JP2021031584A - Caloric material and cooling device including the same - Google Patents
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Classifications
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
Description
本発明は、熱量効果材料及びそれを用いた冷却装置に関する。 The present invention relates to a calorific value effect material and a cooling device using the same.
近年、環境に配慮した、高効率な冷却技術が求められている。例えば、冷蔵庫やエアコンなどの冷却に関する技術では、ノンフロンで高効率なヒートポンプの開発に大きな期待が寄せられている。 In recent years, environmentally friendly and highly efficient cooling technology has been required. For example, in the technology related to cooling of refrigerators and air conditioners, there are great expectations for the development of non-fluorocarbon and highly efficient heat pumps.
冷却技術として近年注目を集めているものの一つに磁気冷却が挙げられる。磁気冷却では強磁性物質に磁場を印加したときのエントロピー変化（-ΔS）を利用する磁気熱量効果により冷凍などの熱変換が可能となる（例えば、特許文献１）。磁気冷却はガス圧縮式冷凍と比べて効率が高く、また冷媒であるフロンが不要なことから、環境に対応した次世代冷却としても大きな注目を集めている。大きな熱量効果を示す材料は、磁気冷却に限らず高効率な次世代冷却に用いることが可能であり、そのような材料の開発は社会から強く求められている。 Magnetic cooling is one of the cooling technologies that has been attracting attention in recent years. In magnetic cooling, heat conversion such as freezing becomes possible by the magnetic calorific value effect utilizing the entropy change (-ΔS) when a magnetic field is applied to a ferromagnetic material (for example, Patent Document 1). Magnetic cooling is more efficient than gas compression refrigeration and does not require chlorofluorocarbon as a refrigerant, so it is attracting a great deal of attention as next-generation cooling that is environmentally friendly. Materials that exhibit a large calorific effect can be used not only for magnetic cooling but also for highly efficient next-generation cooling, and the development of such materials is strongly demanded by society.
本発明の目的は、高効率な熱量効果材料及びそれを用いた冷却装置を提供することにある。 An object of the present invention is to provide a highly efficient calorific value effect material and a cooling device using the same.
本発明者らは、前記課題を解決するため鋭意検討を行った結果、特定のペロブスカイト型酸化物について、所定の条件下で生じる転移により大きなエントロピー変化が生じることを見出し、当該ペロブスカイト型酸化物が、転移に起因する大きなエントロピー変化を利用した高効率な熱量効果材料となることを見出した。ここで、所定の条件とは、ペロブスカイト型酸化物それ自体の物理量、その周囲の物理量、それに加えられる物理量などを変化させることをいう。
本発明は、上記の知見に基づいてさらに検討を重ねて完成したものである。
As a result of diligent studies to solve the above problems, the present inventors have found that, for a specific perovskite-type oxide, a large entropy change occurs due to the transition occurring under predetermined conditions, and the perovskite-type oxide is used. , It was found that it is a highly efficient calorific value effect material utilizing a large entropy change caused by transition. Here, the predetermined condition means changing the physical quantity of the perovskite-type oxide itself, the physical quantity around it, the physical quantity added thereto, and the like.
The present invention has been completed by further studying based on the above findings.
