CN101462759A - Preparation of rare-earth oxide nano magnetic refrigeration material - Google Patents
Preparation of rare-earth oxide nano magnetic refrigeration material Download PDFInfo
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- CN101462759A CN101462759A CNA200810219040XA CN200810219040A CN101462759A CN 101462759 A CN101462759 A CN 101462759A CN A200810219040X A CNA200810219040X A CN A200810219040XA CN 200810219040 A CN200810219040 A CN 200810219040A CN 101462759 A CN101462759 A CN 101462759A
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Abstract
The invention relates to a method for preparing a rare earth oxide nano magnetic refrigerant material. The method comprises: mixing LaCO3, MnCO3, diethylenetriamine pentaacetic acid and glycol, adding deionized water into the mixture, heating and stirring the mixture for dissolution, filtering the mixture and obtaining a noncrystal precursor by drying; and placing the precursor in a box type resistance furnace for heating treatment, controlling the heating speed and temperature, keeping the temperature and then cooling the precursor to obtain the rare earth oxide nano magnetic refrigerant material. The method is simple in technical process, good in repeatability, low in crystallization and sintering temperature, adjustable in metal element proportion according to requirement and low in cost.
Description
Technical field
The present invention relates to magnetic refrigerating function material field, particularly a kind of preparation method of perovskite structure rare-earth oxide nano magnetic refrigeration material.
Background technology
The perovskite structure rare earth oxide, also is attended by huge magnetic entropy and becomes distinctive huge magneto-resistance effect the time owing to the strong current carrier of intrinsic-spin coupling presents.In addition the perovskite structure rare earth oxide have chemical stability height, resistivity big, be easy to make, cost is low and light specific gravity, advantage such as nontoxic, is a kind of rising magnetic refrigeration working substance.Therefore, Chinese scholars is carried out extensive studies to the preparation and the magnetothermal effect of perovskite structure rare earth oxide.
Traditional perovskite structure rare earth oxide material generally all adopts the preparation of solid reaction process, this method needs higher crystallizing and sintering temperature (being generally 1000 ℃-1600 ℃) and long time and multiple high temp sintering just can obtain single-phase sample usually, particle size is a micron order, and size is difficult to control.In order to remedy the deficiency of this traditional preparation process method, people such as Vazquez [C.V.Vazquez, M.C.Blanco, M.A.L.Quintela, etal.J.Mater.Chem.8 (1998) 99] to propose with the citric acid be the sol-gel processing of metal ion network and agent, utilize metal alkoxide decomposition and polymerization at low temperatures to generate gel, sintering under lower sintering temperature (800 ℃-1000 ℃) is prepared evengranular sodium rice perovskite structure rare earth oxide material then.But work as adulterated component element more for a long time, the difficult control of the preparation technology of sample.And the stability of used alkoxide is generally lower in the preparation process, and the composition of hydrolysate is subjected to the influence of hydrolytic process.Therefore, people such as B.Liu [J.B.Liu, H.Wang, M.K.Zhu, etal.Materials Research Bulletin, 2003,38:817-822] adopt hydrothermal synthesis method under 200-240 ℃ low temperature, to prepare perovskite structure nanometer rare earth oxide material, but the synthetic difficulty that exists of hydro-thermal mainly is that the multicomponent complex system is easy to generate not pure phase, the crystalline condition of product is poor, and the distribution of sizes of product is inhomogeneous etc., and this will cause very big influence to the magnetothermal effect of material.Mainly be that the multicomponent complex system is easy to generate not pure phase, the crystalline condition of product is poor, and the distribution of sizes of product is inhomogeneous etc., and this will cause very big influence to the magnetothermal effect of material.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, the preparation method that a kind of low cost, preparation technology are simple, be suitable for the good magnetothermal effect perovskite structure rare-earth oxide nano magnetic refrigeration material of having of suitability for industrialized production is provided.
Method of the present invention may further comprise the steps:
(1) takes by weighing LaCO by stoichiometric ratio
3, MnCO
3, and it is mixed;
(2) by the total metal ion of said mixture: amido poly carboxylic acid title complex: the ethylene glycol mol ratio is that mix 1:1.1～1.5:1～1.5, add appropriate amount of deionized water at said mixture, be heated to 75～85 ℃ and stir make mixture all dissolving obtain clear solution, solution filters the back and is being lower than slowly evaporation under 60 ℃ the condition, remove excessive aqueous solvent up to forming transparent glass state material, after obtain non-crystalline state title complex presoma after 48～56h drying;
(3) the above-mentioned described title complex presoma that makes is put into alumina crucible, place chamber type electric resistance furnace thermal treatment, at first stove is heated to 500～600 ℃, insulation 1～2h with 5～10 ℃/minute rate of heating, after then sample being taken out cooling, being pressed into φ is the 10mm thin slice.Again this thin slice is put into chamber type electric resistance furnace, with 15～20 ℃/minute rate of heating stove is heated to 600 ℃～1000 ℃, being incubated 2～10 hours. outage stops heating, treats stove cooling back taking-up sample, can obtain the perovskite structure rare-earth oxide nano magnetic refrigeration material.
