CN104830284A - Application of rear-earth R2BaCuO5 oxide material to low-temperature magnetic refrigeration - Google Patents
Application of rear-earth R2BaCuO5 oxide material to low-temperature magnetic refrigeration Download PDFInfo
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- CN104830284A CN104830284A CN201510189330.4A CN201510189330A CN104830284A CN 104830284 A CN104830284 A CN 104830284A CN 201510189330 A CN201510189330 A CN 201510189330A CN 104830284 A CN104830284 A CN 104830284A
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- r2bacuo5
- oxide material
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Abstract
The invention relates to an application of a rear-earth R2BaCuO5 oxide material to low-temperature magnetic refrigeration. R represents dysprosium Dy, holmium Ho or erbium Er. The R2BaCuO5 material is of an orthogonal crystal structure, and belongs to a Pnma space group. The rear-earth R2BaCuO5 oxide material for magnetic refrigeration has good magnetic and thermally reversible properties, and has isothermal magnetic entropy changes up to 8.3 J/kgK,10.4 J/kgK and 9.6 J/kgK corresponding to Dy2BaCuO5, Ho2BaCuO5 and Er2BaCuO5 respectively. Therefore, the R2BaCuO5 oxide material can be applied to the aspect of magnetic refrigeration in a low-temperature region. The R2BaCuO5 oxide material is prepared by adopting conventional technological means. The method is simple in process and is suitable for industrialization.
Description
Technical field
The invention belongs to materialogy technical field, relate to a kind of magnetic functional material, particularly a kind of rare earth R
2baCuO
5the application of (R=dysprosium Dy, holmium Ho or erbium Er) oxide material in the magnetic refrigeration of cold zone.
Background technology
Magnetic refrigerating material is a kind of novel magnetic functional materials, and it is the free of contamination refrigerating working material of one utilizing the magnetothermal effect (i.e. magnetocaloric effect, also known as magneto-caloric effect or magnetic entropy effect) of magneticsubstance to realize refrigeration.
Magnetic refrigeration utilizes externally-applied magnetic field and makes orderly, the unordered change (phase transformation) of the magnetic moment of magnetic working medium generation cause the effect of magnet heat absorption and release and carry out refrigeration cycle.Enter region, upfield by magnetic refrigeration working substance, release heat to surrounding environment; Enter zero/low field regions, temperature reduces, and absorbs the object that heat reaches refrigeration; Iterative cycles like this can continuous cooling.
Magnetic refrigeration is considered to the refrigeration modes of a kind of " green ", it does not only discharge as any obnoxious flavoures such as freonll-11, and the energy of consumption 20 ~ 30 ﹪ can be lacked compared with existing best refrigeration system, not only and do not damage the ozone layer but also not emission greenhouse gas, the refrigerator used now and air-conditioning system are then becoming the main body that worldwide energy consumes.
At present, magnetic refrigeration is mainly used in the small-scale device such as pole low temperature and liquefaction helium.Although the restriction of factors makes the widespread use of magnetic Refrigeration Technique not yet ripe, compared with traditional vapor compression refrigeration, magnetic refrigeration has that entropy density is high, volume is little, structure is simple, pollution-free, noise is little, efficiency is high and the advantage such as low in energy consumption, will become a kind of new refrigeration modes having much potentiality future.And depending on that can this technology walk out laboratory, the key of coming into huge numbers of families finds excellent magnetic refrigerating material.Current cold zone magnetic refrigerating material is some rare earth intermetallic compound materials mainly, and such material exists the deficiencies such as the prices of raw and semifnished materials are high, complicated process of preparation.
According to research, rare earth R
2baCuO
5oxide material ministerial level near respective magnetic transition temperature has larger magnetic entropy and becomes, and have with low cost, preparation method simple and good magnetic, heat reversible performance.At low temperature magnetic refrigerating field, there is certain application prospect.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of rare earth R is provided
2baCuO
5(R=dysprosium Dy, holmium Ho or erbium Er) oxide material application in magnetic refrigeration.
Chemical formula of the present invention is R
2baCuO
5the application of oxide material in low temperature magnetic refrigeration, wherein R is dysprosium Dy, holmium Ho or erbium Er.
Described chemical formula is R
2baCuO
5oxide material there is orthogonal type crystalline structure, belong to Pnma spacer.