本発明は、以下の態様を包含する。
項１．
下記式（１）：
Ａ’Ａ３Ｂ４Ｏ１２ （１）
（式中、
Ａ’は、Ｌａ、Ｂｉ、Ｙ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｃａ、Ｓｒ、Ｂａ、及びＰｂからなる群より選ばれる少なくとも一種の元素であり、
Ａは、Ｃｕ、Ｍｎ、Ｆｅ、Ｂｉ、及びＮｉからなる群より選ばれる少なくとも一種の元素であり、
Ｂは、Ｆｅ、Ｔｉ、Ｖ、Ｃｒ、Ｃｕ、Ｍｎ、Ｒｅ、Ｃｏ、Ｎｉ、Ｇｅ、Ｓｎ、Ｚｒ、及びＲｕからなる群より選ばれる少なくとも一種の元素である。）
で表されるペロブスカイト型酸化物を含有する熱量効果材料。
項２．
周囲の圧力、周囲の温度、周囲の磁場、印加する電圧、及び印加する電流からなる群より選ばれる少なくとも一種を変化させることにより発熱又は吸熱が生じる、項１に記載の熱量効果材料。
項３．
周囲の圧力、周囲の温度、周囲の磁場、印加する電圧、及び印加する電流のいずれを変化させても発熱又は吸熱が生じる、項１又は２に記載の熱量効果材料。
項４．
磁気転移に伴って発熱又は吸熱を生じる、項１〜３のいずれか一項に記載の熱量効果材料。
項５．
体積変化に伴って発熱又は吸熱を生じる、項１〜４のいずれか一項に記載の熱量効果材料。
項６．
電気伝導性変化に伴って発熱又は吸熱を生じる、項１〜５のいずれか一項に記載の熱量効果材料。
項７．
構成元素ＡとＢとの間で電荷の移動、又はＢの電荷の分離が生じることにより、発熱又は吸熱を生じる、項１〜６のいずれか一項に記載の熱量効果材料。
項８．
Ａ’は、Ｌａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、及びＴｂからなる群より選ばれる一種又は二種以上である、項１〜７のいずれか一項に記載の熱量効果材料。
項９．
Ａ’が、Ｃａを含む、項１〜７のいずれか一項に記載の熱量効果材料。
項１０．
ペロブスカイト型酸化物が、下記式（２）又は（３）：
ＬｎＣｕ３Ｆｅ４Ｏ１２ （２）
（式中、Ｌｎは、Ｌａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、又はＴｂである。）
ＣａＣｕ３Ｆｅ４Ｏ１２ （３）
で表される、項１〜９のいずれか一項に記載の熱量効果材料。
項１１．
示差走査熱量測定において、１９０Ｋ〜４５０Ｋの範囲に発熱ピーク又は吸熱ピークを有する、項１〜１０のいずれか一項に記載の熱量効果材料。
項１２．
示差走査熱量測定において、１９０Ｋ〜４５０Ｋの範囲でのエントロピー変化量が、３０Ｊｋｇ−１Ｋ−１以上である、項１〜１１のいずれか一項に記載の熱量効果材料。
項１３．
項１〜１２のいずれか一項に記載の熱量効果材料を用いた冷却装置。
The present invention includes the following aspects.
Item 1.
The following formula (1):
A'A 3 B 4 O 12 (1)
(During the ceremony,
A'is at least one selected from the group consisting of La, Bi, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, and Pb. Is an element of
A is at least one element selected from the group consisting of Cu, Mn, Fe, Bi, and Ni.
B is at least one element selected from the group consisting of Fe, Ti, V, Cr, Cu, Mn, Re, Co, Ni, Ge, Sn, Zr, and Ru. )
A calorific effect material containing a perovskite-type oxide represented by.
Item 2.
Item 2. The calorific value effect material according to Item 1, wherein heat is generated or endothermic by changing at least one selected from the group consisting of ambient pressure, ambient temperature, ambient magnetic field, applied voltage, and applied current.
Item 3.
Item 2. The calorific value effect material according to Item 1 or 2, wherein heat is generated or endothermic even if any of the ambient pressure, the ambient temperature, the ambient magnetic field, the applied voltage, and the applied current is changed.
Item 4.
Item 2. The calorific value effect material according to any one of Items 1 to 3, which generates heat or endothermic heat due to magnetic transition.
Item 5.
Item 2. The calorific value effect material according to any one of Items 1 to 4, which generates heat or endothermic with a change in volume.
Item 6.
Item 2. The calorific value effect material according to any one of Items 1 to 5, which generates heat or endothermic with a change in electrical conductivity.
Item 7.
Item 2. The calorific value effect material according to any one of Items 1 to 6, wherein heat generation or endotherm is generated by the transfer of electric charge between the constituent elements A and B or the separation of the electric charge of B.
Item 8.
Item 3. The calorific value effect material according to any one of Items 1 to 7, wherein A'is one or more selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, and Tb.
Item 9.
Item 2. The calorific value effect material according to any one of Items 1 to 7, wherein A'contains Ca.
Item 10.
The perovskite-type oxide has the following formula (2) or (3):
LnCu 3 Fe 4 O 12 (2)
(In the formula, Ln is La, Pr, Nd, Sm, Eu, Gd, or Tb.)
CaCu 3 Fe 4 O 12 (3)
Item 4. The calorific value effect material according to any one of Items 1 to 9.
Item 11.
