KR20150015768A - Magnetocaloric material and method of manufacturing the same and products including the magnetocaloric material - Google Patents

Abstract

The present invention relates to a magnetocaloric material defined as a chemical formula 1 below, and a manufacturing method thereof; and products including the magnetocaloric material. Chemical formula 1 is Al(M_1-aL_a)_2+c(X_1-bY_b)_2+d wherein Al is aluminum; M and L are each independently a transition element; and X and Y are each independently a non-metallic element or a metalloid element, which satisfies 0<=a<=1, 0<=b<=1, -0.5<=c<=0.5, and -0.5<=d<=0.5 respectively wherein a and b are not zero at the same time, and excluding that iron (Fe) and manganese (Mn) exist as transition elements at the same when b is equal to zero.

Description

TECHNICAL FIELD [0001] The present invention relates to a magnetic thermal material, a method of manufacturing the same, and a product including the magnetic thermal material. [0002]

The present invention relates to a magnetic thermal material, a method of manufacturing the same, and a product including the magnetic thermal material.

A cooling device such as a refrigerator or a freezer is a device for lowering the temperature as the refrigerant repeats a refrigerating cycle in which the refrigerant is compressed, condensed, expanded and evaporated. The device lowers the temperature and pressure of the gas refrigerant to a high temperature and high pressure gas refrigerant, A step of condensing high-pressure refrigerant by outside air, depressurizing the condensed refrigerant, and evaporating the reduced-pressure refrigerant at low pressure to absorb heat. Such a cooling device uses a gas refrigerant having a large greenhouse effect, which is limited from an environmental point of view.

Therefore, studies on an environmentally friendly and highly efficient cooling apparatus that does not use gas refrigerant have been actively conducted. One of these measures is the study of self-cooling devices using magnetocaloric materials and permanent magnets.

The self-cooling system is a new cooling technology that can achieve eco-friendly, low noise and high efficiency by cooling using a magnetocaloric effect in which the magnetic thermal material is heated or cooled while the spin alignment is changed according to the magnetic field have.

One embodiment provides a magnetic thermal material capable of controlling the magnetic properties to improve the magnetic thermal effect.

Another embodiment provides a method for manufacturing a magnetic thermal material that is economically mass-producible.

Another embodiment provides a product comprising the magnetically-attracting material.

According to one embodiment, there is provided a magnetorheological material represented by the following formula:

[Chemical Formula 1]

Al (M _{1 - a} L _a ) _{2 + c} (X _{1 - b} Y _b ) _{2 + d}

In Formula 1,

Al is aluminum,

M and L are each independently a transition element,

X and Y are each independently a non-metallic element or a metalloid element,

0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?

a and b are not 0 at the same time,

Provided that when b is 0, iron (Fe) and manganese (Mn) are not present simultaneously as the transition element.

The transition element may be at least one element selected from the group consisting of Fe, Ni, Co, Mn, Cr, V, Ru, Mo, (Zr), tungsten (W), and tantalum (Ta).

The non-metallic or sub-metallic element may be at least one selected from boron (B), carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic (As) It can be one.

The magnetic thermal material may be represented by the following formula (1a).

[Formula 1a]

_{Al (Fe 1 - a L a} ) 2 + c (X 1 - b Y b) 2 + d

In formula (1a)

Al and Fe are aluminum and iron, respectively,

L is at least one element selected from the group consisting of Ni, Co, Mn, Cr, V, Ru, Mo, Nb, Zr, ) And tantalum (Ta).

X and Y are each independently a non-metallic element or a metalloid element,

0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?

a and b are not 0 at the same time,

When b is 0, L is not manganese (Mn).

The magnetoresistive material may be represented by the following formula (1b).

[Chemical Formula 1b]

Al (M _{1 - a} L _a ) _{2 + c} (B _{1 - b} Y _b ) _{2 + d}

In the above formula (1b)

Al and B are aluminum and boron, respectively,

M and L are each independently a transition element,

Y is at least one selected from carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic (As)

0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?

a and b are not 0 at the same time,

Provided that when b is 0, iron (Fe) and manganese (Mn) are not present simultaneously as the transition element.

The magnetoresistive material may be represented by the following Formula 1c:

[Chemical Formula 1c]

_{Al (Fe 1 - a L a} ) 2 + c (B 1- b Y b) 2 + d

In the above formula (1c)

Al, Fe and B are aluminum, iron and boron, respectively,

L is at least one element selected from the group consisting of Ni, Co, Mn, Cr, V, Ru, Mo, Nb, Zr, ) And tantalum (Ta).

