CN113444966A - Mixed rare earth-iron-boron magnetic refrigeration material and preparation method thereof - Google Patents
Mixed rare earth-iron-boron magnetic refrigeration material and preparation method thereof Download PDFInfo
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Abstract
Mixed rare earth iron boronThe magnetic refrigeration material comprises the following chemical components: RExRE’1‑xFe12B 6; wherein RE and RE' are one of the rare earth La, Y, Ce and Nd, and x is more than or equal to 0.2 and less than or equal to 0.8. The invention mixes the rare earth RExRE’1‑ xThe Fe12B6 material belongs to
Space group of SrNi12B6A crystal structure, wherein the isothermal magnetic entropy is changed to 6.4-9.5J/kgK under the change of a 0-3T magnetic field; under the change of a magnetic field of 0-5T, the isothermal magnetic entropy is changed into 10.8-16.6J/kgK. The rare earth iron boron material is prepared by combining electric arc melting of raw materials under the protection of argon gas with a strip casting technology, has simple process, and is suitable for industrial production and application.
Description
Technical Field
The invention belongs to the field of new rare earth materials, and particularly relates to a mixed rare earth ferro-boron magnetic refrigeration material and a preparation method thereof.
Background
The main principle of the magnetic refrigeration technology is to utilize the magnetocaloric effect of the material, also called magnetic card effect, which is a novel refrigeration mode for realizing refrigeration, and the specific expression is that the change of the external magnetic field can cause the change of the temperature of the material, thereby achieving the effect of refrigeration or heating; magnetic refrigeration technology is likely to replace traditional gas compression refrigeration in the future and becomes one of the most promising refrigeration technologies. Compared with the traditional refrigeration technology, the magnetic refrigeration technology has the characteristics of higher refrigeration efficiency, smaller volume of a refrigeration unit, lower noise, longer service life and the like; most importantly, compared with various environmental problems caused by Freon compression refrigeration, the magnetic refrigeration technology is a completely green and environment-pollution-free high-tech technology.
Magnetic refrigeration technology is considered to be one of the most promising refrigeration technologies to replace the traditional gas compression refrigeration in the future. One of the keys to commercialization is to find magnetic refrigeration materials of different temperature zones, depending on whether the technology can be taken out of the laboratory. On one hand, the prior high-performance magnetic refrigeration materials are relatively few, and on the other hand, the prior reported high-performance magnetic refrigeration materials generally contain heavy rare earth elements, and the practical application of the materials is limited due to the fact that the heavy rare earth elements are expensive and rare in content. The development of high-abundance rare earth low-cost magnetic refrigeration materials is of great importance to the strategy of sustainable development of rare earth materials.
Disclosure of Invention
The invention aims to provide a mixed rare earth ferroboron magnetic refrigeration material and a preparation method thereof aiming at the defects of the prior art. The rare earth iron boron material is prepared by combining electric arc melting of raw materials under the protection of argon gas with a strip casting technology, has simple process, and is suitable for industrial production and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
a mixed rare earth-Fe-B magnetic refrigeration material has a chemical composition molecular formula as follows: RExRE'1-xFe12B6(ii) a Wherein RE and RE' are one of the rare earth La, Y, Ce and Nd, and x is more than or equal to 0.2 and less than or equal to 0.8.
Preferably, the mixed rare earth-iron-boron magnetic refrigeration material is SrNi12B6A crystal structure of the form
A space group; the isothermal magnetic entropy of the mixed rare earth ferroboron magnetic refrigeration material is changed to 6.4-9.5J/kgK under the change of a 0-3T magnetic field; under the change of a magnetic field of 0-5T, the isothermal magnetic entropy is changed into 10.8-16.6J/kgK.
Further preferably, the isothermal magnetic entropy of the mixed rare earth ferroboron magnetic refrigeration material is 6.8-9.2J/kgK under the magnetic field change of 0-3T; under the change of a magnetic field of 0-5T, the isothermal magnetic entropy is changed into 12.4-15.8J/kgK.