The alkaline earth carbide of univalent alkaline earth carbide, divalence or LnCO
3(carbonate of Ln-light rare earths or heavy rare earths) can partly replace above-mentioned used LaCO
3Amido poly carboxylic acid title complex is H
5DTPA.
The present invention compared with prior art has following advantage and effect:
(1) technological process is simple relatively, good reproducibility.
(2) adopt amido poly carboxylic acid title complex thermolysis process can realize that the homogeneous phase on the multiple metal ion atomic level mixes, the crystallizing and sintering temperature is low.
(3) ratio of each metallic element can be adjusted arbitrarily as requested, forms the stoichiometry perovskite structure rare-earth oxide nano magnetic refrigeration material of non-stoichiometric when easily.
Embodiment
Embodiment 1
LaCO
3, DyCO
3, SrCO
3,, MnCO
3By stoichiometric ratio is that 0.57:0.1:0.33:1 mixes, and adds the H of 2.4 mole numbers then in this mixture respectively
5The ethylene glycol of DTPA and 2 mole numbers.Said mixture is added appropriate amount of deionized water, be heated to 80 ℃ and stir make mixture all dissolving obtain clear solution, solution filters the back 60 ℃ of slowly evaporations down, remove excessive aqueous solvent up to forming transparent glass state material, after obtain non-crystalline state title complex presoma after the 48h drying.At first stove is heated to 500 ℃ with 10 ℃/minute rate of heating, insulation 2h, then sample is taken out cooling after, being pressed into φ is the 10mm thin slice.Again this thin slice to be put into chamber type electric resistance furnace, stove is heated to 800 ℃, be incubated 6 hours with 18 ℃/minute rate of heating. outage stops heating, treats stove cooling back taking-up sample.Under high resolution transmission electron microscopy the microtexture of observation sample as shown in Figure 1, particle size is 40-50nm.Magnetic performance to above-mentioned sample on superconducting quantum interference device (SQUID) is measured, and the Curie temperature of sample is 358K, the maximum 4.39J/kg.K of sample under 5T magnetic field; Maximum 1.76J/kg.K under 2T magnetic field.
Embodiment 2
LaCO
3, GdCO
3, SrCO
3,, MnCO
3By stoichiometric ratio is that 0.47:0.2:0.33:1 mixes, and adds the H of 3 mole numbers then in this mixture respectively
5The ethylene glycol of DTPA and 2.4 mole numbers.Said mixture is added appropriate amount of deionized water, be heated to 80 ℃ and stir make mixture all dissolving obtain clear solution, solution filters the back 60 ℃ of slowly evaporations down, remove excessive aqueous solvent up to forming transparent glass state material, after obtain non-crystalline state title complex presoma after the 54h drying.At first stove is heated to 500 ℃ with 8 ℃/minute rate of heating, insulation 1h, then sample is taken out cooling after, being pressed into φ is the 10mm thin slice.Again this thin slice to be put into chamber type electric resistance furnace, stove is heated to 800 ℃ ℃, be incubated 10 hours with 15 ℃/minute rate of heating. outage stops heating, treats stove cooling back taking-up sample.The particle size of observation sample is 80-100nm under high resolution transmission electron microscopy, and the magnetic performance to above-mentioned sample on superconducting quantum interference device (SQUID) is measured, and the Curie temperature of sample is 285K, the maximum 4.9J/kg.K of sample under 5T magnetic field; Maximum 1.96J/kg.K under 2T magnetic field.