Y is at least one selected from carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic (As)

0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?

a and b are not 0 at the same time,

When b is 0, L is not manganese (Mn).

The magnetic phase transition temperature can be controlled in accordance with a or b of the above formula (1).

The magnetic phase transition temperature may be about 100K to 400K.

The magnetoresistive material may include a plurality of layers to which the transition element and the non-metal element or the quasi-metal element are bonded, and an aluminum element located between the plurality of layers.

According to another embodiment, there is provided a method for producing a layered crystal material, which comprises preparing a layered crystal material represented by the following formula (3), mixing the layered crystalline material with at least one kind of transition element or at least one kind of transition element precursor, Of the present invention.

(3)

Al (X _{1 - b} Y _b ) _{2 + d}

In Formula 3,

Al is aluminum,

X and Y are each independently a non-metallic element or a metalloid element,

0? B? 1 and -0.5? D? 0.5, respectively.

The non-metallic or sub-metallic element may be at least one selected from boron (B), carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic (As) It can be one.

The transition element may be at least one element selected from the group consisting of Fe, Ni, Co, Mn, Cr, V, Ru, Mo, (Zr), tungsten (W), and tantalum (Ta).

The layered crystal material may include a plurality of layers made of the non-metallic element or the quasi-metallic element and aluminum elements inserted between the plural layers.

The layered crystal material is AlB ₂ Lt; / RTI &gt;

In the mixing step, a reaction catalyst which forms an eutectic melt with aluminum may be provided.

The reaction catalyst may include tin (Sn), indium (In), magnesium (Mg), alloys thereof, or combinations thereof.

The heat treatment may be performed at about 600 to 1000 ° C.

According to another embodiment, there is provided a product comprising the magnetically-heating material.

The product may include different kinds of magnetic thermal materials represented by the formula (1).

The product may include an electromagnetic wave shielding material, a magnetic cooling device, a magnetic heat generator, and a magnetic heat pump.

It is possible to improve the magnetic heat effect by controlling the magnetic property of the magnetic thermal material and simplify the manufacturing process of the magnetic thermal material, thereby realizing economical mass production.

Figs. 1 to 13 are graphs showing the results of the reference synthesis examples and Synthesis Examples 1-1 to 1-3, 2-1 to 2-3, 3-1, 3-2, 4-1, 4-2, 5-1 and 5 -2, which is an X-ray diffraction analysis graph of the magnetic thermal material,
14 is a graph showing changes in magnetization curves according to the temperatures of the magnetic thermal materials according to Synthesis Examples 1-1 and 1-2 and the reference synthesis example,
15 is a graph showing changes in magnetization curves according to the temperatures of magnetic thermal materials according to Synthesis Examples 2-1 to 2-4 and Reference Synthesis Example,
16 is a graph showing changes in magnetization curves according to the temperatures of magnetic thermal materials according to Synthesis Examples 3-1 and 3-2 and Reference Synthesis Example,
17 is a graph showing changes in magnetization curves according to the temperatures of magnetic thermal materials according to Synthesis Examples 4-1 and 4-2 and Reference Synthesis Example,
18 is a graph showing changes in magnetization curves according to the temperatures of the magnetic thermal materials according to Synthesis Examples 5-1 and 5-2 and the reference synthesis example.

Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Hereinafter, the magnetic thermal material according to one embodiment will be described.

A magnetocaloric material is a material capable of generating a magnetic heat effect by magnetic phase transition. In one embodiment, the magnetic thermal material is represented by the following formula (1).

[Chemical Formula 1]

Al (M _{1 - a} L _a ) _{2 + c} (X _{1 - b} Y _b ) _{2 + d}

In Formula 1,

Al is aluminum,

M and L are each independently a transition element,

X and Y are each independently a non-metallic element or a metalloid element,

0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?

a and b are not 0 at the same time,

Provided that when b is 0, iron (Fe) and manganese (Mn) are not present simultaneously as the transition element.

The transition element is an element having a 3d outermost electron. Examples of the transition element include Fe, Ni, Co, Mn, Cr, vanadium, ruthenium, molybdenum, (Mo), niobium (Nb), zirconium (Zr), tungsten (W) and tantalum (Ta).

The nonmetal or metalloid element may be selected from, for example, boron (B), carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic At least one.

