KR20110107136A - Method of preparing micro crystalline particle of magnetocaloric effect material, and micro crystalline particle of magnetocaloric effect material prepared by the same - Google Patents

Method of preparing micro crystalline particle of magnetocaloric effect material, and micro crystalline particle of magnetocaloric effect material prepared by the same Download PDF

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KR20110107136A
KR20110107136A KR1020100026325A KR20100026325A KR20110107136A KR 20110107136 A KR20110107136 A KR 20110107136A KR 1020100026325 A KR1020100026325 A KR 1020100026325A KR 20100026325 A KR20100026325 A KR 20100026325A KR 20110107136 A KR20110107136 A KR 20110107136A
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group
effect material
combinations
microcrystalline particles
magnetothermal effect
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KR1020100026325A
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Korean (ko)
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권순재
김현식
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삼성전자주식회사
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/825—Apparatus per se, device per se, or process of making or operating same
    • Y10S505/888—Refrigeration
    • Y10S505/896—Special refrigerant compound

Abstract

A first precursor comprising at least one selected from the group consisting of metals, metal halides, metal oxides, and combinations thereof; Selected from the group consisting of metalloids, metalloids, metal halides, metal oxides, pnictide-based materials, halides of pnictide-based materials, oxides of pnictide-based materials, and combinations thereof A second precursor comprising at least one; And a reducing agent comprising at least one selected from the group consisting of Group I elements, Group II elements, Group III elements, and combinations thereof to form a mixture, heat treating the mixture and acidifying the thermally treated mixture. Or it provides a method for producing microcrystalline particles of the magnetothermal effect material comprising the step of washing with a base.

Description

METHOD OF PREPARING MICRO CRYSTALLINE PARTICLE OF MAGNETOCALORIC EFFECT MATERIAL, AND MICRO CRYSTALLINE PARTICLE OF MAGNETOCALORIC EFFECT MATERIAL PREPARED BY THE SAME}

The present invention relates to a method for producing microcrystalline particles of a magnetocaloric effect material and to microcrystalline particles of a magnetocaloric effect material prepared according to the above method.

The gas compression cooling method currently used uses a gas refrigerant larger than 1,000 times greater than carbon dioxide, so there is an environmental problem. Therefore, while using a conventional cooling method, but is developing and using a more environmentally friendly refrigerant, but such a refrigerant has a poor cooling efficiency, can not completely eliminate the greenhouse effect.

Therefore, researches on eco-friendly and high-efficiency cooling technologies that do not use gas refrigerant have been actively conducted. For example, research on magnetic cooling technology using ferromagnetic materials and permanent magnets instead of gas refrigerants and compressors has been conducted, and these technologies are in the spotlight as new cooling technologies that can achieve eco-friendly, low noise and high efficiency. In particular, in the above self-cooling technology, it is important to develop materials and devices having excellent productivity due to a simple manufacturing process and excellent cooling efficiency, and a manufacturing method thereof.

Provided is a method for producing microcrystalline particles of a magnetocaloric effect material capable of producing a magnetocaloric effect material having excellent productivity and excellent cooling efficiency due to a simple manufacturing process.

It provides a microcrystalline particles of the magnetothermal effect material produced by the above production method.

According to an aspect of the present invention, a method for producing microcrystalline particles of a magnetocaloric effect material comprises: a first precursor comprising at least one selected from the group consisting of metals, metal halides, metal oxides and combinations thereof; Group consisting of metalloids, metal halides, metal oxides, pnictide-based materials, halides of pnictide-based materials, oxides of pnictide-based materials, and combinations thereof A second precursor comprising at least one selected from; And a reducing agent comprising at least one selected from the group consisting of Group I elements, Group II elements, Group III elements, and combinations thereof to form a mixture, heat treating the mixture and acidifying the thermally treated mixture. Or washing with base.

The metal is manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), niobium (Nb), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb) and combinations thereof, and the metalloid may be boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) And combinations thereof, wherein the pnictide-based material is selected from the group consisting of phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and combinations thereof The halogen may be selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and combinations thereof.

The group I element may be selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof, and the group II element may be beryllium (Be), magnesium (Mg), and calcium (Ca). ), Strontium (Sr), radium (Ra), and combinations thereof. The group III element may be aluminum (Al).

The forming of the mixture may be performed using a ball mill process, an attention mill process, a jet mill process, a spike mill process, or a combination thereof.

The heat treatment of the mixture may be performed at a temperature lower than the melting point of the microcrystalline particles of the magnetothermal effect material to be produced.

The washing with acid or base may be performed by acid leaching or base leaching.

In addition, the step of washing with acid or base may be performed using an aqueous solution of an acid or a base having a concentration of about 0.01 M to about 1 M.

According to another aspect of the present invention, there is provided a microcrystalline particle of the magnetocaloric effect material prepared according to the method for producing microcrystalline particles of the magnetocaloric effect material.

