CN115341262B - Gadolinium-based borate crystal and preparation method and application thereof - Google Patents

Gadolinium-based borate crystal and preparation method and application thereof Download PDF

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CN115341262B
CN115341262B CN202210906326.5A CN202210906326A CN115341262B CN 115341262 B CN115341262 B CN 115341262B CN 202210906326 A CN202210906326 A CN 202210906326A CN 115341262 B CN115341262 B CN 115341262B
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gadolinium
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borate crystal
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CN115341262A (en
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涂衡
陈语葳
沈俊
戴巍
李振兴
张国春
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Technical Institute of Physics and Chemistry of CAS
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    • C—CHEMISTRY; METALLURGY
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
    • C—CHEMISTRY; METALLURGY
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    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
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Abstract

The invention discloses a gadolinium-based borate crystal, a preparation method and application thereof, wherein the chemical formula of the gadolinium-based borate crystal is Ba 5 Gd 3 (BO 3 ) 6 F, the crystal belongs to monoclinic system, and the space group is P2 1 And/c, the unit cell parameters are as follows: α=γ=90°, β= 99.116 (7) °, z=1. The gadolinium-based borate crystal provided by the invention belongs to paramagnetic materials, has negligible hysteresis effect, and is particularly 3K, delta mu 0 Under the condition of h=9t, the maximum magnetic entropy change value is 29.86J kg ‑1 K ‑1 Therefore, the crystalline material has great potential as a magnetic refrigerant. In addition, the invention further provides a preparation method of the gadolinium-based borate crystal, which is convenient and quick, is easy to operate and has a large industrial application prospect.

Description

Gadolinium-based borate crystal and preparation method and application thereof
Technical Field
The invention relates to the technical field of magnetic refrigeration materials. More particularly, to a gadolinium-based borate crystal, a preparation method and application thereof.
Background
The magnetocaloric effect is an inherent property of all magnetic materials. The magnetic refrigeration material mainly depends on isothermal magnetization and adiabatic demagnetization processes to realize cooling of the surrounding environment: when the externally applied magnetic field is zero, the magnetic moment direction in the material is disordered, and the magnetic entropy is larger; applying a magnetic field under isothermal conditions, enabling the magnetic moment orientation to be consistent, reducing magnetic entropy, enabling the adiabatic temperature of a system to rise by applying work to materials by the magnetic field, and releasing heat to the environment; and then the external magnetic field is removed under the adiabatic condition, the magnetic moment is restored to a disordered state, the magnetic entropy is increased, the adiabatic temperature of the system is reduced, and the heat is absorbed into the external environment, so that the aim of refrigeration is fulfilled. The magnetic refrigeration technology is a technology based on the magnetocaloric effect (MCE) of materials to obtain extremely low temperature, has the advantages of high efficiency, low energy consumption and green environmental protection compared with the traditional refrigeration technology, and is known as the green refrigeration technology, so that the technology is also valued in various countries of the world.
The choice of magnetic refrigeration material requires that the magnetic molecules have a large spin ground state, a small magnetic anisotropy, a high magnetic density, a suitable magnetic exchange, and a low energy excited spin state. Gd (Gd) 3+ The ion has a half-full 4f electron shell layer, the ground state is spin-big, the magnetic anisotropy is negligible, and the gadolinium-based compound can be used as a good low-temperature magnetic refrigeration material. Therefore, the invention aims to provide a novel gadolinium-based boric acid paramagnetic salt crystal material with a large application prospect in the field of magnetic refrigeration materials.
Disclosure of Invention
A first object of the present invention is to provide a gadolinium based borate crystal.
The second object of the invention is to provide a method for preparing gadolinium borate crystal.
