of group IIIA or IVA or an alloy of more than one element;
Y为IB族、IIB族、IIIA族、IVA族中的任意一种元素或一种以上元素的合金；Y is any one of Group IB, Group IIB, Group IIIA, Group IVA or an alloy of more than one element;
a、b、c的取值范围为：0.8～1.2；The values of a, b, and c are in the range of 0.8 to 1.2;
A％与B％的和为100％。The sum of A% and B% is 100%.
根据以上方案，所述A％为50％～95％、B％为5％～50％。According to the above scheme, the A% is 50% to 95%, and the B% is 5% to 50%.
根据以上方案，所述A％为60％～90％、B％为10％～40％。According to the above scheme, the A% is 60% to 90%, and the B% is 10% to 40%.
一种MM′X-Y金属复合功能材料的制备方法，包括如下步骤：A preparation method of MM'X-Y metal composite functional material comprises the following steps:
1)按MaM′bXc的化学式配制原料；1) preparing a raw material according to the chemical formula of M a M' b X c ;
2)将配制好的原料放入熔炼炉中，熔炼炉抽真空后用氩气清洗，之后在氩气保护下对配制好的原料进行熔炼，得到MaM′bXc合金；2) The prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed, and then washed with argon gas, and then the prepared raw materials are smelted under argon gas protection to obtain a M a M′ b X c alloy;
3)将MaM′bXc合金进行真空退火处理；3) vacuum annealing the M a M′ b X c alloy;
4)将经真空退火后的MaM′bXc合金、Y材料分别破碎、过筛成粉末；4) The vacuum-annealed M a M′ b X c alloy and the Y material are separately crushed and sieved into a powder;
5)分别量取体积百分比为A％的MaM′bXc合金粉末、B％的Y材料粉末，混合均匀；5) separately taking M a M′ b X c alloy powder and B% Y material powder with a volume percentage of A%, and mixing uniformly;
6)将混合均匀的粉末在磁场下压制成型，得到成型材料；6) press-forming the uniformly mixed powder under a magnetic field to obtain a molding material;
7)将成型材料进行固化，即得到产品MM′X金属复合功能材料。7) The molding material is cured to obtain a product MM'X metal composite functional material.
根据以上方案，所述M或M′为Mn元素时，Mn按1％～10％的原子比过量添加，用于补偿其在制备过程中的挥发和烧损，从而获得单相。According to the above aspect, when the M or M' is a Mn element, Mn is added in an excess of 1% to 10% by atomic ratio to compensate for volatilization and burning during the preparation, thereby obtaining a single phase.
根据以上方案，所述M或M′为Mn元素时，Mn按2％～5％的原子比过量添加。According to the above aspect, when the M or M' is a Mn element, Mn is added in an excess of 2% to 5% by atomic ratio.
根据以上方案，所述熔炼炉抽真空后的压力控制在小于或等于3×10-3Pa，熔炼温度为1300℃以上、熔炼时间为0.5～10min。According to the above aspect, the pressure after the vacuuming of the melting furnace is controlled to be less than or equal to 3 × 10 -3 Pa, the melting temperature is 1300 ° C or higher, and the melting time is 0.5 to 10 min.
根据以上方案，所述熔炼炉抽真空后的压力为2×10-3～3×10-3Pa， 熔炼温度为1300～1700℃、熔炼时间为2～3min。According to the above aspect, the pressure after the vacuuming of the melting furnace is 2 × 10 -3 to 3 × 10 -3 Pa, the melting temperature is 1300 to 1700 ° C, and the melting time is 2 to 3 min.
根据以上方案，所述真空退火的温度为600～1100℃、时间为1～30天。According to the above aspect, the vacuum annealing temperature is 600 to 1100 ° C and the time is 1 to 30 days.
根据以上方案，所述真空退火的温度为700～900℃、时间为5～15天。According to the above aspect, the vacuum annealing temperature is 700 to 900 ° C and the time is 5 to 15 days.
根据以上方案，所述破碎采用研磨、振动磨、滚动磨、球磨、气流磨等中的任意一种或一种以上的组合，所述过筛为过大于10目的标准筛，所述粉末的粒径小于2mm。According to the above aspect, the crushing is performed by any one or a combination of grinding, vibration grinding, rolling mill, ball milling, jet milling, etc., the screening is a standard sieve exceeding 10 mesh, the powder of the powder The diameter is less than 2mm.
根据以上方案，所述过筛为过100～300目的标准筛，所述粉末的粒径为0～0.2mm。According to the above scheme, the sieving is a standard sieve of 100 to 300 mesh, and the powder has a particle diameter of 0 to 0.2 mm.
根据以上方案，所述压制成型为通过压延法、模压法、挤压法、粉末注射成形法、或放电等离子体烧结法将粉末压制成所需的尺寸和形状，所述压制成型的压力为300～1500MPa、温度为0～900℃、时间为1～240min，所述磁场的强度为0～5T。According to the above aspect, the press molding is to press the powder into a desired size and shape by a calendering method, a molding method, an extrusion method, a powder injection molding method, or a discharge plasma sintering method, and the press molding pressure is 300. ～1500 MPa, temperature is 0-900 ° C, time is 1-240 min, and the strength of the magnetic field is 0-5T.
