CN103422014B - Thermoplastic shaping bonding magnetic refrigerating working material and its production and use - Google Patents
Thermoplastic shaping bonding magnetic refrigerating working material and its production and use Download PDFInfo
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- CN103422014B CN103422014B CN201210160345.4A CN201210160345A CN103422014B CN 103422014 B CN103422014 B CN 103422014B CN 201210160345 A CN201210160345 A CN 201210160345A CN 103422014 B CN103422014 B CN 103422014B
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Abstract
The invention provides a kind of magnetic refrigerating working material and its production and use, described material comprises magnetothermal effect alloying pellet and thermoplastics type's tackiness agent, wherein, the particle diameter of described alloying pellet is≤200 μm, and described alloying pellet is bonded to block materials by described tackiness agent by thermoplastic shaping; Wherein, described magnetothermal effect alloying pellet is for having NaZn
13the La (Fe, Si) of type structure
13sill, is preferably La
0.7ce
0.3fe
11.6si
1.4c
x, wherein 0.2≤x≤0.3.The present invention adopts the method for adhesive bonds thermoplastic shaping to obtain the La (Fe, Si) of high strength good toughness
13base magnetothermal effect material, overcomes the intrinsic property of magnetothermal effect material brittle; Although magnetic entropy time-varying amplitude declines compared with before bonding to some extent with effective refrigeration capacity, amplitude is still considerable.Compared with the magneto-caloric material prepared with thermoset forming technology, magneto-caloric material toughness prepared by thermoplastic shaping technology significantly strengthens, and maximum dependent variable of bearing corresponding to pressure enlarges markedly.
Description
Technical field
The invention belongs to magnetic refrigerating working material field.Particularly, the present invention relates to a kind of bonding La (Fe, Si) with high strength
13base magnetic refrigerating working material and preparation method thereof and material applications.More specifically, the present invention relates to a kind of by thermoplastics type's tackiness agent (as PA6(polyamide 6), PP(polyethylene) etc.) La (Fe, Si) with high strength that generates of molding bonded
13base magnetic refrigerating working material, its preparation method and material applications.
Background technology
Refrigeration industry power consumption accounts for more than 15% of the total power consumption of society.Its Carnot's cycle efficiency of vapor compression refrigeration technology generally used at present is only up to about 25%, and the gas refrigerant used in vapor compression refrigeration can destroy atmospheric ozone layer and cause Greenhouse effect.Refrigerating material and research and development Novel low-consumption, the high efficiency Refrigeration Technique of seeking pollution-free, environmental protection are that the world today needs the urgent problems solved.
Magnetic Refrigeration Technique has environmental protection, energy-efficient, reliable and stable feature, has caused worldwide extensive concern in the last few years.A few type high temp that the U.S., China, Holland, Japan find in succession and even room-temperature zone materials with the giant magnetocaloric effect have promoted the expectation of people to environmental protection magnetic Refrigeration Technique greatly, such as: Gd-Si-Ge, LaCaMnO
3, Ni-Mn-Ga, La (Fe, Si)
13the compound such as based compound, Mn-Fe-P-As, MnAs.The common feature of these novel giant magnetio-caloric effects materials is that magnetic entropy becomes all higher than conventional chamber temperature magnetic refrigerating material Gd, and phase transition property is one-level, and majority presents strong magnetocrystalline coupling characteristics, and magnetic phase transition is with the generation of significant crystalline structure phase transformation.These type materials also show different material behaviors, such as, Gd-Si-Ge is expensive, needs to purify further to starting material in preparation process, the compound starting material such as Mn-Fe-P-As, MnAs are poisonous, and NiMn base Heusler alloy has large feature of hysteresis loss etc.
In the nearly a few class novel materials found during the last ten years, accepted extensively in the world at present, that most possibly realize high temperature and even room-temperature zone magnetic refrigeration application is La (Fe, Si)
13based compound, this alloy has that the prices of raw and semifnished materials are cheap, transformation temperature, phase transition property, hysteresis loss can with features such as composition regulations, and near room temperature magnetic entropy uprises one times in Gd.The laboratory of multiple country is one after another by La (Fe, Si)
13base magnetic refrigerating material is used for development test, proves that its refrigeration capacity is better than Gd.
Research shows, La (Fe, Si)
13the phase transition property of based compound can change with the adjustment of component.Such as the Compound Phase change nature of low Si content is generally one-level, increase Curie temperature with Co content rises, first-order phase transition character weakens, and be transitioned into secondary gradually, hysteresis loss reduces gradually (second-order phase transition does not have hysteresis loss), but also declines due to the change magnetothermal effect amplitude of component, exchange interaction thereupon.Being added with of Mn affects exchange interaction makes Curie temperature decline, and first-order phase transition character weakens, and hysteresis loss reduces gradually, and magnetothermal effect amplitude also declines thereupon.On the contrary, it is found that, little rare-earth magnetic atom (such as Ce, Pr, Nd) substitutes La can strengthen first-order phase transition character, and hysteresis loss increases, and magnetothermal effect amplitude increases.Also find: the introducing with the interstitial atom (such as C, H, B etc.) of little atomic radius can improve Curie temperature, makes magnetothermal effect occur in higher warm area scope, such as, as molecular formula LaFe
11.5si
1.5h
αwhen the content of interstitial atoms H is increased to α=1.8 from α=0, transformation temperature (peak temperature of magnetothermal effect) rises to 350K from 200K.People expect to have the first-order phase transition La (Fe, Si) of giant magnetio-caloric effects
13based compound is used for actual magnetic refrigeration application, and obtains desirable refrigeration.
But, La (Fe, Si)
13based compound (especially first-order phase transition material) shows ultimate compression strength difference, the feature that frangible, corrosion resistance is poor due to strong magnetocrystalline coupled characteristic (intrinsic property of material).The sample that some component is newly prepared is cleaved into fragment, and placing in air even can natural degradation.Due to material brittle, as magnetic refrigeration working substance broken pulverized powder blocking circulation passage in refrigeration cycle, reduce the life-span of magnetic refrigerating efficiency and refrigerator.
