WO2018188262A1 - 一种复合磁制冷材料及其制备方法和用途 - Google Patents

一种复合磁制冷材料及其制备方法和用途 Download PDF

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WO2018188262A1
WO2018188262A1 PCT/CN2017/101422 CN2017101422W WO2018188262A1 WO 2018188262 A1 WO2018188262 A1 WO 2018188262A1 CN 2017101422 W CN2017101422 W CN 2017101422W WO 2018188262 A1 WO2018188262 A1 WO 2018188262A1
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magnetic refrigeration
preparation
powder
refrigeration material
composite magnetic
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PCT/CN2017/101422
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English (en)
French (fr)
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张虎
王一旭
吴美玲
陶坤
邢成芬
肖亚宁
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北京科技大学
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    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • 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
    • B22F3/02—Compacting only
    • 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
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0094—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with organic materials as the main non-metallic constituent, e.g. resin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
    • H01F1/017—Compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC

Definitions

  • the invention relates to a magnetic material, in particular to a composite magnetic refrigeration material used for magnetic refrigeration technology and a preparation method thereof, and belongs to the field of preparation of magnetic refrigeration materials.
  • Magnetic refrigeration technology is a kind of green refrigeration technology that uses magnetic material as working medium to cool by means of the magnetocaloric effect of the material itself.
  • the magnetic refrigeration technology has the following advantages: 1) Green environmental protection: Magnetic refrigeration uses solid refrigerant to solve the problem of gas toxic, easy to leak, flammable, ozone layer damage and greenhouse effect.
  • thermodynamic process of magneto-cooling to produce magnetocaloric effect is highly efficient and reversible, and its intrinsic thermodynamic efficiency can reach Carnot efficiency, and the actual efficiency can reach 60-70% of Carnot cycle efficiency;
  • Stable and reliable magnetic refrigeration does not require a gas compressor, vibration and noise are small, long life and high reliability. Therefore, magnetic refrigeration technology has received widespread attention worldwide in recent years.
  • Gd 5 (Si x Ge 1-x ) 4 exhibited a giant magnetocaloric effect near room temperature, marking the first breakthrough in the exploration of room temperature magnetic refrigeration materials, and also caused magnetic The upsurge in the exploration and mechanism of refrigeration materials, especially magnetic refrigeration materials near room temperature. So far, many countries around the world have studied and discovered many magnetic refrigeration materials with giant magnetocaloric effects near room temperature, such as Gd 5 (Si x Ge 1-x ) 4 , LaCaMnO 3 , Ni-Mn-Ga, La(Fe, T).
  • the thermal conductivity of the La(Fe,Si) 13 -based magnetic refrigeration material after bonding is significantly reduced, which seriously affects the heat exchange efficiency.
  • the thermosetting process leads to the decomposition of La(Fe,Si) 13 hydride, which is not suitable for the preparation of La(Fe,Si) 13 hydride materials. . Therefore, the molding process of magnetic refrigeration materials is still a world problem, which seriously hinders the application of magnetic refrigeration materials in refrigerators.
  • Another object of the present invention is to provide a method of preparing a composite magnetic refrigeration material. Another object of the present invention is to provide a composite magnetic refrigeration material prepared by the preparation method. It is still another object of the present invention to provide a composite magnetic body including the same Magnetic refrigerator for refrigerating materials. It is still another object of the present invention to provide an application of the composite magnetic refrigeration material in the manufacture of a refrigerating material.
  • the present invention provides a method of preparing a composite magnetic refrigeration material, specifically comprising the following steps:
  • step 2) pressing the mixed powder in step 2) to a desired size and shape under a certain temperature and magnetic field;
  • the molding material prepared in the step 3) is cured at a certain curing temperature for a certain time, and finally a composite magnetic refrigeration material is obtained.
  • the magnetic refrigerating material X and the material Y are crushed by one or more of grinding, vibration grinding, rolling mill, ball milling, or jet milling,
  • the powder having a particle size of less than 2 mm was screened by a standard sieve of more than 10 mesh.
  • the standard sieve is 100 to 300 mesh, and the powder has a particle diameter of 0 to 0.5 mm.
  • the A% ratio is 40% to 95%; the B% ratio is 5% to 60%; and the C% ratio is 0% to 60%.
  • the A% ratio is 60% to 90%; the B% ratio is 5% to 40%; and the C% ratio is 0% to 30%.
