CN106967923A - A kind of compound magnetic refrigerating material and its production and use - Google Patents
A kind of compound magnetic refrigerating material and its production and use Download PDFInfo
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- CN106967923A CN106967923A CN201710243323.7A CN201710243323A CN106967923A CN 106967923 A CN106967923 A CN 106967923A CN 201710243323 A CN201710243323 A CN 201710243323A CN 106967923 A CN106967923 A CN 106967923A
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- 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
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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
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- 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
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- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- 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
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Abstract
The present invention provides a kind of compound magnetic refrigerating material and its production and use.This is combined specifically comprising for magnetic refrigerating material：X+Y+Z, wherein：X is the one or more in magnetic refrigerating material；Y is the alloy of one or more of elements in IB races, Group IIB, Group IIIA, IVA races；Z is the one or more of various binding agents commonly used in the prior art.The compound magnetic refrigerating material that the present invention is provided has the mechanical performance higher than traditional magnetic refrigerating material, and with good magnetothermal effect, can be good at being applied to magnetic refrigerating field.Meanwhile, the invention also discloses the preparation method of the compound magnetic refrigerating material, the preparation method can make arbitrary shape and the compound magnetic refrigerating material of size according to actual needs.Also, the present invention also has the advantages that abundant raw material, cheap, preparation technology be simple, industrialized production easy to operate and realize, and to practical application, the preparation method has great importance.
Description
Technical field
The present invention relates to a kind of magnetic material, more particularly to a kind of compound magnetic refrigerating material for magnetic Refrigeration Technique and
Its preparation method, belongs to magnetic refrigerating material preparation field.
Background technology
Modern society, Refrigeration ＆ Cryogenic Technique plays very heavy in terms of the living standard and working environment of people is improved
The effect wanted, is related to numerous key areas of national economy, and the annual energy consumption of refrigeration industry accounts for the 15% of social total energy consumption according to statistics
More than.Refrigeration Technique widely used at present is traditional gas compression-swell refrigeration technology, its highest during this technology refrigeration
Efficiency is only 25%, it is seen then that this conventional refrigeration technical efficiency is relatively low.In addition, also there is welding, production in conventional refrigeration technology
The shortcomings of giving birth to noise, be difficult to miniaturization.With the development of modern society, the energy and environmental problem are increasingly serious, therefore find green
Colour circle is protected and energy-efficient Refrigeration Technique turns into urgent problem to be solved in world wide.
In recent years, a kind of magnetic Refrigeration Technique based on magnetothermal effect is widely paid close attention to and studied.Magnetic Refrigeration Technique is
Using magnetic material as working media, a kind of green refrigeration technology freezed by means of the magnetothermal effect of material in itself.With tradition
Gas compression-swell refrigeration technology compare, magnetic Refrigeration Technique has advantages below：1) environmental protection：Magnetic refrigeration uses solid
Refrigeration working medium, solves poisonous gas, easy leakage, inflammable and the problems such as to depletion of the ozone layer and greenhouse effects；2) efficiently save
Energy：Magnetic refrigeration produce magnetothermal effect thermodynamic process be efficiently it is reversible, its intrinsic thermodynamic efficiency up to Carnot efficiency, and
The 60-70% of the actual efficiency that can be realized also up to Carnot's cycle efficiency；3) it is reliable and stable：Magnetic freezes without gas compressor,
Vibration and noise is small, long lifespan, reliability high.Therefore, magnetic Refrigeration Technique obtains global extensive concern in recent years.
1997, the Pecharsky and Gschneidner of U.S.'s Ames Lab reported Gd5(SixGe1-x)4In room temperature
Giant magnetio-caloric effects nearby are shown, the breakthrough first that room temperature magnetic refrigerating material is explored is indicated, meanwhile, also start magnetic refrigeration material
Material, the especially upsurge of the exploration of the magnetic refrigerating material of near room temperature and study mechanism.So far, countries in the world have been studied simultaneously
It is found that many near room temperatures have the magnetic refrigerating material of giant magnetio-caloric effects, such as Gd5(SixGe1-x)4、LaCaMnO3、Ni-Mn-
Ga、La(Fe,T)13(T=Si, Al) based compound, MnAs based compounds, MM ' N (M, M '=magnesium-yttrium-transition metal, N=IIIA or
IVA races element) based compound etc..Although the magnetothermal effect of these magnetic refrigerating materials is significantly higher than traditional room temperature magnetic refrigerating material
Gd, but because they are intermetallic compound mostly, fragility is big, difficult forming, it is difficult to be processed into required shape.Magnetic is freezed
Material is really applied among magnetic refrigerator, then does not need only to have big magnetothermal effect, at the same to possess certain intensity and
Toughness, and meet the different shape of solid-liquid heat exchange needs.