根据以上方案，所述压制成型的压力为600～1000MPa、温度为0～500℃、时间为5～60min，所述磁场的强度为0～2T。According to the above aspect, the pressure of the press molding is 600 to 1000 MPa, the temperature is 0 to 500 ° C, the time is 5 to 60 min, and the strength of the magnetic field is 0 to 2 T.
根据以上方案，所述固化的温度为0～900℃、时间为1～15天。According to the above aspect, the curing temperature is 0 to 900 ° C and the time is 1 to 15 days.
根据以上方案，所述固化的温度为0～500℃、时间为2～7天。According to the above aspect, the curing temperature is 0 to 500 ° C and the time is 2 to 7 days.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
1)本发明提供了一种新型的MM′X-Y金属复合功能材料；2)本发明制备的MM′X-Y金属复合功能材料具有比传统MM′X材料更高的机械性能；3)本发明制备的MM′X-Y金属复合功能材料具有良好的磁热效应，能够很好的应用到制造磁制冷材料方面；4)本发明的制备方法可以根据实际需要制作成任意形状和尺寸的MM′X-Y金属复合功能材料；5)本发明的制备方法工艺简单，易于操作和实现工业化生产，对实际应用具有重要的意义。1) The present invention provides a novel MM'XY metal composite functional material; 2) The MM'XY metal composite functional material prepared by the present invention has higher mechanical properties than the conventional MM'X material; 3) The preparation of the present invention MM'XY metal composite functional material has good magnetocaloric effect and can be applied to the manufacture of magnetic refrigeration materials. 4) The preparation method of the present invention can be fabricated into MM'XY metal composite functional materials of any shape and size according to actual needs. 5) The preparation method of the invention is simple in process, easy to operate and realizes industrial production, and has important significance for practical application.
附图说明 DRAWINGS
图1为本发明实施例1制得的熔炼后的Mn0.6Fe0.4NiSi0.5Ge0.5的形貌图；1 is a topographical view of smelted Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 obtained in Example 1 of the present invention;
图2为本发明实施例1制得的70％Mn0.6Fe0.4NiSi0.5Ge0.5+30％In金属复合功能材料的形貌图；2 is a topographical view of a 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In metal composite functional material prepared in Example 1 of the present invention;
图3为本发明实施例1制得的70％Mn0.6Fe0.4NiSi0.5Ge0.5+30％In金属复合功能材料的应力-应变曲线图；3 is a graph showing a stress-strain curve of a 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In metal composite functional material prepared in Example 1 of the present invention;
图4为本发明实施例1制得的70％Mn0.6Fe0.4NiSi0.5Ge0.5+30％In金属复合功能材料在不同磁场下ΔS对温度的依赖关系图；4 is a graph showing dependence of ΔS on temperature of a 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +30% In composite metal functional material prepared in Example 1 of the present invention under different magnetic fields;
图5为本发明实施例2制得的75％Mn0.6Fe0.4NiSi0.5Ge0.5+25％In金属复合功能材料的应力-应变曲线图；5 is a graph showing a stress-strain curve of a 75% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +25% In metal composite functional material prepared in Example 2 of the present invention;
图6为本发明实施例3制得的80％Mn0.6Fe0.4NiSi0.5Ge0.5+20％In金属复合功能材料的应力-应变曲线图。Fig. 6 is a graph showing the stress-strain curve of an 80% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 + 20% In metal composite functional material obtained in Example 3 of the present invention.
具体实施方式detailed description
下面结合附图与实施例对本发明的技术方案进行说明。The technical solution of the present invention will be described below with reference to the accompanying drawings and embodiments.
实施例1，见图1至图4： Embodiment 1, see Figures 1 to 4:
本发明提供一种70％Mn0.6Fe0.4NiSi0.5Ge0.5+30％In金属复合功能材料及其制备方法，包括如下步骤：The invention provides 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, comprising the following steps:
1)按Mn0.6Fe0.4NiSi0.5Ge0.5的化学式配制原料，原料为纯度高于99.9wt.％的市售金属Mn、Fe、Ni、Si、Ge，其中，Mn按5％的原子比过量添加，用于补偿其在制备过程中的挥发和烧损；1) The raw material is prepared according to the chemical formula of Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 , and the raw material is commercially available metal Mn, Fe, Ni, Si, Ge with a purity higher than 99.9 wt.%, wherein Mn is added in excess of 5% atomic ratio. Used to compensate for its volatilization and burning during the preparation process;