The microcrystalline particles of the magnetothermal effect material may have a particle diameter of about 10 nm to about 20 μm, and may have a particle diameter deviation of about 3 μm or less.

According to yet another aspect of the present invention, a method of preparing a magnetothermal effect material comprises: a first precursor comprising at least one selected from the group consisting of metals, metal halides, metal oxides, and combinations thereof; Selected from the group consisting of metalloids, metalloids, metal halides, metal oxides, pnictide-based materials, halides of pnictide-based materials, oxides of pnictide-based materials, and combinations thereof A second precursor comprising at least one; And a reducing agent comprising at least one selected from the group consisting of Group I elements, Group II elements, Group III elements, and combinations thereof to form a mixture, heat treating the mixture, acidifying the thermally treated mixture Or washing with a base to produce microcrystalline particles of a magnetocaloric effect material, filling the microcrystalline particles of the magnetocaloric effect material into a mold, and the magnetocaloric effect of the microcrystalline particles of a magnetocaloric effect material filled in the mold. Firing to a temperature below the melting point of the microcrystalline particles of the material.

The metal, the metalloid, the pnictide-based material, the halogen, the Group I element, the Group II element, and the Group III element are described in the method for producing microcrystalline particles of the magnetocaloric effect material. As described.

In addition, the description of the step of forming the mixture, the heat treatment of the mixture and the step of washing with the acid or base are as described in the method for producing microcrystalline particles of the magnetothermal effect material.

According to another aspect of the present invention, there is provided a magnetocaloric effect material prepared according to the method for producing a magnetocaloric effect material.

Other aspects of the present invention are included in the following detailed description.

By simplifying the manufacturing process, it is possible to improve processability and economic feasibility of the microcrystalline particles of the magnetocaloric effect material and the process of producing the magnetocaloric effect material. In addition, impurities can be effectively removed, and microcrystalline particles of the magnetothermal effect material having a fine and uniform size can be effectively produced, thereby improving the cooling efficiency of the cooling device using the microcrystalline particles of the magnetocaloric effect material. .

1 is a schematic diagram showing a method for producing microcrystalline particles of a magnetocaloric effect material according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing a method for producing a magnetothermal effect material according to an embodiment of the present invention.
3 is a front view of the magnetothermal effect material of FIG. 2.
Figure 4 is a schematic diagram showing a method for producing a magnetothermal effect material according to an embodiment of the present invention.
5 is an enlarged view of a portion of the magnetothermal effect material of FIGS. 3 and 4.
FIG. 6 is a graph showing an X-ray diffraction pattern of microcrystalline particles of a magnetothermal effect material prepared in Comparative Example 1. FIG.
FIG. 7 is a graph showing an X-ray diffraction pattern before pickling of microcrystalline particles of a magnetocaloric effect material prepared in Example 1. FIG.
8 is a graph showing an X-ray diffraction pattern after pickling of microcrystalline particles of a magnetothermal effect material prepared in Example 1. FIG.
FIG. 9 is a scanning electron microscope (SEM) photograph after pickling of microcrystalline particles of a magnetocaloric effect material prepared in Example 1. FIG.
10 is a scanning electron microscope (SEM) photograph of the magnetothermal effect material prepared in Example 8. FIG.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Method for producing microcrystalline particles of a magnetothermal effect material according to an embodiment of the present invention comprises a first precursor comprising at least one selected from the group consisting of metals, metal halides, metal oxides and combinations thereof; Group consisting of metalloids, metal halides, metal oxides, pnictide-based materials, halides of pnictide-based materials, oxides of pnictide-based materials, and combinations thereof A second precursor comprising at least one selected from; And a reducing agent comprising at least one selected from the group consisting of Group I elements, Group II elements, Group III elements, and combinations thereof to form a mixture, heat treating the mixture and acidifying the thermally treated mixture. Or washing with base.

Hereinafter, a method of preparing microcrystalline particles of a magnetocaloric effect material according to an embodiment of the present invention will be described with reference to FIG. 1. 1 is a schematic diagram showing a method for producing microcrystalline particles of a magnetocaloric effect material according to an embodiment of the present invention.

First, the first precursor (1), metalloid, metalloid halide, metalloid oxide and pnictide-based material comprising at least one selected from the group consisting of metals, metal halides, metal oxides and combinations thereof A second precursor (3) and a group I element and a group II element, including at least one selected from the group consisting of halides of pnictide-based materials, oxides of pnictide-based materials, and combinations thereof And a reducing agent 5 including at least one selected from the group consisting of Group III elements and combinations thereof are uniformly mixed using a ball mill process to form a mixture (S11). Here, although the first precursor 1, the second precursor 3 and the reducing agent 5 are described as being mixed using the ball mill process, the present invention is not limited thereto, and the first precursor 1 and the Any process can be used as long as it is a process which can mix the 2nd precursor 3 and the said reducing agent 5 uniformly. For example, the mixing process may be performed using a ball mill process, an attention mill process, a jet mill process, a spike mill process, or a combination thereof. .