  • the mixed powder in step 2) is pressed into a desired size and shape by calendering, molding, extrusion, powder injection molding, or spark plasma sintering. It is 300 to 1500 MPa; the pressing temperature is 0 to 900 ° C; the magnetic field is 0 to 5 T; and the pressing time is 1 to 240 minutes.
  • the pressure is 600 to 1000 MPa;
  • the temperature is 0 to 500 ° C;
  • the magnetic field is 0 to 2 T; and the pressing time is 5 to 60 minutes.
  • the curing temperature is from 0 to 900 ° C; and the curing time is from 1 to 15 days.
  • the curing temperature is from 0 to 500 ° C; and the curing time is from 2 to 7 days.
  • the present invention provides a composite magnetic refrigeration material having a specific composition of: X + B% of Y + C% of Z of A%, wherein:
  • Y is an alloy of one or more elements of Groups IB, IIB, IIIA, and IVA;
  • Z is one or more kinds of various binders commonly used in the prior art, and may be selected from the group consisting of epoxy resins, phenolic resins, polycarbonates, polyethylene naphthalates, polyethylene terephthalate, and poly One or more of an imide, a polyamide, a polyvinylidene fluoride, a polystyrene, a polybutene, a polyvinyl chloride, a polyethylene, or the like;
  • A% is the volume percentage of X
  • B% is the volume percentage of Y
  • C% is the volume percentage of Z
  • the present invention provides a magnetic refrigerator comprising a composite magnetic refrigeration material provided by the present invention or a magnetic refrigeration material produced by the preparation method provided by the present invention.
  • the present invention provides the use of the magnetic refrigeration material produced by the composite magnetic refrigeration material or the preparation method provided by the present invention in the manufacture of a refrigeration material.
  • the composite magnetic refrigeration material prepared by the preparation method of the invention has higher mechanical properties than the conventional magnetic refrigeration material
  • the composite magnetic refrigeration material of any shape and size can be fabricated according to actual needs;
  • the composite magnetic refrigeration material prepared by the preparation method provided by the invention has a good magnetocaloric effect and can be well applied to the field of magnetic refrigeration;
  • the preparation method provided by the invention has simple process, easy operation and industrialized production, and has important significance for practical application of the preparation method.
  • Example 1 is a stress-strain curve of an 80% LaFe 11.7 Si 1.3 C 0.2 H 1.8 +20% In composite magnetic refrigeration material prepared in Example 1;
  • Example 2 is a DSC curve comparison of an 80% LaFe 11.7 Si 1.3 C 0.2 H 1.8 +20% In composite magnetic refrigeration material prepared in Example 1 and pure LaFe 11.7 Si 1.3 C 0.2 H 1.8 ;
  • Example 3 is a temperature dependence of ⁇ S of 80% LaFe 11.7 Si 1.3 C 0.2 H 1.8 +20% In composite magnetic refrigeration material prepared in Example 1 under different magnetic fields;
  • Example 4 is a DSC curve comparison of a 70% LaFe 11.7 Si 1.3 C 0.2 H 1.8 +20% In+10% epoxy resin composite magnetic refrigeration material prepared in Example 2 and pure LaFe 11.7 Si 1.3 C 0.2 H 1.8 .
  • the conventional La(Fe,Si) 13 hydride material is extremely poor in mechanical properties due to fragmentation of the sample, and the stress-strain curve test cannot be performed.
  • the mechanical properties of the 80% LaFe 11.7 Si 1.3 C 0.2 H 1.8 +20% In composite magnetic refrigeration material obtained by the present embodiment are remarkably improved, and the mechanical properties can be completely tested.
  • the stress-strain curve of 80% LaFe 11.7 Si 1.3 C 0.2 H 1.8 +20%In composite magnetic refrigeration material was measured on a WDW200D microcomputer-controlled universal material testing machine. As shown in Fig. 1, the compressive strength of the metal composite was 138 MPa. The corresponding strain is 4.1%.
  • Figure 3 shows the dependence of ⁇ S on the temperature of the 80% LaFe 11.7 Si 1.3 C 0.2 H 1.8 +20% In composite magnetic refrigeration material under different magnetic fields. It can be seen that the sample exhibits magnetic entropy change near the phase transition temperature of 337K.
  • the maximum value of the magnetic entropy change of the sample is 5.5J/kgK, 8.6J/kgK, and 10.4J/kgK, respectively, when the magnetic field changes are 0-1T, 0-2T, and 0-3T, respectively.