Item 2. The calorific value effect material according to any one of Items 1 to 10, which has an exothermic peak or an endothermic peak in the range of 190K to 450K in differential scanning calorimetry.
Item 12.
The calorific value effect material according to any one of Items 1 to 11, wherein the amount of change in entropy in the range of 190K to 450K is 30 Jkg -1 K -1 or more in the differential scanning calorimetry.
Item 13.
A cooling device using the calorific value effect material according to any one of Items 1 to 12.
本発明によれば、高効率な熱量効果材料及びそれを用いた冷却装置が提供される。 According to the present invention, a highly efficient calorific value effect material and a cooling device using the same are provided.
＜熱量効果材料＞
本明細書において、熱量効果材料とは、物理量の変化により発熱又は吸熱が生じる材料をいう。物理量は、熱量効果材料自体の物理量であってもよいし、熱量効果材料周囲の物理量や熱量効果材料に加えられる物理量であってもよい。物理量は、例えば、熱量効果材料自体の体積、熱量効果材料周囲の圧力、熱量効果材料周囲の温度、熱量効果材料周囲の磁場、熱量効果材料に加えられる電圧、熱量効果材料に加えられる電流、及び熱量効果材料自体の電気抵抗などから選ばれる一種又は二種以上であってもよい。また、熱量効果材料は、熱交換材料、蓄熱材料、又は蓄冷材料であってもよい。
<Chemical effect material>
In the present specification, the calorific value effect material refers to a material that generates heat or endothermic due to a change in physical quantity. The physical quantity may be the physical quantity of the calorific value effect material itself, the physical quantity around the calorie effect material, or the physical quantity added to the calorie effect material. The physical quantities are, for example, the volume of the calorie effect material itself, the pressure around the calorie effect material, the temperature around the calorie effect material, the magnetic field around the calorie effect material, the voltage applied to the calorie effect material, the current applied to the calorie effect material, and It may be one kind or two or more kinds selected from the electric resistance of the calorific value effect material itself. Further, the heat quantity effect material may be a heat exchange material, a heat storage material, or a cold storage material.
本発明の熱量効果材料は、下記式（１）：
Ａ’Ａ３Ｂ４Ｏ１２ （１）
（式中、
Ａ’は、Ｌａ、Ｂｉ、Ｙ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｃａ、Ｓｒ、Ｂａ、及びＰｂからなる群より選ばれる少なくとも一種の元素であり、
Ａは、Ｃｕ、Ｍｎ、Ｆｅ、Ｂｉ、及びＮｉからなる群より選ばれる少なくとも一種の元素であり、
Ｂは、Ｆｅ、Ｔｉ、Ｖ、Ｃｒ、Ｃｕ、Ｍｎ、Ｒｅ、Ｃｏ、Ｎｉ、Ｇｅ、Ｓｎ、Ｚｒ、及びＲｕからなる群より選ばれる少なくとも一種の元素である。）
で表されるペロブスカイト型酸化物を含有する。
The calorific value effect material of the present invention has the following formula (1):
A'A 3 B 4 O 12 (1)
(During the ceremony,
A'is at least one selected from the group consisting of La, Bi, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, and Pb. Is an element of
A is at least one element selected from the group consisting of Cu, Mn, Fe, Bi, and Ni.
B is at least one element selected from the group consisting of Fe, Ti, V, Cr, Cu, Mn, Re, Co, Ni, Ge, Sn, Zr, and Ru. )
Contains a perovskite-type oxide represented by.
式（１）において、通常、Ａ’及びＡは、ペロブスカイト型酸化物のＡサイトを占める元素であり、Ｂは、ペロブスカイト型酸化物のＢサイトを占める元素であり、Ａ’、Ａ、及びＢは、互いに異なる種類の元素である。 In formula (1), A'and A are usually elements that occupy the A site of the perovskite-type oxide, B is an element that occupies the B site of the perovskite-type oxide, and A', A, and B. Are different types of elements.
一実施態様において、Ａ’は、Ｌａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、及びＴｂからなる群より選ばれる一種又は二種以上であることが好ましい。Ａ’を二種以上の元素の組合せとすることにより、発熱又は吸熱が生じる温度を調整することができる。 In one embodiment, A'is preferably one or more selected from the group consisting of La, Pr, Nd, Sm, Eu, Gd, and Tb. By combining A'with two or more elements, the temperature at which heat generation or endotherm occurs can be adjusted.