Chinese patent application CN101755312A discloses a kind of reaction sintering article for magnetic heat exchange and preparation method thereof, and these goods comprise one (La
1-am
a) (Fe
1-b-ct
by
c)
13-dbase phase alloy, its preparation method is to comprise the precursor powder mixing of La precursor, Fe precursor and Y precursor etc., is pressed into base, sinters 2 ~ 24 hours at the temperature then between 1000 ~ 1200 DEG C, formed and have (La
1-am
a) (Fe
1-b-ct
by
c)
13-dthe phase of composition.Adopt the way of this powder metallurgy can by La (Fe, Si)
13base magnetothermal effect material is prepared into the working medium shape of magnetic refrigerator device requirement.Such as mix the La (Fe, Si) of Co
13base room temperature magnetothermal effect material phase transformation character is generally secondary, and (magnetocrystalline coupling is more weak, the adjoint lattice dilatation of magnetic phase transition is relatively slow, more weak), the working medium shape that model machine requires can be made by the way of powder metallurgy, there is certain ultimate compression strength, in working cycle, substantially do not occur tiny crack (or tiny crack is less).But, for first-order phase transition La (Fe, Si)
13(magnetocrystalline coupling is strong for sill, magnetic phase transition is with significant lattice dilatation), can inevitably there is tiny crack or fracture in the working material of the regular shape made by the way of powder metallurgy, mechanical property is undesirable, limits the practical application of material in working cycle.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of high strength, non-friable and be suitable for the La (Fe, Si) of magnetic refrigeration application of having
13base magnetothermal effect material, its preparation method and comprise the magnetic refrigerator device of this material and this material is manufacturing the application in refrigerating material.
The object of the present invention is to provide a kind of high strength, non-friable and be suitable for the La (Fe, Si) of magnetic refrigeration application of having
13base magnetic refrigerating working material, its preparation method and comprise the magnetic refrigerator device of this material and this material is manufacturing the application in refrigerating material.La
0.7ce
0.3fe
11.6si
1.4c
xalloy is La (Fe, Si)
13one in base magnetic refrigerating material, phase transition property is one-level, and Curie temperature is positioned at 212K.
Specifically, the invention provides a kind of by thermoplastics type's tackiness agent (as PA6(polyamide 6, having another name called polycaprolactam), PP etc.) La (Fe, Si) with high strength good toughness of molding bonded
13base magnetic refrigerating working material, its preparation method and material applications.The present inventor studies discovery, introduces the method that PA6 tackiness agent adopts thermoplastic shaping, can obtain the bonding La (Fe, Si) of high strength, good toughness
13base magnetothermal effect material, magnetic entropy becomes (characterizing the parameter of magnetothermal effect), and amplitude, effectively refrigeration capacity decline to some extent compared with before bonding, but amplitude is still considerable, and magnetic lag loss reduces.And arbitrary shape, size can be made according to the actual needs of magnetic refrigerator to working material.Thermoplastics type's tackiness agent cheap (as: PA6 about 40 ~ 50 yuan/kilogram), utilizes thermoplastic shaping way to obtain the La (Fe, Si) of high strength good toughness
13base magnetothermal effect material is significant for the magnetic refrigeration application of this kind of material reality.It is strong that the material that thermoplastic shaping bonding generates has toughness compared with thermoset forming material, and the not feature of easy fracture, the magnetic refrigeration application for reality acquires a special sense.
The object of the invention is to, a kind of La (Fe, Si) not only with high strength but also good toughness is provided
13base magnetic refrigerating working material.
Another object of the present invention is, provide a kind of described in not only there is the La (Fe, Si) of high strength but also good toughness
13the preparation method of base magnetic refrigerating working material.
Another object of the present invention is, provides the La (Fe, Si) not only described in a kind of comprising with high strength but also good toughness
13the magnetic refrigerator device of base magnetic refrigerating working material.
Another object of the present invention is, provide a kind of described in not only there is the La (Fe, Si) of high strength but also good toughness
13base magnetic refrigerating working material is manufacturing the application in refrigerating material.
The object of the invention is to be achieved through the following technical solutions.
The invention provides a kind of magnetic refrigerating working material, described magnetic refrigerating working material comprises magnetothermal effect alloying pellet and thermoplastics type's tackiness agent, wherein, the particle diameter of described magnetothermal effect alloying pellet is≤200 μm, and described magnetothermal effect alloying pellet is bonded to block materials by described thermoplastics type's tackiness agent by thermoplastic shaping; Wherein, described magnetothermal effect alloying pellet is for having NaZn
13the La (Fe, Si) of type structure
13sill, is preferably La
0.7ce
0.3fe
11.6si
1.4c
x, wherein 0.2≤x≤0.3.
Preferably, in magnetic refrigerating working material of the present invention, relative to the described magnetothermal effect alloying pellet of 100 weight parts, the content of described thermoplastics type's tackiness agent can be 5 ~ 25 weight parts, is preferably 10 ~ 20 weight parts.
Can be various conventional thermoplastics type's tackiness agent for tackiness agent of the present invention, as: PA(polymeric amide, comprises polyamide 6, polyamide 66, polyamide 1010 etc.), PPS(polyphenylene sulfide), PP(polypropylene), EVA(ethylene-vinyl acetate copolymer), LCP(TLCP), PET(polyethylene terephthalate), PE(polyethylene) in one or more.Preferably, be PA6(polyamide 6 for tackiness agent of the present invention).
Thermoplastics type's tackiness agent is different from thermosetting type adhesion agent, and thermoplastics type's tackiness agent is the not sex change with temperature change after solidifying below denaturation temperature, and thermosetting type adhesion agent (as epoxy resin) is once solidification and sex change.Thermoplastics type's tackiness agent is combined by physical action by many molecular chains, so thermoplastics type's tackiness agent presents softening or molten state, now plastic processing after being heated, cooling after fixing, reheats and still can soften.And thermosetting type adhesion agent is by chemical bond netted molecular chain crosslinked together, also can soften or melting when its feature is then and starts to be heated, but just no longer softening once curing molding.Now, also cannot soften close to softening temperature even if be heated to, and also can not dissolve in a solvent.
According to magnetic refrigerating working material provided by the invention, wherein, the particle size range of described magnetothermal effect alloying pellet is preferably 15 ~ 200 μm.
The present inventor finds, when the particle diameter of magnetothermal effect alloying pellet of the present invention is not more than 200 μm, the present invention bonds La (Fe, Si)
13base magnetothermal effect material is except having high strength good toughness, and its hysteresis loss also significantly reduces.The embodiment of the present invention 3 research shows, hysteresis loss reduces gradually with the reduction of granularity, and when being reduced to particle size range and being 15 ~ 50 μm, hysteresis loss declines to a great extent 64%.
Present invention also offers the preparation method of above-mentioned magnetic refrigerating working material, comprise the steps:
1) by La (Fe, Si)
13the chemical formula of sill is (as La
0.7ce
0.3fe
11.6si
1.4c
x) preparation raw material;
2) raw material that step 1) prepares is put into electric arc furnace, vacuumize, by inert gas purge, and melting under protection of inert gas, obtain alloy pig, wherein said rare gas element is preferably argon gas;
3) by step 2) melted alloy pig vacuum annealing, then at liquid nitrogen or quenching-in water, prepare and there is NaZn
13the La (Fe, Si) of structure
13base magnetothermal effect alloy;
4) obtained to step 3) magnetothermal effect alloy carries out fragmentation, obtains the magnetothermal effect alloying pellet of particle diameter≤200 μm;
5) magnetothermal effect alloying pellet obtained with step 4) for thermoplastics type's tackiness agent is mixed, compression moulding, and thermoplastic solidification obtains block materials.