2)采用电弧熔炼法，将配制好的原料放入熔炼炉中，熔炼炉抽真空至2×10-3Pa后用氩气清洗，之后在氩气保护下对配制好的原料在1500℃下熔炼3min，得到铸锭Mn0.6Fe0.4NiSi0.5Ge0.5；2) Using the arc melting method, the prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed to 2×10 -3 Pa, and then washed with argon gas, and then the prepared raw materials are protected at 1500 ° C under argon gas protection. After smelting for 3 min, the ingot Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 was obtained ;
3)将Mn0.6Fe0.4NiSi0.5Ge0.5在真空度为5×10-3Pa的石英管内，850℃下退火处理7天；3) Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 in a quartz tube with a vacuum of 5 × 10 -3 Pa, and annealed at 850 ° C for 7 days;
4)利用玛瑙研钵分别将真空退火后的Mn0.6Fe0.4NiSi0.5Ge0.5、金属In破碎、150目的标准筛筛选出小于0.1mm的不规则颗粒粉末； 4) using agate mortar, vacuum-annealed Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 , metal In broken, 150 mesh standard sieve to screen irregular particle powder of less than 0.1 mm;
5)分别量取体积百分比为70％的Mn0.6Fe0.4NiSi0.5Ge0.5粉末、30％的In粉末，混合均匀；5) Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 powder and 30% In powder with a volume percentage of 70% were separately weighed and uniformly mixed;
6)将混合均匀的粉末在150℃、900MPa压力、零磁场下压制5min得到Φ10mm的圆柱形70％Mn0.6Fe0.4NiSi0.5Ge0.5+30％In金属复合功能材料；6) The uniformly mixed powder is pressed at 150 ° C, 900 MPa pressure and zero magnetic field for 5 min to obtain a cylindrical 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 + 30% In metal composite functional material of Φ 10 mm;
7)在500℃下固化7天，即得到产品70％Mn0.6Fe0.4NiSi0.5Ge0.5+30％In金属复合功能材料。7) Curing at 500 ° C for 7 days gave a product of 70% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 + 30% In metal composite functional material.
本实施例制得的熔炼后的Mn0.6Fe0.4NiSi0.5Ge0.5样品的形貌见图1，由图可知，传统熔炼后，样品由于从高温冷却至室温的过程中经历了马氏体相变，相变过程中产生的巨大内应力导致样品碎化，无法进行成型和机械加工，限制了这类功能材料的应用。本实施例产品的形貌见图2，产品具有很好的成型和加工性能，很好地解决了以上难题。The morphology of the smelted Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 sample prepared in this example is shown in Fig. 1. It can be seen from the figure that after the conventional smelting, the sample undergoes martensite transformation due to cooling from high temperature to room temperature. The large internal stress generated during the phase change causes the sample to be fragmented and cannot be formed and machined, which limits the application of such functional materials. The appearance of the product of this embodiment is shown in Fig. 2, and the product has good molding and processing properties, and the above problems are well solved.
传统MM′X合金由于样品碎化，机械性能极差，无法进行应力-应变曲线测试。而通过本实施例产品的机械性能显著提高，完全可以进行机械性能测试。在WDW200D型微机控万能材料试验机上测定本实施例产品的应力-应变曲线，如图3所示，本实施例产品的抗压强度为45MPa，对应的应变为9.2％。Conventional MM'X alloys have poor mechanical properties due to sample fragmentation and are not capable of stress-strain curve testing. The mechanical properties of the product of this embodiment are significantly improved, and the mechanical property test can be completely performed. The stress-strain curve of the product of this example was measured on a WDW200D type microcomputer-controlled universal material testing machine. As shown in Fig. 3, the compressive strength of the product of this example was 45 MPa, and the corresponding strain was 9.2%.
在磁性测量***(美国Quantum Design公司设计的Versalab Free测量***)上测定本实施例产品的等温磁化曲线(M-H曲线)，再根据麦克斯韦关系：
Figure PCTCN2017086889-appb-000001
可从等温磁化曲线计算磁熵变ΔS。图4示出了本实施例产品在不同磁场下ΔS对温度的依赖关系，可以看出，样品在相变温度311K附近出现磁熵变的极大值，在磁场变化分别为0-1T、0-2T、0-3T下，样品的最大磁熵变分别为4.5J/kgK、9.9J/kgK、15.3J/kgK。目前，利用永磁体NdFeB可获得2T的磁场，故在0-2T磁场变化下的材料的磁熵变倍受关注。 可以看出，在0-2T磁场变化下，本实施例产品的最大磁熵变(9.9J/kgK)，显著高于传统室温磁制冷材料Gd的磁熵变(2T磁场下，磁熵变为5.0J/kgK)，说明本实施例产品可以作为更优的室温功能材料。The isothermal magnetization curve (MH curve) of the product of this example was measured on a magnetic measurement system (Versalab Free measurement system designed by Quantum Design, USA), and then according to Maxwell's relationship:
Figure PCTCN2017086889-appb-000001