2010, Lyubina researchs were found, the La (Fe, Si) with loose structure is prepared by hot-forming mode13
Material, can not only be greatly enhanced the mechanical performance of material, and can reduce heat stagnation and magnetic hystersis loss.Then, China is special
Profit application CN103137281A discloses a kind of bonding La (Fe, Si) with high intensity13Base magnetic refrigerating material and its preparation side
Method, bonding agent and the La (Fe, Si) such as the patent utilization epoxide-resin glue, polyimides glue13Material powder mixing and thermoset forming,
So as to obtain the La (Fe, Si) of high intensity13Base magnetic refrigerating material.However, because the thermal conductivity of the bonding agent is low, causing to bond
La (Fe, Si) afterwards13The thermal conductivity of base magnetic refrigerating material is remarkably decreased, and has had a strong impact on its heat exchange efficiency.Simultaneously as La (Fe,
Si)13The heat endurance of hydride material is poor, therefore, and thermoset forming technique can cause La (Fe, Si)13Hydride decomposition, it is uncomfortable
In preparation La (Fe, Si)13Hydride material.Therefore, the moulding process of magnetic refrigerating material is still a world-famous puzzle, serious resistance
Application of the magnetic refrigerating material on refrigeration machine is hindered.
The content of the invention
Therefore, it is an advantage of the invention to provide a kind of preparation method of compound magnetic refrigerating material.The present invention's is another
One purpose is that there is provided compound magnetic refrigerating material prepared by the preparation method.It is still another object of the present invention to provide
It is a kind of to include the magnetic refrigerator of the compound magnetic refrigerating material.A further object of the present invention is that there is provided the compound magnetic system
Application of the cold material in manufacture refrigerating material.
The purpose of the present invention is achieved through the following technical solutions：
On the one hand, the present invention provides the method for preparing compound magnetic refrigerating material, specifically includes following steps：
1) magnetic refrigerating material X and material Y are broken into the powder of certain size；
2) by step 1) in magnetic refrigerating material X, Y powder for preparing and bonding agent Z mix equal in A%+B%+C% ratios
It is even；
3) by step 2) in mixed powder the size and dimensions of needs is pressed under certain temperature and magnetic field；
4) by step 3) in the moulding material prepared solidify certain time under certain solidification temperature, be finally combined
Magnetic refrigerating material.
The preparation method provided according to the present invention, it is preferable that in step 1) in, by magnetic refrigerating material X and material Y by grinding
Mill, vibromill, the one or more rolled in the modes such as mill, ball milling or airflow milling crush, and pass through the standard more than 10 mesh
Sieve, filters out the powder that particle diameter is less than 2mm.
It is highly preferred that in step 1) in, the standard screen is 100~300 mesh, and the powder diameter is 0~0.5mm.
Preferably, in step 2) in, the A% ratios are 40%~95%；The B% ratios are 5%~60%；It is described
C% ratios are 0%~60%.
It is highly preferred that in step 2) in, the A% ratios are 60%~90%；The B% ratios are 5%~40%；Institute
It is 0%~30% to state C% ratios.
Preferably, in step 3) in, by step 2) in mixed powder pass through rolling process, die pressing, extrusion, powder
Injection moulding or discharge plasma sintering process are pressed into the size and dimension of needs, and the pressure is 300~1500MPa；Institute
Press temperature is stated for 0~900 DEG C；The magnetic field is 0~5T；The press time is 1~240 minute.
It is highly preferred that in step 3) in, the pressure is 600~1000MPa；The press temperature is 0~500 DEG C；Institute
Magnetic field is stated for 0~2T；The press time is 5~60 minutes.
Preferably, in step 4) in, the solidification temperature is 0~900 DEG C；The hardening time is 1~15 day.
It is highly preferred that in step 4) in, the solidification temperature is 0~500 DEG C；The hardening time is 2~7 days.