  • 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.
  • the maximum magnetic entropy change (8.6 J/kgK) of 80% LaFe 11.7 Si 1.3 C 0.2 H 1.8 +20% In composite magnetic refrigeration material is significantly higher than that of the traditional room temperature magnetic refrigeration material Gd under the change of 0-2T magnetic field.
  • Magnetic entropy change (magnetic entropy becomes 5.0 J/kgK under 2T magnetic field), indicating that the 80% LaFe 11.7 Si 1.3 C 0.2 H 1.8 +20% In composite magnetic refrigeration material prepared in Example 1 can be used as a better room temperature. Functional Materials.
  • step 2) The powder after mixing in step 2) is pressed at a pressing temperature of 130 ° C, a pressure of 900 MPa, and a zero magnetic field for 5 minutes to obtain a cylindrical 70% LaFe 11.7 Si 1.3 C 0.2 H 1.8 +20% In+10% ring of ⁇ 10 mm. Molding material for oxygen resin;
  • the conventional Mn 0.6 Fe 0.4 NiSi 0.6 Ge 0.4 generates a large internal stress due to the martensitic transformation, which causes the sample to be broken and cannot be mechanically formed, which limits the application of such functional materials.
  • the 60% Mn 0.6 Fe 0.4 NiSi 0.6 Ge 0.4 +20%Sn+20% epoxy resin composite magnetic refrigeration material obtained by the invention has good molding and processing properties, and the above problems are well solved.
  • the magnetic heating effect of 60% Mn 0.6 Fe 0.4 NiSi 0.6 Ge 0.4 +20%Sn+20% epoxy resin composite magnetic refrigeration material is higher than that of the traditional room temperature magnetic refrigeration material Gd.
  • step 2) The powder after mixing in step 2) is pressed at a pressing temperature of 20 ° C, a pressure of 1000 MPa, and a magnetic field of 1.0 T for 30 minutes to obtain a cylindrical 90% Mn 1.2 Fe 0.8 P 0.48 Si 0.52 +5% InSn + 5% of ⁇ 10 mm. Molding material for epoxy resin;
  • the 90% Mn 1.2 Fe 0.8 P 0.48 Si 0.52 +5% InSn+5% epoxy resin composite magnetic refrigeration material obtained by the invention has good molding and processing properties.
  • the magnetic heating effect of 90% Mn 1.2 Fe 0.8 P 0.48 Si 0.52 +5% InSn+5% epoxy resin composite magnetic refrigeration material is higher than that of the traditional room temperature magnetic refrigeration material Gd.
  • the 80% Gd 5 Si 2 Ge 2 +5% Al + 155% epoxy resin composite magnetic refrigeration material obtained by the invention has good molding and processing properties.
  • the magnetic heating effect of 80% Gd 5 Si 2 Ge 2 +5% Al + 15% epoxy resin composite magnetic refrigeration material is higher than that of the traditional room temperature magnetic refrigeration material Gd.
  • step 3 The powder obtained by mixing the step 2) uniformly is pressed at a pressing temperature of 500 ° C, a pressure of 900 MPa, and a zero magnetic field for 40 minutes to obtain a cylindrical 70% Ni 50 Mn 34 Co 2 Sn 14 + 25% Ag + 5% ring of ⁇ 15 mm. Molding material for oxygen resin;
  • the 70% Ni 50 Mn 34 Co 2 Sn 14 + 25% Ag + 5% epoxy resin composite magnetic refrigeration material obtained by the invention has good molding and processing properties.
  • the magnetic heating effect of 70% Ni 50 Mn 34 Co 2 Sn 14 +25%Ag+5% epoxy resin composite magnetic refrigeration material is higher than that of the traditional room temperature magnetic refrigeration material Gd.