The magnetic entropy change ΔS can be calculated from the isothermal magnetization curve. Fig. 4 shows the dependence of ΔS on the temperature of the product in the present embodiment under different magnetic fields. It can be seen that the maximum value of the magnetic entropy change occurs in the sample near the phase transition temperature 311K, and the magnetic field changes are 0-1T, 0, respectively. At -2T and 0-3T, the maximum magnetic entropy change of the samples was 4.5 J/kg K, 9.9 J/kg K, and 15.3 J/kg K, respectively. At present, a magnetic field of 2T is obtained by using the permanent magnet NdFeB, so the magnetic entropy of the material under the change of the 0-2T magnetic field is attracting attention. It can be seen that under the change of 0-2T magnetic field, the maximum magnetic entropy change (9.9J/kgK) of the product of this embodiment is significantly higher than that of the traditional room temperature magnetic refrigeration material Gd (under 2T magnetic field, the magnetic entropy becomes 5.0J/kgK), indicating that the product of this embodiment can be used as a better room temperature functional material.
实施例2，见图5： Embodiment 2, see Figure 5:
本发明提供一种75％Mn0.6Fe0.4NiSi0.5Ge0.5+25％In金属复合功能材料及其制备方法，包括如下步骤：The invention provides 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, comprising the following steps:
1)按Mn0.6Fe0.4NiSi0.5Ge0.5的化学式配制原料，原料为纯度高于99.9wt.％的市售金属Mn、Fe、Ni、Si、Ge，其中，Mn按5％的原子比过量添加，用于补偿其在制备过程中的挥发和烧损；1) The raw material is prepared according to the chemical formula of Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 , and the raw material is commercially available metal Mn, Fe, Ni, Si, Ge with a purity higher than 99.9 wt.%, wherein Mn is added in excess of 5% atomic ratio. Used to compensate for its volatilization and burning during the preparation process;
2)采用电弧熔炼法，将配制好的原料放入熔炼炉中，熔炼炉抽真空至2.5×10-3Pa后用氩气清洗，之后在氩气保护下对配制好的原料在1700℃下熔炼2min，得到铸锭Mn0.6Fe0.4NiSi0.5Ge0.5；2) Using the arc melting method, the prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed to 2.5×10 -3 Pa, and then washed with argon gas, and then the prepared raw materials are protected at 1700 ° C under argon gas protection. After smelting for 2 min, the ingot Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 was obtained ;
3)将Mn0.6Fe0.4NiSi0.5Ge0.5在真空度为5×10-3Pa的石英管内，850℃下退火处理8天；3) Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 in a quartz tube with a vacuum of 5 × 10 -3 Pa, and annealed at 850 ° C for 8 days;
4)利用玛瑙研钵分别将真空退火后的Mn0.6Fe0.4NiSi0.5Ge0.5、金属In破碎、200目的标准筛筛选出小于0.07mm的不规则颗粒粉末；4) using agate mortar, vacuum-annealed Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 , metal In broken, 200 mesh standard sieve to screen out irregular particle powder of less than 0.07 mm;
5)分别量取体积百分比为75％的Mn0.6Fe0.4NiSi0.5Ge0.5粉末、25％的In粉末，混合均匀；5) Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 powder and 25% In powder with a volume percentage of 75% were separately weighed and uniformly mixed;
6)将混合均匀的粉末在140℃、900MPa压力、零磁场下压制10min得到Φ10mm的圆柱形75％Mn0.6Fe0.4NiSi0.5Ge0.5+25％In金属复合功能材料；6) The uniformly mixed powder is pressed at 140 ° C, 900 MPa pressure and zero magnetic field for 10 min to obtain a cylindrical 75% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 + 25% In metal composite functional material of Φ 10 mm;
7)在500℃下固化7天，即得到产品75％Mn0.6Fe0.4NiSi0.5Ge0.5+25％In金属复合功能材料。7) Curing at 500 ° C for 7 days gave a product of 75% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 + 25% In metal composite functional material.
在WDW200D型微机控万能材料试验机上测定本实施例产品75％Mn0.6Fe0.4NiSi0.5Ge0.5+25％In金属复合材料的应力-应变曲线，如图5所示，本实施例产品的抗压强度为48MPa，对应的应变为15.6％。 同时，经磁性测试，本实施例产品的磁热效应高于传统室温磁制冷材料Gd。The stress-strain curve of the 75% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +25% In metal composite of the product of this example was measured on a WDW200D type microcomputer-controlled universal material testing machine. As shown in FIG. 5, the compression resistance of the product of this example was as shown in FIG. The strength is 48 MPa and the corresponding strain is 15.6%. At the same time, the magnetothermal effect of the product of this embodiment is higher than that of the conventional room temperature magnetic refrigeration material Gd.
