CN105836755A - Gadolinium borate and preparation method and application thereof - Google Patents
Gadolinium borate and preparation method and application thereof Download PDFInfo
- Publication number
- CN105836755A CN105836755A CN201610167697.0A CN201610167697A CN105836755A CN 105836755 A CN105836755 A CN 105836755A CN 201610167697 A CN201610167697 A CN 201610167697A CN 105836755 A CN105836755 A CN 105836755A
- Authority
- CN
- China
- Prior art keywords
- boric acid
- preparation
- gadolinium
- acid gadolinium
- magnetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/127—Borates of heavy metals
-
- H—ELECTRICITY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention relates to gadolinium borate and a preparation method and application thereof. According to preparation of gadolinium borate, Gd<3+> is used as a raw material, and small molecular weight BO3<3-> is used as a ligand. The preparation method comprises the following steps: placing gadolinium oxide and boric acid into a quartz porcelain boat, grinding solids into powders, uniformly mixing, drying, transferring the quartz porcelain boat into a quartz tube furnace, heating to 400 DEG C and keeping the temperature for 10 h, heating to 1000 DEG C and keeping the temperature for 6h, cooling to room temperature to obtain a white powdery solid, washing and carrying out suction filtration, and drying to obtain gadolinium borate. The gadolinium borate which is white powdery crystal can be applied in preparation of magnetic refrigeration materials. Synthetic equipment is simple, and the preparation method is fast and easy to operate. The gadolinium borate is a borate compound and has very strong stability and good heat stability from a strong acid environment to a strong base environment. By raising mass ratio of rare earth to the ligand, magnetic density is raised, and magnetic refrigeration effect of the material is greatly enhanced.
Description
Technical field
The present invention relates to boric acid gadolinium, especially relate to boric acid gadolinium and preparation method and application.
Background technology
Traditional vapor compression refrigeration technology is widely used in daily life.But along with people's living standard
Improving constantly, the poor efficiency that traditional gas compression refrigerator has can not meet the requirement of people.Meanwhile, conventional refrigeration
Cold-producing medium freon used in machine also can heavy damage ozone layer, people start to seek a kind of novel Refrigeration Technique, have both
Energy-efficient and the big advantage of non-environmental-pollution two.1997, Ames Laboratory of USDOE found a kind of by Gd, Si, Ge
The alloy constituted can at room temperature demonstrate huge magnetothermal effect, and since then, Astronics Corp starts to research and develop one and do not uses
Compressor, and novel refrigerating machine based on magnet.Owing to it is compared with traditional vapor compression refrigeration refrigerator, has and need not pressure
The advantages such as contracting machine, noise is little, reliability is high in vibrations, working cycle length, efficient, pollution-free, operating temperature and cold scope are wide, because of
These people have put into more attention rate to magnetic refrigerating field, and magnetic refrigeration research is the most progressively to low temperature magnetic based on coordination compound
Refrigeration research transition.
One good magnetic refrigerating material must be had relatively great magnetic entropy variation value, and it requires that magnetic molecule has big spin
Ground state, little magnetic anisotropy, high magnetic density, suitable magnetic exchange and low-energy excite spin
(M.Evangelisti；O.Roubeau；E.Palacios；A.Camón；T.N.Hooper；E.K.Brechin；
J.J.Alonso；Cryogenic Magnetocaloric Effect in a Ferromagnetic Molecular Dimer
[J].Angew.Chem.Int.Ed.,2011,50,6606-6609.).And the metal complex molecular magnet of high-spin compares rare earth
Alloy, magnetic nanometer particles show bigger MCE value, particularly in very low temperature region territory, due to the long-range order of coordination compound, weak
Intermolecular interaction can avoid magnetic entropy become reduce (R.Sibille；T.Mazet；B.Malaman；M.Francois；A
Metal-Organic Framework as Attractive Cryogenic Magnetorefrigerant[J]
.Chem.Eur.J.；2012,18,12970-12973.).
Summary of the invention
It is an object of the invention to provide boric acid gadolinium and preparation method and application.
Described boric acid gadolinium is with Gd3+For raw material, the BO of small-molecular-weight3 3-For part.
The preparation method of described boric acid gadolinium is as follows:
Gadolinia., boric acid being placed in quartz porcelain boat, clayed into power by solid, mix homogeneously, after drying by quartz porcelain boat
Transfer in quartz tube furnace, be warming up to 400 DEG C and constant temperature 10h, then heat to 1000 DEG C and constant temperature 6h, be then cooled to room
Temperature, obtains white powder solid, then washs sucking filtration, the most i.e. obtains boric acid gadolinium (GdBO3), gained boric acid gadolinium is white powder
Crystal.