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Abstract

一种复合磁制冷材料及其制备方法，该复合磁制冷材料的具体组成为：X+Y+Z，其中：X为磁制冷材料中的一种或几种；Y为IB族、IIB族、IIIA族、IVA族中一种或几种元素的合金；Z为现有技术中常用的各种粘结剂的一种或几种。该复合制冷材料通过将组分X、Y、Z均匀混合后压制，固化成形制得。

Description

一种复合磁制冷材料及其制备方法和用途 技术领域
本发明涉及一种磁性材料，特别是涉及一种用于磁制冷技术的复合磁制冷材料及其制备方法，属于磁制冷材料制备领域。
背景技术
现代社会，制冷及低温技术在改善人们的生活水平和工作环境等方面起着十分重要的作用，关系到国计民生的众多重要领域，据统计制冷业每年能耗占社会总能耗的15％以上。目前广泛采用的制冷技术是传统的气体压缩-膨胀制冷技术，这种技术制冷时其最高效率仅为25％，可见，这种传统制冷技术效率较低。此外，传统制冷技术还存在破坏环境、产生噪音、难以小型化等缺点。随着现代社会的发展，能源和环境问题日益严峻，因此寻找绿色环保且高效节能的制冷技术已成为世界范围内亟待解决的问题。
近年来，一种基于磁热效应的磁制冷技术受到广泛的关注和研究。磁制冷技术是以磁性材料为工作介质，借助于材料本身的磁热效应来制冷的一种绿色制冷技术。与传统的气体压缩-膨胀制冷技术相比，磁制冷技术具有以下优点：1)绿色环保：磁制冷采用固体制冷工质，解决了气体有毒、易泄露、易燃以及对臭氧层破坏和温室效应等问题；2)高效节能：磁制冷产生磁热效应的热力学过程是高效可逆的，其本征热力学效率可达卡诺效率，而实际能实现的效率也可达卡诺循环效率的60-70％；3)稳定可靠：磁制冷无需气体压缩机，振动与噪声小、寿命长、可靠性高。因此，磁制冷技术近年来得到全世界的广泛关注。
1997年，美国Ames实验室的Pecharsky和Gschneidner报道了Gd5(SixGe1-x)4在室温附近表现出巨磁热效应，标志着室温磁制冷材 料探索的首次突破，同时，也掀起了磁制冷材料，尤其是室温附近的磁制冷材料的探索和机理研究的热潮。迄今为止，世界各国已研究并发现了许多室温附近具有巨磁热效应的磁制冷材料，如Gd5(SixGe1-x)4、LaCaMnO3、Ni-Mn-Ga、La(Fe,T)13(T＝Si、Al)基化合物、MnAs基化合物，MM′N(M,M′＝过渡族金属，N＝IIIA或IVA族元素)基化合物等。尽管这些磁制冷材料的磁热效应显著高于传统室温磁制冷材料Gd，但由于它们大多是金属间化合物，脆性大，成型困难，难于加工成所需形状。要将磁制冷材料真正应用到磁制冷机当中，则不仅需要具有大的磁热效应，同时要具备一定的强度和韧性，并满足固液换热需要的不同形状。
2010年，Lyubina研究发现，通过热压成型的方式制备具有多孔结构的La(Fe,Si)13材料，不仅能够极大地提高材料的机械性能，而且能够降低热滞和磁滞损耗。随后，中国专利申请CN103137281A公开了一种具有高强度的粘结La(Fe,Si)13基磁制冷材料及其制备方法，该专利利用环氧树脂胶、聚酰亚胺胶等粘接剂与La(Fe,Si)13材料粉末混合并热固成型，从而获得了高强度的La(Fe,Si)13基磁制冷材料。然而，由于该粘接剂的热导率低，导致粘结后La(Fe,Si)13基磁制冷材料的热导率显著下降，严重影响了其换热效率。同时，由于La(Fe,Si)13氢化物材料的热稳定性差，因此，热固成型工艺会导致La(Fe,Si)13氢化物分解，不适于制备La(Fe,Si)13氢化物材料。因此，磁制冷材料的成型工艺仍然是一个世界难题，严重阻碍了磁制冷材料在制冷机上的应用。
发明内容
因此，本发明的一个目的在于，提供一种复合磁制冷材料的制备方法。本发明的另一个目的在于，提供所述制备方法制备的复合磁制冷材料。本发明的再一个目的在于，提供一种包括所述复合磁 制冷材料的磁制冷机。本发明的又一个目的在于，提供所述复合磁制冷材料在制造制冷材料中的应用。
本发明的目的是通过以下技术方案实现的：
一方面，本发明提供制备复合磁制冷材料的方法，具体包括以下步骤：
1)将磁制冷材料X和材料Y破碎成一定尺寸的粉末；
2)将步骤1)中制备出的磁制冷材料X、Y粉末与粘接剂Z按A％+B％+C％比例混合均匀；
3)将步骤2)中混合后的粉末在一定温度和磁场下压制成需要的尺寸和形状；
4)将步骤3)中制备出的成型材料在一定固化温度下固化一定时间，最终获得复合磁制冷材料。
