CN107855518A - A kind of preparation method of the hot composite of magnetic bonded by low-melting alloy - Google Patents

A kind of preparation method of the hot composite of magnetic bonded by low-melting alloy Download PDF

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Publication number
CN107855518A
CN107855518A CN201711118700.0A CN201711118700A CN107855518A CN 107855518 A CN107855518 A CN 107855518A CN 201711118700 A CN201711118700 A CN 201711118700A CN 107855518 A CN107855518 A CN 107855518A
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low
magnetic
melting alloy
magneto
melting
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李领伟
刘振刚
丁錾
武启明
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Northeastern University China
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Northeastern University China
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    • B22F1/0003
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/1035Liquid phase sintering
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/012Magnets 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
    • H01F1/015Metals or alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

The invention belongs to technical field of magnetic, and in particular to a kind of preparation method of the hot composite of magnetic bonded by low-melting alloy.Technical scheme is as follows:Comprise the following steps:1) iron-based magneto-caloric material is prepared using arc-melting furnace;2) by iron-based magneto-caloric material vacuum annealing, then in room temperature quenching-in water, 1 with NaZn structures is made:13 phase La (Fe, Si)13Base magneto-caloric material;3) by the La (Fe, Si) after annealing13Base magneto-caloric material carries out mechanical lapping, crosses the powder for filtering out that particle diameter is 30 300 μm;4) by La (Fe, Si)13Base magneto-caloric material powder is mixed in proportion with low-melting alloy powder and cold moudling, and pressing pressure is 0.1 1.4GPa, and the press time is 1 30 minutes;5) pressing pressure is kept, 5 30 minutes is being incubated higher than on low-melting alloy melting temperature, furnace cooling, is being stripped at room temperature.The present invention can obtain the hot composite of magnetic with high resistance to compression toughness, big magnetothermal effect and good pyroconductivity.