In the mixture, the metal is manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), niobium (Nb), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium ( Pr, Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium ( Tm), ytterbium (Yb) and combinations thereof, and the metalloid may be boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), or tellurium. It may be selected from the group consisting of rulium (Te) and combinations thereof, the pnictide-based material is phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi) and combinations thereof The halogen may be selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and combinations thereof.

In addition, the group I element may be selected from the group consisting of lithium (Li), sodium (Na), potassium (K) and combinations thereof, and the group II element may be beryllium (Be), magnesium (Mg), calcium ( Ca), strontium (Sr), radium (Ra), and combinations thereof. The group III element may be aluminum (Al). Specifically, the group II element contained in the reducing agent is preferably magnesium (Mg), and the group III element is preferably aluminum (Al).

In the mixture, the first precursor and the second precursor may be included in an appropriate amount to suit the composition of the microcrystalline particles of the desired magnetothermal effect material. In addition, in the mixture, the reducing agent may be included in an amount sufficient to reduce both the first precursor and the second precursor.

The mixture includes a reducing agent, so that the preparation process of the microcrystalline particles of the magnetocaloric effect material according to one embodiment of the present invention may be carried out in an inert atmosphere such as argon (Ar) gas, a reducing atmosphere such as hydrogen gas, a vacuum atmosphere, It may also be performed in an atmospheric atmosphere containing oxygen gas. For this reason, the manufacturing process of the microcrystal grain of a magnetothermal effect material can be simplified. In addition, the reducing agent is uniformly dispersed in the mixture, and the reaction in which the reducing agent is oxidized is an exothermic reaction, so that the mixture is heated uniformly so that the reaction between materials contained in the mixture proceeds uniformly as a whole. have.

In addition, the oxide formed by oxidizing the reducing agent is formed between the microcrystalline particles of the resulting magnetothermal effect material, the oxide formed by oxidizing the reducing agent and the microcrystalline particles of the resulting magnetothermal effect material do not react with each other. Thus, the oxide formed by oxidizing the reducing agent can control the growth of the microcrystalline particles of the magnetocaloric effect material, thereby controlling the size and uniformity of the microcrystalline particles of the magnetocaloric effect material.

Subsequently, a mixture of the first precursor 1, the second precursor 3, and the reducing agent 5 is molded into a cylinder using a press (S12). When forming by pressing as described above, the contact between the first precursor (1), the second precursor (3) and the reducing agent (5) can be facilitated so that their reaction can be effectively performed during the subsequent heat treatment. However, the molding is not limited thereto, and the molding may be performed by other methods and forms. In addition, although the forming step is illustrated in FIG. 1, the forming step is not limited thereto, and the forming step may be omitted.

Subsequently, the molded mixture is heat-treated (S13). By the heat treatment, the reducing agent is oxidized to an oxide 5 ', and the first precursor and the second precursor are reduced while reacting with each other to form microcrystalline particles 7 of a magnetothermal effect material. The oxide 5 'formed by oxidizing the reducing agent may be particles having a size of nanometers.

The heat treatment may be performed by, for example, conventional heating, microwave heating, induction heating, spark plasma sintering, or the like, but is not limited thereto.

In addition, the heat treatment may be performed at a temperature lower than the melting point of the microcrystalline particles of the magnetothermal effect material to be formed, specifically, may be performed at a temperature of about 900 ℃ to about 1,200 ℃. When the heat treatment is performed within the temperature range, the first precursor and the second precursor may be efficiently reacted to effectively form microcrystalline particles of the magnetothermal effect material. More specifically, the heat treatment of the mixture may be performed at a temperature of about 950 ℃ to about 1,150 ℃.

Subsequently, the heat-treated mixture is washed with acid or base (S14). By performing the pickling or base washing, the microcrystalline particles 7 of the magnetothermal effect material having less reactivity with acids or bases are kept intact, while the selective removal of the oxides 5 'formed by oxidizing the reducing agent. Can be effectively achieved. As a result, the microcrystalline particles 7 of the magnetothermal effect material which are not mixed with impurities can be obtained. When washing with water other than pickling or base washing, impurities may remain, making it difficult to obtain fine crystal particles of a high purity magnetothermal effect material.

The washing with acid or base is a method for removing an oxide formed by oxidizing a reducing agent, and may be performed, for example, by acid leaching or base leaching.

The washing with the acid or the base may be performed using an aqueous acid solution or an aqueous base solution having a concentration of about 0.01 M to about 1 M. When the concentration of the acid aqueous solution or the base aqueous solution is within the above range, the cleaning effect is excellent, and damage to the microcrystalline particles of the magnetocaloric effect material can be suppressed. Specifically, the concentration of the acid or base aqueous solution may be about 0.1 M to about 0.5 M.