根据本发明提供的制备方法，优选地，在步骤1)中，将磁制冷材料X和材料Y通过研磨、振动磨、滚动磨、球磨、或气流磨等方式中的一种或几种破碎，并通过大于10目的标准筛，筛选出粒径小于2mm的粉末。
更优选地，在步骤1)中，所述标准筛为100～300目，所述粉末粒径为0～0.5mm。
优选地，在步骤2)中，所述A％比例为40％～95％；所述B％比例为5％～60％；所述C％比例为0％～60％。
更优选地，在步骤2)中，所述A％比例为60％～90％；所述B％比例为5％～40％；所述C％比例为0％～30％。
优选地，在步骤3)中，将步骤2)中混合后的粉末通过压延法、模压法、挤压法、粉末注射成形、或放电等离子体烧结法压制成需要的尺寸和形状，所述压力为300～1500MPa；所述压制温度为0～900℃；所述磁场为0～5T；所述压制时间为1～240分钟。
更优选地，在步骤3)中，所述压力为600～1000MPa；所述压 制温度为0～500℃；所述磁场为0～2T；所述压制时间为5～60分钟。
优选地，在步骤4)中，所述固化温度为0～900℃；所述固化时间为1～15天。
更优选地，在步骤4)中，所述固化温度为0～500℃；所述固化时间为2～7天。
另一方面，本发明提供一种复合磁制冷材料，其具体组成为：A％的X+B％的Y+C％的Z，其中：
X为磁制冷材料中的一种或几种，可选自Gd、Gd5(SixGe1-x)4、LaCaMnO3、Ni-Mn-D(D＝Ga,In,Sn,等)Heusler合金、La(Fe,T)13(T＝Si、Al)基化合物、MnAs基化合物，MM′N(M,M′＝过渡族金属，N＝IIIA或IVA族元素)基磁制冷材料中的一种或几种；
Y为IB族、IIB族、IIIA族、IVA族中一种或几种元素的合金；
Z为现有技术中常用的各种粘结剂的一种或几种，可选自环氧树脂、酚醛树脂、聚碳酸酯、聚乙烯萘酸脂、聚对苯二甲酸二乙酯、聚酰亚胺、聚酰胺、聚偏氟乙烯、聚苯乙烯、聚丁烯、聚氯乙烯、聚乙烯等中的一种或几种；
A％为X的体积百分含量；
B％为Y的体积百分含量；
C％为Z的体积百分含量；
A％+B％+C％的和为100％。
再一方面，本发明提供了一种磁制冷机，所述制冷机包括本发明提供的复合磁制冷材料或者按照本发明提供的制备方法制得的磁制冷材料。
又一方面，本发明提供所述复合磁制冷材料或者按照本发明提供的制备方法制得的磁制冷材料在制造制冷材料中的应用。
本发明的有益技术效果：
与现有技术相比，本发明的优势在于：
1)利用本发明提供了一种以往未报道过的复合磁制冷材料；
2)利用本发明的制备方法制备的复合磁制冷材料具有比传统磁制冷材料更高的机械性能；
3)利用本发明提供的制备方法可以根据实际需要制作任意形状和尺寸的复合磁制冷材料；
4)利用本发明提供的制备方法制备的复合磁制冷材料具有很好的磁热效应，能够很好的应用到磁制冷领域；
5)本发明提供的制备方法工艺简单，易于操作和实现工业化生产，对实际应用该制备方法具有重要的意义。
附图说明
图1为实施例1制得的80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料的应力-应变曲线；
图2为实施例1制得的80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料与纯LaFe11.7Si1.3C0.2H1.8的DSC曲线对比；
图3为实施例1制得的80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料在不同磁场下ΔS对温度的依赖关系；
图4为实施例2制得的70％LaFe11.7Si1.3C0.2H1.8+20％In+10％环氧树脂复合磁制冷材料与纯LaFe11.7Si1.3C0.2H1.8的DSC曲线对比。
具体实施方式
下面结合具体实施方式及附图对本发明进行进一步的详细描述，给出的实施例仅为了阐明本发明，而不是为了限制本发明的范围。
实施例1：
80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料及其制备方法：
1)利用玛瑙研钵分别将LaFe11.7Si1.3C0.2H1.8材料和金属In破碎， 并通过150目的标准筛筛选出小于0.1mm的不规则颗粒粉末；
2)按80％LaFe11.7Si1.3C0.2H1.8+20％In的体积比例将步骤1)所得粉末混合均匀；