Embodiment 3
LaCO
3, CeCO
3, SrCO
3,, MnCO
3By stoichiometric ratio is that 0.57:0.1:0.33:1 mixes, and adds the H of 2.6 mole numbers then in this mixture respectively
5The ethylene glycol of DTPA and 3 mole numbers.Said mixture is added appropriate amount of deionized water, be heated to 80 ℃ and stir make mixture all dissolving obtain clear solution, solution filters the back 60 ℃ of slowly evaporations down, remove excessive aqueous solvent up to forming transparent glass state material, after obtain non-crystalline state title complex presoma after the 56h drying.At first stove is heated to 500 ℃ with 5 ℃/minute rate of heating, insulation 1.5h, then sample is taken out cooling after, being pressed into φ is the 10mm thin slice.Again this thin slice to be put into chamber type electric resistance furnace, stove is heated to 1000 ℃, be incubated 10 hours with 18 ℃/minute rate of heating. outage stops heating, treats stove cooling back taking-up sample.The particle size of observation sample is 140-150nm under high resolution transmission electron microscopy, and the magnetic performance to above-mentioned sample on superconducting quantum interference device (SQUID) is measured, and the Curie temperature of sample is 368K, the maximum 3.24J/kg.K of sample under 5T magnetic field; Maximum 1.16J/kg.K under 2T magnetic field.
Claims (4)
1, a kind of preparation method of rare-earth oxide nano magnetic refrigeration material is characterized in that comprising the steps:
(1) takes by weighing LaCO by stoichiometric ratio
3, MnCO
3, and it is mixed;
(2) by the total metal ion of said mixture: amido poly carboxylic acid title complex: the ethylene glycol mol ratio is that mix 1:1.1～1.5:1～1.5, add appropriate amount of deionized water at said mixture, be heated to 75～85 ℃ and stir make mixture all dissolving obtain clear solution, solution filters the back and is being lower than slowly evaporation under 60 ℃ the condition, remove excessive aqueous solvent up to forming transparent glass state material, after obtain non-crystalline state title complex presoma after 48～56h drying;
(3) the above-mentioned described title complex presoma that makes is put into alumina crucible, place chamber type electric resistance furnace thermal treatment, at first stove is heated to 500～600 ℃, insulation 1～2h with 5～10 ℃/minute rate of heating, after then sample being taken out cooling, being pressed into φ is the 10mm thin slice.Again this thin slice is put into chamber type electric resistance furnace, with 15～20 ℃/minute rate of heating stove is heated to 600 ℃～1000 ℃, be incubated outage in 2～10 hours and stop heating, treat stove cooling back taking-up sample, can obtain the perovskite structure rare-earth oxide nano magnetic refrigeration material.
2, the preparation method of a kind of rare-earth oxide nano magnetic refrigeration material according to claim 1 is characterized in that described amido poly carboxylic acid title complex is H
5DTPA..
3, the preparation method of a kind of rare-earth oxide nano magnetic refrigeration material according to claim 1 is characterized in that described LaCO
3Can part be replaced by the alkaline earth carbide of univalent alkaline earth carbide and divalence.
4. the preparation method of a kind of rare-earth oxide nano magnetic refrigeration material according to claim 1, LaCO
3Can be partly by LnCO
3, Ln-light rare earths or heavy rare earths carbonate replace.
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| CNA200810219040XA CN101462759A (en) | 2008-11-06 | 2008-11-06 | Preparation of rare-earth oxide nano magnetic refrigeration material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358248A (en) * | 2018-04-10 | 2018-08-03 | 武汉理工大学 | Ln0.3Sr0.7Fe0.7Cr0.3O3-δThe synthetic method of ion-electron mixed conductor material |
| CN110088224A (en) * | 2016-12-22 | 2019-08-02 | 株式会社三德 | Cool storage material and its manufacturing method, regenerator and refrigeration machine |
| CN112175587A (en) * | 2020-10-20 | 2021-01-05 | 厦门大学 | Application of gadolinium carbonate dihydrate |
-
2008
- 2008-11-06 CN CNA200810219040XA patent/CN101462759A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110088224A (en) * | 2016-12-22 | 2019-08-02 | 株式会社三德 | Cool storage material and its manufacturing method, regenerator and refrigeration machine |
| CN108358248A (en) * | 2018-04-10 | 2018-08-03 | 武汉理工大学 | Ln0.3Sr0.7Fe0.7Cr0.3O3-δThe synthetic method of ion-electron mixed conductor material |
| CN108358248B (en) * | 2018-04-10 | 2020-01-31 | 武汉理工大学 | Ln0.3Sr0.7Fe0.7Cr0.3O3-δSynthesis method of ion-electron mixed conductor material |
| CN112175587A (en) * | 2020-10-20 | 2021-01-05 | 厦门大学 | Application of gadolinium carbonate dihydrate |
| CN112175587B (en) * | 2020-10-20 | 2021-08-17 | 厦门大学 | Application of gadolinium carbonate dihydrate |
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