Magnetic refrigeration R of the present invention
2baCuO
5(R=dysprosium Dy, holmium Ho or erbium Er) oxide material not only has good magnetic, heat reversible performance, under 0 ~ 7T changes of magnetic field, (should be Dy corresponding to dysprosium Dy, holmium Ho or erbium Er
2baCuO
5, Ho
2baCuO
5, Er
2baCuO
5) its isothermal magnetic entropy variation is up to 8.3,10.4 and 9.6J/kgK.Therefore R
2baCuO
5(R=dysprosium Dy, holmium Ho or erbium Er) oxide material can be applicable to magnetic refrigeration aspect, cold zone.R of the present invention
2baCuO
5oxide material adopts the preparation of routine techniques means, and the method technique is simple, be applicable to industrialization.
Accompanying drawing explanation
Fig. 1 is Dy of the present invention
2baCuO
5material cold (FC) on the scene and null field cold (ZFC) specific magnetising moment are with pyromagnetic (M-T) change curve of temperature;
Fig. 2 is the lower Dy of the present invention of different magnetic field change
2baCuO
5the isothermal magnetic entropy of material becomes variation with temperature graphic representation;
Fig. 3 is Ho of the present invention
2baCuO
5material cold (FC) on the scene and null field cold (ZFC) specific magnetising moment are with pyromagnetic (M-T) change curve of temperature;
Fig. 4 is the lower Ho of the present invention of different magnetic field change
2baCuO
5the isothermal magnetic entropy of material becomes variation with temperature graphic representation;
Fig. 5 is Er of the present invention
2baCuO
5material cold (FC) on the scene and null field cold (ZFC) specific magnetising moment are with pyromagnetic (M-T) change curve of temperature;
Fig. 6 is the lower Er of the present invention of different magnetic field change
2baCuO
5the isothermal magnetic entropy of material becomes variation with temperature graphic representation.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further analyzed, but concrete case study on implementation is not limited in any way the present invention.
Embodiment 1.Dy
2baCuO
5the preparation of material and magnetic refrigeration performance measure
Step (1). by 7.459g (0.02 mole) Holmium trioxide Dy
2o
3, 3.946g (0.02 mole) barium carbonate BaCO
3with 1.431g (0.01 mole) Red copper oxide Cu
2o is uniformly mixed into raw material according to mol ratio 2:2:1;
Step (2). after utilizing mortar that raw mill is even, put into corundum crucible and sinter 48 hours at retort furnace is heated to 900 DEG C;
Step (3). by the raw material regrind powdered after process, after utilizing tabletting machine shaping, again put into corundum crucible and sinter 72 hours at retort furnace is heated to 920 DEG C; Cool to room temperature with the furnace and can obtain finished product;
Step (4). obtained finished product turns out to be Dy through X-ray diffraction
2baCuO
5monophase materials, this material is that orthogonal type crystalline structure belongs to Pnma spacer.
Step (5). the obtained Dy of above-described embodiment 1 that annex measures measured by the vibrating sample magnetometer (VSM) of physical measurement system (PPMS-9) produced in Quantum Design, Inc. of the U.S.
2baCuO
5pyromagnetic (M-T) curve under material cold-peace on the scene null field is cold as shown in Figure 1.Dy can be determined from M-T curve
2baCuO
5material does not have thermal hysteresis, its magnetic transition temperature is 11K.
Step (6). the Dy that the embodiment 1 measured on vibrating sample magnetometer measurement (VSM) annex of physical measurement system (PPMS) prepares
2baCuO
5the isothermal magnetization of material near transformation temperature (M-H) curve.Utilize formula:
the isothermal magnetic entropy calculated under different magnetic field change becomes.The isothermal magnetic entropy change-Δ S calculated
mfig. 2 is seen with the relation of temperature T.Embodiment 1 prepares Dy
2baCuO
5under the changes of magnetic field of 0-5T and 0-7T, its isothermal magnetic entropy becomes maximum value and reaches 5.9J/kgK and 8.3J/kgK respectively.
As seen from Figure 1, Figure 2, the Dy for preparing of embodiment 1
2baCuO
5material has larger magnetic entropy and becomes near 11K temperature, and has good magnetic, heat reversible performance.Therefore the Dy for preparing of known embodiment 1
2baCuO
5material has certain application prospect at low temperature magnetic refrigerating field.