3)将步骤2)混合均匀后的粉末在140℃的压制温度、900MPa压力、零磁场下压制10分钟得到Φ10mm的圆柱形80％LaFe11.7Si1.3C0.2H1.8+20％In成型材料；
4)将步骤3)中制备出的成型材料在20℃下固化2天，最终获得80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料。
本领域技术人员公知的是，传统La(Fe,Si)13氢化物材料在氢化处理后呈粉末状，无法进行机械加工成型，限制了这类功能材料的应用。而利用本发明所获得的80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料具有很好的成型和加工性能，很好地解决了以上难题。
进一步，传统La(Fe,Si)13氢化物材料由于样品碎化，机械性能极差，无法进行应力-应变曲线测试。而通过本实施例所获得的80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料机械性能显著提高，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80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料的应力-应变曲线，如图1所示，该金属复合材料的抗压强度为138MPa，对应的应变为4.1％。
在差示扫描量热仪(日本精工公司设计的DSC 6220系统)上测试80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料与纯LaFe11.7Si1.3C0.2H1.8的DSC曲线，如图2所示，可以看出80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料和纯LaFe11.7Si1.3C0.2H1.8的居里温度TC都是337K，说明本实施例1的制备方法并未改变原有磁制冷材料的磁性相变，使复合磁制冷材料保持了与原有磁制冷材料相同的相变温度，非常有利于实际应用。
在磁性测量系统(美国Quantum Design公司设计的Versalab  Free测量系统)上测定80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料的等温磁化曲线(M-H曲线)，再根据麦克斯韦关系：
Figure PCTCN2017101422-appb-000001
可从等温磁化曲线计算磁熵变ΔS。图3示出了该80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料在不同磁场下ΔS对温度的依赖关系，可以看出，样品在相变温度337K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5.5J/kgK、8.6J/kgK、10.4J/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，80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料的最大磁熵变(8.6J/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)，说明实施例1制得的80％LaFe11.7Si1.3C0.2H1.8+20％In复合磁制冷材料可以作为更优的室温功能材料。
实施例2：
70％LaFe11.7Si1.3C0.2H1.8+20％In+10％环氧树脂复合磁制冷材料及其制备方法：
1)利用玛瑙研钵分别将LaFe11.7Si1.3C0.2H1.8材料和金属In破碎，并通过200目的标准筛筛选出小于0.07mm的不规则颗粒粉末；
2)按70％LaFe11.7Si1.3C0.2H1.8+20％In+10％环氧树脂的体积比例将步骤1)所得粉末混合均匀；
3)将步骤2)混合均匀后的粉末在130℃的压制温度、900MPa压力、零磁场下压制5分钟得到Φ10mm的圆柱形70％LaFe11.7Si1.3C0.2H1.8+20％In+10％环氧树脂的成型材料；
4)将步骤3)中制备出的成型材料在20℃下固化7天，最终获得70％LaFe11.7Si1.3C0.2H1.8+20％In+10％环氧树脂复合磁制冷材料。