实施例3，见图6：Embodiment 3, see Figure 6:
本发明提供一种80％Mn0.6Fe0.4NiSi0.5Ge0.5+20％In金属复合功能材料及其制备方法，包括如下步骤：The invention provides 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, comprising the following steps:
1)按Mn0.6Fe0.4NiSi0.5Ge0.5的化学式配制原料，原料为纯度高于99.9wt.％的市售金属Mn、Fe、Ni、Si、Ge，其中，Mn按3％的原子比过量添加，用于补偿其在制备过程中的挥发和烧损；1) The raw material is prepared according to the chemical formula of Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 , and the raw material is a commercially available metal Mn, Fe, Ni, Si, Ge having a purity higher than 99.9 wt.%, wherein Mn is excessively added in an atomic ratio of 3%. Used to compensate for its volatilization and burning during the preparation process;
2)采用电弧熔炼法，将配制好的原料放入熔炼炉中，熔炼炉抽真空至3×10-3Pa后用氩气清洗，之后在氩气保护下对配制好的原料在1700℃下熔炼2min，得到铸锭Mn0.6Fe0.4NiSi0.5Ge0.5；2) Using the arc melting method, the prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed to 3×10 -3 Pa, and then washed with argon gas, and then the prepared raw materials are protected at 1700 ° C under argon gas protection. After smelting for 2 min, the ingot Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 was obtained ;
3)将Mn0.6Fe0.4NiSi0.5Ge0.5在真空度为5×10-3Pa的石英管内，750℃下退火处理15天；3) Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 in a quartz tube with a vacuum of 5 × 10 -3 Pa, and annealed at 750 ° C for 15 days;
4)利用玛瑙研钵分别将真空退火后的Mn0.6Fe0.4NiSi0.5Ge0.5、金属In破碎、150目的标准筛筛选出小于0.1mm的不规则颗粒粉末；4) using agate mortar, vacuum-annealed Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 , metal In broken, 150 mesh standard sieve to screen irregular particle powder of less than 0.1 mm;
5)分别量取体积百分比为80％的Mn0.6Fe0.4NiSi0.5Ge0.5粉末、20％的In粉末，混合均匀；5) Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 powder and 20% In powder with a volume percentage of 80% were separately measured and uniformly mixed;
6)将混合均匀的粉末在140℃、900MPa压力、零磁场下压制6min得到Φ10mm的圆柱形80％Mn0.6Fe0.4NiSi0.5Ge0.5+20％In金属复合功能材料；6) The uniformly mixed powder is pressed at 140 ° C, 900 MPa pressure and zero magnetic field for 6 min to obtain a cylindrical 80% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 + 20% In metal composite functional material of Φ 10 mm;
7)在500℃下固化7天，即得到产品80％Mn0.6Fe0.4NiSi0.5Ge0.5+20％In金属复合功能材料。7) After curing at 500 ° C for 7 days, a product of 80% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 + 20% In metal composite functional material was obtained.
在WDW200D型微机控万能材料试验机上测定本实施例产品80％Mn0.6Fe0.4NiSi0.5Ge0.5+20％In金属复合材料的应力-应变曲线，如图6所示，本实施例产品的抗压强度为41MPa，对应的应变为14.9％。The stress-strain curve of the 80% Mn 0.6 Fe 0.4 NiSi 0.5 Ge 0.5 +20% In metal composite of the product of this example was measured on a WDW200D type microcomputer-controlled universal material testing machine. As shown in Fig. 6, the compression resistance of the product of this example was as shown in Fig. 6. The strength is 41 MPa and the corresponding strain is 14.9%.
实施例4：Example 4:
本发明提供一种60％MnCoCu0.08Ge0.92+40％Sn金属复合功能材料及 其制备方法，包括如下步骤：The invention provides a 60% MnCoCu 0.08 Ge 0.92 +40%Sn metal composite functional material and a preparation method thereof, comprising the following steps:
1)按MnCoCu0.08Ge0.92的化学式配制原料，原料为纯度高于99.9wt.％的市售金属Mn、Co、Cu、Ge，其中，Mn按3％的原子比过量添加，用于补偿其在制备过程中的挥发和烧损；1) The raw material is prepared according to the chemical formula of MnCoCu 0.08 Ge 0.92 , and the raw material is commercially available metal Mn, Co, Cu, Ge having a purity higher than 99.9 wt.%, wherein Mn is excessively added in an atomic ratio of 3% to compensate for Volatilization and burning during preparation;
2)采用电弧熔炼法，将配制好的原料放入熔炼炉中，熔炼炉抽真空至2×10-3Pa后用氩气清洗，之后在氩气保护下对配制好的原料在1600℃下熔炼3min，得到铸锭MnCoCu0.08Ge0.92；2) Using the arc melting method, the prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed to 2×10 -3 Pa, and then washed with argon gas, and then the prepared raw materials are protected at 1600 ° C under argon gas protection. After smelting for 3 min, the ingot MnCoCu 0.08 Ge 0.92 was obtained .