On the other hand, the present invention provides a kind of compound magnetic refrigerating material, and it is specifically comprised：A% X+B% Y+C%
Z, wherein：
X is the one or more in magnetic refrigerating material, may be selected from Gd, Gd5(SixGe1-x)4、LaCaMnO3、Ni-Mn-D(D
=Ga, In, Sn, etc.) Heusler alloys, La (Fe, T)13(T=Si, Al) based compound, MnAs based compounds, MM ' N (M, M '
=magnesium-yttrium-transition metal, N=IIIA or IVA races element) one or more in base magnetic refrigerating material；
Y is the alloy of one or more of elements in IB races, Group IIB, Group IIIA, IVA races；
Z is the one or more of various binding agents commonly used in the prior art, may be selected from epoxy resin, phenolic resin, gathers
It is carbonic ester, polyethylene naphthoic acid fat, polyethylene terephthalate, polyimides, polyamide, Kynoar, polystyrene, poly-
One or more in butylene, polyvinyl chloride, polyethylene etc.；
A% is X volumn concentration；
B% is Y volumn concentration；
C% is Z volumn concentration；
A%+B%+C%'s and for 100%.
Another further aspect, the invention provides a kind of magnetic refrigerator, the refrigeration machine includes the compound magnetic system that the present invention is provided
Cold material or according to magnetic refrigerating material made from the preparation method that provides of the present invention.
Another aspect, the preparation method that the present invention provides the compound magnetic refrigerating material or provided according to the present invention is made
Magnetic refrigerating material manufacture refrigerating material in application.
The advantageous effects of the present invention：
Compared with prior art, advantage of the invention is that：
1) using in the past the invention provides a kind of compound magnetic refrigerating material do not reported；
2) the compound magnetic refrigerating material prepared using the preparation method of the present invention has higher than traditional magnetic refrigerating material
Mechanical performance；
3) preparation method provided using the present invention can make arbitrary shape and the compound magnetic of size according to actual needs
Refrigerating material；
4) compound magnetic refrigerating material prepared by the preparation method provided using the present invention has good magnetothermal effect, can
It is applied to magnetic refrigerating field well；
5) the preparation method technique that the present invention is provided is simple, it is easy to operate and realize industrialized production, should to practical application
Preparation method has great importance.
Brief description of the drawings
Fig. 1 is 80%LaFe made from embodiment 111.7Si1.3C0.2H1.8The stress of the compound magnetic refrigerating materials of+20%In-should
Varied curve；
Fig. 2 is 80%LaFe made from embodiment 111.7Si1.3C0.2H1.8+ 20%In is combined magnetic system
Cold material and pure LaFe11.7Si1.3C0.2H1.8DSC curve contrast；
Fig. 3 is 80%LaFe made from embodiment 111.7Si1.3C0.2H1.8+ 20%In is combined magnetic refrigerating material in different magnetic
Dependences of the Δ S to temperature off field；
Fig. 4 is 70%LaFe made from embodiment 211.7Si1.3C0.2H1.8+ 20%In+10% epoxy resin is combined magnetic refrigeration
Material and pure LaFe11.7Si1.3C0.2H1.8DSC curve contrast.
Embodiment
The present invention is further described in detail with reference to embodiment and accompanying drawing, the embodiment provided is only
In order to illustrate the present invention, the scope being not intended to be limiting of the invention.
Embodiment 1：
80%LaFe11.7Si1.3C0.2H1.8+ 20%In is combined magnetic refrigerating material and preparation method thereof：
1) using agate mortar respectively by LaFe11.7Si1.3C0.2H1.8Material and metal In are broken, and pass through the mark of 150 mesh
Standard filters out the irregular particle powder less than 0.1mm；
2) 80%LaFe is pressed11.7Si1.3C0.2H1.8+ 20%In volume ratio is by step 1) gained powder is well mixed；
3) by step 2) it is well mixed after powder suppress 10 under 140 DEG C of press temperature, 900MPa pressure, zero magnetic field
Minute obtains Φ 10mm cylindrical 80%LaFe11.7Si1.3C0.2H1.8+ 20%In moulding materials；
4) by step 3) in the moulding material prepared solidify 2 days at 20 DEG C, finally obtain 80%
LaFe11.7Si1.3C0.2H1.8+ 20%In is combined magnetic refrigerating material.