Described Gadolinia. can be 1: 1.5 with the mol ratio of boric acid；Described being clayed into power by solid can use agate mortar to incite somebody to action
Solid is clayed into power；The described heating rate being warming up to 400 DEG C can be 5 DEG C/h；The described heating rate being warming up to 1000 DEG C can
It is 100 DEG C/h；The described rate of temperature fall being cooled to room temperature can be 50 DEG C/h；Described washing can use dehydrated alcohol and deionization washing
Wash.
Crystal structure analysis: available X-ray powder diffractometer carries out crystal structure survey to boric acid gadolinium magnetic refrigerating material
Examination, test temperature is 298K.This material is by Gd3+And BO3 3-Carry out what coordination synthesis obtained.Can obtain from crystal structure analysis
Knowing, compound belongs to hexagonal crystal system, space group 6mm, and molecular formula is GdBO3, cell parameter is a=3.829, b=3.829, c=
8.89, V=112.9.
Having carried out magnetothermal effect research on Quantum Design SQUID MPMS gaussmeter, concrete scheme is as follows:
In 2～9K temperature ranges, test under the conditions of magnetic field 0～7T.Magnetic entropy curve is processed to obtain from method of approximation
Along with temperature reduction, magnetic field strengthen, the magnetic entropy value of boric acid gadolinium magnetic refrigerating material raises, and at T=3K, Δ H=7T, magnetic entropy value reaches
To maximum, 47.28J kg-1K-1(173.52mJ cm-3K-1), business can at applying a magnetic field Δ H=3T magnetic entropy up to 18.81J
kg-1K-1(69.13mJ cm-3K-1)。
Described boric acid gadolinium can be applied in preparing magnetic refrigerating material.
The present invention controls Gd3+And BO3 3-Be coordinated for part, simply prepare have under condition of ultralow temperature aobvious
Write the magnetic refrigerating material of magnetothermal effect.The present invention utilizes regulation and control reaction ratio, the method for experimental temperature controls Gd3+And BO3 3-It is main
Part be coordinated, carry out the preparation of Rare-Earth Magnetic refrigerating material, obtain boric acid gadolinium magnetic refrigerating material (GdBO3)。
The present invention selects has high spin ground state and the rare-earth Gd of less magnetic anisotropy3+As cation, select little point
The BO of son amount3 3-As part, improve the mass values of rare earth/part to improve magnetic density.It is a discovery of the invention that with rare-earth Gd3+With
BO3 3-Compound for part synthesis has high magnetic entropy under ultralow temperature, embodies its pole as low-temperature magnetic refrigeration material
Big potentiality, have important research and application prospect.
The remarkable advantage of the present invention is:
(1) boric acid gadolinium synthesizer is simple, and preparation method is quick, it is easy to operation, has bigger synthesis application prospect.
(2) boric acid gadolinium is borate compound, under from strong acid to strong alkali environment, all has extremely strong stability, thermally-stabilised
Property is good.
(3) boric acid gadolinium selects the rare-earth Gd 3+ with high spin ground state and less magnetic anisotropy as cation, selects
The BO of small-molecular-weight3 3-As major ligand, the mass values of raising rare earth/part, to improve magnetic density, makes the magnetic of material freeze
Effect has lifting greatly, and the magnetic entropy value under commercial magnetic field condition is higher than existing business magnetic refrigerating material.
The present invention utilizes rare-earth Gd3+As cation, select the BO of small-molecular-weight3 3-As part, prepare simply
Boric acid gadolinium magnetic refrigerating material.Research proves, such material has high magnetothermal effect under ultralow temperature, low-intensity magnetic field, is replacing costliness
Noble gas carry out the fields such as low temperature magnetic refrigeration and have broad application prospects.
Accompanying drawing explanation
The XRD spectra of Fig. 1 boric acid gadolinium magnetic refrigerating material.
The variable temperature magnetic susceptibility figure of Fig. 2 boric acid gadolinium magnetic refrigerating material.
The magnetic entropy change figure of Fig. 3 boric acid gadolinium magnetic refrigerating material.
Detailed description of the invention
The invention will be further described to combine accompanying drawing below by embodiment.