他の実施態様において、Ａ’は、Ｌａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、又はＴｂを含むことが好ましく、Ｌａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、又はＴｂであることがより好ましい。 In other embodiments, A'preferably comprises La, Pr, Nd, Sm, Eu, Gd, or Tb, more preferably La, Pr, Nd, Sm, Eu, Gd, or Tb. ..
別の実施態様において、Ａ’は、Ｎｄ、Ｓｍ、又はＧｄを含むことが好ましく、Ｎｄ、Ｓｍ、又はＧｄであることがより好ましい。 In another embodiment, A'preferably comprises Nd, Sm, or Gd, more preferably Nd, Sm, or Gd.
更に別の実施態様において、Ａ’は、Ｃａを含むことが好ましく、Ｃａであることがより好ましい。 In yet another embodiment, A'preferably contains Ca, more preferably Ca.
一実施態様において、Ａは、Ｃｕ、Ｍｎ、及びこれらの組合せであることが好ましい。 In one embodiment, A is preferably Cu, Mn, or a combination thereof.
他の実施態様において、Ａは、Ｃｕを含むことが好ましく、Ｃｕであることがより好ましい。 In other embodiments, A preferably contains Cu, more preferably Cu.
一実施態様において、Ｂは、Ｆｅ、Ｒｅ、及びこれらの組合せであることが好ましい。 In one embodiment, B is preferably Fe, Re, or a combination thereof.
他の実施態様において、Ｂは、Ｆｅを含むことが好ましく、Ｆｅであることがより好ましい。 In other embodiments, B preferably contains Fe, more preferably Fe.
式（１）で表されるペロブスカイト型酸化物は、下記式（２）又は（３）：
ＬｎＣｕ３Ｆｅ４Ｏ１２ （２）
（式中、Ｌｎは、Ｌａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、又はＴｂである。）
ＣａＣｕ３Ｆｅ４Ｏ１２ （３）
で表されるペロブスカイト型酸化物であることが好ましい。
The perovskite-type oxide represented by the formula (1) is represented by the following formula (2) or (3):
LnCu 3 Fe 4 O 12 (2)
(In the formula, Ln is La, Pr, Nd, Sm, Eu, Gd, or Tb.)
CaCu 3 Fe 4 O 12 (3)
It is preferably a perovskite-type oxide represented by.
式（１）で表されるペロブスカイト型酸化物の形状、大きさなどは特に限定されない。形状は、目的の部品などに応じて適宜設定すればよいが、部品の加工容易性などの観点から、粒子状であることが好ましい。形状が粒子状である場合、平均粒径は１〜１０００μｍ程度が好ましい。平均粒径の測定方法としては、公知の方法を採用することができ、例えば、透過型電子顕微鏡法などが挙げられる。 The shape and size of the perovskite-type oxide represented by the formula (1) are not particularly limited. The shape may be appropriately set according to the target parts and the like, but is preferably in the form of particles from the viewpoint of ease of processing of the parts. When the shape is particulate, the average particle size is preferably about 1 to 1000 μm. As a method for measuring the average particle size, a known method can be adopted, and examples thereof include a transmission electron microscope method.
式（１）で表されるペロブスカイト型酸化物は、例えば、Ａ’の酸化物、Ａの酸化物、及びＢの酸化物を混合し、熱処理（焼成）することにより製造できる。 The perovskite-type oxide represented by the formula (1) can be produced, for example, by mixing an oxide of A', an oxide of A, and an oxide of B and heat-treating (calcining) the oxide.
Ａ’の酸化物、Ａの酸化物、及びＢの酸化物の配合割合は、特に限定されず、式（１）で表されるペロブスカイト型酸化物が得られるように適宜設定すればよい。例えば、ＬｎＣｕ３Ｆｅ４Ｏ１２を製造する場合、Ｌｎ２Ｏ３、ＣｕＯ、及びＦｅ２Ｏ３をモル比で１：６：４の割合で用いればよい。また、ＣａＣｕ３Ｆｅ４Ｏ１２を製造する場合、ＣａＣＯ３、ＣｕＯ、及びＦｅ２Ｏ３をモル比で１：３：２の割合で用いればよい。 The blending ratio of the oxide of A', the oxide of A, and the oxide of B is not particularly limited, and may be appropriately set so as to obtain the perovskite type oxide represented by the formula (1). For example, when producing LnCu 3 Fe 4 O 12 , Ln 2 O 3 , CuO, and Fe 2 O 3 may be used in a molar ratio of 1: 6: 4. When CaCu 3 Fe 4 O 12 is produced, CaCO 3 , CuO, and Fe 2 O 3 may be used in a molar ratio of 1: 3: 2.