A third object of the present invention is to provide the use of gadolinium based borate crystals as magnetic refrigeration material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a gadolinium based borate crystal having the formula Ba 5 Gd 3 (BO 3 ) 6 F。
Further, the gadolinium borate crystal is monoclinic, and the space group is P2 1 And/c, the unit cell parameters are as follows: α＝γ＝90°，β＝99.116(7)°，Z＝1。
wherein, rare earth ion Gd 3+ Has a high spin ground state and a small magnetic anisotropy, but is a magnetic cationic Gd 3+ The invention selects ligand with small volume and relative molecular mass, which can provide as much filling space for magnetic cations with larger volume when constructing compound basic frame, and ensure that certain interval exists between magnetic cations to have less magnetic interaction, and the mass ratio of rare earth/ligand is improved to improve crystal magnetic density. In addition, small molecular weight BO 3 3- As a ligand, the processing difficulty of the crystal in the practical application process can be reduced, and the refrigeration stability of the crystal can be improved.
In a second aspect, the present invention provides a method for preparing the gadolinium borate crystal, comprising the steps of:
uniformly mixing a Ba-containing compound, a Gd-containing compound, a B-containing compound and an F-containing compound, uniformly heating to 650-700 ℃ in an aerobic environment, presintering at a constant temperature, cooling for one time, and grinding; and (3) in a vacuum environment, heating to 800-810 ℃ again at a constant speed, reacting at a constant temperature, cooling for the second time, and grinding to obtain gadolinium-based borate crystals.
Further, in the above method, the molar ratio of Ba, gd, B and F in the Ba-containing compound, gd-containing compound, B-containing compound and F-containing compound is 4-6:2-4:5-7:1; preferably 5:3:6:1. Wherein, the proportion of the raw materials is in the range of the invention, and the proportion of the impurity phase of the target product can be further reduced.
The Ba-containing compound is carbonate containing Ba or fluoride containing Ba.
The Gd-containing compound is an oxide containing Gd.
The B-containing compound is H 3 BO 3 Or B is a 2 O 3 。
The F-containing compound is BaF 2 。
The temperature rising speed of the uniform temperature rising or the uniform temperature rising again is 30 ℃/h to 40 ℃/h.
The constant-temperature presintering time is 1d-3d. Wherein the constant temperature calcination aims at removing H in the reactant 2 O and CO 2 And a preliminary solid phase reaction is carried out, the aerobic environment being preferably an air atmosphere.
The primary cooling is performed at a cooling rate of 40 ℃/h to 50 ℃/h.
The secondary cooling is performed at a cooling rate of 30 ℃/h to 40 ℃/h.
In a fifth aspect, the present invention provides the use of a gadolinium based borate crystal as described above as a magnetic refrigeration material.
It should be noted that any range recited in the present invention includes any value between the endpoints and any sub-range formed by any value between the endpoints or any value between the endpoints unless specifically stated otherwise. The preparation processes according to the invention are conventional processes unless otherwise indicated, and the starting materials used are commercially available from the public sources or are prepared according to the prior art.
The beneficial effects of the invention are that
1) The gadolinium-based borate crystal provided by the invention belongs to paramagnetic salt materials, has negligible hysteresis effect, and has higher refrigeration efficiency when being used as a magnetic refrigeration material.
2) The gadolinium borate crystal provided by the invention has the following structure that the gadolinium borate crystal is 3K, delta mu 0 The maximum magnetic entropy change value shown under the condition of h=9t is 29.86J kg -1 K -1 Has great potential in being used as magnetic refrigerant.
3) The preparation method of the gadolinium-based borate crystal is convenient and quick, is easy to operate and has a large application prospect.
Drawings
FIG. 1 shows Ba prepared in example 1 5 Gd 3 (BO 3 ) 6 XRD pattern of F crystal.
FIG. 2 shows Ba prepared in example 1 5 Gd 3 (BO 3 ) 6 F structural schematic diagram of crystal.
FIG. 3 shows the process of example 1Prepared Ba 5 Gd 3 (BO 3 ) 6 Infrared spectrogram of the F crystal.
FIG. 4 shows Ba prepared in example 1 5 Gd 3 (BO 3 ) 6 Thermal weight graph of F crystal.
FIG. 5 shows Ba prepared in example 1 5 Gd 3 (BO 3 ) 6 F, a temperature change susceptibility curve and a Curie-Curie fitting curve of the crystal.