The embodiment of method produced according to the present invention; preferably; in described step 5); be dry mixed by the method that thermoplastics type's tackiness agent mixes with magnetothermal effect alloying pellet; preferably pulverous thermoplastics type's tackiness agent (as PA6, PP etc.) and described magnetothermal effect alloying pellet are mixed in proportion.
The embodiment of method produced according to the present invention, wherein, in described step 5), the method for compression moulding comprises: pressing pressure can be 0.1 ~ 1.5GPa, and be preferably 0.8 ~ 1.2GPa, the press time can be 1 ~ 10 minute.
Particularly, can be by the mixture compression moulding of thermoplastics type's tackiness agent and alloying pellet the working medium shape that needs of magnetic refrigerator and size.Concrete operations can be: the mixture of tackiness agent and alloying pellet is put into mould (shape, the size of mould are prepared according to the actual needs of magnetic refrigerator to material), compression moulding under room temperature, room temperature bottom knockout after compression moulding.
The embodiment of method produced according to the present invention, wherein, in described step 5), thermoplastic solidification is carried out in a vacuum, and the condition of solidification comprises: solidification value 215 ~ 290 DEG C, is preferably 240 ~ 280 DEG C, is preferably 30 ~ 60 minutes set time, vacuum tightness≤10
-1pa.Wherein, the selective dependency of solidification value is in the softening temperature of thermoplastics type's tackiness agent (as PA6, PP etc.), fusing point and denaturation temperature, and the PA6 tackiness agent vicat softening temperature (0.45Mpa heat-drawn wire), fusing point and the denaturation temperature that use in the embodiment of the present application are 160 DEG C, 220 DEG C and 290 DEG C respectively.The tackiness agent model that different company produces is different, depend on the difference of a small amount of additive that different purposes is introduced, softening temperature, fusing point and denaturation temperature can slightly difference, normally, the melting range of PA6 tackiness agent: 215 ~ 230 DEG C, denaturation temperature >=290 ~ 300 DEG C, the PA6 for dissimilar thermoplastics type's tackiness agent, different model all can realize thermoplastic solidification at warm area (melting temperature≤T≤denaturation temperature).
The embodiment of method produced according to the present invention, wherein, in described step 1), carbon can preferably be provided by FeC alloy.Owing to also containing Fe element in FeC alloy, need suitably to reduce the simple substance Fe added, make the proportioning of the various elements of interpolation still meet the atom ratio of magneticsubstance chemical formula.
Present invention also offers a kind of magnetic refrigerator, the magnetic refrigerating working material that described refrigerator comprises magnetic refrigerating working material provided by the invention or obtains according to preparation method provided by the invention.
Present invention also offers described magnetic refrigerating working material or manufacture the application in refrigerating material according to the magnetic refrigerating working material that the inventive method obtains.
Compared with prior art, advantage of the present invention is:
(1) at La (Fe, Si)
13a small amount of thermoplastics type's tackiness agent (as PA6, PP etc.) introduced by base magnetothermal effect material, adopts the method for thermoplastic shaping can obtain the bonding magnetic heat effect material not only with high strength but also good toughness, overcomes the intrinsic property of material brittle, impact resistance difference;
(2) after bonding, magnetic entropy change (characterizing the parameter of magnetothermal effect) amplitude, the effectively refrigeration capacity of material still maintains considerable amplitude;
(3) refrigerating working material of arbitrary shape and size can be made to the actual needs of refrigerating working material according to magnetic refrigerator;
(4) compared with preparing magneto-caloric material with thermoset forming technology, magneto-caloric material toughness prepared by thermoplastic shaping technology significantly strengthens, and maximum dependent variable of bearing corresponding to pressure enlarges markedly;
(5) the bonding La (Fe, Si) of high strength good toughness of the present invention
13preparation method's technique of base magnetothermal effect material is simple, easy handling and realize suitability for industrialized production, and for thermoplastics type's tackiness agent of the present invention cheap (as: PA6 about 40 ~ 50 yuan/kilogram), the La (Fe, Si) of the high strength good toughness utilizing thermoplastic formation process to obtain
13base magnetothermal effect material still has price advantage, and the magnetic refrigeration application for this kind of material reality is significant.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 is La in embodiment 1
0.7ce
0.3fe
11.6si
1.4c
0.3alloying pellet solidifies room temperature X-ray diffraction (XRD) collection of illustrative plates that is front and different-grain diameter particle different condition thermoplastic shaping solidification rear (material 1, material 2).
Fig. 2 is La in embodiment 1
0.7ce
0.3fe
11.6si
1.4c
0.3pyromagnetic (M-T) curve before alloying pellet solidification and after the solidification of different-grain diameter particle different condition thermoplastic shaping under (material 1, material 2, material 3, material 4) 0.02T magnetic field.
Fig. 3 is La in embodiment 1
0.7ce
0.3fe
11.6si
1.4c
0.3rise field under (material 1, material 2, material 3, material 4) (a) differing temps before alloying pellet solidification and after the solidification of different-grain diameter particle different condition thermoplastic shaping, the magnetzation curve (MH curve) of a process and (b) different magnetic field fall and under magnetic entropy become (Δ S) dependence (calculating rises field Δ S) to temperature.
Fig. 4 is La in embodiment 1
0.7ce
0.3fe
11.6si
1.4c
0.3the relation of bearing pressure and strain of different-grain diameter particle different condition thermoplastic shaping solidification rear (material 1, material 2, material 3, material 4).
Fig. 5 is La in embodiment 2
0.7ce
0.3fe
11.6si
1.4c
0.2pyromagnetic (M-T) curve before alloying pellet solidification and after thermoplastic shaping solidification under 0.02T magnetic field.
Fig. 6 is La in embodiment 2
0.7ce
0.3fe
11.6si
1.4c
0.2(Δ S) dependence (calculate and rise field Δ S) to temperature is become with magnetic entropy under the rear 0-5T changes of magnetic field of thermoplastic shaping solidification before alloying pellet solidification.
Fig. 7 is La in embodiment 2
0.7ce
0.3fe
11.6si
1.4c
0.2the relation of bearing pressure and strain after thermoplastic shaping solidification.
Fig. 8 is La in comparative example 1
0.7ce
0.3fe
11.6si
1.4c
0.2the relation of bearing pressure and strain of the block materials of alloying pellet after different typed pressure compacted under, vacuum solidification (thermoset forming technology), illustration illustrates the pattern under the pattern of block materials and pressure after fragmentation.
Fig. 9 is that the ultimate compression strength of the block materials that comparative example 1 step (7) obtains is to the dependence of typed pressure.