熱処理は、公知の方法に従って行うことができる。例えば、カプセル（例：白金カプセル）に、Ａ’の酸化物、Ａの酸化物、及びＢの酸化物の混合物を充填し、得られたカプセルを公知の装置を用いて熱処理（例：加圧及び加熱）する方法が挙げられる。公知の装置としては、例えば、立方体アンビル型高圧発生装置などが挙げられる。 The heat treatment can be performed according to a known method. For example, a capsule (eg, a platinum capsule) is filled with a mixture of an oxide of A', an oxide of A, and an oxide of B, and the obtained capsule is heat-treated using a known device (eg, pressurization). And heating). Known devices include, for example, a cubic anvil type high voltage generator.
熱処理の圧力は、６ＧＰａ以上が好ましく、６〜１５ＧＰａが更に好ましい。 The heat treatment pressure is preferably 6 GPa or more, more preferably 6 to 15 GPa.
熱処理の温度は、８００℃以上が好ましく、１０００℃以上がより好ましく、１０００℃〜１２００℃が更に好ましい。 The temperature of the heat treatment is preferably 800 ° C. or higher, more preferably 1000 ° C. or higher, and even more preferably 1000 ° C. to 1200 ° C.
熱処理の時間は、原料の酸化物が十分に反応するように適宜調整すればよいが、通常、３０分〜２４時間である。 The heat treatment time may be appropriately adjusted so that the oxide of the raw material reacts sufficiently, but is usually 30 minutes to 24 hours.
熱処理に先立って、Ａ’の酸化物、Ａの酸化物、及びＢの酸化物の混合物には、公知の添加剤を含有させてもよい。公知の添加剤としては、例えば、ＫＣｌＯ４などの酸化剤が挙げられる。 Prior to the heat treatment, the mixture of the oxide of A', the oxide of A, and the oxide of B may contain a known additive. Known additives, for example, oxidizing agents such as KClO 4.
本発明の熱量効果材料は、周囲の圧力、周囲の温度、周囲の磁場、印加する電圧、及び印加する電流からなる群より選ばれる少なくとも一種を変化させることにより発熱又は吸熱が生じる材料であることが好ましい。 The calorific value effect material of the present invention is a material that generates heat or endothermic by changing at least one selected from the group consisting of ambient pressure, ambient temperature, ambient magnetic field, applied voltage, and applied current. Is preferable.
周囲の圧力の変化（正又は負の圧力の印加も含む）により体積を変化させることにより発熱又は吸熱が生じる熱量効果材料を「圧力熱量効果材料」と呼ぶことができる。周囲の磁場を変化（正又は負の磁場の印加も含む）させることにより発熱又は吸熱が生じる熱量効果材料を「磁気熱量効果材料」と呼ぶことができる。印加する電圧、電流を変化（正又は負の電圧、電流の印加も含む）させることにより発熱又は吸熱が生じる熱量効果材料を「電気熱量効果材料」と呼ぶことができる。本発明の熱量効果材料は、圧力熱量効果材料、磁気熱量効果材料、及び電気熱量効果材料のいずれの材料にもなり得る。 A calorific value effect material that generates heat or endothermic by changing its volume due to a change in ambient pressure (including application of a positive or negative pressure) can be called a "pressure calorie effect material". A calorific value effect material that generates heat or endothermic by changing the ambient magnetic field (including application of a positive or negative magnetic field) can be called a "magnetic calorie effect material". A calorific value effect material that generates heat or endothermic by changing the applied voltage and current (including application of a positive or negative voltage and current) can be called an "electric calorific value effect material". The calorific value effect material of the present invention can be any of a pressure calorie effect material, a magnetic calorie effect material, and an electrocalorie effect material.