FIG. 6 shows Ba prepared in example 1 5 Gd 3 (BO 3 ) 6 And F, changing the temperature and changing the field magnetization intensity of the crystal.
FIG. 7 shows Ba prepared in example 1 5 Gd 3 (BO 3 ) 6 Arrott plot of F crystals.
FIG. 8 shows Ba prepared in example 1 5 Gd 3 (BO 3 ) 6 And F, magnetic entropy change diagram of the crystal.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration only and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and adaptations can be made by those skilled in the art in light of the foregoing disclosure. Embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Example 1
Preparing powdered Ba by high-temperature solid phase method 5 Gd 3 (BO 3 ) 6 F crystal comprising the steps of:
BaCO is weighed 3 ：2.22g(11.25mmol)，BaF 2 ：0.22g(1.25mmol)，Gd 2 O 3 ：1.36g(3.75mmol)，B 2 O 3 :0.52g (7.5 mmol) of the mixture is uniformly mixed, the mixture is filled into an open platinum crucible with phi of 20mm multiplied by 20mm, compacted, placed into a muffle furnace, heated to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintered for 2d at a constant temperature, cooled to room temperature at a rate of 50 ℃/h, and ground to obtain a preliminary presintered product. Pouring the presintered product into quartzVacuum sealing in glass tube, heating to 810 deg.C at 30 deg.C/h in muffle furnace, reacting at constant temperature for 2d, cooling to room temperature at 40 deg.C/h, grinding to obtain Ba 5 Gd 3 (BO 3 ) 6 Powder sample of F crystals.
Ba prepared in this example 5 Gd 3 (BO 3 ) 6 The F crystal samples were tested as follows:
structural characterization:
XRD was used for the Ba obtained in this example 5 Gd 3 (BO 3 ) 6 F crystal is characterized, and the result is shown in FIG. 1, in which Ba 5 Gd 3 (BO 3 ) 6 F is monoclinic system, and the space group is P2 1 And/c, the unit cell parameters are as follows: α＝γ＝90°，β＝99.116(7)°，Z＝1。
ba prepared in this example 5 Gd 3 (BO 3 ) 6 The F structure is schematically shown in FIG. 2.
FIG. 3 shows the Ba obtained in this example 5 Gd 3 (BO 3 ) 6 F crystal infrared spectrum characterization result, BO is shown in the figure 3 3- Asymmetric stretching vibration peaks of 1265, 1213 and 1165cm -1 ，BO 3 3- The symmetrical telescopic vibration peak of (C) is 916cm -1 ，BO 3 3- Bending vibration peaks at 740 and 586cm -1 . The infrared spectrum shows Ba 5 Gd 3 (BO 3 ) 6 The coordination mode of B in the F crystal is BO 3 Is matched with the actual structure.
Thermal stability test:
the Ba is 5 Gd 3 (BO 3 ) 6 The thermogravimetric analysis result of the F crystal is shown in FIG. 4, which shows that the crystal material has good stability in the temperature range from room temperature to the melting point of 1235 ℃, and no phase change exists toAnd loss of quality.
Magnetic testing:
the following magnetocaloric effect study was performed with a Quantum Design PPMS-9 complex system in the range of 2K-300K under a magnetic field of 0T-9T:
ba is measured under the condition of temperature range of 2K-300K and magnetic field range of 0-9T 5 Gd 3 (BO 3 ) 6 The temperature change magnetic susceptibility and the temperature change magnetic susceptibility reciprocal curve of the F crystal are shown in figure 5. The reciprocal curve of the variable-temperature magnetic susceptibility is linearly fitted according to the Curie-Curie theorem, so that the compound is a paramagnetic salt material, and C=7.56 emu K mol -1 θ=0.98K, and a positive gaussian constant indicates Ba 5 Gd 3 (BO 3 ) 6 The extremely weak ferromagnetic coupling effect of the F crystal is suitable for being used as a magnetic refrigeration material.