Embodiment 1
The preparation process of boric acid gadolinium magnetic refrigerating material: 0.5mmol Gadolinia., 1mmol boric acid are placed in quartz porcelain boat.Adopt
With agate mortar, solid is clayed into power, mix homogeneously, it is dried overnight.Porcelain boat is transferred to 120cm × Φ 50 quartz tube furnace
In, it is warming up to 400 DEG C and constant temperature 600min with the speed of 300 DEG C/h, is then warming up to 1000 DEG C and perseverance with the speed of 200 DEG C/h
Temperature 6h, is then cooled to room temperature with the speed of 50 DEG C/h, obtains white powder solid.Produce with dehydrated alcohol and deionized water wash
Thing, sucking filtration, it is dried overnight, obtains white powder crystal.
Embodiment 2
Structural characterization
The powder sample crystal structure of boric acid gadolinium magnetic refrigerating material uses Rigaku Ultima IV X-ray single crystal diffraction
Instrument is collected under 298K and is obtained.Fig. 1 is the XRD figure of boric acid gadolinium magnetic refrigerating material.From figure 1 it appears that the experiment of its XRD is spread out
Penetrate peak basically identical with the XRD data (straight line) according to mono-crystalline structures matching.Each characteristic diffraction peak peak shape is preferable, and baseline is more flat
Surely, illustrate sample without dephasign, purity is higher, and crystalline phase is good.
Boric acid gadolinium magnetic refrigerating material: belong to hexagonal crystal system, space group 6mm, molecular formula is GdBO3, cell parameter is a=
3.829, b=3.829, c=8.89, V=112.9.
Embodiment 3
Magnetic Test
Use Quantum Design SQUID MPMS gaussmeter to boric acid gadolinium magnetic refrigerating material temperature range be 2～
Test under the conditions of the external magnetic field of 300K and 1000Oe.Fig. 2 is the variable temperature magnetic susceptibility figure of boric acid gadolinium magnetic refrigerating material.And
In 2～10K temperature ranges, test under the conditions of magnetic field 0～7T.Fig. 3 is the magnetic entropy change figure of boric acid gadolinium magnetic refrigerating material.
Fig. 2 shows, at room temperature, and the χ of boric acid gadolinium magnetic refrigerating materialMT value is 7.62cm3mol-1K, and according to Curie's theorem
Calculate 1 Gd not coupled3+χ obtained by ionMT theoretical value 7.88cm3mol-1K is sufficiently close to.At 300～100K temperature models
In enclosing, along with temperature declines χMT value has almost no change, during less than 100K, and χMT value starts slowly to decline, along with temperature is the lowest,
χMT value declines the fastest, when temperature reaches 2K, and its χMT value is 6.25cm3K mol-1.In the range of 50～300K, to χMT～T
Curve be fitted according to Curie-weiss theorem, can obtain: Weiss constant θ=-3.76K, negative Weiss constant is also from side
Illustrate the anti-ferromagnetic coupling interaction of boric acid gadolinium magnetic refrigerating material.
Boric acid gadolinium magnetic refrigerating material magnetic entropy change can be according to Maxwell formula:
Estimate with the magnetization data (i.e. Fig. 3) of alternating temperature variable field, acquired results such as Fig. 3.
Fig. 3 shows, in the range of test, boric acid gadolinium magnetic refrigerating material reaches maximum-Δ Sm value when T=3K, Δ H=7T
47.28J kg-1K-1(173.52mJ cm-3K-1), business can at applying a magnetic field Δ H=3T magnetic entropy up to 18.81J kg-1K-1
(69.13mJ cm-3K-1).This value is less than with an isolated Gd3+(S=7/2) the theoretical value Δ Sm=nRln that ion calculates
(2s+1)/Mw=Rln (8)/Mw=80.02J kg-1K-1(293.68mJ cm-3K-1).Being likely due to of reduction of magnetic entropy value
The intermetallic antiferromagnetic reaction of compound causes.T=3K, Δ H=3T can be under applying a magnetic field range of condition, magnetic entropy variate is still
So up to 18.81J kg-1K-1(69.13mJ cm-3K-1)。
The present invention utilizes simple raw material, controls Gd by the method for regulation and control reaction ratio, experimental temperature3+And BO3 3-For part
It is coordinated, reacting by heating in high temperature resistant quartz ampoule, obtains boric acid gadolinium magnetic refrigerating material (GdBO3).Selection has high-spin
Ground state and the rare-earth Gd of less magnetic anisotropy3+As cation, the BO of small-molecular-weight3 3-As major ligand, improve rare earth/
The mass values of part, to improve magnetic density, makes the material magnetic refrigeration effect of synthesis have lifting greatly, at commercial magnetic field condition
Under magnetic entropy value higher than existing business magnetic refrigerating material, have great application prospect.