Embodiment 2.Ho
2baCuO
5the preparation of material and magnetic refrigeration performance measure
Step (1). by 7.555g (0.02 mole) Holmium trioxide Ho
2o
3, 3.946g (0.02 mole) barium carbonate BaCO
3with 1.431g (0.01 mole) Red copper oxide Cu
2o is uniformly mixed into raw material according to mol ratio 2:2:1;
Step (2). after utilizing mortar that raw mill is even, put into corundum crucible and sinter 50 hours at retort furnace is heated to 910 DEG C;
Step (3). by the raw material regrind powdered after process, after utilizing tabletting machine shaping, again put into corundum crucible and sinter 70 hours at retort furnace is heated to 930 DEG C; Cool to room temperature with the furnace and can obtain finished product;
Step (4). obtained finished product turns out to be Ho through X-ray diffraction
2baCuO
5monophase materials, this material is that orthogonal type crystalline structure belongs to Pnma spacer.
Step (5). the obtained Ho of above-described embodiment 2 that annex measures measured by the vibrating sample magnetometer (VSM) of physical measurement system (PPMS-9) produced in Quantum Design, Inc. of the U.S.
2baCuO
5pyromagnetic (M-T) curve under material cold-peace on the scene null field is cold as shown in Figure 3.Ho can be determined from M-T curve
2baCuO
5material does not have thermal hysteresis, its magnetic transition temperature is 9K.
Step (6). the Ho that the embodiment 2 measured on vibrating sample magnetometer measurement (VSM) annex of physical measurement system (PPMS) prepares
2baCuO
5the isothermal magnetization of material near transformation temperature (M-H) curve.Utilize formula:
the isothermal magnetic entropy calculated under different magnetic field change becomes.The isothermal magnetic entropy change-Δ S calculated
mfig. 4 is seen with the relation of temperature T.Embodiment 2 prepares Ho
2baCuO
5under the changes of magnetic field of 0-5T and 0-7T, its isothermal magnetic entropy becomes maximum value and reaches 7.0J/kgK and 10.4J/kgK respectively.
From Fig. 3, Fig. 4, the Ho that embodiment 2 prepares
2baCuO
5material has larger magnetic entropy and becomes near 9K temperature, and has good magnetic, heat reversible performance.Therefore the Ho for preparing of known embodiment 2
2baCuO
5material has certain application prospect at low temperature magnetic refrigerating field.
Embodiment 3.Er
2baCuO
5the preparation of material and magnetic refrigeration performance measure
Step (1). by 7.65g (0.02 mole) Holmium trioxide Er
2o
3, 3.946g (0.02 mole) barium carbonate BaCO
3with 1.431g (0.01 mole) Red copper oxide Cu
2o is uniformly mixed into raw material according to mol ratio 2:2:1;
Step (2). after utilizing mortar that raw mill is even, put into corundum crucible and sinter 45 hours at retort furnace is heated to 880 DEG C;
Step (3). by the raw material regrind powdered after process, after utilizing tabletting machine shaping, again put into corundum crucible and sinter 75 hours at retort furnace is heated to 910 DEG C; Cool to room temperature with the furnace and can obtain finished product;
Step (4). obtained finished product turns out to be Er through X-ray diffraction
2baCuO
5monophase materials, this material is that orthogonal type crystalline structure belongs to Pnma spacer.
Step (5). the obtained Er of above-described embodiment 3 that annex measures measured by the vibrating sample magnetometer (VSM) of physical measurement system (PPMS-9) produced in Quantum Design, Inc. of the U.S.
2baCuO
5pyromagnetic (M-T) curve under material cold-peace on the scene null field is cold as shown in Figure 5.Er can be determined from M-T curve
2baCuO
5material does not have thermal hysteresis, its magnetic transition temperature is 9K.