3)将MnCoCu0.08Ge0.92在真空度为5×10-3Pa的石英管内，800℃下退火处理15天；3) MnCoCu 0.08 Ge 0.92 in a quartz tube with a vacuum of 5 × 10 -3 Pa, annealed at 800 ° C for 15 days;
4)利用气流磨分别将真空退火后的MnCoCu0.08Ge0.92、金属Sn破碎、300目的标准筛筛选出小于0.05mm的不规则颗粒粉末；4) using a jet mill to separately vacuum-anneal MnCoCu 0.08 Ge 0.92 , metal Sn, and 300 mesh standard sieve to screen irregular particle powder of less than 0.05 mm;
5)分别量取体积百分比为60％的MnCoCu0.08Ge0.92粉末、40％的Sn粉末，混合均匀；5) MnCoCu 0.08 Ge 0.92 powder and 40% Sn powder with a volume percentage of 60% were separately weighed and mixed uniformly;
6)将混合均匀的粉末在室温、960MPa压力、1.5T磁场下压制15min得到Φ10mm的圆柱形60％MnCoCu0.08Ge0.92+40％Sn金属复合功能材料；6) The uniformly mixed powder is pressed at room temperature, 960 MPa pressure, 1.5T magnetic field for 15 min to obtain a cylindrical 60% MnCoCu 0.08 Ge 0.92 +40% Sn metal composite functional material of Φ10 mm;
7)在500℃下固化7天，即得到产品60％MnCoCu0.08Ge0.92+40％Sn金属复合功能材料。7) Curing at 500 ° C for 7 days, the product 60% MnCoCu 0.08 Ge 0.92 + 40% Sn metal composite functional material was obtained.
实施例5：Example 5:
本发明提供一种75％Mn0.95CoCe0.9Si0.1+25％InSn金属复合功能材料及其制备方法，包括如下步骤：The invention provides a 75% Mn 0.95 CoCe 0.9 Si 0.1 +25% InSn metal composite functional material and a preparation method thereof, comprising the following steps:
1)按Mn0.95CoCe0.9Si0.1的化学式配制原料，原料为纯度高于99.9wt.％的市售金属Mn、Co、Ge、Si，其中，Mn按4％的原子比过量添加，用于补偿其在制备过程中的挥发和烧损；1) The raw material is prepared according to the chemical formula of Mn 0.95 CoCe 0.9 Si 0.1 , and the raw material is commercially available metal Mn, Co, Ge, Si with a purity higher than 99.9 wt.%, wherein Mn is added in excess of 4% atomic ratio for compensation Its volatilization and burning during the preparation process;
2)采用电弧熔炼法，将配制好的原料放入熔炼炉中，熔炼炉抽真空至3×10-3Pa后用氩气清洗，之后在氩气保护下对配制好的原料在1400℃下熔炼3min，得到铸锭Mn0.95CoCe0.9Si0.1； 2) Using the arc melting method, the prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed to 3×10 -3 Pa, and then washed with argon gas, and then the prepared raw materials are protected at 1400 ° C under argon gas protection. After smelting for 3 min, the ingot Mn 0.95 CoCe 0.9 Si 0.1 was obtained .
3)将Mn0.95CoCe0.9Si0.1在真空度为5×10-3Pa的石英管内，900℃下退火处理5天；3) Mn 0.95 CoCe 0.9 Si 0.1 was annealed at 900 ° C for 5 days in a quartz tube having a vacuum of 5 × 10 -3 Pa;
4)利用高能球磨机分别将真空退火后的Mn0.95CoCe0.9Si0.1、金属InSn破碎、250目的标准筛筛选出小于0.06mm的不规则颗粒粉末；4) using a high-energy ball mill to separately filter the Mn 0.95 CoCe 0.9 Si 0.1 , the metal InSn, and the 250-mesh standard sieve after vacuum annealing to obtain irregular particle powder of less than 0.06 mm;
5)分别量取体积百分比为75％的Mn0.95CoCe0.9Si0.1粉末、25％的InSn粉末，混合均匀；5) Mn 0.95 CoCe 0.9 Si 0.1 powder and 25% InSn powder with a volume percentage of 75% were separately weighed and mixed uniformly;
6)将混合均匀的粉末在800℃、600MPa压力、零磁场下压制15min得到Φ10mm的圆柱形75％Mn0.95CoCe0.9Si0.1+25％InSn金属复合功能材料；6) The uniformly mixed powder is pressed at 800 ° C, 600 MPa pressure and zero magnetic field for 15 min to obtain a cylindrical 75% Mn 0.95 CoCe 0.9 Si 0.1 + 25% InSn metal composite functional material of Φ 10 mm;
7)在500℃下固化7天，即得到产品75％Mn0.95CoCe0.9Si0.1+25％InSn金属复合功能材料。7) Curing at 500 ° C for 7 days gave a product of 75% Mn 0.95 CoCe 0.9 Si 0.1 + 25% InSn metal composite functional material.
以上实施例仅用以说明而非限制本发明的技术方案，尽管上述实施例对本发明进行了详细说明，本领域的相关技术人员应当理解：可以对本发明进行修改或者同等替换，但不脱离本发明精神和范围的任何修改和局部替换均应涵盖在本发明的权利要求范围内。 The above embodiments are only intended to illustrate and not to limit the technical solutions of the present invention. Although the above embodiments are described in detail, those skilled in the art will understand that the invention may be modified or equivalently substituted without departing from the invention. Any modifications and partial substitutions of the spirit and scope are intended to be included within the scope of the appended claims.