Claims (9)
1. boric acid gadolinium, it is characterised in that it is with Gd3+For raw material, the BO of small-molecular-weight3 3-For part.
2. the preparation method of boric acid gadolinium as claimed in claim 1, it is characterised in that it specifically comprises the following steps that
Gadolinia., boric acid are placed in quartz porcelain boat, solid is clayed into power, mix homogeneously, shifts quartz porcelain boat after drying
In quartz tube furnace, it is warming up to 400 DEG C and constant temperature 10h, then heats to 1000 DEG C and constant temperature 6h, be then cooled to room temperature,
Obtaining white powder solid, then wash sucking filtration, the most i.e. obtain boric acid gadolinium, gained boric acid gadolinium is white powder crystal.
3. the preparation method of boric acid gadolinium as claimed in claim 2, it is characterised in that described Gadolinia. is 1 with the mol ratio of boric acid:
1.5。
4. the preparation method of boric acid gadolinium as claimed in claim 2, it is characterised in that described being clayed into power by solid is to use Achates
Solid is clayed into power by mortar.
5. the preparation method of as claimed in claim 2 boric acid gadolinium, it is characterised in that described in be warming up to the heating rate of 400 DEG C be 5
℃/h。
6. the preparation method of as claimed in claim 2 boric acid gadolinium, it is characterised in that described in be warming up to the heating rate of 1000 DEG C and be
100℃/h。
7. the preparation method of as claimed in claim 2 boric acid gadolinium, it is characterised in that described in be cooled to the rate of temperature fall of room temperature be 50
℃/h。
8. the preparation method of boric acid gadolinium as claimed in claim 2, it is characterised in that described washing is with dehydrated alcohol and deionization
Water washs.
9. boric acid gadolinium is applied in preparing magnetic refrigerating material as claimed in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610167697.0A CN105836755A (en) | 2016-03-23 | 2016-03-23 | Gadolinium borate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610167697.0A CN105836755A (en) | 2016-03-23 | 2016-03-23 | Gadolinium borate and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105836755A true CN105836755A (en) | 2016-08-10 |
Family
ID=56583034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610167697.0A Pending CN105836755A (en) | 2016-03-23 | 2016-03-23 | Gadolinium borate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105836755A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277545A (en) * | 2021-05-12 | 2021-08-20 | 厦门大学 | Gadolinium fluorocarbonate, and preparation method and application thereof |
| CN115557513A (en) * | 2022-10-17 | 2023-01-03 | 中国科学院理化技术研究所 | Gadolinium-based borate compound, preparation and application thereof |
| CN117586755A (en) * | 2024-01-19 | 2024-02-23 | 镧明材料技术(上海)有限公司 | Refrigerating material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5484200A (en) * | 1977-12-16 | 1979-07-04 | Tokushiyu Muki Zairiyou Kenkiy | Neutron absorbent and its preparation |
| JPS56155281A (en) * | 1980-04-11 | 1981-12-01 | Toshiba Corp | Red-luminescent fluorescent substance |
| CN1780074A (en) * | 2004-11-28 | 2006-05-31 | 中国科学院福建物质结构研究所 | Laser crystal materials doped with thulium borate rolled aluminium, preparation and use thereof |
| CN1778999A (en) * | 2004-11-28 | 2006-05-31 | 中国科学院福建物质结构研究所 | Aluminium borate with non-linear optical materials |
| CN101831703A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Borate compound gadolinium-lanthanum-scandium borate and mono-crystal, preparation method and application thereof |
| CN102633276A (en) * | 2012-04-16 | 2012-08-15 | 浙江师范大学 | Preparation method of mono-disperse gadolinium borate nanometer crystal |
-
2016
- 2016-03-23 CN CN201610167697.0A patent/CN105836755A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5484200A (en) * | 1977-12-16 | 1979-07-04 | Tokushiyu Muki Zairiyou Kenkiy | Neutron absorbent and its preparation |
| JPS56155281A (en) * | 1980-04-11 | 1981-12-01 | Toshiba Corp | Red-luminescent fluorescent substance |
| CN1780074A (en) * | 2004-11-28 | 2006-05-31 | 中国科学院福建物质结构研究所 | Laser crystal materials doped with thulium borate rolled aluminium, preparation and use thereof |