According to another embodiment of the present invention provides a microcrystalline particles of a magnetocaloric effect material prepared according to the method for producing microcrystalline particles of the magnetocaloric effect material. The microcrystalline particles of the magnetocaloric effect material may include, but are not limited to, a metal-metalloid-based material, a metal-phentide-based material, a metal-metalloid-phentide-based material, or a combination thereof. Specifically, the microcrystalline particles of the magnetothermal effect material are MnAs-based material, MnFeSi-based material, MnFeGe-based material, MnFe (Si, Ge) -based material, MnFe (P, Si) -based material, MnFe (P, Si, B) ) -Based material, MnFe (P, Si, Ge) -based material, MnFe (P, As) -based material, MnFe (P, Sb) -based material, MnFe (P, Bi) -based material, MnFe (P, As, Sb, Bi) material, Gd (Si, Ge) material, CoMn (Si, Ge) material, RMnSi material (where R is La, Ce, Pr, Nd, Pm or Sm), RFeSi material (here , R may be La, Ce, Pr, or Nd) or a combination thereof, but is not limited thereto. More specifically, the fine crystal grains of the magnetic heat effect materials MnFe (P 0 .5, Si 0 .5), MnFe (P 0 .5, Si 0 .5- x B x) ( where, 0 <x < 0.5), MnFe (P 0.5, Si 0 .5- y Ge y) ( where, 0 <y <0.5), Gd 5 (Si 1 -x, Ge x) 4) ( where, 0 <x <1), Mn (As 1- x , Sb x ) (where 0 <x <1) or a combination thereof, but is not limited thereto. Since the microcrystalline particles of the prepared magnetothermal effect material are stable to water, alcohol and acid, they can be easily applied to a magnetic cooling system using water or alcohol as a heat exchange fluid.

The microcrystalline particles of the magnetocaloric material prepared according to the method for producing microcrystalline particles of the magnetocaloric effect material contain little impurities, and may be formed of microparticles having considerable uniformity.

The microcrystalline particles of the magnetothermal effect material may have a particle diameter of about 10 nm to about 20 μm. When the particle diameter of the microcrystalline particles of the magnetothermal effect material is within the above range, it is possible to prevent or alleviate the generation of cracks due to the magnetic history and the thermal history, thereby improving the self cooling efficiency and lifespan characteristics. Specifically, the microcrystalline particles of the magnetothermal effect material may have a particle diameter of about 50 nm to about 5 μm, and more specifically, may have a particle diameter of about 500 nm to about 5 μm.

The microcrystalline particles of the magnetothermal effect material may have a particle diameter deviation of about 3 μm or less, for example, about 5 nm to about 3 μm. When the particle diameter variation of the microcrystalline particles of the magnetocaloric effect material is within the above range, it is possible to effectively prevent or alleviate the occurrence of cracks due to the magnetic history and the thermal history, thereby effectively improving the self cooling efficiency and life characteristics. Specifically, the microcrystalline particles of the magnetothermal effect material may have a particle diameter deviation of about 20 nm to about 2 μm, and more specifically, may have a particle diameter deviation of about 100 nm to about 1 μm.

According to the manufacturing method of the microcrystalline particles of the magnetothermal effect material according to an embodiment of the present invention, the reaction can proceed in the air as well as inert atmosphere, reducing atmosphere using a reducing agent, the microcrystalline particles of the magnetothermal effect material Can simplify the manufacturing process. In addition, the oxide in which the reducing agent is oxidized is formed in nanometer size to serve as a spacer to control the growth of the microcrystalline particles of the magnetothermal effect material, thereby facilitating the microcrystalline particles of the magnetothermal effect material of the microstructure. Can be formed. In addition, the oxide after the reducing agent is oxidized can be effectively removed by washing with an acid or a base. Therefore, by using the method for producing microcrystalline particles of the magnetothermal effect material according to an embodiment of the present invention, the microcrystalline particles of the magnetothermal effect material of the desired microstructure and high purity without the use of complicated processes and expensive equipment Can be manufactured effectively and can also be manufactured in large quantities. This can contribute to the implementation and commercialization of new environmentally friendly, high efficiency and low noise self cooling systems, such as room temperature self cooling systems.

According to another embodiment of the present invention, the method for producing a magnetothermal effect material is to fill the mold with the microcrystalline particles of the magnetothermal effect material, and to bake at a temperature below the melting point of the microcrystalline particles of the magnetothermal effect material Steps.

Hereinafter, a method of manufacturing a magnetothermal effect material according to an embodiment of the present invention will be described with reference to FIGS. 2 to 5. 2 and 4 is a schematic diagram showing a method of manufacturing a magnetothermal effect material according to an embodiment of the present invention.

Referring to FIGS. 2 and 4, first, the microcrystalline particles 7 of the magnetothermal effect material are filled in a mold and fired at a temperature below the melting point of the microcrystalline particles of the magnetothermal effect material (S15).

Description of the microcrystalline particles 7 of the magnetothermal effect material is the same as described in the method of manufacturing the microcrystalline particles of the magnetothermal effect material.