The magnetoresistive material represented by Formula 1 may be a non-rare-earth material including aluminum, at least one kind of transition element, and at least one kind of non-metal element or sub-metal element, and may have a plurality of layered structures. The plurality of layered structures may have, for example, a structure in which a plurality of layers in which the transition element and the non-metallic element or the quasi-metallic element are bonded and an aluminum element is positioned between the plurality of layers, And may be arranged in a zigzag manner. The magnetoresistive material represented by Formula 1 may have an orthorhombic system structure, for example.

The magnetic thermal material represented by Formula 1 may have a two-dimensional magnetic structure resulting from the layered structure, and thus may have a magnetic phase transition temperature (Tc) near room temperature (about 300K). The self-phase transition temperature is the temperature at which the magnetic thermal material changes from the ferromagnetic state to the paramagnetic state, the ferromagnetic state at the temperature lower than the magnetic phase transition temperature, and the paramagnetic state at the temperature higher than the magnetic phase transition temperature. Therefore, it can be advantageously applied to a cooling device such as a refrigerator or an air conditioner by having a self-phase transition temperature at a room temperature body.

In addition, the magnetic thermal material represented by the formula (1) does not involve structural phase transition due to the two-dimensional magnetic structure and thus does not generate thermal hysteresis and magnetic hysteresis. Therefore, when the magnetic heating material is applied to a cooling device such as a refrigerator or an air conditioner, energy loss can be reduced and high efficiency can be realized.

The magnetic thermal material represented by the formula (1) includes at least one of the transition element and the nonmetal element or the metalloid element. For example, when a is not 0 in the above formula (1), it includes plural kinds of transition elements, and when b is not 0, plural kinds of non-metallic elements or sub-metallic elements are included. Also, for example, when a and b are not all 0 in the above formula (1), plural kinds of transition elements and plural kinds of nonmetal elements or submetallic elements are included. By including a plurality of kinds of transition elements and / or a plurality of kinds of nonmetal elements or quasimetric elements in this way, the self phase transition temperature can be changed.

For example, when the magnetic thermal material includes the first and second transition elements, the magnetic phase transition temperature can be lowered as compared with the case where only the first transition element is included, and the degree of change in the magnetic phase transition temperature Can be controlled.

For example, when the magnetoresistive material includes the first and second nonmetallic elements or the quasi-metallic element, the magnetic phase transition temperature can be increased as compared with the case where only the first nonmetal element or the quasi-metallic element is included. The degree of change of the magnetic phase transition temperature can be controlled according to the content of the metal element.

Accordingly, the phase transition temperature of the magnetic thermal material can be lowered or increased by changing the composition of the magnetic thermal material, and the desired magnetic phase transition temperature can be controlled by selecting the kind and content of the transition element and / or the nonmetal element or the quasi metal element .

In addition, by using two or more kinds of magnetic thermal materials having different magnetic phase transition temperatures, it is possible to enlarge the temperature range in which magnetism can be attained and thereby to widen the operating temperature range.

The magnetic thermal material represented by the formula (1) may be represented by, for example, the following formula (1a).

[Formula 1a]

_{Al (Fe 1 - a L a} ) 2 + c (X 1 - b Y b) 2 + d

In formula (1a)

Al and Fe are aluminum and iron, respectively,

L is a transition element other than iron (Fe), and examples thereof include transition metals such as Ni, Co, Mn, Cr, V, Ru, Mo, Nb), zirconium (Zr), tungsten (W), and tantalum (Ta)

X and Y are each independently a non-metallic element or a metalloid element,

0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?

a and b are not 0 at the same time,

When b is 0, L is not manganese (Mn).

The magnetic thermal material represented by Formula 1a may be a magnetic thermal material represented by the following Formula 1aa.

(1aa)

_{Al (Fe 1 - a L a} ) 2+ c B 2

In the above formula (1aa)

Al, Fe and B are aluminum, iron and boron, respectively,

L is a transition element except for iron (Fe) and manganese (Mn)

0 &lt; a? 1 and -0.5? C? 0.5, respectively.

The magnetoresistive material represented by Formula 1 may be represented by, for example, the following Formula 1b.

[Chemical Formula 1b]

Al (M _{1 - a} L _a ) _{2 + c} (B _{1 - b} Y _b ) _{2 + d}

In the above formula (1b)

Al and B are aluminum and boron, respectively,

M and L are each independently a transition element,

Y is a nonmetal element or a submetallic element other than boron (B), for example, carbon, silicon, phosphorus, sulfur, ), &Lt; / RTI &gt;

0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?

a and b are not 0 at the same time,

Provided that when b is 0, iron (Fe) and manganese (Mn) are not present simultaneously as the transition element.