Claims (16)

  1. 一种MM′X-Y金属复合功能材料，其特征在于，包括如下组分及其体积百分比：A％的MaM′bXc和B％的Y，其中：A MM'XY metal composite functional material characterized by comprising the following components and their volume percentages: A% of M a M' b X c and B% of Y, wherein:
    M、M′为过渡族元素中的任意一种元素或一种以上元素的合金；M, M' is any one of transition elements or an alloy of more than one element;
    X为IIIA或IVA族元素中的任意一种元素或一种以上元素的合金；X is any one of the elements of group IIIA or IVA or an alloy of more than one element;
    Y为IB族、IIB族、IIIA族、IVA族中的任意一种元素或一种以上元素的合金；Y is any one of Group IB, Group IIB, Group IIIA, Group IVA or an alloy of more than one element;
    a、b、c的取值范围为：0.8～1.2；The values of a, b, and c are in the range of 0.8 to 1.2;
    A％与B％的和为100％。The sum of A% and B% is 100%.
  2. 根据权利要求1所述的MM′X-Y金属复合功能材料，其特征在于，所述A％为50％～95％、B％为5％～50％。The MM'X-Y metal composite functional material according to claim 1, wherein the A% is 50% to 95% and the B% is 5% to 50%.
  3. 根据权利要求1所述的MM′X-Y金属复合功能材料，其特征在于，所述A％为60％～90％、B％为10％～40％。The MM'X-Y metal composite functional material according to claim 1, wherein the A% is 60% to 90% and the B% is 10% to 40%.
  4. 一种MM′X-Y金属复合功能材料的制备方法，其特征在于，包括如下步骤：A method for preparing a MM'X-Y metal composite functional material, comprising the steps of:
    1)按MaM′bXc的化学式配制原料；1) preparing a raw material according to the chemical formula of M a M' b X c ;
    2)将配制好的原料放入熔炼炉中，熔炼炉抽真空后用氩气清洗，之后在氩气保护下对配制好的原料进行熔炼，得到MaM′bXc合金；2) The prepared raw materials are placed in a smelting furnace, the smelting furnace is vacuumed, and then washed with argon gas, and then the prepared raw materials are smelted under argon gas protection to obtain a M a M′ b X c alloy;
    3)将MaM′bXc合金进行真空退火处理；3) vacuum annealing the M a M′ b X c alloy;
    4)将经真空退火后的MaM′bXc合金、Y材料分别破碎、过筛成粉末；4) The vacuum-annealed M a M′ b X c alloy and the Y material are separately crushed and sieved into a powder;
    5)分别量取体积百分比为A％的MaM′bXc合金粉末、B％的Y材料粉末，混合均匀；5) separately taking M a M′ b X c alloy powder and B% Y material powder with a volume percentage of A%, and mixing uniformly;
    6)将混合均匀的粉末在磁场下压制成型，得到成型材料；6) press-forming the uniformly mixed powder under a magnetic field to obtain a molding material;
    7)将成型材料进行固化，即得到产品MM′X金属复合功能材料。 7) The molding material is cured to obtain a product MM'X metal composite functional material.
  5. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述M或M′为Mn元素时，Mn按1％～10％的原子比过量添加。The method for producing a MM'X-Y metal composite functional material according to claim 4, wherein when M or M' is a Mn element, Mn is added in an excess of 1% to 10% by atomic ratio.
  6. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述M或M′为Mn元素时，Mn按2％～5％的原子比过量添加。The method for producing a MM'X-Y metal composite functional material according to claim 4, wherein when M or M' is a Mn element, Mn is added in an excess of 2% to 5% by atomic ratio.
  7. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述熔炼炉抽真空后的压力控制在小于或等于3×10-3Pa，熔炼温度为1300℃以上、熔炼时间为0.5～10min。The method for preparing a MM'XY metal composite functional material according to claim 4, wherein the pressure after the vacuuming of the melting furnace is controlled to be less than or equal to 3 × 10 -3 Pa, the melting temperature is 1300 ° C or more, and smelting The time is 0.5 to 10 minutes.
  8. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述熔炼炉抽真空后的压力为2×10-3～3×10-3Pa，熔炼温度为1300～1700℃、熔炼时间为2～3min。The method for preparing a MM'XY metal composite functional material according to claim 4, wherein the pressure of the melting furnace after vacuuming is 2×10 -3 to 3×10 -3 Pa, and the melting temperature is 1300 to 1700. °C, melting time is 2 ~ 3min.
  9. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述真空退火的温度为600～1100℃、时间为1～30天。The method for preparing a MM'X-Y metal composite functional material according to claim 4, wherein the vacuum annealing temperature is 600 to 1100 ° C and the time is 1 to 30 days.
  10. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述真空退火的温度为700～900℃、时间为5～15天。The method for preparing a MM'X-Y metal composite functional material according to claim 4, wherein the vacuum annealing temperature is 700 to 900 ° C and the time is 5 to 15 days.
  11. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述破碎采用研磨、振动磨、滚动磨、球磨、气流磨中的任意一种或一种以上的组合，所述过筛为过大于10目的标准筛，所述粉末的粒径小于2mm。The method for preparing a MM'XY metal composite functional material according to claim 4, wherein the crushing is performed by any one or a combination of grinding, vibration grinding, rolling mill, ball milling, and jet milling. The sieve is a standard sieve having a size greater than 10 mesh, and the powder has a particle size of less than 2 mm.
  12. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述过筛为过100～300目的标准筛，所述粉末的粒径为0～0.2mm。The method for preparing a MM'X-Y metal composite functional material according to claim 4, wherein the sieving is a standard sieve of 100 to 300 mesh, and the powder has a particle diameter of 0 to 0.2 mm.
  13. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述压制成型为通过压延法、模压法、挤压法、粉末注射成形法、或放电等离子体烧结法将粉末压制成所需的尺寸和形状，所述压制成型的压力为300～1500MPa、温度为0～900℃、时间 为1～240min，所述磁场的强度为0～5T。The method for preparing a MM'XY metal composite functional material according to claim 4, wherein the press molding is performed by a calendering method, a molding method, an extrusion method, a powder injection molding method, or a discharge plasma sintering method. Pressed into a desired size and shape, the compression molding pressure is 300-1500 MPa, the temperature is 0-900 ° C, time The intensity of the magnetic field is 0 to 5 T for 1 to 240 min.
  14. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述压制成型的压力为600～1000MPa、温度为0～500℃、时间为5～60min，所述磁场的强度为0～2T。The method for preparing a MM'XY metal composite functional material according to claim 4, wherein the press molding has a pressure of 600 to 1000 MPa, a temperature of 0 to 500 ° C, and a time of 5 to 60 min, and the strength of the magnetic field. It is 0~2T.
  15. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述固化的温度为0～900℃、时间为1～15天。The method for preparing a MM'X-Y metal composite functional material according to claim 4, wherein the curing temperature is 0 to 900 ° C and the time is 1 to 15 days.
  16. 根据权利要求4所述的MM′X-Y金属复合功能材料制备方法，其特征在于，所述固化的温度为0～500℃、时间为2～7天。 The method for preparing a MM'X-Y metal composite functional material according to claim 4, wherein the curing temperature is 0 to 500 ° C and the time is 2 to 7 days.
PCT/CN2017/086889 2017-04-13 2017-06-01 Functional mm'x-y metal composite material and preparation method therefor WO2018188178A1 (en)