Figure 10 is the La that embodiment 3 obtains
0.7ce
0.3fe
11.6si
1.4c
0.2room temperature X-ray diffraction (XRD) collection of illustrative plates of alloy block.
Figure 11 is the La that embodiment 3 obtains
0.7ce
0.3fe
11.6si
1.4c
0.2sample pyromagnetic (M-T) curve under 0.02T magnetic field of alloy block and 3 particle size range.
Figure 12 is the La that embodiment 3 obtains
0.7ce
0.3fe
11.6si
1.4c
0.2magnetization (M-H) curve rising field, fall a process that the sample of alloy block and 3 particle size range a) is measured under differing temps; B) hysteresis loss is to the dependence graph of temperature.
Figure 13 is the La that embodiment 3 obtains
0.7ce
0.3fe
11.6si
1.4c
0.2the sample of alloy block and 3 particle size range rises the Δ S of field process to the dependence graph of temperature under different magnetic field.
Figure 14 is a) magnetization (M-H) curve of the sample of particle size range <10 μm that embodiment 3 obtains; B) the Δ S of field process is risen under different magnetic field to the dependence graph of temperature.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, the embodiment provided only in order to illustrate the present invention, instead of in order to limit the scope of the invention.
About being described as follows of the raw material used in embodiment and equipment:
(1) starting material La, Ce, Fe, Si, FeC and purity thereof are respectively: simple substance La, purity 99.52wt.%, purchased from Hunan distillation rare-earth metal material limited liability company.Commercially pure LaCe alloy purchased from rare earth International Trading Company Ltd of Inner Mongol Baogang, purity: 99.17wt.% (97.03at.%), La, Ce atomic ratio: 1:1.88.Simple substance Fe, purity 99.9wt.%, purchased from Beijing Non-Fervoous Metal Inst..FeC(99.9wt.%, Fe, C weight ratio are 95.76:4.24), the simple substance Fe melting being 99.9wt.% by simple substance C and purity forms.Si(99.91wt.%), purchased from Beijing Non-Fervoous Metal Inst..Raw material is all block.
(2) starting material PA6(polyamide 6) purchased from Nanjing Hong Rui engineering plastics company limited, Powdered (particle diameter ~ 200 micron), vicat softening temperature (under 0.45Mpa heat-drawn wire), fusing point and denaturation temperature are 160 DEG C, 220 DEG C and 290 DEG C respectively.Starting material " epoxy resin glue BT-801 powder (having mixed corresponding solidifying agent and promotor in product) " are purchased from Chinese Dongguan City Bang Te finish materials company limited.
(3) electric arc furnace used is that Beijing WuKe opto-electrical Technology Co., Ltd produces, model: WK-II type non-consumable arc furnace.Cu target X-ray diffractometer is that Rigaku company produces, and model is RINT2400.Superconductive quantum interference vibrating sample magnetometer (MPMS(SQUID) VSM), be QuantumDesign(USA) company's production, model is MPMS(SQUID) VSM.Oil press is purchased from Tianjin Keqi High Technology Corp., and model is: 769YP-24B.Electronic universal tester newly thinks carefully material tests company limited purchased from Shenzhen, and model is: CMT4305.
embodiment 1: the La of preparation high strength good toughness
0.7
ce
0.3
fe
11.6
si
1.4
c
0.3
magnetic refrigerating working material
1) by La
0.7ce
0.3fe
11.6si
1.4c
0.3chemical formula is prepared burden, raw material is technical pure LaCe alloy, Fe, Si, La and FeC, wherein, simple substance La is used for the part of La deficiency in supplementary LaCe alloy, FeC alloy is used to provide C, owing to also containing Fe element in FeC alloy, need suitably to reduce the simple substance Fe added, make the proportioning of the various elements of interpolation still meet the atom ratio of magneticsubstance chemical formula.
2) by the raw material mixing in step 1), put into electric arc furnace, be evacuated to 2 × 10
-3pa, furnace chamber is cleaned 2 times with the high-purity argon gas that purity is 99.996wt%, being filled with purity afterwards in furnace chamber is 99.996wt% high-purity argon gas to normal atmosphere, Arc (after Arc, starting material are just molten becomes alloy together), obtain alloy pig, each alloy spindle melt back 4 times, smelting temperature is 2000 DEG C, after melting terminates, in copper crucible, cooling obtains cast alloy ingot.
3) by step 2) in the cast alloy ingot for preparing wrap with molybdenum foil respectively, be sealed in high vacuum (1 × 10
-4pa) in silica tube, anneal 30 days at 1080 DEG C, break silica tube Quenching in liquid nitrogen, obtain and there is NaZn
13the La of type structure
0.7ce
0.3fe
11.6si
1.4c
0.3alloy.
4) La will prepared in step 3)
0.7ce
0.3fe
11.6si
1.4c
0.3the irregular particle of particle diameter≤200 μm is made in alloy segmentation, and sieves out the particulate samples of different-grain diameter scope, particle diameter 1:120 ~ 200 μm, particle diameter 2:75 ~ 120 μm.
The alloying pellet of particle diameter 120 ~ 200 μm of scopes is sieved out with 120 orders and 75 object standard sieves;
The alloying pellet of particle diameter 75 ~ 125 μm of scopes is sieved out with 200 orders and 120 object standard sieves;
5) La of two kinds of particle size range will prepared in step 4)
0.7ce
0.3fe
11.6si
1.4c
0.3particle respectively with (tackiness agent PA6 proportion: 10wt%, 20wt%) Homogeneous phase mixing in varing proportions of the thermoplastic shaping plastics PA6 purchased from Nanjing Hong Rui engineering plastics company limited, prepare following four kinds of mixed glue materials:
Material 1-particle diameter: 120 ~ 200 μm, PA6 ratio: 10wt%, solidification value: 280 DEG C;
Material 2-particle diameter: 75 ~ 120 μm, PA6 ratio: 10wt%, solidification value: 280 DEG C;
Material 3-particle diameter: 120 ~ 200 μm, PA6 ratio: 20wt%, solidification value: 290 DEG C;
Material 4-particle diameter: 75 ~ 120 μm, PA6 ratio: 20wt%, solidification value: 290 DEG C.
6) four kinds of materials after mixed glue step 5) prepared respectively compression moulding are right cylinder (diameter: 5 millimeters, high: 7 millimeters).Step: the alloying pellet after mixed glue being put into material is that the mould of high chromium carbamide tool steel is (cylindrical, diameter 5 millimeters), oil press compression moulding is used under room temperature, typed pressure: 1.0GPa, the molding time of material 1, material 2 is: 2 minutes, and the molding time of material 3, material 4 is: 10 minutes.Room temperature bottom knockout after compression moulding.