It is well known by those skilled in the art that tradition La (Fe, Si)13Hydride material after hydrogenation treatment in powdered,
Machining shaping can not be carried out, the application of this kind of functional material is limited.And 80% obtained using the present invention
LaFe11.7Si1.3C0.2H1.8+ 20%In be combined magnetic refrigerating material have well shaping and processing characteristics, solve well with
Upper problem.
Further, traditional La (Fe, Si)13Hydride material is due to sample fragmentation, mechanical performance extreme difference, it is impossible to answered
Force-strain curve is tested.And the 80%LaFe obtained by the present embodiment11.7Si1.3C0.2H1.8+ 20%In is combined magnetic refrigeration
The mechanical property of materials is significantly improved, and measuring mechanical property can be carried out completely.In WDW200D type microcomputer control universal testing machines
Upper measure 80%LaFe11.7Si1.3C0.2H1.8+ 20%In is combined the load-deformation curve of magnetic refrigerating material, as shown in figure 1, should
The compression strength of metallic composite is 138MPa, and corresponding strain is 4.1%.
80% is tested on differential scanning calorimeter (systems of DSC 6220 of NSK company design)
LaFe11.7Si1.3C0.2H1.8+ 20%In is combined magnetic refrigerating material and pure LaFe11.7Si1.3C0.2H1.8DSC curve, such as Fig. 2 institutes
Show, it can be seen that 80%LaFe11.7Si1.3C0.2H1.8+ 20%In is combined magnetic refrigerating material and pure LaFe11.7Si1.3C0.2H1.8Residence
In temperature TCAll it is 337K, illustrates that the preparation method of the present embodiment 1 does not change the magnetic phase transition of original magnetic refrigerating material, makes multiple
Close magnetic refrigerating material maintain with original magnetic refrigerating material identical phase transition temperature, be very beneficial for practical application.
Surveyed in magnetic measurement systems (the Versalab Free measuring systems of Quantum Design companies of U.S. design)
Determine 80%LaFe11.7Si1.3C0.2H1.8+ 20%In is combined the isothermal magnetization curve (M-H curves) of magnetic refrigerating material, further according to wheat
Ke Siwei relations：Magnetic entropy can be calculated from isothermal magnetization curve become Δ S.Fig. 3 shows this
80%LaFe11.7Si1.3C0.2H1.8+ 20%In is combined magnetic refrigerating material, and Δ S, can to the dependence of temperature under different magnetic field
To find out, there is the maximum of magnetic entropy change near phase transition temperature 337K in sample, is respectively 0-1T, 0-2T, 0- in changes of magnetic field
Under 3T, the maximum magnetic entropy variable of sample is respectively 5.5J/kgK, 8.6J/kgK, 10.4J/kgK.At present, can using permanent magnet NdFeB
2T magnetic field is obtained, therefore the magnetic entropy change of the material under 0-2T changes of magnetic field receives much attention.As can be seen that in 0-2T changes of magnetic field
Under, 80%LaFe11.7Si1.3C0.2H1.8The maximum magnetic entropy variable (8.6J/kgK) that+20%In is combined magnetic refrigerating material is significantly higher than biography
System room temperature magnetic refrigerating material Gd magnetic entropy becomes (under 2T magnetic fields, magnetic entropy is changed into 5.0J/kgK), illustrates 80% made from embodiment 1
LaFe11.7Si1.3C0.2H1.8+ 20%In, which is combined magnetic refrigerating material, can be used as more excellent room temperature functional material.
Embodiment 2：
70%LaFe11.7Si1.3C0.2H1.8+ 20%In+10% epoxy resin is combined magnetic refrigerating material and preparation method thereof：
1) using agate mortar respectively by LaFe11.7Si1.3C0.2H1.8Material and metal In are broken, and pass through the mark of 200 mesh
Standard filters out the irregular particle powder less than 0.07mm；
2) 70%LaFe is pressed11.7Si1.3C0.2H1.8The volume ratio of+20%In+10% epoxy resin is by step 1) gained powder
End is well mixed；
3) by step 2) it is well mixed after powder suppress 5 under 130 DEG C of press temperature, 900MPa pressure, zero magnetic field
Minute obtains Φ 10mm cylindrical 70%LaFe11.7Si1.3C0.2H1.8The moulding material of+20%In+10% epoxy resin；
4) by step 3) in the moulding material prepared solidify 7 days at 20 DEG C, finally obtain 70%
LaFe11.7Si1.3C0.2H1.8+ 20%In+10% epoxy resin is combined magnetic refrigerating material.