Step (6). the Er that the embodiment 3 measured on vibrating sample magnetometer measurement (VSM) annex of physical measurement system (PPMS) prepares
2baCuO
5the isothermal magnetization of material near transformation temperature (M-H) curve.Utilize formula:
the isothermal magnetic entropy calculated under different magnetic field change becomes.The isothermal magnetic entropy change-Δ S calculated
mfig. 6 is seen with the relation of temperature T.Embodiment 3 prepares Er
2baCuO
5under the changes of magnetic field of 0-5T and 0-7T, its isothermal magnetic entropy becomes maximum value and reaches 6.9J/kgK and 9.6J/kgK respectively.
From Fig. 5, Fig. 6, the Er that embodiment 3 prepares
2baCuO
5material has larger magnetic entropy and becomes near 9K temperature, and has good magnetic, heat reversible performance.Therefore the Er for preparing of known embodiment 3
2baCuO
5material has certain application prospect at low temperature magnetic refrigerating field.
Claims (2)
1. a rare earth R
2baCuO
5the application of oxide material in low temperature magnetic refrigeration, wherein R=dysprosium Dy, holmium Ho or erbium Er.
2. a kind of rare earth R as claimed in claim 1
2baCuO
5the application of oxide material in low temperature magnetic refrigeration, is characterized in that described rare earth R
2baCuO
5oxide material material has orthogonal type crystalline structure, belongs to Pnma spacer.
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|---|---|---|---|
| CN201510189330.4A CN104830284A (en) | 2015-04-20 | 2015-04-20 | Application of rear-earth R2BaCuO5 oxide material to low-temperature magnetic refrigeration |
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|---|---|---|---|
| CN201510189330.4A CN104830284A (en) | 2015-04-20 | 2015-04-20 | Application of rear-earth R2BaCuO5 oxide material to low-temperature magnetic refrigeration |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347797A (en) * | 2015-10-10 | 2016-02-24 | 东北大学 | R2Cu2O5 oxide material used for low-temperature magnetic refrigeration and preparation method thereof |
| CN110168043A (en) * | 2016-12-28 | 2019-08-23 | 株式会社三德 | Rare earth cool storage material and regenerator and refrigeration machine with it |
| CN110993230A (en) * | 2019-11-05 | 2020-04-10 | 杭州电子科技大学 | Rare earth RE applied to low-temperature magnetic refrigeration2MnCuO6Material and preparation method |
Citations (2)
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|---|---|---|---|---|
| EP0978885A2 (en) * | 1998-08-06 | 2000-02-09 | International Superconductivity Technology Center | Superconductor of high electromagnetic force |
| CN1464869A (en) * | 2001-06-29 | 2003-12-31 | 财团法人国际超电导产业技术研究中心 | Method of joining oxide superconductor and oxide superconductor joiner |
-
2015
- 2015-04-20 CN CN201510189330.4A patent/CN104830284A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0978885A2 (en) * | 1998-08-06 | 2000-02-09 | International Superconductivity Technology Center | Superconductor of high electromagnetic force |
| CN1464869A (en) * | 2001-06-29 | 2003-12-31 | 财团法人国际超电导产业技术研究中心 | Method of joining oxide superconductor and oxide superconductor joiner |
Non-Patent Citations (4)
| Title |
|---|
| R. BURRIEL等: "Calorimetric study of the green phases R2BaCuO5(R = Gd, Dy, Ho, Er, Lu, Y)", 《JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS》 * |
| R.Z. LEVITIN等: "Two magnetic transitions and metamagnetism in the R2BaCuO5(R = Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb) compounds", 《JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS》 * |
| V.V.MOSHCHALKOV等: "MAGNETIC INTERACTIONS IN R2BaCuO 5 (R=Y,Sm,Eu,Gd,Dy,Ho,Er,Tm,Yb,LH)COMPOUNDS", 《SOLID STATE COMMUNICATION》 * |
| 唐勇柏等: "稀土系磁制冷材料的研究与发展", 《四川稀土》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347797A (en) * | 2015-10-10 | 2016-02-24 | 东北大学 | R2Cu2O5 oxide material used for low-temperature magnetic refrigeration and preparation method thereof |
| CN110168043A (en) * | 2016-12-28 | 2019-08-23 | 株式会社三德 | Rare earth cool storage material and regenerator and refrigeration machine with it |
| CN110993230A (en) * | 2019-11-05 | 2020-04-10 | 杭州电子科技大学 | Rare earth RE applied to low-temperature magnetic refrigeration2MnCuO6Material and preparation method |
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