7) step 6) is suppressed the right cylinder that obtains in vacuum (1 × 10
-2pa) solidification in.The solidification value of material 1 and material 2 is 280 DEG C, and the solidification value of material 3 and material 4 is 290 DEG C, is 60 minutes set time.The first-order phase transition La of high strength good toughness is then obtained after solidification
0.7ce
0.3fe
11.6si
1.4c
0.3magnetic refrigerating working material.After solidification the density of material 1, material 2, material 3, material 4 be 3.58 respectively, 3.67,3.02,3.12g/cm
3.
performance test:
One, the La that Cu target X-ray diffractometer determination step (4) obtains is utilized
0.7ce
0.3fe
11.6si
1.4c
0.3room temperature X-ray diffraction (XRD) collection of illustrative plates of (material 1, material 2, material 3 and material 4) before alloying pellet bonding and after the solidification of different-grain diameter particle different condition thermoplastic shaping, as shown in Figure 1, can find out La
0.7ce
0.3fe
11.6si
1.4c
0.3alloying pellet crystallization is NaZn
13type structure, XRD does not detect obvious dephasign.Sample after mixed glue thermoplastic solidification does not all detect the appearance of obvious α-Fe or other dephasign.The tackiness agent PA6 introduced is organism, and Cu target X-ray diffraction technology does not detect its diffraction peak.
Two, at MPMS(SQUID) La that obtains of the upper determination step of VSM (4)
0.7ce
0.3fe
11.6si
1.4c
0.3pyromagnetic (M-T) curve before alloying pellet bonding and after the solidification of different-grain diameter particle different condition thermoplastic shaping under (material 1 ~ 4) 0.02T magnetic field, as shown in Figure 2, can find out, before alloying pellet bonding, transformation temperature is positioned at 212K.After the solidification of different-grain diameter particle different condition thermoplastic shaping, phase transformation slows down, and transformation temperature is to high temperature movement a little.Fig. 3 (a) illustrates La
0.7ce
0.3fe
11.6si
1.4c
0.3rise field under (material 1 ~ 4) differing temps before alloying pellet bonding and after the solidification of different-grain diameter particle different condition thermoplastic shaping, fall the magnetzation curve (MH curve) of a process, after can finding out thermoplastic shaping adhesive solidification, sample hysteresis loss declines to a great extent, and is similar to and levels off to zero.Before bonding, the maximum hysteresis loss of alloying pellet is 42J/kg.
Three, according to Maxwell relations:
Δ S can be become from isothermal magnetization curve calculation magnetic entropy.Fig. 3 (b) illustrates the La that step (4) obtains
0.7ce
0.3fe
11.6si
1.4c
0.3before alloying pellet bonding and after the solidification of different-grain diameter particle different condition thermoplastic shaping, under (material 1 ~ 4) different magnetic field, Δ S is to the dependence (calculate and rise field Δ S) of temperature, and Δ S peak shape is along with the increase in magnetic field is to high-temperature zone asymptotic expansion.There are some researches show, the Δ S flat reaction essence of magnetothermal effect.Δ S podium level is 25.1J/kgK, 16.6J/kgK, 16.3J/kgK, 13.5J/kgK, 13.0J/kgK respectively under (material 1 ~ 4) 0-5T changes of magnetic field before alloying pellet bonding and after the solidification of different grain size particle different condition thermoplastic shaping, halfwidth is 20.6K, 26.4K, 24.9K, 28.9K, 27.0K respectively, and deducting the effective refrigeration capacity after maximum hysteresis loss is 428J/kg, 350J/kg, 330J/kg, 311J/kg, 302J/kg respectively.Although can find out that the magnetic entropy time-varying amplitude after solidification, effectively refrigeration capacity decline to some extent, still there is considerable amplitude.
The relation of bearing pressure and strain of the block materials after four, measuring vacuum thermoplastic solidification with CMT4305 electronic universal tester (is shown in Fig. 4, pattern after illustration illustrates material cured and under pressure after fragmentation), can find out that the bill of material that the different condition of cure of different-grain diameter obtains reveals different ultimate compression strength and toughness.Identical tackiness agent PA6 ratio 10wt%, 240 DEG C of solidifications small particle size (material 2:75 ~ 120 μm) are compared with Large stone (material 1:120 ~ 200 μm) material and are shown higher ultimate compression strength and more obdurability, small particle size (material 2), Large stone (material 1) material ultimate compression strength are 34.9 and 20.5MPa respectively, maximum strain of bearing corresponding to pressure is 11.7% and 9.5% respectively, shows that small particle size sample toughness strengthens.When tackiness agent PA6 ratio be increased to 20wt% and 280 DEG C of solidifications (comparatively high temps can make tackiness agent fully melt flowing with the object reaching even clad alloy particle surface) time ultimate compression strength and toughness be significantly increased, material 3(particle diameter: 120 ~ 200 μm, PA6 ratio: 20wt%, solidification value: 280 DEG C), material 4(particle diameter: 75 ~ 120 μm, PA6 ratio: 20wt%, solidification value: 280 DEG C) ultimate compression strength reach 56.3 and 53.6MPa respectively, maximum maximum strain of bearing corresponding to pressure can reach 19.5% respectively, 20.7%, show that toughness significantly strengthens.Compared with preparing magneto-caloric material with thermoset forming technology in comparative example 1, thermoplastic shaping technology is prepared magneto-caloric material toughness and is significantly strengthened.In comparative example 1, the maximum maximum strain of bearing corresponding to pressure of (Fig. 8) thermoset forming material is only 2.5%.
embodiment 2: the La of preparation high strength good toughness
0.7
ce
0.3
fe
1.6
si
1.4
c
0.2
magnetic refrigerating working material
1) by La
0.7ce
0.3fe
11.6si
1.4c
0.2chemical formula is prepared burden, raw material is technical pure LaCe alloy, Fe, Si, La and FeC, wherein, simple substance La is used for the part of La deficiency in supplementary LaCe alloy, FeC alloy is used to provide C, owing to also containing Fe element in FeC alloy, need suitably to reduce the simple substance Fe added, make the proportioning of the various elements of interpolation still meet the atom ratio of magneticsubstance chemical formula.
2) by the raw material mixing in step 1), put into electric arc furnace, be evacuated to 2 × 10
-3pa, furnace chamber is cleaned 2 times with the high-purity argon gas that purity is 99.996wt%, being filled with purity afterwards in furnace chamber is 99.996wt% high-purity argon gas to normal atmosphere, Arc (after Arc, starting material are just molten becomes alloy together), obtain alloy pig, each alloy spindle melt back 4 times, smelting temperature is 2000 DEG C, after melting terminates, in copper crucible, cooling obtains cast alloy ingot.
3) by step 2) the cast alloy ingot for preparing wraps with molybdenum foil respectively, is sealed in high vacuum (1 × 10
-4pa) in silica tube, anneal 30 days at 1080 DEG C, break silica tube Quenching in liquid nitrogen, obtain and there is NaZn
13the La of type structure
0.7ce
0.3fe
11.6si
1.4c
0.2alloy.