Description

A kind of preparation method of the hot composite of magnetic bonded by low-melting alloy
Technical field
The invention belongs to technical field of magnetic, and in particular to a kind of hot composite wood of magnetic bonded by low-melting alloy The preparation method of material.
Background technology
The main flow refrigeration machine used at present is all based on the mode of vapor compression refrigeration.Vapor compression refrigeration agent is mainly fluorine Leon or HFC, they have serious destruction to air, can cause destruction and the greenhouse effects of ozone layer.Based on magnetic Fuel factor (MCE), environmental protection and energy-conservation substitute of the magnetic Refrigeration Technique as conventional gas compression refrigeration have huge potentiality.By In this solid material technology without using compressed gas, so will not be damaged to air, it is referred to as green refrigeration skill Art.In addition, traditional vapor compression refrigeration efficiency is low, the 5%-10% of Carnot cycle can only achieve, the efficiency of magnetic refrigeration can be with Reach the 30%-60% of Carnot cycle, power savings advantages are notable.Meanwhile magnetic refrigeration also have the close height of entropy, small volume, it is simple in construction, Noise is small, long lifespan and be easy to maintenance the features such as.It is whole world model to study and produce with efficient magnetic refrigerator Enclose interior researcher urgent problem to be solved.
Good magnetic refrigeration solid coolant agent has the characteristics that:Larger adiabatic temperature changes, higher chemically stable Property and mechanical stability and there is high pyroconductivity between heat exchanger.Simple metal gadolinium is most common room temperature magnetic refrigerating material Material, it has good magnetic heating performance, and often by the normative reference as other magneto-caloric materials, but its high price limits its business Industry purposes, and functionally gradient material (FGM) can not be produced to expand it in AMR (Active Magnetic Regenerator) experiments Refrigeration scope.The intermetallic compound of people's exploitation at present mainly has iron-based, manganese base, Ni-based and gadolinium base to close as solid coolant agent Gold.Its structure is respectively NaZn13The La (Fe, Si) of structure13Based alloy, the MnFeP (Ge, Si) and Mn (Co, Ni) of hexagonal structure Ge alloys, Heusler types Ni2Mn(Ga,In,Sn,Sb).It is different from traditional room temperature magnetic refrigerating material Gd two level magnetic phase transition, this There is the first order phase change of magnetic structure coupling in a little new giant magnetio-caloric effects materials, when magnetic phase transition occurs, its crystal structure can also be sent out Raw significant change.These new materials also have some respective material characteristics, such as Gd- due to its component and structure Si-Ge is expensive, and, NiMn toxic to compound starting materials such as the further purification of raw material, MnAs is needed in preparation process Base Heusler alloys have the characteristics of hysteresis loss is big etc..
La(Fe,Si)13Magnetic refrigerating material has NaZn13Type structure (1:13 phases), it is considered to be most promising room temperature magnetic One of refrigerant, because it shows big magnetothermal effect and adjustable Curie temperature (T c).Curie temperature, interconvertibility Matter, magnetic hystersis loss change with the change of component, and countries in the world researchers show keen interest to this, and It investigated than influence of the more comprehensive component change to magnetic refrigerating material, while it be actively applied to AMR and tested, attempt to make Produce more efficient magnetic refrigerating system.Research shows that the compound of low Si contents is generally first order phase change;The increase of Co contents Can be that Curie temperature rises, first order phase change property weakens, and is gradually transitions two level, and hysteresis loss is gradually reduced, yet with The change of component, exchange interaction, magnetothermal effect amplitude also decline therewith;Mn addition makes Curie temperature by influenceing exchange interaction Decline, small rare-earth magnetic atom, which substitutes La, can strengthen first order phase change property;The less interstitial atom of atomic radius (such as C, H, B etc.) introducing can improve Curie temperature, make magnetothermal effect occur in the range of 250-340K.Although La (Fe, Si)13Base magnetic Refrigerating material near room temperature magnetic entropy becomes one times higher than Gd, and adjustable Curie temperature can produce functionally gradient material (FGM) expansion Refrigeration scope, but its strong magnetocrystalline coupled characteristic (intrinsic property of material) is shown that compression strength is poor, frangible, corrosion resistant The characteristics of losing ability, and chemicals are difficult into the thin plate less than 0.5mm between brittle metal, especially for La (Fe, Si)13Hx, because generally inevitably a large amount of rare-earth compounds hydrogenation explosion, this for practical application very It is unfavorable.The shortcomings that inherent fragility and relatively low thermal conductivity of La-Fe-Si sills are two inevitable.
Powder metallurgy process is considered as the effective way (U.S. Patent Publication No. of scale manufacture magnetic refrigeration alloy US2011/0114031 A1), for example, Matthias Katter etc. using powder metallurgy method be prepared for block La (Fe, Co, Si)13Base magnetic refrigerating material, research show block La (Fe, Co, Si) prepared by powder metallurgic method13Material possesses anneals with as cast condition Handle the equivalent magnetic property of sample, but it is this by the mechanical property of powdered reaction sintering and compressing block materials less It is preferable.Magnetic refrigerating material moves in circles disengaging high-intensity magnetic field in AMR, in constantly cutting magnetic induction line, is subjected to tens to several The magnetic pull of hectonewton, this tests the mechanical property of magnetic refrigerating material very much.
It is to improve magnetic refrigeration that high-thermal conductive metal particle (copper, silver) is mixed with metal-base composites with magneto-caloric material particle Effective concept (U.S. Patent Publication No. US2011/0168363 A9) of material mechanical performance.It is but cold extrusion shaped compound Adhesion is weaker between material has metallic particles, caused during large deformation magnetic thermalloy magnetic property reduce the deficiencies of.It is Chinese public Open patent CN102764887A and disclose a kind of preparation method of the magnetic refrigeration composite material by polymer bonding, polymer is in magnetic Solidification is carried out off field and obtains magnetocrystalline anisotropy and magnetic thermal anisotropy energy, and resistance to compression toughness also has preferably compared to the above method Lifting, but the limitation of polymer thermal conductivity is constrained to, between the magnetic refrigeration composite material and heat exchanger that finally obtain Pyroconductivity is unsatisfactory.Preparation method (the China Patent Publication No. of magnetic refrigeration working substance is bonded on thermoplastic shaping CN103422014A) compared with sample prepared by thermoset forming technology, its toughness significantly strengthens the magnetic refrigeration composite material obtained, But it can not also avoid this problem of pyroconductivity.