在差示扫描量热仪(日本精工公司设计的DSC 6220系统)上测试70％LaFe11.7Si1.3C0.2H1.8+20％In+10％环氧树脂复合磁制冷材料与纯LaFe11.7Si1.3C0.2H1.8的DSC曲线，如图4所示，可以看出70％LaFe11.7Si1.3C0.2H1.8+20％In+10％环氧树脂复合磁制冷材料和纯LaFe11.7Si1.3C0.2H1.8的居里温度TC都是337K，说明本实施例2的制备方法并未改变原有磁制冷材料的磁性相变，使复合磁制冷材料保持了与原有磁制冷材料相同的相变温度，非常有利于实际应用。
本领域技术人员公知的是，传统La(Fe,Si)13氢化物材料在氢化处理后呈粉末状，无法进行机械加工成型，限制了这类功能材料的应用。而利用本发明所获得的70％LaFe11.7Si1.3C0.2H1.8+20％In+10％环氧树脂复合磁制冷材料具有很好的成型和加工性能，很好地解决了以上难题。同时，经磁性测试，70％LaFe11.7Si1.3C0.2H1.8+20％In+10％环氧树脂复合磁制冷材料的磁热效应高于传统室温磁制冷材料Gd。
实施例3：
60％Mn0.6Fe0.4NiSi0.6Ge0.4+20％Sn+20％环氧树脂复合磁制冷材料及其制备方法：
1)利用玛瑙研钵分别将Mn0.6Fe0.4NiSi0.6Ge0.4材料和金属Sn破碎，并通过100目的标准筛筛选出小于0.15mm的不规则颗粒粉末；
2)按60％Mn0.6Fe0.4NiSi0.6Ge0.4+20％Sn+20％环氧树脂的体积比例将步骤1)所得粉末混合均匀；
3)将步骤2)混合均匀后的粉末在20℃的压制温度、960MPa压力、1.5T磁场下压制15分钟得到Φ10mm的圆柱形60％Mn0.6Fe0.4NiSi0.6Ge0.4+20％Sn+20％环氧树脂的成型材料；
4)将步骤3)中制备出的成型材料在150℃下固化5天，最终获得60％Mn0.6Fe0.4NiSi0.6Ge0.4+20％Sn+20％环氧树脂复合磁制冷材料。
本领域技术人员公知的是，传统Mn0.6Fe0.4NiSi0.6Ge0.4由于马氏体相变产生巨大的内应力，导致样品碎化，无法进行机械加工成型，限制了这类功能材料的应用。而利用本发明所获得的60％Mn0.6Fe0.4NiSi0.6Ge0.4+20％Sn+20％环氧树脂复合磁制冷材料具有很好的成型和加工性能，很好地解决了以上难题。同时，经磁性测试，60％Mn0.6Fe0.4NiSi0.6Ge0.4+20％Sn+20％环氧树脂复合磁制冷材料的磁热效应高于传统室温磁制冷材料Gd。
实施例4：
90％Mn1.2Fe0.8P0.48Si0.52+5％InSn+5％环氧树脂复合磁制冷材料及其制备方法：
1)利用高能球磨机分别将Mn1.2Fe0.8P0.48Si0.52和InSn合金破碎，并通过300目的标准筛筛选出小于0.05mm的不规则颗粒粉末；
2)按90％Mn1.2Fe0.8P0.48Si0.52+5％InSn+5％环氧树脂的体积比例将步骤1)所得粉末混合均匀；
3)将步骤2)混合均匀后的粉末在20℃的压制温度、1000MPa压力、1.0T磁场下压制30分钟得到Φ10mm的圆柱形90％Mn1.2Fe0.8P0.48Si0.52+5％InSn+5％环氧树脂的成型材料；
4)将步骤3)中制备出的成型材料在150℃下固化7天，最终获得90％Mn1.2Fe0.8P0.48Si0.52+5％InSn+5％环氧树脂复合磁制冷材料。
经过力学性能测试，本发明所获得的90％Mn1.2Fe0.8P0.48Si0.52+5％InSn+5％环氧树脂复合磁制冷材料具有很好的成型和加工性能。同时，经磁性测试，90％Mn1.2Fe0.8P0.48Si0.52+5％InSn+5％环氧树脂复合磁制冷材料的磁热效应高于传统室温磁制冷材料Gd。
实施例5：
80％Gd5Si2Ge2+5％Al+15％环氧树脂复合磁制冷材料及其制备方法：
1)利用气流磨分别将Gd5Si2Ge2材料和金属Al破碎，并通过300目的标准筛筛选出小于0.05mm的不规则颗粒粉末；
2)按80％Gd5Si2Ge2+5％Al+15％环氧树脂的体积比例将步骤1)所得粉末混合均匀；
3)将步骤2)混合均匀后的粉末在600℃的压制温度、600MPa压力、零磁场下压制20分钟得到Φ10mm的圆柱形80％Gd5Si2Ge2+5％Al+15％环氧树脂的成型材料；
4)将步骤3)中制备出的成型材料在300℃下固化5天，最终获得80％Gd5Si2Ge2+5％Al+15％环氧树脂复合磁制冷材料。