The invention relates to a preparation method of a mixed rare earth-iron-boron magnetic refrigeration material, which comprises the following steps:
the method comprises the following steps: according to RExRE'1-xFe12B6Respectively weighing raw materials containing RE, RE ', Fe and B according to the stoichiometric ratio of the chemical elements, wherein the RE and the RE' are one of any different elements in the rare earth La, Y, Ce and Nd, and x is more than or equal to 0.2 and less than or equal to 0.8; the volatilization loss amount of the rare earth elements RE and RE ' in the smelting process is considered, and the raw materials containing RE and RE ' with the volatilization loss amount are supplemented, so that the raw materials containing RE and RE ' are excessive;
step two: under the protection of inert gas, smelting the raw materials in the step one in an electric arc smelting furnace until the raw materials are completely molten, and preserving heat for 30-120 seconds to finish the first smelting; then, after cooling, turning over the material obtained by melting and solidifying the mixed raw material, heating the material again to be molten, and preserving heat for 30-120 seconds to finish the second melting; then repeating the second smelting step for at least 2 times to obtain a smelting product;
step three: placing the smelting product obtained in the second step in a quartz tube of a melt-spinning furnace, carrying out induction heating under the protection of inert gas until the smelting product is completely molten, and starting melt-spinning after continuously smelting for 10-20 seconds, wherein the pressure difference between the inside and the outside of the quartz tube in the melt-spinning process is 0.09-0.11 MPa, and the tangential linear velocity of a copper rod is 26-32 m/s, so as to obtain a thin strip-shaped product;
step four: crushing the thin strip product obtained in the third step, performing cold press molding to obtain a calcined precursor, sealing the calcined precursor into a quartz tube, heating to 850-1200 ℃, preserving heat for 80-200 hours in vacuum, and performing annealing treatment to obtain uniform RExRE'1-xFe12B6And (5) obtaining a finished product of the polycrystalline block.
Preferably, in the step one, the purity of the adopted raw materials containing rare earth, iron and boron is more than or equal to 99.9 percent.
Preferably, in the second step, in order to compensate for volatilization of the rare earth, the addition amount of the rare earth raw material is 2-4% in excess.
Preferably, in the second step, the second smelting step is repeated for 2-4 times to obtain a smelting product.
Preferably, in the second step or the third step, the inert gas is argon, and the purity is more than or equal to 99.9%.
Preferably, in the second step, the raw materials in the first step are smelted to be completely molten, and the temperature is kept for 40-100 seconds to complete the first smelting; and then, turning over the material after the mixed raw material is melted and solidified after cooling, heating the material again to be melted, and preserving heat for 40-100 seconds to finish the second melting.
Preferably, in the second step, the tangential linear velocity of the copper rod is 28-32 m/s when the strip throwing is carried out.
Preferably, in the second step, the temperature is heated to 900-.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the mixed rare earth-iron-boron magnetic refrigeration material has high magnetic performance and lower cost;
2. the mixed rare earth iron boron material provided by the invention is prepared by adopting a conventional electric arc melting technical means, has a simple process, and is suitable for industrial production and application.
Detailed Description
The present invention is further analyzed, but the specific embodiments do not limit the present invention.
Example 1:
a mixed rare earth-Fe-B magnetic refrigeration material has a chemical composition molecular formula as follows: la0.8Y0.2Fe12B6Is SrNi12B6A crystal structure of the form
And (4) space group.
The mixed rare earth-iron-boron magnetic refrigeration material La of the embodiment0.8Y0.2Fe12B6The preparation method comprises the following steps:
the method comprises the following steps: according to the formula La: y: fe: the molar ratio of B is 0.824:0.206:12:6, and La, Pr, Fe and B raw materials with the purity of 99.9 percent are respectively weighed;
step two: mixing the weighed raw materials, putting the mixed raw materials into an electric arc melting furnace, heating the mixed raw materials to be molten under the protection of Ar gas, and preserving heat for 45 seconds to finish primary melting; then, after cooling, turning over the material obtained by melting and solidifying the mixed raw material, heating the material again to be molten, and preserving heat for 40 seconds to finish the second melting; then repeating the second smelting step for 3 times to obtain a smelting product;
step three: placing the smelting product obtained in the second step in a quartz tube of a melt-spinning furnace, carrying out induction heating under the protection of Ar gas until the smelting product is completely melted, and starting melt-spinning after continuously smelting for 15 seconds, wherein the pressure difference between the inside and the outside of the quartz tube in the melt-spinning process is 0.09MPa, and the tangential linear velocity of a copper rod is 30m/s, so as to obtain a thin strip-shaped product;
step four: crushing the thin strip-shaped product obtained in the third step, performing cold press molding to obtain a calcined precursor, and performing cold press molding on the calcined precursorSealing the calcined precursor into a quartz tube, heating to 900 ℃, preserving heat for 80 hours in vacuum, and annealing to obtain uniform La0.8Y0.2Fe12B6And (5) obtaining a finished product of the polycrystalline block.