The content of the invention
The present invention provides a kind of preparation method of the hot composite of magnetic bonded by low-melting alloy, obtains with high anti- Press toughness, the hot composite of the magnetic of big magnetothermal effect and good pyroconductivity.
Technical scheme is as follows:
A kind of preparation method of the hot composite of magnetic bonded by low-melting alloy, comprises the following steps:
1) iron-based magneto-caloric material is prepared using arc-melting furnace, wherein protective atmosphere is argon gas;
2) by melted iron-based magneto-caloric material vacuum annealing, then in room temperature quenching-in water, prepare and tied with NaZn The 1 of structure:13 phase La (Fe, Si)13Iron-based magneto-caloric material;
3) by the La (Fe, Si) after annealing13Base magneto-caloric material carries out mechanical lapping, and it is 30- to select particle diameter by sieving 300 μm of powder;
4) by La (Fe, Si)13Base magneto-caloric material powder is mixed in proportion and is cold-pressed into low-melting alloy powder Type, wherein pressing pressure are 0.1-1.4GPa, and the press time is 1-30 minutes;
5) continue to keep pressing pressure, 5-30 minutes are being incubated higher than on low-melting alloy melting temperature, then with stove Cooling, is stripped at room temperature.
The preparation method of the described hot composite of the magnetic bonded by low-melting alloy, wherein the iron-based magneto-caloric material is Iron-based magnetic refrigeration alloy.
The preparation method of the described hot composite of the magnetic bonded by low-melting alloy, its preferred scheme are the La (Fe,Si)13Base magneto-caloric material powder diameter is 50-100 μm.
The preparation method of the described hot composite of the magnetic bonded by low-melting alloy, wherein the low-melting alloy is molten Alloy of the point between 340-500K, the mass fraction of the low-melting alloy is 5%-25%, the low-melting alloy powder Size be 10-20nm.
The preparation method of the described hot composite of the magnetic bonded by low-melting alloy, its preferred scheme are the eutectic The mass fraction of point alloy is 5%-15%.
The preparation method of the described hot composite of the magnetic bonded by low-melting alloy, its preferred scheme are the compacting Pressure is 0.5-1.2GPa.
Beneficial effects of the present invention are:The present invention is at La (Fe, Si)13A small amount of low-melting alloy is introduced in base magneto-caloric material, Keep pressure low-melting alloy is in molten condition after cold moudling, then cooled down in room temperature, fill low-melting alloy More holes, metallurgical chain, the considerable heat biography for improving magnetic hot composite are formd between the hot composite material granular of magnetic Conductance, and the magnetic hot composite higher than block materials consistency is obtained, intensity is not only increased, and overcome material Expect frangible, the intrinsic property of impact resistance difference;Compared with the hot composite of hot-forming magnetic, magnetic entropy time-varying amplitude of the invention, Adiabatic temperature change is still considerable, can also prevent it is hot-forming under the conditions of high temperature to oozing hydrogen magnetic refrigeration alloy Curie temperature Influence;With metal-non-metal composite ratio, the present invention introduces low-melting alloy in matrix material, and significantly reduces Porosity, the pyroconductivity between the hot composite of magnetic and heat exchanger substantially increase, and freeze for the actual magnetic of this kind of material Using significant.
Brief description of the drawings
Fig. 1 is mass ratio 10:1 LaFe11.6Si1.4H1.4Magnetic thermalloy and Pb55.7Bi31.2Cd13.1Low-melting alloy is suppressed It is molded the SEM schematic diagrames of the hot composite of magnetic;
Fig. 2 be different quality than LaFe11.6Si1.4H1.4Magnetic thermalloy and Pb55.7Bi31.2Cd13.1Low-melting alloy is suppressed It is molded the hot composite of magnetic, the M-T curves under 0.01T magnetic fields;
Fig. 3 is mass ratio 10:1 LaFe11.6Si1.4H1.4Magnetic thermalloy and Pb55.7Bi31.2Cd13.1Low-melting alloy is suppressed The hot composite of magnetic is molded, field is risen at different temperatures, drops the M-H curves of field process;
Fig. 4 be different quality than LaFe11.6Si1.4H1.4Magnetic thermalloy and Pb55.7Bi31.2Cd13.1Low-melting alloy is suppressed The hot composite of magnetic is molded under different magnetic field, magnetic entropy becomes the dependence curve to temperature;
Fig. 5 be different quality than LaFe11.6Si1.4H1.4Magnetic thermalloy and Pb55.7Bi31.2Cd13.1Low-melting alloy is suppressed It is molded the stress strain diagram of the hot composite of magnetic.
Embodiment
Using Pb55.7Bi31.2Cd13.1Low-melting alloy (fusing point is 88 DEG C) and iron-based magneto-caloric material particle cold moudling system The good LaFe of standby high intensity thermal conductivity11.6Si1.4H1.4, the compressing hot composite of magnetic.
Preparation process is as follows:It is LaFe to make composition with arc-melting furnace11.6Si1.4Ingot casting, under vacuo 1050 DEG C of annealing Quenched after seven days in room temperature water;Block after annealing is subjected to mechanical lapping, the particle size selected of sieving is at 50-100 μm Between, by LaFe11.6Si1.4Grain is placed under 20MPa Hydrogen Vapor Pressure, and hydrogen is inhaled at 500 DEG C and obtains LaFe11.6Si1.4H2.3, with Pb55.7Bi31.2Cd13.1Low-melting alloy powder presses 10:1 mass ratio is well mixed, and is incubated 10 minutes at 110 DEG C, Ran Housui Stove cools down, and is stripped at room temperature.
Measurement result shows, LaFe11.6Si1.4H1.4The Tc of alloy material is 298k, block LaFe11.6Si1.4Alloy Maximum compressive strength is 155MPa, and the low melting point Pb-Bi-Cd alloy powders containing mass fraction 5%, 10% and 15% bond sample The maximum compressive strength of product is 259MPa, 344MPa and 495MPa, than block LaFe11.6Si1.4The maximum compressive strength of alloy point About 69%, 122% and 219% are not enhanced.
Pure LaFe11.6Si1.4H1.4Maximum magnetic entropy variable be 14.6J/kg K, be respectively 5%, 10% and containing mass fraction The bond samples LaFe of 15% low-melting alloy11.6Si1.4H1.4/ Pb-Bi-Cd maximum magnetic entropy variable be respectively 12.52J/kg K, 12.3J/kg K and 11.3J/kg K.
From figure 1 it appears that the low-melting alloy of white is full of in the magnetic thermalloy particulate interspaces of grey, black Hole only has a small amount of presence.The magnetic refrigeration composite material finally obtained shows uniform microstructure, good magnetic heat Effect and mechanical performance, and thermal conductivity.