The mold may be variously selected and used according to the size, shape, etc. of the magnetothermal effect material to be obtained, and is not limited to the size and shape of the magnetothermal effect material shown in FIGS. 2 and 4.

Subsequently, the microcrystalline particles 7 of the magnetothermal effect material filled in the mold are fired at a temperature below the melting point of the microcrystalline particles 7 of the magnetothermal effect material (S16). When firing at a temperature below the melting point of the microcrystalline particles 7 of the magnetothermal effect material, since crystal growth of the microcrystalline particles 7 of the magnetothermal effect material does not occur, It is possible to easily form the magnetothermal effect material 10 in which the microcrystalline particles 7 of these magnetocaloric effect materials are collected while the microcrystalline particles 7 maintain the microstructure.

3 is a front view of the magnetothermal effect material 10 produced according to the manufacturing method shown in FIG. FIG. 5 is an enlarged view of a portion A of the magnetothermal effect material 10 manufactured according to the manufacturing method shown in FIGS. 2 and 4. Referring to FIG. 5, the prepared magnetothermal effect material 10 includes microcrystalline particles 7 of the magnetothermal effect material, which maintain the microstructure.

As such, when the microcrystalline particles 7 of the magnetothermal effect material are included in the magnetothermal effect material 10 while maintaining the microstructure, the magnetothermal effect material 10 generates a thermal history and a magnetic history. Even if the microcrystalline particles (7) of the magnetothermal effect material contained in them buffer each other, it is possible to prevent or alleviate the occurrence of cracks to prevent or alleviate the performance degradation. In addition, the magnetothermal effect material 10 may have excellent mechanical strength.

For example, spark plasma sintering and hot press may be used as a method of firing at a temperature below the melting point of the microcrystalline particles of the magnetothermal effect material, but is not limited thereto.

Specifically, the temperature below the melting point of the microcrystalline particles of the magnetothermal effect material may be about 900 ℃ to about 1,200 ℃, more specifically may be about 950 ℃ to about 1,150 ℃, but is not limited thereto.

According to another embodiment of the present invention provides a magnetothermal effect material prepared according to the method for producing a magnetothermal effect material.

The size and shape of the magnetothermal effect material is not limited, and may be manufactured in a desired size and a desired shape.

Hereinafter, the Example and comparative example of this description are described. However, the following examples are merely examples of the present disclosure, and the present disclosure is not limited by the following examples.

Example

Example  One: Magnetothermal effect  Microcrystalline particles of material ( MnFe ( P 0 .5 , Si 0 .5 Manufacture of))

Fe 2 O 3 , Mn, Si, P and Mg were quantified in a molar ratio of 1: 2: 1: 1: 3, and then mixed in air using a ball mill for 5 hours to form a mixture. The mixture is charged into a metal mold and pressurized by a press to form a cylinder having a diameter of 1 cm x 1 cm in height. The molded mixture is placed in an alumina crucible, the alumina crucible is placed in a quartz tube, sealed in a vacuum state, and reacted by heat treatment at 1,150 ° C. for 5 hours, and then slowly cooled. When the reaction is carried out in a vacuum state, the reaction of Mg and Fe 2 O 3 can be promoted. By the heat treatment, the mixture is reacted according to the following Scheme 1.

Scheme 1

Fe 2 O 3 + 2Mn + Si + P + 3Mg → 2MnFe (P 0 .5, Si 0 .5) + 3MgO

The heat-treated mixture is pulverized in agate mortar, and then put into a hydrochloric acid solution of 1 mol (M) and stirred for 1 hour with a magnetic stirrer or a mechanical stirrer to wash and remove MgO generated in the reaction process. It is then washed three times with water and then dried. Thus, MnFe (P 0 .5, Si 0 .5) on a pure crystal to produce the fine crystal grains of the magnetic heat effect material.

The MnFe (P 0 .5, Si 0 .5) magnetic particle size of the fine crystal grains of the thermal effect material is about 20 to about 100 nm ㎛, and the deviation of the particle diameter is from about 2 ㎛ below.

Example  2: Magnetothermal effect  Microcrystalline particles of material ( MnFe ( P 0 .5 , Si 0 .5 Manufacture of))

Fe 2 O 3 , Mn, Si, P and Mg were quantified in a molar ratio of 1: 2: 1: 1: 3, and then mixed in air using a ball mill for 5 hours to form a mixture. The mixture is charged into a metal mold and pressurized by a press to form a cylinder having a diameter of 1 cm x 1 cm in height. The molded mixture is placed in an alumina crucible, the alumina crucible is placed in a tubular electric furnace, vacuumed and filled with argon gas. The pressure of the argon gas is maintained at 1 atm, and reacted by heat treatment at 1,150 ° C. for 5 hours, followed by slow cooling. When the reaction is carried out in an argon atmosphere, the reaction of Mg and Fe 2 O 3 can be promoted. By the heat treatment, the mixture is reacted according to Scheme 1.