4) La step 3) prepared
0.7ce
0.3fe
11.6si
1.4c
0.2the irregular particle of particle diameter≤200 μm is made in alloy segmentation, and sieves out the alloying pellet of particle diameter 120 ~ 200 μm of scopes with 120 orders and 75 object standard sieves.
5) La step 4) prepared
0.7ce
0.3fe
11.6si
1.4c
0.2particle and the thermoplastic shaping plastics PA6 Homogeneous phase mixing purchased from Nanjing Hong Rui engineering plastics company limited, tackiness agent PA6 proportion: 20wt%.
6) after mixed glue step 5) prepared, material compression moulding is right cylinder (diameter: 5 millimeters, high: 7 millimeters).Step: the alloying pellet after mixed glue is put into the mould (cylindrical, diameter 5 millimeters) that material is high chromium carbamide tool steel, use oil press compression moulding under room temperature, typed pressure: 1.0GPa, molding time is 10 minutes.Room temperature bottom knockout after compression moulding.
7) step 6) is suppressed the right cylinder that obtains in vacuum (1 × 10
-1pa) solidification in.Solidification value is 280 DEG C, and set time is 30 minutes.The first-order phase transition La of high strength good toughness is then obtained after solidification
0.7ce
0.3fe
11.6si
1.4c
0.2magnetic refrigerating working material.After solidification, the density of material is 3.0g/cm
3.
performance test:
One, the La that Cu target X-ray diffractometer determination step (4) obtains is utilized
0.7ce
0.3fe
11.6si
1.4c
0.2room temperature X-ray diffraction (XRD) collection of illustrative plates before alloying pellet bonding and after thermoplastic shaping solidification, La
0.7ce
0.3fe
11.6si
1.4c
0.3alloying pellet crystallization is NaZn
13type structure, XRD does not detect obvious dephasign.Sample after mixed glue thermoplastic solidification does not all detect the appearance of obvious α-Fe or other dephasign.The tackiness agent PA6 introduced is organism, and Cu target X-ray diffraction technology does not detect its diffraction peak.
Two, at MPMS(SQUID) La that obtains of the upper determination step of VSM (4)
0.7ce
0.3fe
11.6si
1.4c
0.2pyromagnetic (M-T) curve before alloying pellet bonding and after thermoplastic shaping solidification under 0.02T magnetic field, as shown in Figure 5.Can find out, before alloying pellet bonding, transformation temperature is positioned at 200K.After thermoplastic shaping solidification, phase transformation slows down, and transformation temperature is to high temperature movement a little.Fig. 6 provides the La that step (4) obtains
0.7ce
0.3fe
11.6si
1.4c
0.2before alloying pellet bonding and after thermoplastic shaping solidification under 0-5T changes of magnetic field Δ S to the dependence (utilize Maxwell relations to calculate and rise field Δ S) of temperature, it is 26.4J/kgK and 13.6J/kgK respectively that effective magnetic entropy becomes Δ S, halfwidth is 19.6K and 27.3K respectively, and deducting the effective refrigeration capacity after maximum hysteresis loss is 375J/kg and 305J/kg respectively.Although can find out that the magnetic entropy time-varying amplitude after solidification, effectively refrigeration capacity decline to some extent, still there is considerable amplitude.
Three, the relation (being shown in Fig. 7) of bearing pressure and strain of the block materials after vacuum thermoplastic solidification is measured with CMT4305 electronic universal tester, La
0.7ce
0.3fe
11.6si
1.4c
0.2after thermoplastic shaping solidification, ultimate compression strength is 58.5MPa, and maximum maximum strain of bearing corresponding to pressure can reach 21.5%(and show that toughness significantly strengthens).
comparative example 1: utilize thermoset forming technology to prepare La
0.7
ce
0.3
fe
11.6
si
1.4
c
0.2
magnetothermal effect material
Step 1) ~ step 3) prepares La according to the mode that the step 1) ~ step 3) with embodiment 2 is same
0.7ce
0.3fe
11.6si
1.4c
0.2alloy.
4) La step 3) prepared
0.7ce
0.3fe
11.6si
1.4c
0.2alloy is pulverized and is made irregular particle, average particle size range: 20 ~ 200 microns.
5) " epoxy resin glue BT-801 powder (having mixed corresponding solidifying agent and promotor in product) " purchased from Chinese Dongguan City Bang Te finish materials company limited is made into glue.Configuration proportion (weight ratio) is acetone: dehydrated alcohol: BT-801 epoxy resin glue=1:1:1; Dissolving method: mixed acetone and ethanol solution are poured in BT-801 epoxy resin glue powder, is stirred to powder and is dissolved completely in solution, and glue preparation is complete.Then, by the glue be mixed with by weight: alloying pellet: BT-801 epoxy resin glue powder=100:4.5 pours La prepared by step 4) into
0.7ce
0.3fe
11.6si
1.4c
0.2in alloying pellet, mix, shakeout and put into 50 DEG C of baking ovens until dry, drying time is 180 minutes.
6) La after the mixed glue prepared by step 5)
0.7ce
0.3fe
11.6si
1.4c
0.2alloying pellet compression moulding is right cylinder (diameter: 5 millimeters, high: 7 millimeters).Step: the alloying pellet after mixed glue being put into material is that the mould of high chromium carbamide tool steel is (cylindrical, diameter 5 millimeters), oil press compression moulding is used under room temperature, the pressure selected in the moulding process of parallel test is respectively: 0.5GPa, 0.75GPa, 1.0GPa, 1.3GPa, and the time is: 2 minutes.Room temperature bottom knockout after compression moulding.
7) step 6) is suppressed the right cylinder (vacuum tightness: 1 × 10 in a vacuum obtained
-2pa) solidify, solidification value is 160 DEG C, and set time is 20 minutes.The first-order phase transition La of high strength is then obtained after solidification
0.7ce
0.3fe
11.6si
1.4c
0.2magnetothermal effect material.
performance test:
The relation (being shown in Fig. 8) of bearing pressure and strain of different typed pressure compacted under, the rear sample of solidification is measured with CMT4305 electronic universal tester, thus obtain ultimate compression strength to the dependence (being shown in Fig. 9) of typed pressure, can find out that ultimate compression strength raises with the rising of typed pressure, when typed pressure is raised to 1.3GPa from 0.75GPa, after solidification, material ultimate compression strength significantly rises to 136.7MPa from 47.6MPa.With virgin alloy Particle Phase ratio, magnetic entropy diminish width decline while hysteresis loss decline, effective refrigeration capacity remains unchanged or rises to some extent.