Claims (6)

1. a kind of preparation method of the hot composite of magnetic bonded by low-melting alloy, it is characterised in that comprise the following steps:
1) iron-based magneto-caloric material is prepared using arc-melting furnace, wherein protective atmosphere is argon gas;
2) by melted iron-based magneto-caloric material vacuum annealing, then in room temperature quenching-in water, 1 with NaZn structures is prepared : 13 phase La (Fe, Si)13Base magneto-caloric material;
3) by the La (Fe, Si) after annealing13Base magneto-caloric material carries out mechanical lapping, and particle diameter is selected as 30-300 μm by sieving Powder;
4) by La (Fe, Si)13Base magneto-caloric material powder is mixed in proportion with low-melting alloy powder and cold moudling, its Middle pressing pressure is 0.1-1.4GPa, and the press time is 1-30 minutes;
5) continue to keep pressing pressure, 5-30 minutes are being incubated higher than on low-melting alloy melting temperature, then furnace cooling, It is stripped at room temperature.
2. the preparation method of the magnetic hot composite according to claim 1 bonded by low-melting alloy, it is characterised in that The iron-based magneto-caloric material is iron-based magnetic refrigeration alloy.
3. the preparation method of the magnetic hot composite according to claim 1 bonded by low-melting alloy, it is characterised in that The La (Fe, Si)13Base magneto-caloric material powder diameter is 30-300 μm, and optimal is 50-100 μm.
4. the preparation method of the magnetic hot composite according to claim 1 bonded by low-melting alloy, it is characterised in that The low-melting alloy is alloy of the fusing point between 340-500K, and the mass fraction of the low-melting alloy is 5%-25%, The size of the low-melting alloy powder is 10-20nm.
5. the preparation method of the magnetic hot composite according to claim 4 bonded by low-melting alloy, it is characterised in that The mass fraction of the low-melting alloy is 5%-15%.
6. the preparation method of the magnetic hot composite according to claim 1 bonded by low-melting alloy, it is characterised in that The pressing pressure is 0.5-1.2GPa.
CN201711118700.0A 2017-11-14 2017-11-14 A kind of preparation method of the hot composite of magnetic bonded by low-melting alloy Pending CN107855518A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109763049A (en) * 2019-03-21 2019-05-17 中国科学院物理研究所 Compound magnetic refrigerating material and preparation method thereof, magnetic refrigeration apparatus
CN110172631A (en) * 2019-04-25 2019-08-27 天津市京建建筑防水工程有限公司 Cobalt manganese kamash alloy material and preparation method thereof
CN114561580A (en) * 2022-03-03 2022-05-31 杭州电子科技大学 RE4TCd magnetic refrigeration material and preparation method thereof

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WO2016140350A1 (en) * 2015-03-05 2016-09-09 株式会社三徳 Manufacturing method for magnetic freezing module
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CN106906408A (en) * 2015-12-22 2017-06-30 中国科学院宁波材料技术与工程研究所 LaFeSi base magnetic refrigeration composite materials and preparation method and application

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CN103137281A (en) * 2011-11-22 2013-06-05 中国科学院物理研究所 Bonding La (Fe, Si) 13 base magnetocaloric effect material and preparation method and use thereof
CN103422014A (en) * 2012-05-22 2013-12-04 中国科学院物理研究所 Thermoplastic molding adhesion magnetic refrigerant materials, preparation method and applications
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Publication number Priority date Publication date Assignee Title
CN109763049A (en) * 2019-03-21 2019-05-17 中国科学院物理研究所 Compound magnetic refrigerating material and preparation method thereof, magnetic refrigeration apparatus
CN110172631A (en) * 2019-04-25 2019-08-27 天津市京建建筑防水工程有限公司 Cobalt manganese kamash alloy material and preparation method thereof
CN114561580A (en) * 2022-03-03 2022-05-31 杭州电子科技大学 RE4TCd magnetic refrigeration material and preparation method thereof

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Application publication date: 20180330