经过力学性能测试，本发明所获得的80％Gd5Si2Ge2+5％Al+15％环氧树脂复合磁制冷材料具有很好的成型和加工性能。同时，经磁性测试，80％Gd5Si2Ge2+5％Al+15％环氧树脂复合磁制冷材料的磁热效应高于传统室温磁制冷材料Gd。
实施例6：
70％Ni50Mn34Co2Sn14+25％Ag+5％环氧树脂复合磁制冷材料及其制备方法：
1)利用高能球磨机分别将Ni50Mn34Co2Sn14材料和金属Ag破碎，并通过250目的标准筛筛选出小于0.06mm的不规则颗粒粉末；
2)按70％Ni50Mn34Co2Sn14+25％Ag+5％环氧树脂的体积比例将步骤1)所得粉末混合均匀；
3)将步骤2)混合均匀后的粉末在500℃的压制温度、900MPa压力、零磁场下压制40分钟得到Φ15mm的圆柱形70％Ni50Mn34Co2Sn14+25％Ag+5％环氧树脂的成型材料；
4)将步骤3)中制备出的成型材料在700℃下固化2天，最终获得70％Ni50Mn34Co2Sn14+25％Ag+5％环氧树脂复合磁制冷材料。
经过力学性能测试，本发明所获得的70％Ni50Mn34Co2Sn14+25％Ag+5％环氧树脂复合磁制冷材料具有很好的成型和加工性能。同时，经磁性测试，70％Ni50Mn34Co2Sn14+25％Ag+5％环氧树脂复合磁制冷材料的磁热效应高于传统室温磁制冷材料Gd。
以上已经参照具体实施方式详细地描述了本发明，对本领域技术人员而言，应当理解的是，上述具体实施方式不应该被理解为限定本发明的范围。因此，在不脱离本发明精神和范围的情况下可以对本发明的实施方案作出各种改变和改进。

Claims (8)

  1. 一种复合磁制冷材料的制备方法，其特征在于，所述方法包括如下步骤：
    1)将材料X和材料Y破碎成一定尺寸的粉末；
    2)将步骤1)中制备出的材料X、Y的粉末与粘接剂Z按A％+B％+C％比例混合均匀；所述比例为体积百分比；
    3)将步骤2)中混合后的粉末在一定温度和磁场下压制成需要的尺寸和形状；
    4)将步骤3)中制备出的成型材料在一定固化温度下固化一定时间，获得复合磁制冷材料；
    其中，材料X为磁制冷材料中的一种或几种；
    材料Y为IB族、IIB族、IIIA族、IVA族中一种或几种元素的合金；
    Z为粘结剂的一种或几种。
  2. 根据权利要求1所述的制备方法，其特征在于，所述步骤1)包括：所述破碎采用研磨、振动磨、滚动磨、球磨、或气流磨中的一种或几种；破碎后材料通过大于10目的标准筛，筛选出粒径小于2mm的粉末；优选地，所述标准筛为100～300目，所述粉末的粒径为0～0.5mm。
  3. 根据权利要求1所述的制备方法，其特征在于，所述步骤2)所述A％为40％～95％；所述B％为5％～60％；所述C％为0％～60％；优选地，所述A％为60％～90％；所述B％为5％～40％；所述C％为0％～30％。
  4. 根据权利要求1所述的制备方法，其特征在于，所述步骤3)包括：将步骤2)中混合后的粉末通过压延法、模压法、挤压法、粉末注射成形、或放电等离子体烧结法压制成需要的尺寸和形状，压制时压力为300～1500MPa；压制温度为0～900℃；所述磁场为0～5T；压制时间为1～240分钟；优选地，所述压制压力为600～1000MPa；所述压制温度为0～500℃；所述磁场为0～2T；所述压制时间为5～60分钟。
  5. 根据权利要求1所述的制备方法，其特征在于，所述步骤4)中所述固化温度为0～900℃；固化时间为1～15天；优选地，所述固化温度为0～500℃；所述固化时间为2～7天。
  6. 一种复合磁制冷材料，其具体组成为：A％的X+B％的Y+C％的Z，其中：
    X为磁制冷材料中的一种或几种；
    Y为IB族、IIB族、IIIA族、IVA族中一种或几种元素的合金；
    Z为粘结剂的一种或几种；
    A％为X的体积百分含量；
    B％为Y的体积百分含量；
    C％为Z的体积百分含量；
    A％+B％+C％的和为100％。
  7. 一种磁制冷机，其特征在于，所述磁制冷机包括权利要求6所述的复合磁制冷材料或者按照权利要求1-5中任一项所述的制备方法得到的磁制冷材料。
  8. 一种权利要求6中所述的复合磁制冷材料或者按照权利要求1-5中任一项所述的制备方法得到的磁制冷材料在制造制冷材料中的应用。
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