70% is tested on differential scanning calorimeter (systems of DSC 6220 of NSK company design)
LaFe11.7Si1.3C0.2H1.8+ 20%In+10% epoxy resin is combined magnetic refrigerating material and pure LaFe11.7Si1.3C0.2H1.8DSC
Curve, as shown in Figure 4, it can be seen that 70%LaFe11.7Si1.3C0.2H1.8+ 20%In+10% epoxy resin is combined magnetic refrigeration material
Material and pure LaFe11.7Si1.3C0.2H1.8Curie temperature TCAll it is 337K, illustrates that the preparation method of the present embodiment 2 does not change original
Have the magnetic phase transition of magnetic refrigerating material, make compound magnetic refrigerating material maintain with original magnetic refrigerating material identical phase transition temperature,
It is very beneficial for practical application.
It is well known by those skilled in the art that tradition La (Fe, Si)13Hydride material after hydrogenation treatment in powdered,
Machining shaping can not be carried out, the application of this kind of functional material is limited.And 70% obtained using the present invention
LaFe11.7Si1.3C0.2H1.8+ 20%In+10% epoxy resin, which is combined magnetic refrigerating material, has shaping and processing characteristics well,
Above problem is solved well.Meanwhile, through Magnetic Test, 70%LaFe11.7Si1.3C0.2H1.8+ 20%In+10% asphalt mixtures modified by epoxy resin
The magnetothermal effect that fat is combined magnetic refrigerating material is higher than traditional room temperature magnetic refrigerating material Gd.
Embodiment 3：
60%Mn0.6Fe0.4NiSi0.6Ge0.4+ 20%Sn+20% epoxy resin is combined magnetic refrigerating material and preparation method thereof：
1) using agate mortar respectively by Mn0.6Fe0.4NiSi0.6Ge0.4Material and metal Sn are broken, and pass through 100 purposes
Standard screen filters out the irregular particle powder less than 0.15mm；
2) 60%Mn is pressed0.6Fe0.4NiSi0.6Ge0.4The volume ratio of+20%Sn+20% epoxy resin is by step 1) gained
Powder is well mixed；
3) by step 2) it is well mixed after powder suppressed under 20 DEG C of press temperature, 960MPa pressure, 1.5T magnetic fields
Obtain within 15 minutes Φ 10mm cylindrical 60%Mn0.6Fe0.4NiSi0.6Ge0.4The moulding material of+20%Sn+20% epoxy resin；
4) by step 3) in the moulding material prepared solidify 5 days at 150 DEG C, finally obtain 60%
Mn0.6Fe0.4NiSi0.6Ge0.4+ 20%Sn+20% epoxy resin is combined magnetic refrigerating material.
It is well known by those skilled in the art that tradition Mn0.6Fe0.4NiSi0.6Ge0.4Because martensitic traoformation generation is huge
Internal stress, causes sample fragmentation, it is impossible to carry out machining shaping, limits the application of this kind of functional material.And utilize this hair
Bright obtained 60%Mn0.6Fe0.4NiSi0.6Ge0.4+ 20%Sn+20% epoxy resin, which is combined magnetic refrigerating material, to be had well
Shaping and processing characteristics, solve above problem well.Meanwhile, through Magnetic Test, 60%Mn0.6Fe0.4NiSi0.6Ge0.4+
The magnetothermal effect that 20%Sn+20% epoxy resin is combined magnetic refrigerating material is higher than traditional room temperature magnetic refrigerating material Gd.