The heat-treated mixture was pulverized in agate induction, and then put into a 1 molar (M) hydrochloric acid aqueous solution and stirred for 1 hour using a magnetic stirrer or a mechanical stirrer to wash and remove the MgO produced in the reaction process. It is then washed three times with water and then dried. Thus, MnFe (P 0 .5, Si 0 .5) on a pure crystal to produce the fine crystal grains of the magnetic heat effect material. The MnFe (P 0 .5, Si 0 .5) magnetic particle size of the fine crystal grains of the thermal effect material is about 20 to about 100 nm ㎛, and the deviation of the particle diameter is from about 2 ㎛ below.

Example  3: Magnetothermal effect  Microcrystalline particles of material ( MnFe (P, Si , Ge ))

Fe 2 O 3 , Mn, P, Si, Ge and Mg fine of the magnetothermal effect material in the same manner as in Example 1 except that the quantitative ratio of 1: 2: 1: 0.8: 0.2: 3 Prepare crystal particles.

By heat treatment, the mixture is reacted according to Scheme 2 below.

Scheme 2

Fe 2 O 3 + 2Mn + P + 0.8Si + 0.2Ge + 3Mg → 2MnFe (P 0 .5, Si 0 .4 Ge 0 .1) + 3MgO

The MnFe (P 0 .5, Si 0 .5- x Ge x) particle size of the fine crystal grains of the magnetic heat effect material is about 100 nm to about 20 ㎛, and the deviation of the particle diameter is from about 2 ㎛ below.

Example  4: Magnetothermal effect  The microcrystalline particles of the material (boron (B) Doped  MnFe ( P 0 .5 , Si 0.5 Manufacture of))

Self-heating effect in the same manner as in Example 1 except that Fe 2 O 3 , Mn, P, Si, B 2 O 3 and Mg were used in a quantitative ratio of 1: 2: 1: 0.9: 0.1: 3 Prepare microcrystalline particles of material.

By heat treatment, the mixture is reacted according to Scheme 3 below.

Scheme 3

Fe 2 O 3 + 2Mn + P + 0.9Si + 0.1B 2 O 3 + 3Mg → 2MnFe (P 0 .5, Si 0 .45 B 0.05) + 3.3 MgO

The MnFe (P 0 .5, Si 0 .45 B 0.05) magnetic column particle size of the fine crystal grains of the effect material is about 100 nm to about 20 ㎛, and the deviation of the particle diameter is from about 2 ㎛ below.

Example  5: Magnetothermal effect  Microcrystalline particles of material ( MnFe ( P 0 .5 , Si 0 .5 Manufacture of))

Fe, MnO 2 , Si, P and Mg was prepared in the same manner as in Example 1 except that the quantitative ratio of 2: 2: 1: 1: 4 was used to prepare microcrystalline particles of a magnetothermal effect material.

By heat treatment, the mixture is reacted according to Scheme 4 below.

Scheme 4

2Fe + 2MnO 2 + Si + P + 4Mg → 2MnFe (P 0 .5, Si 0 .5) + 4MgO

The MnFe (P 0 .5, Si 0 .5) magnetic particle size of the fine crystal grains of the thermal effect material is about 20 to about 100 nm ㎛, and the deviation of the particle diameter is from about 2 ㎛ below.

Example  6: Magnetothermal effect  Microcrystalline particles of material ( MnFe ( P 0 .5 , Si 0 .5 Manufacture of))

Fine crystal particles of the magnetothermal effect material were prepared in the same manner as in Example 1, except that Fe, Mn, SiO 2 , P, and Mg were used in a quantitative ratio of 2: 2: 1: 1: 2.

By heat treatment, the mixture is reacted according to Scheme 5 below.

Scheme 5

2Fe + 2Mn + SiO 2 + P + 2Mg → 2MnFe (P 0 .5, Si 0 .5) + 2MgO

The MnFe (P 0 .5, Si 0 .5) magnetic particle size of the fine crystal grains of the thermal effect material is about 20 to about 100 nm ㎛, and the deviation of the particle diameter is from about 2 ㎛ below.

Example  7: Magnetothermal effect  Microcrystalline particles of material ( MnFe ( P 0 .5 , Si 0 .5 Manufacture of))

Fe 2 O 3 , Mn, P, Si and Al were prepared in the same manner as in Example 1 except that the quantitative ratio of 1: 2: 1: 1: 2 was used to prepare microcrystalline particles of a magnetothermal effect material. do.

By heat treatment, the mixture is reacted according to Scheme 6 below.

Scheme 6

Fe 2 O 3 + 2Mn + P + Si + 2Al → 2MnFe (P 0 .5, Si 0 .5) + Al 2 O 3

The MnFe (P 0 .5, Si 0 .5) magnetic heat effect fine particle size of the crystal grains is about 200 nm to about 25 ㎛ of material while deviation of the particle diameter is about 3 ㎛ below.

Example  8: Magnetothermal effect  Manufacture of substances

Example 1 was subjected to fine crystals of the magnetic heat effect material prepared in particles (MnFe (P 0 .5, Si 0 .5)) and sintered using spark plasma sintering (spark plama sintering, SPS). The spark plasma sintering is carried out at about 800 ° C. to about 1,000 ° C. for 10 minutes.