XRD and magnetic measurements show that the La of this example0.8Y0.2Fe12B6The material belongs to
Space group of SrNi12B6A crystal structure, wherein the isothermal magnetic entropy is changed into 6.8J/kgK under the change of a 0-3T magnetic field; under the change of a magnetic field of 0-5T, the isothermal magnetic entropy is changed into 12.4J/kgK. The mixed rare earth-iron-boron magnetic refrigeration material has high magnetic performance and low cost; the mixed rare earth iron boron material provided by the embodiment is prepared by adopting a conventional electric arc melting technical means, has a simple process, and is suitable for industrial production and application.
Example 2:
a mixed rare earth-Fe-B magnetic refrigeration material has a chemical composition molecular formula as follows: nd (neodymium)0.5Ce0.5Fe12B6Is SrNi12B6A crystal structure of the form
And (4) space group.
The mixed rare earth-iron-boron magnetic refrigeration material Nd of the embodiment0.5Ce0.5Fe12B6The preparation method comprises the following steps:
the method comprises the following steps: according to Nd: ce: fe: the molar ratio of B is 0.516:0.514:12:6, and Nd, Ce, Fe and B raw materials with the purity of 99.9 percent are respectively weighed;
step two: mixing the weighed raw materials, putting the mixed raw materials into an electric arc melting furnace, heating the mixed raw materials to be molten under the protection of Ar gas, and preserving heat for 80 seconds to finish primary melting; then, after cooling, turning over the material obtained by melting and solidifying the mixed raw material, heating the material again to be molten, and preserving heat for 60 seconds to finish the second melting; then repeating the second smelting step for 2 times to obtain a smelting product;
step three: placing the smelting product obtained in the second step in a quartz tube of a melt-spinning furnace, carrying out induction heating under the protection of Ar gas until the smelting product is completely melted, and starting melt-spinning after continuously smelting for 10 seconds, wherein the pressure difference between the inside and the outside of the quartz tube in the melt-spinning process is 0.10MPa, and the tangential linear velocity of a copper rod is 28m/s, so as to obtain a thin strip-shaped product;
step four: crushing the thin strip-shaped product obtained in the third step, performing cold press molding to obtain a calcined precursor, sealing the calcined precursor into a quartz tube, heating to 1100 ℃, preserving heat for 100 hours in vacuum, and performing annealing treatment to obtain uniform Nd0.5Ce0.5Fe12B6And (5) obtaining a finished product of the polycrystalline block.
XRD and magnetic measurement showed that the Nd in this example0.5Ce0.5Fe12B6The material belongs to
Space group of SrNi12B6A crystal structure, wherein the isothermal magnetic entropy is changed into 9.2J/kgK under the change of a magnetic field of 0-3T; under the change of a magnetic field of 0-5T, the isothermal magnetic entropy is changed to be 15.8J/kgK. The mixed rare earth-iron-boron magnetic refrigeration material has high magnetic performance and low cost; the mixed rare earth iron boron material provided by the embodiment is prepared by adopting a conventional electric arc melting technical means, has a simple process, and is suitable for industrial production and application.
Example 3:
a mixed rare earth-Fe-B magnetic refrigeration material has a chemical composition molecular formula as follows: y is0.7Ce0.3Fe12B6Is SrNi12B6A crystal structure of the form
And (4) space group.