As seen from Figure 8, comparative example 1 adopts the La that thermoset forming technology bonds
0.7ce
0.3fe
11.6si
1.4c
0.2the maximum maximum strain of bearing corresponding to pressure of material is only 2.5%, the maximum maximum strain of bearing corresponding to pressure of the material adopting thermoplastic shaping technology to obtain in embodiment 1 and embodiment 2.Similar compositions La in embodiment 1
0.7ce
0.3fe
11.6si
1.4c
0.3the maximum maximum strain of bearing corresponding to pressure that different-grain diameter different condition thermoplastic shaping solidifies material 1, material 2, material 3 and the material 4 obtained is 11.7%, 9.5%, 19.5% and 20.7% respectively, (form identical with the material of comparative example 1) in embodiment 2 adopting thermoplastic shaping to solidify rear maximum maximum strain of bearing corresponding to pressure is 21.5%, show to adopt thermoplastic shaping bonding technology can obtain the novel La (Fe, Si) that ultimate compression strength is considerable, toughness significantly strengthens
13base magnetic refrigerating working material.
embodiment 3: the La with little hysteresis loss
0.7
ce
0.3
fe
11.6
si
1.4
c
0.2
magnetothermal effect material
1) by La
0.7ce
0.3fe
11.6si
1.4c
0.2chemical formula is prepared burden, raw material is technical pure LaCe alloy, Fe, Si, La and FeC, wherein, simple substance La is used for the part of La deficiency in supplementary LaCe alloy, FeC alloy is used to provide C, owing to also containing Fe element in FeC alloy, need suitably to reduce the simple substance Fe added, make the proportioning of the various elements of interpolation still meet the atom ratio of magneticsubstance chemical formula;
2) by the raw material mixing in step 1), put into electric arc furnace, be evacuated to 2 × 10
-3pa, furnace chamber is cleaned 2 times with the high-purity argon gas that purity is 99.996%, being filled with purity afterwards in furnace chamber is 99.996% high-purity argon gas to normal atmosphere, Arc (after Arc, starting material are just molten becomes alloy together), obtain alloy pig, each alloy spindle melt back 4 times, smelting temperature is 2000 DEG C, after melting terminates, in copper crucible, cooling obtains cast alloy ingot;
3) by step 2) in the cast alloy ingot for preparing wrap with molybdenum foil respectively, be sealed in high vacuum (1 × 10
-4pa) in silica tube, anneal 30 days at 1080 DEG C, break silica tube Quenching in liquid nitrogen, obtain and there is NaZn
13the La of type structure
0.7ce
0.3fe
11.6si
1.4c
0.2alloy block.
4) alloy block step 3) obtained breaks the coarse particles being divided into particle diameter to be less than 1mm into pieces in metal mortar; under acetone protection, with agate mortar coarse particles ground to form further the irregular alloying pellet of particle diameter≤200 μm afterwards; sieve with the standard sieve alloy particle of different meshes afterwards, thus prepare the particle with different-grain diameter scope.For anti-oxidation, screening process carries out in acetone liquid.Concrete screening mode is as follows:
The alloying pellet of particle diameter 90 ~ 120 μm of scopes is sieved out with 170 orders and 120 object standard sieves;
The alloying pellet of particle diameter 50 ~ 90 μm of scopes is sieved out with 270 orders and 170 object standard sieves;
The alloying pellet of particle diameter 15 ~ 50 μm of scopes is sieved out with 800 orders and 270 object standard sieves;
Sieve out particle diameter with 1600 object standard sieves and be less than 10 μm of alloying pellets.
sample detection and interpretation of result:
One, Cu target X-ray diffractometer is utilized to measure La
0.7ce
0.3fe
11.6si
1.4c
0.2room temperature X-ray diffraction (XRD) collection of illustrative plates of alloy block, result as shown in Figure 10, can find out that sample is clean NaZn
13type phase structure, does not almost have dephasign to occur.
Two, on superconductive quantum interference vibrating sample magnetometer [MPMS(SQUID) VSM], La is measured
0.7ce
0.3fe
11.6si
1.4c
0.2alloy block (individual particle, weight: 2.7mg) and different-grain diameter scope sample (90 ~ 120 μm (weight: 2.31mg), 50 ~ 90 μm (weight: 1.86mg), 15 ~ 50 μm (weight: 1.28mg), <10 μm (weight: 0.86mg) pyromagnetic (M-T) curve under 0.02T magnetic field, as shown in figure 11.Result shows: except the Curie temperature of the alloying pellet of particle diameter <10 μm to high-temperature mobile to 203K except (because the accumulation material introducing stress in process of lapping may separate out α-Fe, relative Si content increases), the Curie temperature of the alloying pellet of other 3 particle size range is all consistent with alloy block, is positioned at 200K.
Three, at MPMS(SQUID) VSM measures La
0.7ce
0.3fe
11.6si
1.4c
0.2alloy block (individual particle, weight: 2.7mg) and different-grain diameter scope sample (90 ~ 120 μm (weight: 2.31mg), 50 ~ 90 μm (weight: 1.86mg), 15 ~ 50 μm (weight: 1.28mg), <10 μm (weight: 0.86mg) rise field at different temperatures, fall the magnetzation curve of a process (M-H curve), rising field, to fall field speed degree identical, is 500 oersteds/second.(a) and (b) group of Figure 12 illustrates alloy block and 3 particle size range samples in the M-H curve of ascending, descending field process and hysteresis loss respectively to the dependence of temperature.On M-H curve, the appearance of remarkable flex point shows the existence becoming magnetic transition behavior from paramagnetic to ferrimagnetic state of induced by magnetic field.Each suite line is carried out contrast can find out: hysteresis loss declines to a great extent with the reduction of granularity, the 35.4J/kg that maximum magnetic flux is delayed when dropping to particle size range 15 ~ 50 μm from 98.4J/kg during alloy block, down ratio reaches 64%.The M-H curve of high-temperature zone (the paramagnetic region of 1:13 phase) is straight line, and indirect proof alloy block and 3 particle size range samples are clean 1:13 phase, substantially do not have the appearance of α-Fe phase.
Four, according to Maxwell relations:
Δ S can be become from isothermal magnetization curve calculation magnetic entropy.Figure 13 illustrates the La of alloy block and 3 particle size range
0.7ce
0.3fe
11.6si
1.4c
0.2alloying pellet rises the Δ S of field process to the dependence of temperature under different magnetic field.Can find out in Figure 13, Δ S peak shape is along with the increase in magnetic field is to high-temperature zone asymptotic expansion, and spike heel platform, this is La (Fe, Si)
13the characteristic feature of base first-order phase transition system, derives from the change magnetic transition behavior of the above induced by magnetic field of Curie temperature.Δ S peak shape demonstrates the existence of the first-order phase transition characteristic sum change magnetic transition behavior of system further.There are some researches show, the appearance of Δ S spike produces due to the two-phase coexistent of first-order phase transition process, is the illusion that there is not heat effect, the Δ S flat reaction essence of magnetothermal effect.Can find out, the La of alloy block and 3 particle size range
0.7ce
0.3fe
11.6si
1.4c
0.2sample all keeps large effective magnetic entropy time-varying amplitude, and mean value is 26J/kgK.