Comparative example  One: Magnetothermal effect  matter( MnFe ( P 0 .5 , Si 0 .5 Manufacturing

Fe 2 P, Mn and Si were quantified in a molar ratio of 1: 2: 1, and then mixed for 5 hours using a ball mill to form a mixture. The mixture is charged into a metal mold and pressurized by a press to form a cylinder having a diameter of 1 cm x 1 cm in height. The molded mixture was placed in a quartz tube, sealed in vacuum, and reacted by heat treatment at 1,200 ° C. for 5 hours, followed by slow cooling. By the heat treatment, the mixture is reacted according to the following Scheme 7, to form a magnetothermal effect material.

Scheme 7

Fe 2 P + 2Mn + Si → 2MnFe (P 0 .5, Si 0 .5)

Preparative a MnFe (P 0 .5, Si 0 .5) the magnetic material is heat effect does not control the grain growth is formed of a particle (particle) rather than the ingot (ingot) or lumps (bulk) type of material. Therefore, the manufacturing method of Comparative Example 1 cannot form a magnetothermal effect material in the form of microcrystalline particles.

Test Example  1: X-ray diffraction (X- ray diffraction , XRD ) Measure

X-ray diffraction analysis is performed before and after pickling of the microcrystalline particles of the magnetothermal effect materials prepared in Examples 1 to 7, respectively. X-ray diffraction analysis after the pickling is performed after pickling and drying. In addition, X-ray diffraction analysis of the microcrystalline particles of the magnetothermal effect material prepared in Comparative Example 1 is carried out. The result about the comparative example 1 is shown in FIG. In addition, the results before pickling of the microcrystalline particles of the magnetocaloric effect material prepared in Example 1 are shown in FIG. 7, and the results after pickling are shown in FIG. 8.

In the X-ray diffraction analysis, Cu-Kα ray having a wavelength of 0.154 nm is used as a light source.

From what shown in Figure 6, Comparative Example 1 A fine crystal grains of the magnetic heat effect, the material prepared in MnFe (P 0 .5, Si 0 .5) determines, as well as impurities such as Mn 3 Si, Fe 2 MnSi equivalent You can see that it is included.

As shown in FIG. 7, before pickling the microcrystalline particles of the magnetothermal effect material prepared in Example 1, X-ray diffraction peaks indicating MgO were clearly observed, but Mn 3 Si and Fe 2 MnSi were observed. X-ray diffraction peaks due to impurities are not observed. When using the metal from which the oxide (Fe 2 O 3) and Mg to produce substances MnFe (P 0 .5, Si 0 .5) type, has an effect of inhibiting Si and Mn 3 Fe 2 MnSi impurities generated You can check it.

As shown in FIG. 8, after pickling the microcrystalline particles of the magnetothermal effect material prepared in Example 1, X-ray diffraction peaks showing MgO observed in FIG. 7 and Mn 3 Si and Fe observed in FIG. 6. 2 MnSi without the X- ray diffraction peak due to impurities was observed, such as, MnFe (P 0 .5, Si 0 .5) of X- ray materials, only the diffraction peak is observed. As a result, it can be confirmed that the microcrystalline particles of the magnetothermal effect material synthesized according to Example 1 are pure MnFe (P, Si) -based materials.

Test Example  2: scanning electron microscope ( scanning electron microscope , SEM ) Picture

SEM images are taken after the microcrystalline particles of the magnetothermal effect material prepared in Examples 1 to 7 are pickled. The result about Example 1 is shown in FIG.

In addition, SEM photographs of the magnetothermal effect material prepared in Example 8 were taken, and the results are shown in FIG. 10.

As shown in FIG. 9, the size of the microcrystalline particles of the magnetothermal effect material prepared in Example 1 is about 500 nm to about 10 μm. As a result, it can be seen that the microcrystalline particles of the magnetothermal effect material prepared in Example 1 are formed in a fine size.

As shown in FIG. 10, it can be seen that in the magnetothermal effect material prepared in Example 8, the microcrystalline particles of the magnetothermal effect material of Example 1 gathered without crystal growth.