Ba measured at a temperature ranging from 2K to 10K and a magnetic field ranging from 0 to 9T 5 Gd 3 (BO 3 ) 6 The temperature and field magnetization diagram of the F crystal is shown in fig. 6. The curve shows that Ba as the strength of the magnetic field increases 5 Gd 3 (BO 3 ) 6 The magnetization of the F crystal gradually increases and reaches a saturation value of 6.72N mu at a temperature of 2K and a magnetic field of 9T Β And theoretical value 7N mu Β Is very close.
Ba 5 Gd 3 (BO 3 ) 6 The phase change type of the F crystal can be according to Banerjee criterion: the magnetization data of the variable temperature and variable field are used for estimation, the obtained result is shown as an Arrott curve in FIG. 7, the slope of each point on the curve is positive, and the magnetic phase transition of the crystal material is indicated to belong to the second-level magnetic phase transition.
Ba 5 Gd 3 (BO 3 ) 6 The change in magnetic entropy of the F crystal can be according to the Maxwell formula: the magnetization data of the temperature and field change are used for estimation, the obtained result is shown as a magnetic entropy curve in fig. 8, and the crystal material in the test range is 3K, delta mu 0 The maximum magnetic entropy change value of 29.86J kg is shown when H=9T -1 K -1 。
Example 2
Preparing powdered Ba by high-temperature solid phase method 5 Gd 3 (BO 3 ) 6 F crystal comprising the steps of:
BaCO is weighed 3 ：2.22g(11.25mmol)，BaF 2 ：0.22g(1.25mmol)，Gd 2 O 3 ：1.36g(3.75mmol)，H 3 BO 3 : mixing 0.93g (15 mmol), loading into an open platinum crucible with phi 20mm multiplied by 20mm, compacting, placing into a muffle furnace, heating to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintering at a constant temperature for 2d, cooling to room temperature at a rate of 50 ℃/h, and grinding to obtain a preliminary presintering product. Pouring the presintered product into a quartz glass tube, vacuumizing and sealing, placing into a muffle furnace, heating to 810 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 5 Gd 3 (BO 3 ) 6 Powder sample of F crystals.
XRD was used for the Ba obtained in this example 5 Gd 3 (BO 3 ) 6 The F crystal was characterized and the results were substantially identical to example 1.
Example 3
Preparing powdered Ba by high-temperature solid phase method 5 Gd 3 (BO 3 ) 6 F crystal comprising the steps of:
BaCO is weighed 3 ：2.22g(11.25mmol)，BaF 2 ：0.22g(1.25mmol)，Gd 2 O 3 ：1.36g(3.75mmol)，H 3 BO 3 :0.46g (7.5 mmol) and B 2 O 3 :0.26g (3.75 mmol) of the mixture is uniformly mixed, the mixture is filled into an open platinum crucible with phi 20mm multiplied by 20mm, compacted and put into a muffle furnace, the temperature is raised to 700 ℃ at a heating rate of 30 ℃/h in an air environment, the mixture is presintered for 2d at a constant temperature, then the mixture is cooled to room temperature at a rate of 50 ℃/h, and the preliminary presintered product is obtained after grinding. Pouring the presintered product into a quartz glass tube, vacuumizing and sealing, placing into a muffle furnace, heating to 810 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 5 Gd 3 (BO 3 ) 6 Powder sample of F crystals.
XRD was used for the Ba obtained in this example 5 Gd 3 (BO 3 ) 6 The F crystal was characterized and the results were substantially identical to example 1.
Example 4
Preparing powdered Ba by high-temperature solid phase method 5 Gd 3 (BO 3 ) 6 F crystal comprising the steps of:
BaCO is weighed 3 ：2.22g(11.25mmol)，BaF 2 ：0.22g(1.25mmol)，Gd 2 O 3 ：1.36g(3.75mmol)，H 3 BO 3 :0.46g (7.5 mmol) and B 2 O 3 :0.26g (3.75 mmol) of the mixture is uniformly mixed, the mixture is filled into an open platinum crucible with phi 20mm multiplied by 20mm, compacted and put into a muffle furnace, the temperature is raised to 700 ℃ at a heating rate of 30 ℃/h in an air environment, the mixture is presintered for 1d at a constant temperature, then the mixture is cooled to room temperature at a rate of 50 ℃/h, and the mixture is ground to obtain a preliminary presintered product. Pouring the presintered product into a quartz glass tube, vacuumizing and sealing, placing into a muffle furnace, heating to 810 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain Ba 5 Gd 3 (BO 3 ) 6 Powder sample of F crystals.