| CN1778999A (en) * | 2004-11-28 | 2006-05-31 | 中国科学院福建物质结构研究所 | Aluminium borate with non-linear optical materials |
| CN101831703A (en) * | 2009-03-13 | 2010-09-15 | 中国科学院福建物质结构研究所 | Borate compound gadolinium-lanthanum-scandium borate and mono-crystal, preparation method and application thereof |
| CN102633276A (en) * | 2012-04-16 | 2012-08-15 | 浙江师范大学 | Preparation method of mono-disperse gadolinium borate nanometer crystal |
Non-Patent Citations (2)
| Title |
|---|
| RADHA VELCHURI ETC.: "Preparation and characterization of rare earth orthoborates, LnBO3 (Ln = Tb, La, Pr,Nd, Sm, Eu, Gd, Dy, Y) and LaBO3:Gd, Tb, Eu by metathesis reaction:ESR of LaBO3:Gd and luminescence of LaBO3:Tb, Eu", 《MATERIALS RESEARCH BULLETIN》 * |
| YAN-CONG CHEN ETC.: ""A brilliant cryogenic magnetic coolant: magnetic and magnetocaloric study of ferromagnetically coupled GdF3"", 《JOURNAL OF MATERIALS CHEMISTRY C》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277545A (en) * | 2021-05-12 | 2021-08-20 | 厦门大学 | Gadolinium fluorocarbonate, and preparation method and application thereof |
| CN115557513A (en) * | 2022-10-17 | 2023-01-03 | 中国科学院理化技术研究所 | Gadolinium-based borate compound, preparation and application thereof |
| CN115557513B (en) * | 2022-10-17 | 2024-01-23 | 中国科学院理化技术研究所 | Gadolinium-based borate compound, preparation and application thereof |
| CN117586755A (en) * | 2024-01-19 | 2024-02-23 | 镧明材料技术(上海)有限公司 | Refrigerating material and preparation method and application thereof |
| CN117586755B (en) * | 2024-01-19 | 2024-04-09 | 镧明材料技术(上海)有限公司 | Refrigerating material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Giant anisotropy of magnetocaloric effect in TbMnO 3 single crystals | |
| Chen et al. | Study of a magnetic-cooling material Gd (OH) CO 3 | |
| US20150033763A1 (en) | Material for magnetic refrigeration and magnetic refrigeration device | |
| CN105347797B (en) | R in freezing applied to low temperature magnetic2Cu2O5Oxide material and preparation method thereof | |
| CN115346744B (en) | Magnetic refrigeration material and preparation method and application thereof | |
| Zhu et al. | Magnetocaloric effect in layered perovskite manganese oxide La1. 4Ca1. 6Mn2O7 | |
| CN105836755A (en) | Gadolinium borate and preparation method and application thereof | |
| Wu et al. | Giant reversible magnetocaloric effect in orthorhombic GdScO3 | |
| Zhang et al. | Structural and cryogenic magnetic properties of rare earth rich RE 11 Co 4 In 9 (RE= Gd, Dy and Ho) intermetallic compounds | |
| CN115353149A (en) | Perovskite manganese oxide porous nanosphere and preparation method and application thereof | |
| Cheng et al. | Refrigeration effect of La (FeCoSi) 13B0. 25 compounds and gadolinium metal in reciprocating magnetic refrigerator | |
| Yang et al. | Large magnetic entropy change in weberite-type oxides Gd3MO7 (M= Nb, Sb, and Ta) | |
| CN102383018A (en) | Rare earth-chrome-silicone-based magnetic refrigerating material and preparation method thereof | |
| CN102127396B (en) | Magnetic refrigeration material compound prepared under high pressure and preparation method thereof | |
| CN103334043B (en) | Magnetic alloy serving as magnetic refrigeration material | |
| Huang et al. | Preparation, crystal structure and magnetocaloric properties of Tb 5 (Si x Ge 4− x) | |
| Cui et al. | Large reversible magnetocaloric effect in the ferromagnetic pyrochlores R2Mn2O7 (R= Dy, Ho, Yb) | |
| CN104830284A (en) | Application of rear-earth R2BaCuO5 oxide material to low-temperature magnetic refrigeration | |
| CN102383017B (en) | Preparation method for europium-based low-temperature magnetic refrigeration material of ThCr2Si2 structure | |
| Gschneidner Jr et al. | Magnetic refrigeration | |
| CN113277545B (en) | Gadolinium fluorocarbonate, and preparation method and application thereof | |
| CN103468224B (en) | The application in low temperature magnetic freezes of a kind of rare earth RPdIn material | |
| CN104531085A (en) | Application of gadolinium hydroxide | |
| CN102465225A (en) | Magnetic refrigerant material, its preparation method and application | |
| CN112175587A (en) | Application of gadolinium carbonate dihydrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160810 |
|
| RJ01 | Rejection of invention patent application after publication |