The mixed rare earth-iron-boron magnetic refrigeration material Y of the embodiment0.7Ce0.3Fe12B6The preparation method comprises the following steps:
the method comprises the following steps: according to Y: ce: fe: the molar ratio of B is 0.728:0.312:12:6, and Y, Ce, Fe and B raw materials with the purity of 99.9% are respectively weighed;
step two: mixing the weighed raw materials, putting the mixed raw materials into an electric arc melting furnace, heating the mixed raw materials to be molten under the protection of Ar gas, and preserving heat for 100 seconds to finish primary melting; then, after cooling, turning over the material obtained by melting and solidifying the mixed raw material, heating the material again to be molten, and preserving heat for 100 seconds to finish the second melting; then repeating the second smelting step for 4 times to obtain a smelting product;
step three: placing the smelting product obtained in the second step in a quartz tube of a melt-spinning furnace, carrying out induction heating under the protection of Ar gas until the smelting product is completely melted, and starting melt-spinning after continuously smelting for 20 seconds, wherein the pressure difference between the inside and the outside of the quartz tube in the melt-spinning process is 0.11MPa, and the tangential linear velocity of a copper rod is 32m/s, so as to obtain a thin strip-shaped product;
step four: crushing the thin strip-shaped product obtained in the third step, performing cold press molding to obtain a calcined precursor, sealing the calcined precursor into a quartz tube, heating to 1000 ℃, preserving heat for 120 hours in vacuum, and performing annealing treatment to obtain uniform Y0.7Ce0.3Fe12B6And (5) obtaining a finished product of the polycrystalline block.
XRD and magnetic measurements show that Y is the same as that of example0.7Ce0.3Fe12B6The material belongs to
Space group of SrNi12B6A crystal structure, wherein the isothermal magnetic entropy is changed to 7.7J/kgK under the change of a magnetic field of 0-3T; under the change of a magnetic field of 0-5T, the isothermal magnetic entropy is changed to 13.6J/kgK. The mixed rare earth-iron-boron magnetic refrigeration material has high magnetic performance and low cost; the mixed rare earth iron boron material provided by the embodiment is prepared by adopting a conventional electric arc melting technical means, has a simple process, and is suitable for industrial production and application.
Example 4:
a mixed rare-earth-Fe-B magnetic refrigerating material contains the chemical componentsThe subformula is: la0.3Nd0.7Fe12B6Is SrNi12B6A crystal structure of the form
And (4) space group.
The mixed rare earth-iron-boron magnetic refrigeration material La of the embodiment0.3Nd0.7Fe12B6The preparation method comprises the following steps:
the method comprises the following steps: according to the formula La: nd: fe: the molar ratio of B is 0.306:0.714:12:6, and La, Nd, Fe and B raw materials with the purity of 99.9 percent are respectively weighed;
step two: mixing the weighed raw materials, putting the mixed raw materials into an electric arc melting furnace, heating the mixed raw materials to be molten under the protection of Ar gas, and preserving heat for 40 seconds to finish primary melting; then, after cooling, turning over the material obtained by melting and solidifying the mixed raw material, heating the material again to be molten, and preserving heat for 60 seconds to finish the second melting; then repeating the second smelting step for 2 times to obtain a smelting product;
step three: placing the smelting product obtained in the second step in a quartz tube of a melt-spinning furnace, carrying out induction heating under the protection of Ar gas until the smelting product is completely melted, and starting melt-spinning after continuously smelting for 10 seconds, wherein the pressure difference between the inside and the outside of the quartz tube in the melt-spinning process is 0.10MPa, and the tangential linear velocity of a copper rod is 29m/s, so as to obtain a thin strip-shaped product;
step four: crushing the thin strip-shaped product obtained in the third step, performing cold press molding to obtain a calcined precursor, sealing the calcined precursor into a quartz tube, heating to 900 ℃, preserving heat for 100 hours in vacuum, and performing annealing treatment to obtain uniform La0.3Nd0.7Fe12B6And (5) obtaining a finished product of the polycrystalline block.
XRD and magnetic measurements show that the La of this example0.3Nd0.7Fe12B6The material belongs to
Space group of SrNi12B6Form crystalThe structure is characterized in that under the condition of 0-3T magnetic field change, the isothermal magnetic entropy is changed into 7.1J/kgK; under the change of a magnetic field of 0-5T, the isothermal magnetic entropy is changed into 12.9J/kgK. The mixed rare earth-iron-boron magnetic refrigeration material has high magnetic performance and low cost; the mixed rare earth iron boron material provided by the embodiment is prepared by adopting a conventional electric arc melting technical means, has a simple process, and is suitable for industrial production and application.
While the embodiments of the present invention have been described, the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the present invention may be made in the form of equivalent substitutions without departing from the technical principle and inventive concept of the present invention.