As the contrast with the above results, (a) and (b) of Figure 14 respectively illustrates M-H curve when particle size range is reduced to <10 μm and magnetic entropy temperature curve.As can be seen from Figure 14: reduce granularity to <10 μm, although maximum magnetic flux is delayed be further reduced to 27J/kg, the precipitation of the dephasigns such as α-Fe or the mutually unstable decomposition caused make magnetothermal effect amplitude drop to 21J/kgK.The M-H curve of Figure 14 (a) still bends at the paramagnetic high-temperature area of 1:13 phase, indicates precipitation or the unstable decomposition caused mutually of the dephasigns such as α-Fe.
Below describe in detail the present invention with reference to embodiment, to those skilled in the art, should be understood that, above-mentioned embodiment should not be understood to limit scope of the present invention.Therefore, various changes and improvements can made to embodiment of the present invention without departing from the spirit and scope of the present invention.
Claims (16)
1. a magnetic refrigerating working material, described magnetic refrigerating working material comprises magnetothermal effect alloying pellet and thermoplastics type's tackiness agent, wherein, the particle diameter of described magnetothermal effect alloying pellet is 15 ~ 200 μm, and described magnetothermal effect alloying pellet is bonded to block materials by described thermoplastics type's tackiness agent by thermoplastic shaping; Wherein, described magnetothermal effect alloying pellet is for having NaZn
13the La (Fe, Si) of type structure
13sill, wherein, described thermoplastics type's tackiness agent be selected from polymeric amide, polyphenylene sulfide, polypropylene, ethylene-vinyl acetate copolymer, TLCP, polyethylene terephthalate, polyethylene one or more; Relative to the described magnetothermal effect alloying pellet of 100 weight parts, the content of described thermoplastics type's tackiness agent is 5 ~ 25 weight parts.
2. magnetic refrigerating working material according to claim 1, wherein, described in there is NaZn
13the La (Fe, Si) of type structure
13sill is La
0.7ce
0.3fe
11.6si
1.4c
x, wherein 0.2≤x≤0.3.
3. magnetic refrigerating working material according to claim 1, wherein, relative to the described magnetothermal effect alloying pellet of 100 weight parts, the content of described thermoplastics type's tackiness agent is 10 ~ 20 weight parts.
4. magnetic refrigerating working material according to claim 1, wherein, described polymeric amide comprises polyamide 6, polyamide 66, polyamide 1010.
5. magnetic refrigerating working material according to claim 1, wherein, described thermoplastics type's tackiness agent is polyamide 6.
6. the preparation method of the magnetic refrigerating working material according to any one of claim 1 to 5, the method comprises the steps:
1) by La (Fe, Si)
13the chemical formula preparation raw material of sill;
2) by step 1) raw material for preparing puts into electric arc furnace, vacuumizes, by inert gas purge, and melting under protection of inert gas, obtain alloy pig;
3) by step 2) melted alloy pig vacuum annealing, then at liquid nitrogen or quenching-in water, prepare and there is NaZn
13the La (Fe, Si) of structure
13base magnetothermal effect alloy;
4) to step 3) obtained magnetothermal effect alloy carries out fragmentation, obtains the magnetothermal effect alloying pellet that particle diameter is 15 ~ 200 μm;
5) by thermoplastics type's tackiness agent and step 4) obtained magnetothermal effect alloying pellet mixes, compression moulding, and thermoplastic shaping solidification obtains block materials.
7. preparation method according to claim 6, wherein, in described step 5) in, be dry mixed by the method that thermoplastics type's tackiness agent mixes with magnetothermal effect alloying pellet.
8. preparation method according to claim 7, wherein, described dry mixed comprises: mixed with described magnetothermal effect alloying pellet by pulverous thermoplastics type's tackiness agent.
9. preparation method according to claim 6, wherein, in described step 5) in, the condition of compression moulding comprises: pressing pressure is 0.1 ~ 1.5GPa, and the press time is 1 ~ 10 minute.
10. preparation method according to claim 9, wherein, pressing pressure is 0.8 ~ 1.2GPa.
11. preparation methods according to claim 6, wherein, in described step 5) in, solidification is carried out in a vacuum, and the condition of solidification comprises: solidification value 215 ~ 290 DEG C, 30 ~ 60 minutes set times, vacuum tightness≤10
-1pa.
12. preparation methods according to claim 11, wherein, solidification value is 240 ~ 280 DEG C.
13. preparation methods according to claim 6, wherein, in described step 1) in, the carbon in chemical formula is provided by FeC alloy.
14. preparation methods according to claim 6, wherein, described rare gas element is argon gas.
15. 1 kinds of magnetic refrigerators, the magnetic refrigerating working material that described refrigerator comprises the magnetic refrigerating working material according to any one of claim 1 to 5 or obtains according to method according to any one of claim 6 to 14.
Magnetic refrigerating working material according to any one of 16. claims 1 to 5 or the application of magnetic refrigerating working material in manufacture refrigerating material obtained according to method according to any one of claim 6 to 14.
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| KR20170097131A (en) * | 2014-12-18 | 2017-08-25 | 바스프 에스이 | Magnetocaloric cascade and method for fabricating a magnetocaloric cascade |
| CN104694813B (en) * | 2015-03-04 | 2017-07-28 | 中国科学院宁波材料技术与工程研究所 | LaFeSi base magnetic refrigerating materials and preparation method and application |
| WO2016140350A1 (en) * | 2015-03-05 | 2016-09-09 | 株式会社三徳 | Manufacturing method for magnetic freezing module |
| DE102015015240A1 (en) * | 2015-11-20 | 2017-05-24 | Licence | Device for cooling |
| CN106086738B (en) * | 2016-05-31 | 2018-04-13 | 北京科技大学 | Adjust NaZn13Structure rare earth ferro-silicium Curie temperature and the method for reducing dephasign |
| CN106917029B (en) * | 2017-04-13 | 2018-08-21 | 佛山市程显科技有限公司 | A kind of ferromagnetic martensitic traoformation MM ' X-Y metal composite functional materials and preparation method thereof |
| CN107855518A (en) * | 2017-11-14 | 2018-03-30 | 东北大学 | A kind of preparation method of the hot composite of magnetic bonded by low-melting alloy |
| CN115109984A (en) * | 2022-07-04 | 2022-09-27 | 中国科学院宁波材料技术与工程研究所 | Preparation method of La-Fe-Si-based magnetic refrigeration alloy |
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| CN101226801A (en) * | 2007-11-27 | 2008-07-23 | 浙江大学 | Method for manufacturing iron base alloy electromagnetic-interference-resistance |
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