The magnetic thermal material represented by the formula 1b may be a magnetic thermal material represented by the following formula 1ba.

[Chemical Formula 1ba]

AlFe ₂ (B _{1 - b} Y _b ) _{2 + d}

In the above formula (1ba)

Al, Fe and B are aluminum, iron and boron, respectively,

Y may be at least one selected from carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic (As)

0 &lt; b? 1 and -0.5? D? 0.5, respectively

The magnetoresistive material represented by Formula 1 may be represented by, for example, the following Formula 1c.

[Chemical Formula 1c]

_{Al (Fe 1 - a L a} ) 2 + c (B 1- b Y b) 2 + d

In the above formula (1c)

Al, Fe and B are aluminum, iron and boron, respectively,

L is a transition element other than iron (Fe), and examples thereof include transition metals such as Ni, Co, Mn, Cr, V, Ru, Mo, Nb), zirconium (Zr), tungsten (W), and tantalum (Ta)

Y is a nonmetal element or a submetallic element other than boron (B), for example, carbon, silicon, phosphorus, sulfur, ), &Lt; / RTI &gt;

0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?

a and b are not 0 at the same time,

When b is 0, L is not manganese (Mn).

The magnetic thermal material may be contained in the form of particles, and the particles may be, for example, microcrystalline particles.

The magnetic thermal material may have a particle diameter of about 1 nm to 100 탆. By having the particle diameter within the above range, the generation of cracks due to the magnetic hysteresis and thermal history can be prevented or alleviated, and the self cooling efficiency and the life characteristics can be improved. And may have a particle diameter of about 10 nm to 100 탆 within the above range, and a particle diameter of about 100 nm to 5 탆 within the above range.

Hereinafter, a method of manufacturing a magnetic thermal material according to one embodiment will be described.

A method for manufacturing a magnetic thermal material according to an embodiment includes preparing a layered crystal material represented by the following Chemical Formula 3, mixing the layered crystalline material with at least one kind of transition element or at least one kind of transition element precursor , And a heat treatment step.

(3)

Al (X _{1 - b} Y _b ) _{2 + d}

In Formula 3,

Al is aluminum,

X and Y are each independently a non-metallic element or a metalloid element,

0? B? 1 and -0.5? D? 0.5, respectively.

The nonmetal or metalloid element may be selected from, for example, boron (B), carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic At least one.

First, a layered crystal material represented by the above formula (3) is prepared.

The layered crystal material represented by Formula 3 is a raw material containing aluminum and a non-metallic element or a quasi-metallic element and includes a plurality of layers made of the non-metallic element or the quasi-metallic element and aluminum elements inserted between the plural layers . Each layer constituting the layered crystal material may be, for example, a net-like planar shape, and may be, for example, a graphene-like layer. The layered crystal material may be, for example, AlB ₂ , and AlB ₂ may have a plurality of boron (B) in the form of net-like planar layers and aluminum (Al) may be located between the layers.

And then the layered crystalline material is mixed with at least one kind of transition element or at least one type of transition element precursor.

The transition element may be, for example, Fe, Ni, Co, Mn, Cr, V, Ru, Mo, Zirconium (Zr), tungsten (W) and tantalum (Ta), and the transition element precursor may be at least one selected from the group consisting of hydroxide, alkoxide, citrate, Acetylacetonate, halide, sulfonate, phosphate or hydrate form thereof.

The reducing agent may be mixed together. The reducing agent may include at least one selected from, for example, Group I elements, Group II elements, Group III elements, and combinations thereof. The Group I element may be, for example, lithium (Li), sodium (Na), potassium (K) or a combination thereof. The Group II element may be, for example, beryllium (Be), magnesium (Mg) (Sr), radium (Ra), or a combination thereof, and the Group III element may be aluminum (Al), for example.

The reducing agent is uniformly dispersed in the mixture and the oxidation reaction of the reducing agent is an exothermic reaction so that the mixture is heated uniformly so that the reaction between the substances contained in the mixture can be uniformly performed as a whole . Also, the oxide formed by oxidizing the reducing agent is formed between the generated magnetic thermal materials, and the material formed by oxidizing the reducing agent and the generated magnetic thermal material do not react with each other. Thus, the material formed by oxidizing the reducing agent can control the growth of the magnetic thermal material, thereby controlling the particle size and uniformity of the magnetic thermal material.