The present invention is not limited to the above embodiments, but may be manufactured in various different forms, and a person having ordinary knowledge in the art to which the present invention pertains does not change the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

1: first precursor 3: second precursor
5: reducing agent 5 ': oxide formed by oxidizing the reducing agent
7: microcrystalline particles of magnetothermal effect material
10: magnetothermal effect material A: part of the magnetothermal effect material

Claims (18)

A first precursor comprising at least one selected from the group consisting of metals, metal halides, metal oxides, and combinations thereof; Group consisting of metalloids, metal halides, metal oxides, pnictide-based materials, halides of pnictide-based materials, oxides of pnictide-based materials, and combinations thereof A second precursor comprising at least one selected from; And a reducing agent comprising at least one selected from the group consisting of Group I elements, Group II elements, Group III elements, and combinations thereof to form a mixture,
Heat treating the mixture and
Washing the heat-treated mixture with an acid or a base
Method for producing microcrystalline particles of a magnetocaloric effect material comprising a.
The method of claim 1,
The metal is manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), niobium (Nb), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb) and combinations thereof
The metalloid is selected from the group consisting of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), and combinations thereof,
The pnictide-based material is selected from the group consisting of phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and combinations thereof,
And the halogen is selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and combinations thereof.
The method of claim 1,
The group I element is selected from the group consisting of lithium (Li), sodium (Na), potassium (K) and combinations thereof,
The Group II element is selected from the group consisting of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), radium (Ra), and combinations thereof,
The group III element is aluminum (Al) is a method for producing microcrystalline particles of the magnetothermal effect material.
The method of claim 1,
The step of forming the mixture is carried out using a ball mill process, an attention mill process, a jet mill process, a spike mill process, or a combination thereof. Method for producing microcrystalline particles of heat effect material.
The method of claim 1,
Heat-treating the mixture is carried out at a temperature lower than the melting point of the microcrystalline particles of the magnetothermal effect material to be produced.
The method of claim 1,
The washing with acid or base is performed by acid leaching or base leaching.
The method of claim 1,
The washing with acid or base is a method for producing microcrystalline particles of a magnetocaloric effect material that is performed using an aqueous acid solution or a base solution having a concentration of 0.01 M to 1 M.
Microcrystalline particles of the magnetothermal effect material according to the method for producing microcrystalline particles of the magnetothermal effect material according to claim 1.
The method of claim 8,
The microcrystalline particles of the magnetothermal effect material has a particle diameter of 10 nm to 20 ㎛ microcrystalline particles of the magnetothermal effect material.
The method of claim 8,
The microcrystalline particles of the magnetocaloric effect material has a particle diameter deviation of 3 μm or less.
A first precursor comprising at least one selected from the group consisting of metals, metal halides, metal oxides, and combinations thereof; Selected from the group consisting of metalloids, metalloids, metal halides, metal oxides, pnictide-based materials, halides of pnictide-based materials, oxides of pnictide-based materials, and combinations thereof A second precursor comprising at least one; And a reducing agent comprising at least one selected from the group consisting of Group I elements, Group II elements, Group III elements, and combinations thereof to form a mixture,
Heat treating the mixture,
Washing the heat-treated mixture with an acid or a base to prepare microcrystalline particles of a magnetocaloric effect material,
Filling the mold with microcrystalline particles of the magnetothermal effect material and
Calcining the microcrystalline particles of the magnetothermal effect material filled in the mold to a temperature below the melting point of the microcrystalline particles of the magnetothermal effect material.
Method for producing a magnetothermal effect material comprising a.
The method of claim 11,
The metal is manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), niobium (Nb), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb) and combinations thereof
The metalloid is selected from the group consisting of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te), and combinations thereof,
The pnictide-based material is selected from the group consisting of phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and combinations thereof,
And the halogen is selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and combinations thereof.
The method of claim 11,
The group I element is selected from the group consisting of lithium (Li), sodium (Na), potassium (K) and combinations thereof,
The Group II element is selected from the group consisting of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), radium (Ra), and combinations thereof,
The group III element is a method of producing a magnetothermal effect material is aluminum (Al).
The method of claim 11,
The step of forming the mixture is carried out using a ball mill process, an attention mill process, a jet mill process, a spike mill process, or a combination thereof. Method of making a thermally effective material.
The method of claim 11,
Heat-treating the mixture is carried out at a temperature lower than the melting point of the microcrystalline particles of the magneto-thermal effect material to be produced.
The method of claim 11,
The washing with acid or base is carried out by acid washing or base washing.
The method of claim 11,
The washing with acid or base is a method of producing a magnetothermal effect material is carried out using an aqueous solution of an acid or a base having a concentration of 0.01 M to 1 M.
Magnetothermal effect material prepared according to the method for producing a magnetothermal effect material according to claim 11.
KR1020100026325A 2010-03-24 2010-03-24 Method of preparing micro crystalline particle of magnetocaloric effect material, and micro crystalline particle of magnetocaloric effect material prepared by the same KR20110107136A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130121546A (en) * 2012-04-27 2013-11-06 삼성전자주식회사 Thermoelectric material improved in figure of merit and method of producing same
KR20160081657A (en) * 2014-12-31 2016-07-08 삼성전자주식회사 Magnetocaloric material, products including the magnetocaloric material, and method of manufacturing the magnetocaloric material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130121546A (en) * 2012-04-27 2013-11-06 삼성전자주식회사 Thermoelectric material improved in figure of merit and method of producing same
KR20160081657A (en) * 2014-12-31 2016-07-08 삼성전자주식회사 Magnetocaloric material, products including the magnetocaloric material, and method of manufacturing the magnetocaloric material

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