XRD was used for the Ba obtained in this example 5 Gd 3 (BO 3 ) 6 Characterization was performed with F, and the results were substantially identical to example 1.
Comparative example 1
The method for preparing the crystal by adopting the high-temperature solid phase method comprises the following steps:
BaCO is weighed 3 ：2.96g(15mmol)，Gd 2 O 3 ：1.45g(4mmol)，GdF 3 :0.21g (1 mmol) and B 2 O 3 :0.63g (9 mmol) of the mixture is uniformly mixed, the mixture is filled into an open platinum crucible with phi 20mm multiplied by 20mm, the mixture is compacted and put into a muffle furnace, the temperature is raised to 700 ℃ at a heating rate of 30 ℃/h in an air environment, the mixture is presintered for 1d at a constant temperature, then the mixture is cooled to room temperature at a rate of 50 ℃/h, and a preliminary presintered product is obtained after grinding. And pouring the presintered product into a quartz glass tube, vacuumizing and sealing, putting into a muffle furnace, heating to 810 ℃ at a heating rate of 30 ℃/h, reacting at a constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sample.
Characterization of the powder sample obtained in this example by XRD revealed that XRD of the powder sample in this example was not consistent with that in example 1, i.e., the target product Ba could not be synthesized 5 Gd 3 (BO 3 ) 6 And F, crystal.
Comparative example 2
The method for preparing the crystal by adopting the high-temperature solid phase method comprises the following steps:
BaCO is weighed 3 ：2.22g(11.25mmol)，BaCl 2 ：0.26g(1.25mmol)，Gd 2 O 3 ：1.36g(3.75mmol)，B 2 O 3 :0.52g (7.5 mmol) of the mixture is uniformly mixed, the mixture is filled into an open platinum crucible with phi of 20mm multiplied by 20mm, compacted, placed into a muffle furnace, heated to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintered for 2d at a constant temperature, cooled to room temperature at a rate of 50 ℃/h, and ground to obtain a preliminary presintered product. And pouring the presintered product into a quartz glass tube, vacuumizing and sealing, putting into a muffle furnace, heating to 810 ℃ at a heating rate of 30 ℃/h, reacting at a constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sample.
Characterization of the powder sample obtained in this example by XRD revealed that the XRD spectrum of the powder sample in this example is not identical to that of example 1, i.e., the target product Ba could not be synthesized 5 Gd 3 (BO 3 ) 6 And F, crystal.
Comparative example 4
The method for preparing the crystal by adopting the high-temperature solid phase method comprises the following steps:
BaCO is weighed 3 ：2.22g(11.25mmol)，BaF 2 ：0.22g(1.25mmol)，Gd 2 O 3 ：1.36g(3.75mmol)，B 2 O 3 :0.52g (7.5 mmol) of the mixture is uniformly mixed, the mixture is filled into an open platinum crucible with phi of 20mm multiplied by 20mm, compacted, placed into a muffle furnace, heated to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintered for 2d at a constant temperature, cooled to room temperature at a rate of 50 ℃/h, and ground to obtain a preliminary presintered product. Pouring the presintered product into a quartz glass tube in air, placing into a muffle furnace, heating to 810 ℃ at a heating rate of 30 ℃/h, reacting at constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sampleThe product is obtained.
Characterization of the powder sample obtained in this example by XRD revealed that the XRD spectrum of the powder sample in this example is not identical to that of example 1, i.e., the target product Ba could not be synthesized 5 Gd 3 (BO 3 ) 6 And F, crystal.