During the mixing, the reaction catalyst may be mixed together. The reaction catalyst may be used for promoting the reaction between the layered crystal material and the transition element or the transition element precursor. For example, a material capable of acting as a flux to facilitate diffusion of the transition element into the layered crystal material Lt; / RTI &gt; Such a material may be an element forming eutectic melt with aluminum constituting the layered crystal material, for example, including tin (Sn), indium (In), magnesium (Mg) .

The mixing may be, for example, a ball mill process, an attrition mill process, a jet mill process, a spike mill process, or a combination thereof, but is not limited thereto.

The mixing may be performed in an inert atmosphere such as argon gas, a reducing atmosphere such as hydrogen gas, a vacuum atmosphere, or an atmospheric atmosphere containing oxygen gas.

The mixture is then heat treated.

The heat treatment may be performed by, for example, conventional heating, microwave heating, induction heating, spark plasma sintering, or the like, for example, at about 600 to 1000 ° C .

By the heat treatment, the transition element can be diffused into the layered crystal structure, for example, a layer made of the nonmetal element or the metalloid element to form a chemical bond with the nonmetal element and the metalloid element.

By the heat treatment, a plurality of layered magnetic recording materials including aluminum, a nonmetal element or a metalloid element and a transition element can be obtained. The plurality of layered structures may have, for example, a structure in which a plurality of layers in which the transition element and the non-metallic element or the quasi-metallic element are bonded and an aluminum element is positioned between the plurality of layers, And can be arranged in a zigzag.

Subsequently, the magnetic thermal material may be subjected to additional heat treatment at about 700 to 1100 ° C.

The above-described manufacturing method does not require a high-energy process such as arc melting or induction heating, thereby reducing manufacturing cost and mass production.

The magnetic thermal material may be processed into various shapes and manufactured into various products requiring a magnetic heating effect. The product may include, but is not limited to, electromagnetic shielding materials, magnetic cooling devices, magnetic heat generators, and magnetic heat pumps.

At this time, by using two or more types of magnetic thermal materials having different magnetic phase transition temperatures as described above, it is possible to widen the temperature range where magnetism can be attained to widen the application temperature range.

Examples and comparative examples of the present invention will be described below. However, the following examples are only examples of the present invention, and the present invention is not limited by the following examples.

Reference synthesis example : AlFe ₂ B ₂  of  Produce

Aluminum (Al) and boron (B) are mixed at a molar ratio of 1: 2 and heat-treated at 800 ° C for 6 hours in an argon atmosphere to synthesize AlB ₂ . Then, 0.3033 g of the synthesized AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn) were mixed in an atmosphere of nitrogen using an agate mortar to obtain a mixed powder. The mixing can be carried out in air or an anoxic atmosphere, but it is safe to mix in an oxygen-free atmosphere in consideration of the reactivity of aluminum (Al) powder and the like. Then, the mixed powder is filled in a metal mold, and the mixture is compressed in the form of a cylinder having a diameter of 1 cm by applying pressure (300 kgf / cm 2) to the press. Subsequently, the cylindrical compact is placed in a quartz tube, and the quartz tube is sealed in a vacuum. The quartz tube is then heat-treated in an electric furnace at 800 DEG C for 8 hours. The reaction in the heat treatment process is shown in the following reaction formula.

[Reaction Scheme]

AlB ₂ + 2Fe + 0.5 Al + 0.3 Sn -> AlFe ₂ B ₂ + 0.5 Al + 0.3 Sn

Subsequently, the heat-treated reaction mixture is pulverized in an agate mortar, and is then stirred in an aqueous 3 vol.% Hydrochloric acid solution for 1 hour to remove by-products such as aluminum (Al) and tin (Sn). Then washed three times with water, once with acetone and then dried to obtain AlFe ₂ B ₂ .

Synthetic example  1-1: AlFe _{One .9} Mn _{0 .One} B ₂  Manufacturing

Except that 0.3033 g of AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn), 0.3033 g of AlB _2, 0.6621 g of iron (Fe), 0.0343 g of manganese (Mn) g and 0.2222 g of tin (Sn) were used in the same manner as in Reference Synthesis Example to obtain AlFe _{1 .9} Mn _{0 .1} B _{2 .}

Synthetic example  1-2: AlFe _{One .7} Mn _{0 .3} B ₂  Manufacturing

0.3033 g of AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn), 0.3033 g of AlB _2, 0.5924 g of iron (Fe), 0.1028 g of manganese (Mn) g and 0.2222 g of tin (Sn) were used in the same manner as in Reference Synthesis Example to obtain AlFe _{1 .7} Mn _{0 .3} B _{2 .}

Synthetic example  1-3: AlMn ₂ B ₂  of  Produce

Except that 0.3033 g of AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn) were replaced with 0.3033 g of AlB _2, 0.6856 g of manganese (Mn) and 0.0842 g of aluminum Except that 1 vol% hydrochloric acid aqueous solution was used instead of hydrochloric acid aqueous solution, AlMn ₂ B ₂ was obtained _.