Embodiment 4：
90%Mn1.2Fe0.8P0.48Si0.52+ 5%InSn+5% epoxy resin is combined magnetic refrigerating material and preparation method thereof：
1) using high energy ball mill respectively by Mn1.2Fe0.8P0.48Si0.52With InSn alloy breaks downs, and pass through the mark of 300 mesh
Standard filters out the irregular particle powder less than 0.05mm；
2) 90%Mn is pressed1.2Fe0.8P0.48Si0.52The volume ratio of+5%InSn+5% epoxy resin is by step 1) gained powder
End is well mixed；
3) by step 2) it is well mixed after powder suppressed under 20 DEG C of press temperature, 1000MPa pressure, 1.0T magnetic fields
Obtain within 30 minutes Φ 10mm cylindrical 90%Mn1.2Fe0.8P0.48Si0.52The moulding material of+5%InSn+5% epoxy resin；
4) by step 3) in the moulding material prepared solidify 7 days at 150 DEG C, finally obtain 90%
Mn1.2Fe0.8P0.48Si0.52+ 5%InSn+5% epoxy resin is combined magnetic refrigerating material.
The 90%Mn obtained by Mechanics Performance Testing, the present invention1.2Fe0.8P0.48Si0.52+ 5%InSn+5% asphalt mixtures modified by epoxy resin
Fat, which is combined magnetic refrigerating material, has shaping and processing characteristics well.Meanwhile, through Magnetic Test, 90%Mn1.2Fe0.8P0.48Si0.52
The magnetothermal effect that+5%InSn+5% epoxy resin is combined magnetic refrigerating material is higher than traditional room temperature magnetic refrigerating material Gd.
Embodiment 5：
80%Gd5Si2Ge2+ 5%Al+15% epoxy resin is combined magnetic refrigerating material and preparation method thereof：
1) using airflow milling respectively by Gd5Si2Ge2Material and metal Al are broken, and are filtered out by 300 the polished standard screens
Irregular particle powder less than 0.05mm；
2) 80%Gd is pressed5Si2Ge2The volume ratio of+5%Al+15% epoxy resin is by step 1) gained powder mixes equal
It is even；
3) by step 2) it is well mixed after powder suppress 20 under 600 DEG C of press temperature, 600MPa pressure, zero magnetic field
Minute obtains Φ 10mm cylindrical 80%Gd5Si2Ge2The moulding material of+5%Al+15% epoxy resin；
4) by step 3) in the moulding material prepared solidify 5 days at 300 DEG C, finally obtain 80%Gd5Si2Ge2+ 5%
Al+15% epoxy resin is combined magnetic refrigerating material.
The 80%Gd obtained by Mechanics Performance Testing, the present invention5Si2Ge2+ 5%Al+15% epoxy resin is combined magnetic
Refrigerating material has shaping and processing characteristics well.Meanwhile, through Magnetic Test, 80%Gd5Si2Ge2+ 5%Al+15% epoxies
The magnetothermal effect of resin compounded magnetic refrigerating material is higher than traditional room temperature magnetic refrigerating material Gd.
Embodiment 6：
70%Ni50Mn34Co2Sn14+ 25%Ag+5% epoxy resin is combined magnetic refrigerating material and preparation method thereof：
1) using high energy ball mill respectively by Ni50Mn34Co2Sn14Material and metal Ag are broken, and pass through the standard of 250 mesh
Filter out the irregular particle powder less than 0.06mm；
2) 70%Ni is pressed50Mn34Co2Sn14The volume ratio of+25%Ag+5% epoxy resin is by step 1) gained powder mixes
Close uniform；
3) by step 2) it is well mixed after powder suppress 40 under 500 DEG C of press temperature, 900MPa pressure, zero magnetic field
Minute obtains Φ 15mm cylindrical 70%Ni50Mn34Co2Sn14The moulding material of+25%Ag+5% epoxy resin；
4) by step 3) in the moulding material prepared solidify 2 days at 700 DEG C, finally obtain 70%
Ni50Mn34Co2Sn14+ 25%Ag+5% epoxy resin is combined magnetic refrigerating material.
The 70%Ni obtained by Mechanics Performance Testing, the present invention50Mn34Co2Sn14+ 25%Ag+5% epoxy resin is answered
Closing magnetic refrigerating material has shaping and processing characteristics well.Meanwhile, through Magnetic Test, 70%Ni50Mn34Co2Sn14+ 25%Ag
The magnetothermal effect that+5% epoxy resin is combined magnetic refrigerating material is higher than traditional room temperature magnetic refrigerating material Gd.
The present invention is describe in detail with reference to embodiment above, to those skilled in the art, should
Understand, above-mentioned embodiment is not construed as limiting the scope of the present invention.Therefore, essence of the invention is not being departed from
Embodiment of the present invention can be made various changes and modifications in the case of god and scope.