Claims (10)
1. A mixed rare earth-iron-boron magnetic refrigeration material is characterized in that: the chemical composition molecular formula of the material is as follows: RExRE'1- xFe12B6(ii) a Wherein RE and RE' are one of the rare earth La, Y, Ce and Nd, and x is more than or equal to 0.2 and less than or equal to 0.8.
2. The mixed rare earth-iron-boron magnetic refrigeration material of claim 1, characterized in that: it is SrNi12B6A crystal structure of the form
A space group; the isothermal magnetic entropy of the mixed rare earth ferroboron magnetic refrigeration material is changed to 6.4-9.5J/kgK under the change of a 0-3T magnetic field; under the change of a magnetic field of 0-5T, the isothermal magnetic entropy is changed into 10.8-16.6J/kgK.
3. A preparation method of the mixed rare earth ferroboron magnetic refrigeration material of claim 1 is characterized by comprising the following steps:
the method comprises the following steps: according to RExRE'1-xFe12B6Chemical element meteringRespectively weighing raw materials containing RE, RE ', Fe and B according to the ratio, wherein the RE and the RE' are one of any different elements in the rare earth La, Y, Ce and Nd, and x is more than or equal to 0.2 and less than or equal to 0.8; the volatilization loss amount of the rare earth elements RE and RE ' in the smelting process is considered, and the raw materials containing RE and RE ' with the volatilization loss amount are supplemented, so that the raw materials containing RE and RE ' are excessive;
step two: under the protection of inert gas, smelting the raw materials in the step one in an electric arc smelting furnace until the raw materials are completely molten, and preserving heat for 30-120 seconds to finish the first smelting; then, after cooling, turning over the material obtained by melting and solidifying the mixed raw material, heating the material again to be molten, and preserving heat for 30-120 seconds to finish the second melting; then repeating the second smelting step for at least 2 times to obtain a smelting product;
step three: placing the smelting product obtained in the second step in a quartz tube of a melt-spinning furnace, carrying out induction heating under the protection of inert gas until the smelting product is completely molten, and starting melt-spinning after continuously smelting for 10-20 seconds, wherein the pressure difference between the inside and the outside of the quartz tube in the melt-spinning process is 0.09-0.11 MPa, and the tangential linear velocity of a copper rod is 26-32 m/s, so as to obtain a thin strip-shaped product;
step four: crushing the thin strip product obtained in the third step, performing cold press molding to obtain a calcined precursor, sealing the calcined precursor into a quartz tube, heating to 850-1200 ℃, preserving heat for 80-200 hours in vacuum, and performing annealing treatment to obtain uniform RExRE'1-xFe12B6And (5) obtaining a finished product of the polycrystalline block.
4. The preparation method of the mixed rare earth ferroboron magnetic refrigeration material according to claim 3, wherein the purity of the raw materials containing rare earth, iron and boron adopted in the step one is more than or equal to 99.9%.
5. The preparation method of the mixed rare earth ferroboron magnetic refrigeration material according to claim 3, wherein in the second step, in order to compensate volatilization of rare earth, the addition amount of the rare earth raw material is 2-4% excessive.
6. The method for preparing the mixed rare earth ferroboron magnetic refrigeration material as claimed in claim 3, wherein in the second step, the second smelting step is repeated for 2-4 times to obtain a smelted product.
7. The method for preparing the mixed rare earth ferroboron magnetic refrigeration material according to claim 3, wherein in the second step or the third step, the inert gas is argon gas, and the purity is more than or equal to 99.9%.
8. The method for preparing the mixed rare earth ferroboron magnetic refrigeration material according to claim 3, wherein in the second step, the raw material in the first step is smelted until the raw material is completely melted, and the temperature is maintained for 40-100 seconds to complete the first smelting; and then, turning over the material after the mixed raw material is melted and solidified after cooling, heating the material again to be melted, and preserving heat for 40-100 seconds to finish the second melting.
9. The preparation method of the mixed rare earth ferroboron magnetic refrigeration material according to claim 3, wherein in the second step, the tangential linear velocity of the copper rod is 28-32 m/s when the strip casting is carried out.
10. The method for preparing the mixed rare earth ferroboron magnetic refrigeration material as recited in claim 3, wherein in the second step, the annealing treatment is performed by heating to 900-.
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