Synthetic example  2-1: AlFe _{One .95} Co _{0 .05} B ₂  Manufacturing

AlB ₂ 0.3033g, iron (Fe) 0.6981g, aluminum (Al) 0.0842g, and tin (Sn) 0.2222g 0.3033g instead of AlB _2, iron (Fe) 0.6621g, cobalt (Co) 0.0368g, aluminum (Al) 0.0842 g and 0.2222 g of tin (Sn) were used in the same manner as in Reference Synthesis Example to obtain AlFe _{1 .95} Co _{0 .05} B _{2 .}

Synthetic example  2-2: AlFe _{One .85} Co _{0 .15} B ₂  Manufacturing

0.3033 g of AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn), 0.3033 g of AlB _2, 0.6447 g of iron (Fe), 0.0552 g of cobalt (Co) synthesized by g and tin in the same manner as in synthesis example basis, except for using (Sn) 0.2222g to obtain the _{AlFe 1 .85 Co 0 .15 B 2} .

Synthetic example  2-3: AlFe _{One .8} Co _{0 .2} B ₂  Manufacturing

0.3033 g of AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn), 0.3033 g of AlB _2, 0.6273 g of iron (Fe), 0.0736 g of cobalt (Co) , except that the g and tin (Sn) 0.2222g synthesized in the same manner as the reference example is obtained by synthesizing the _{AlFe 1 .8 Co 0 .2 B 2} .

Synthetic example  2-4: AlFe _{One .7} Co _{0 .3} B ₂  Manufacturing

0.3033 g of AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn), 0.3033 g of AlB _2, 0.5924 g of iron (Fe), 0.1103 g of cobalt (Co) , except that the g and tin (Sn) 0.2222g synthesized in the same manner as the reference example is obtained by synthesizing the _{AlFe 1 .7 Co 0 .3 B 2} .

Synthetic example  3-1: AlFe _{One .9} Cr _{0 .One} B ₂  Manufacturing

AlB ₂ 0.3033g, iron (Fe) 0.6981g, aluminum (Al) 0.0842g, and tin (Sn) 0.2222g 0.3033g instead of AlB _2, iron (Fe) 0.6621g, chromium (Cr) 0.0325g, aluminum (Al) 0.0842 , except that the g and tin (Sn) 0.2222g synthesized in the same manner as the reference example is obtained by synthesizing the _{AlFe 1 .9 Cr 0 .1 B 2} .

Synthetic example  3-2: AlFe _{One .8} Cr _{0 .2} B ₂  Manufacturing

0.3033 g of AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn), 0.3033 g of AlB _2, 0.6273 g of iron (Fe), 0.0649 g of chromium (Cr) , except that the g and tin (Sn) 0.2222g synthesized in the same manner as the reference example is obtained by synthesizing the _{AlFe 1 .8 Cr 0 .2 B 2} .

Synthetic example  4-1: AlFe ₂ B _{One .9} Si _{0 . One}  of  Produce

0.3033 g of AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn), 0.3033 g of AlB _2, 0.6970 g of iron (Fe), 0.0479 g of Mg ₂ Si, And 0.2222 g of tin (Sn) were used in the same manner as in Reference Synthesis Example to obtain AlFe ₂ B _1.9 Si _{0.1 .}

Synthetic example  4-2: AlFe ₂ B _{One .8} Si _{0 . 2}  of  Produce

0.303 g of AlB _2, 0.0982 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn), 0.3033 g of AlB _2, 0.6970 g of iron (Fe), 0.0958 g of Mg ₂ Si, And 0.2222 g of tin (Sn) were used in the same manner as in Reference Synthesis Example to obtain AlFe ₂ B _1.8 Si _{0.2 .}

Synthetic example  5-1: AlFe ₂ B _{One .9} P _{0 . One}  of  Produce

0.3033 g of AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn), 0.3033 g of AlB _2, 0.6970 g of iron (Fe), 0.0193 g of phosphorus (P) g and 0.2222 g of tin (Sn) were used in the same manner as in Reference Synthesis Example to obtain AlFe ₂ B _1.9 P _{0.1 .}