Claims (8)
1. a kind of preparation method of compound magnetic refrigerating material, it is characterised in that methods described comprises the following steps：
1）Material X and material Y are broken into the powder of certain size；
2）By step 1）In material X, Y powder prepared and bonding agent Z it is well mixed in A%+B%+C% ratios；The ratio
For percent by volume；
3）By step 2）In mixed powder the size and dimensions of needs is pressed under certain temperature and magnetic field；
4）By step 3）In the moulding material prepared solidify certain time under certain solidification temperature, obtain compound magnetic refrigeration material
Material；
Wherein, material X is the one or more in magnetic refrigerating material；
Material Y is the alloy of one or more of elements in IB races, Group IIB, Group IIIA, IVA races；
Z is the one or more of binding agent.
2. preparation method according to claim 1, it is characterised in that the step 1）Including：The broken use grinding,
Vibromill, the one or more rolled in mill, ball milling or airflow milling；Material passes through more than 10 the polished standard screens, screening after broken
Go out the powder that particle diameter is less than 2mm;Preferably, the standard screen is 100 ~ 300 mesh, and the particle diameter of the powder is 0 ~ 0.5 mm.
3. preparation method according to claim 1, it is characterised in that the step 2）The A% is 40% ~ 95%；The B%
For 5% ~ 60%；The C% is 0% ~ 60%;Preferably, the A% is 60% ~ 90%；The B% is 5% ~ 40%；The C% is 0% ~ 30%.
4. preparation method according to claim 1, it is characterised in that the step 3）Including：By step 2）After middle mixing
Powder needs are pressed into by rolling process, die pressing, extrusion, powder injection forming or discharge plasma sintering process
Size and dimension, pressure is 300 ~ 1500 MPa during compacting；Press temperature is 0 ~ 900 C；The magnetic field is 0 ~ 5T；Press time
For 1 ~ 240 minute;Preferably, the pressing pressure is 600 ~ 1000 MPa；The press temperature is 0 ~ 500 C；The magnetic field
For 0 ~ 2T；The press time is 5 ~ 60 minutes.
5. preparation method according to claim 1, it is characterised in that the step 4）Described in solidification temperature be 0 ~ 900
C；Hardening time is 1 ~ 15 day;Preferably, the solidification temperature is 0 ~ 500 C；The hardening time is 2 ~ 7 days.
6. a kind of compound magnetic refrigerating material, it is specifically comprised：A% X+B% Y+C% Z, wherein：
X is the one or more in magnetic refrigerating material；
Y is the alloy of one or more of elements in IB races, Group IIB, Group IIIA, IVA races；
Z is the one or more of binding agent；
A% is X volumn concentration；
B% is Y volumn concentration；
C% is Z volumn concentration；
A%+B%+C%'s and for 100%.
7. a kind of magnetic refrigerator, it is characterised in that the magnetic refrigerator include compound magnetic refrigerating material described in claim 6 or
The magnetic refrigerating material that person obtains according to the preparation method any one of claim 1-5.
8. compound magnetic refrigerating material described in a kind of claim 6 or according to the system any one of claim 1-5
Application of the magnetic refrigerating material that Preparation Method is obtained in manufacture refrigerating material.
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| CN201710243323.7A CN106967923A (en) | 2017-04-14 | 2017-04-14 | A kind of compound magnetic refrigerating material and its production and use |
| PCT/CN2017/101422 WO2018188262A1 (en) | 2017-04-14 | 2017-09-12 | Magnetic refrigeration composite material, preparation method therefor and use thereof |
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| CN107603573A (en) * | 2017-08-09 | 2018-01-19 | 同济大学 | A kind of Multi-layer composite regenerative material and its application |
| CN108531139A (en) * | 2018-05-08 | 2018-09-14 | 武汉博茗低碳产业股份有限公司 | A kind of forming and sintering carbon is the shaping phase-change material and preparation method thereof of carrier |
| WO2018188262A1 (en) * | 2017-04-14 | 2018-10-18 | 北京科技大学 | Magnetic refrigeration composite material, preparation method therefor and use thereof |
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| CN112850781A (en) * | 2020-12-31 | 2021-05-28 | 鄂尔多斯应用技术学院 | Rare earth gadolinium-based complex crystal and preparation method thereof |
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