Priority Applications (1)

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

Applications Claiming Priority (2)

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

Publications (1)

Publication Number Publication Date
WO2018188178A1 true WO2018188178A1 (en) 2018-10-18

Family

ID=59568323

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/086889 WO2018188178A1 (en) 2017-04-13 2017-06-01 Functional mm'x-y metal composite material and preparation method therefor

Country Status (3)

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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201711184D0 (en) * 2017-07-12 2017-08-23 Ibm Efficiently populating a phase diagram for modeling of multiple substances
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1389536A (en) * 2002-07-15 2003-01-08 南京大学 Composite room temperature magnetic refrigerating material and its prepn.
CN105448443A (en) * 2015-11-26 2016-03-30 北京科技大学 Preparation method of bonding martensitic phase change material
CN105714173A (en) * 2016-04-27 2016-06-29 上海电力学院 Manganese-cobalt-germanium-base alloy magnetic refrigeration material and preparing method thereof
WO2016104739A1 (en) * 2014-12-26 2016-06-30 大電株式会社 Production method for magnetic refrigeration material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1389536A (en) * 2002-07-15 2003-01-08 南京大学 Composite room temperature magnetic refrigerating material and its prepn.
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
CN105714173A (en) * 2016-04-27 2016-06-29 上海电力学院 Manganese-cobalt-germanium-base alloy magnetic refrigeration material and preparing method thereof

Also Published As

Publication number Publication date
CN106917029B (en) 2018-08-21
CN106917029A (en) 2017-07-04
US20200024693A1 (en) 2020-01-23

Similar Documents

Publication Publication Date Title
WO2022041693A1 (en) Tic strengthened cocrni medium-entropy alloy composite material and preparation method therefor
JP2022543491A (en) RTB Permanent Magnet Material, Manufacturing Method, and Application
JP2015506090A (en) Adhesive La (Fe, Si) 13-based magnetocaloric material and its production method and application
JP2014500611A (en) High corrosion resistance sintered NdFeB magnet and method for preparing the same
CN108364736A (en) A kind of Nd-Fe-B permanent magnet material and preparation method thereof
CN106435323A (en) Oxide dispersion strengthened (ODS) high-entropy alloy and preparation method thereof
CN104372230A (en) High-strength high-toughness ultrafine-grained high-entropy alloy and preparation method thereof
CN106868379A (en) A kind of high-entropy alloy with big magnetostriction coefficient and preparation method thereof
CN102751064A (en) Nano toughening NdFeB magnetic material and preparation method thereof
CN109524190B (en) Rare earth-iron-silicon-based magnetic refrigeration composite material and preparation method thereof
Bai et al. Excellent mechanical properties and large magnetocaloric effect of spark plasma sintered Ni-Mn-In-Co alloy
Wu et al. LaFe11. 6Si1. 4/Pr40Co60 magnetocaloric composites for refrigeration near room temperature
CN105448443A (en) Preparation method of bonding martensitic phase change material
Chen et al. Martensitic transformation and magnetic properties of Ti-doped NiCoMnSn shape memory alloy
Zhong et al. Improvement in mechanical and magnetocaloric properties of hot-pressed La (Fe, Si) 13/La70Co30 composites by grain boundary engineering
WO2018188178A1 (en) Functional mm'x-y metal composite material and preparation method therefor
Zhong et al. Microstructural evolution, magnetocaloric effect, mechanical and thermal properties of hot-pressed LaFe11. 6Si1. 4/Ce2Co7 composites prepared using strip-cast master alloy flakes
Zhong et al. Influence of particle size on the mechanical properties and magnetocaloric effect of La0. 8Ce0. 2 (Fe0. 95Co0. 05) 11.8 Si1. 2/Sn composites
Xin et al. Martensitic transformation and mechanical properties of NiMnGaV high-temperature shape memory alloys
CN103805839B (en) The preparation method of magnetic hardening FeGa alloy
Zhong et al. Attractive properties of magnetocaloric spark plasma sintered LaFe11. 6Si1. 4/Pr2Co7 composites for near room temperature cooling applications
US9418779B2 (en) Process for preparing scalable quantities of high purity manganese bismuth magnetic materials for fabrication of permanent magnets
Kuang et al. Simultaneously achieved good mechanical properties and large magnetocaloric effect in spark plasma sintered Ni-Mn-In alloys
Zhang et al. Tailored thermal expansion and electrical properties of α-Cu2V2O7/Al
Peng et al. Microstructure, phase evolution and magnetocaloric properties of LaFe11. 6Si1. 4/La70Co30 composite

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17905077

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17905077

Country of ref document: EP

Kind code of ref document: A1