Comparative example 5
The preparation method of the crystal by adopting the aqueous solution method comprises the following steps:
BaCO is weighed 3 ：2.22g(11.25mmol)，BaF 2 ：0.22g(1.25mmol)，Gd 2 O 3 ：1.36g(3.75mmol)，B 2 O 3 :0.52g (7.5 mmol) was mixed and placed in a 100mL glass beaker, dissolved in 40% strength by volume concentrated nitric acid, and placed in an oven at 200℃until oven-dried. Placing the obtained white powder into an open platinum crucible with the diameter of 20mm multiplied by 20mm, compacting the white powder, placing the compact powder into a muffle furnace, heating the compact powder to 700 ℃ at a heating rate of 30 ℃/h in an air environment, presintering the compact powder at a constant temperature for 2d, cooling the compact powder to room temperature at a rate of 50 ℃/h, and grinding the compact powder to obtain a preliminary presintering product. And pouring the presintered product into a quartz glass tube, vacuumizing and sealing, putting into a muffle furnace, heating to 810 ℃ at a heating rate of 30 ℃/h, reacting at a constant temperature for 2 days, cooling to room temperature at a rate of 40 ℃/h, and grinding to obtain a powder sample.
Characterization of the powder sample obtained in this example by XRD revealed that the XRD spectrum of the powder sample in this example is not identical to that of example 1, i.e., the target product Ba could not be synthesized 5 Gd 3 (BO 3 ) 6 And F, crystal.
It should be understood that the foregoing examples of the present invention are merely illustrative of the present invention and not limiting of the embodiments of the present invention, and that various other changes and modifications can be made by those skilled in the art based on the above description, and it is not intended to be exhaustive of all of the embodiments, and all obvious changes and modifications that come within the scope of the invention are defined by the following claims.

Claims (13)

1. Gadolinium-based borateThe crystal is characterized in that the gadolinium based borate crystal has a chemical formula of Ba 5 Gd 3 (BO 3 ) 6 F, the gadolinium borate crystal belongs to a monoclinic system, and the space group is P2 1 And/c, the unit cell parameters are as follows: α＝γ＝90°，β＝99.116(7)°，Z＝1。
2. a method of preparing a gadolinium based borate crystal according to claim 1, comprising the steps of:
uniformly mixing a Ba-containing compound, a Gd-containing compound, a B-containing compound and an F-containing compound, uniformly heating to 650-700 ℃ in an aerobic environment, presintering at a constant temperature, cooling for one time, and grinding; and in a vacuum environment, heating to 800-810 ℃ again at a constant speed, reacting at a constant temperature, cooling for the second time, and grinding to obtain the gadolinium-based borate crystal.
3. The method according to claim 2, wherein the molar ratio of Ba, gd, B and F in the Ba-containing compound, gd-containing compound, B-containing compound and F-containing compound is 4-6:2-4:5-7:1.
4. The method according to claim 2, wherein the molar ratio of Ba, gd, B and F in the Ba-containing compound, gd-containing compound, B-containing compound and F-containing compound is 5:3:6:1.
5. The method according to claim 2, wherein the Ba-containing compound is a Ba-containing carbonate or a Ba-containing fluoride.
6. The method of claim 2, wherein the Gd-containing compound is a Gd-containing oxide.
7. The method according to claim 2, wherein the B-containing compound is H 3 BO 3 Or B is a 2 O 3 。
8. The method according to claim 2, wherein the F-containing compound is BaF 2 。
9. The method according to claim 2, wherein the temperature rising rate of the constant temperature rising or the constant temperature rising again is 30 ℃/h to 40 ℃/h.
10. The method according to claim 2, wherein the constant temperature pre-firing time is 1d-3d.
11. The method of claim 2, wherein the primary cooling is performed at a cooling rate of 40 ℃/h to 50 ℃/h.
12. The method of claim 2, wherein the secondary cooling is performed at a cooling rate of 30 ℃/h to 40 ℃/h.
13. Use of a gadolinium borate crystal according to claim 1 or a gadolinium borate crystal produced by the method of any one of claims 2 to 12 as a magnetic refrigeration material.
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