Synthetic example  5-2: AlFe ₂ B _{One .7} P _{0 . 3}  of  Produce

0.3033 g of AlB _2, 0.6981 g of iron (Fe), 0.0842 g of aluminum (Al) and 0.2222 g of tin (Sn), 0.3033 g of AlB _2, 0.6970 g of iron (Fe), 0.0580 g of phosphorus (P) g and 0.2222 g of tin (Sn) were used in the same manner as in Reference Synthesis Example to obtain AlFe ₂ B _1.7 P _{0.3 .}

Rating 1

The crystal structure of the magnetic thermal materials obtained in Reference Synthesis Example and Synthesis Examples 1-1 to 5-2 is confirmed by X-ray diffraction analysis.

The results are shown in Figs.

Figs. 1 to 13 are graphs showing the results of the reference synthesis examples and Synthesis Examples 1-1 to 1-3, 2-1 to 2-3, 3-1, 3-2, 4-1, 4-2, 5-1 and 5 -2 is an X-ray diffraction analysis graph of the magnetorheological material.

1 to 13, the reference synthesis example and Synthesis Examples 1-1 to 1-3, 2-1 to 2-3, 3-1, 3-2, 4-1, 4-2, and 5-1 And 5-2 can all be confirmed to have an orthorhombic crystal structure.

Rating 2

The change in magnetization curve according to the temperature of the magnetocrystalline material obtained in Reference Synthesis Example and Synthesis Examples 1-1 to 5-2 is evaluated.

The results are described with reference to Figs. 14 to 18. Fig.

FIG. 14 is a graph showing changes in magnetization curves according to the temperatures of magnetic thermal materials according to Synthesis Examples 1-1 and 1-2 and Reference Synthesis Example, and FIG. 15 is a graph showing the change of magnetization curves according to Synthesis Examples 2-1 to 2-4 and Reference Synthesis Example FIG. 16 is a graph showing changes in magnetization curves according to the temperature of the magnetic thermal material according to Synthesis Examples 3-1 and 3-2 and the reference synthesis example. FIG. 17 is a graph showing changes in magnetization curves according to the temperatures of magnetic thermal materials according to Synthesis Examples 4-1 and 4-2 and Reference Synthesis Example, FIG. 5 is a graph showing the change of the magnetization curve according to the temperature of the magnetic thermal material according to the synthesis example. FIG.

14 to 18, the temperature at the point representing the maximum slope of each curve can be defined as the magnetic phase transition temperature.

14 to 18, the magnetic thermal material according to the reference synthesis example exhibits a magnetic phase transition temperature near about 300 K and the magnetic thermal material according to Synthesis Examples 1-1 to 3-2 is a magnetic thermal substance according to the reference synthesis example It can be confirmed that the magnetostrictive materials according to Synthesis Examples 4-1 to 5-2 exhibit the magnetostatic transition temperature at a temperature lower than that of the magnetostrictive material according to the reference synthesis example.

From this, the magnetic thermal material including the first and second transition elements can lower the magnetic phase transition temperature as compared with the magnetic thermal material including the first transition element. At this time, depending on the content of the second transition element, And the like.

Likewise, the magnetic thermal material including the first and second nonmetallic elements or the quasi-metallic element can increase the temperature of the magnetic phase transition compared to the magnetic thermal material including the first nonmetal element or the quasi-metallic element, It can be confirmed that the degree of change of the magnetic phase transition temperature varies depending on the content of the metal element.

Accordingly, the phase transition temperature of the magnetic thermal material can be lowered or increased by changing the composition of the magnetic thermal material, and the desired magnetic phase transition temperature can be controlled by selecting the kind and content of the transition element and / or the nonmetal element or the quasi metal element . In addition, by including two or more kinds of magnetic thermal materials having different magnetic phase transition temperatures, it can be seen that the temperature range in which magnetism can be increased can be expanded and thus the operating temperature range can be widened.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (20)

Magnetic thermal material represented by the following formula (1)
[Chemical Formula 1]
Al (M _{1 - a} L _a ) _{2 + c} (X _{1 - b} Y _b ) _{2 + d}
In Formula 1,
Al is aluminum,
M and L are each independently a transition element,
X and Y are each independently a non-metallic element or a metalloid element,
0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?
a and b are not 0 at the same time,
Provided that when b is 0, iron (Fe) and manganese (Mn) are not present simultaneously as the transition element.
The method of claim 1,
The transition element may be at least one element selected from the group consisting of Fe, Ni, Co, Mn, Cr, V, Ru, Mo, (Zr), tungsten (W), and tantalum (Ta).
The method of claim 1,
The non-metallic or sub-metallic element may be at least one selected from boron (B), carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic (As) One of the self-heating substances.
The method of claim 1,
A magnetorheological substance represented by the following formula (1a).
[Formula 1a]
_{Al (Fe 1 - a L a} ) 2 + c (X 1 - b Y b) 2 + d
In formula (1a)
Al and Fe are aluminum and iron, respectively,
L is at least one element selected from the group consisting of Ni, Co, Mn, Cr, V, Ru, Mo, Nb, Zr, ) And tantalum (Ta).
X and Y are each independently a non-metallic element or a metalloid element,
0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?
a and b are not 0 at the same time,
When b is 0, L is not manganese (Mn).
The method of claim 1,
A magnetorheological substance represented by the following formula (1b).
[Chemical Formula 1b]
Al (M _{1 - a} L _a ) _{2 + c} (B _{1 - b} Y _b ) _{2 + d}
In the above formula (1b)
Al and B are aluminum and boron, respectively,
M and L are each independently a transition element,
Y is at least one selected from carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic (As)
0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?
a and b are not 0 at the same time,
Provided that when b is 0, iron (Fe) and manganese (Mn) are not present simultaneously as the transition element.
The method of claim 1,
Magnetic thermal material represented by the following formula 1c:
[Chemical Formula 1c]
_{Al (Fe 1 - a L a} ) 2 + c (B 1- b Y b) 2 + d
In the above formula (1c)
Al, Fe and B are aluminum, iron and boron, respectively,
L is at least one element selected from the group consisting of Ni, Co, Mn, Cr, V, Ru, Mo, Nb, Zr, ) And tantalum (Ta).
Y is at least one selected from carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic (As)
0? A? 1, 0? B? 1, -0.5? C? 0.5 and -0.5? D?
a and b are not 0 at the same time,
When b is 0, L is not manganese (Mn).
The method of claim 1,
Wherein the magnetic phase transition temperature is controlled in accordance with a or b in the above formula (1).
The method of claim 1,
Wherein the magnetic phase transition temperature is 100K to 400K.
The method of claim 1,
Wherein the magnetocaloric material comprises a plurality of layers to which the transition element and the nonmetal or submetal element are bonded and an aluminum element located between the plurality of layers.
Preparing a layered crystal material represented by the following formula (3)
Mixing the layered crystalline material with at least one kind of transition element or at least one type of transition element precursor, and
Step of heat treatment
A method for producing a magnetic thermal material comprising:
(3)
Al (X _{1 - b} Y _b ) _{2 + d}
In Formula 3,
Al is aluminum,
X and Y are each independently a non-metallic element or a metalloid element,
0? B? 1 and -0.5? D? 0.5, respectively.
11. The method of claim 10,
The non-metallic or sub-metallic element may be at least one selected from boron (B), carbon (C), silicon (Si), phosphorus (P), sulfur (S), germanium (Ge), arsenic (As) / RTI &gt; as claimed in any one of the preceding claims.
11. The method of claim 10,
The transition element may be at least one element selected from the group consisting of Fe, Ni, Co, Mn, Cr, V, Ru, Mo, (Zr), tungsten (W), and tantalum (Ta).
11. The method of claim 10,
Wherein the layered crystal material includes a plurality of layers made of the non-metallic element or the quasi-metallic element and aluminum elements inserted between the plurality of layers.
11. The method of claim 10,
The layered crystal material is AlB ₂ The method of producing a self-heat material.
11. The method of claim 10,
Wherein the mixing step comprises providing a reaction catalyst that forms an eutectic melt with aluminum in the mixing step.
16. The method of claim 15,
Wherein the reaction catalyst comprises tin (Sn), indium (In), magnesium (Mg), an alloy thereof, or a combination thereof.
11. The method of claim 10,
Wherein the heat treatment is performed at 600 to 1000 占 폚.
10. An article comprising a magnetically-attracting substance according to any one of claims 1 to 9.
The method of claim 18,
The product comprising different types of magnetic thermal materials represented by the formula (1).
The method of claim 18,
An electromagnetic shielding material, a magnetic cooling device, a magnetic heat generator, and a magnetic heat pump.

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