本発明の熱量効果材料は、周囲の圧力、周囲の温度、周囲の磁場、印加する電圧、及び印加する電流のいずれを変化させても発熱又は吸熱が生じる材料であることがより好ましい。このような熱量効果材料を「マルチ熱量効果材料」と呼ぶことができる。 It is more preferable that the calorific value effect material of the present invention is a material that generates heat or endothermic even if any of the ambient pressure, the ambient temperature, the ambient magnetic field, the applied voltage, and the applied current is changed. Such a calorific value effect material can be called a "multi calorie effect material".
本発明の熱量効果材料は、好ましくは、温度変化において発熱又は吸熱が生じる材料であり、より好ましくは、示差走査熱量測定において１７０Ｋ〜４５０Ｋの範囲に発熱ピーク又は吸熱ピークを有する材料であり、更に好ましくは、示差走査熱量測定において１９０Ｋ〜４５０Ｋの範囲に発熱ピーク又は吸熱ピークを有する材料であり、更により好ましくは、示差走査熱量測定において２５０Ｋ〜３５０Ｋの範囲に発熱ピーク又は吸熱ピークを有する材料であり、特に好ましくは、示差走査熱量測定において２７０Ｋ〜３１０Ｋの範囲に発熱ピーク又は吸熱ピークを有する材料である。 The calorific effect material of the present invention is preferably a material that generates heat or endothermic with a temperature change, and more preferably a material having a heat generation peak or endothermic peak in the range of 170K to 450K in differential scanning calorimetry. A material having an endothermic peak or endothermic peak in the range of 190K to 450K in the differential scanning calorimetry is preferable, and a material having an endothermic peak or endothermic peak in the range of 250K to 350K in the differential scanning calorimetry is even more preferable. A material having an endothermic peak or an endothermic peak in the range of 270K to 310K in differential scanning calorimetry is particularly preferable.
前記発熱ピーク又は吸熱ピークの半値幅は、均質性の点から、４０Ｋ以下が好ましく、３５Ｋ以下がより好ましく、３０Ｋ以下が更に好ましい。 The half width of the exothermic peak or endothermic peak is preferably 40 K or less, more preferably 35 K or less, and even more preferably 30 K or less from the viewpoint of homogeneity.
本発明の熱量効果材料の示差走査熱量測定において、発熱ピーク又は吸熱ピークが現れる温度範囲（例えば、１７０Ｋ〜４５０Ｋ、好ましくは１９０Ｋ〜４５０Ｋ）でのエントロピー変化量は、例えば、３０Ｊｋｇ−１Ｋ−１以上、好ましくは３５Ｊｋｇ−１Ｋ−１以上、更に好ましくは４０Ｊｋｇ−１Ｋ−１以上、更により好ましくは４５Ｊｋｇ−１Ｋ−１以上、特に好ましくは５０Ｊｋｇ−１Ｋ−１以上、特により好ましくは５５Ｊｋｇ−１Ｋ−１以上、最も好ましくは６０Ｊｋｇ−１Ｋ−１以上である。 In the differential scanning calorie measurement of the calorific value effect material of the present invention, the amount of change in entropy in the temperature range in which the exothermic peak or heat absorption peak appears (for example, 170K to 450K, preferably 190K to 450K) is, for example, 30 Jkg -1 K -1. or more, preferably 35Jkg -1 K -1 or higher, more preferably 40Jkg -1 K -1 or higher, even more preferably 45Jkg -1 K -1 or higher, particularly preferably 50Jkg -1 K -1 or higher, particularly more preferably 55 Jkg -1 K -1 or more, most preferably 60 Jkg -1 K -1 or more.
本発明の熱量効果材料の示差走査熱量測定において、発熱ピーク又は吸熱ピークが現れる温度範囲（例えば、１７０Ｋ〜４５０Ｋ、好ましくは１９０Ｋ〜４５０Ｋ）でのエンタルピー変化量は、例えば、５Ｊｇ−１以上、好ましくは１０Ｊｇ−１以上、更に好ましくは１５Ｊｇ−１以上、特に好ましくは２０Ｊｇ−１以上である。 In the differential scanning calorimetry of the calorimetric effect material of the present invention, the amount of change in enthalpy in the temperature range in which the exothermic peak or endothermic peak appears (for example, 170K to 450K, preferably 190K to 450K) is, for example, 5Jg -1 or more, preferably. Is 10 Jg -1 or more, more preferably 15 Jg -1 or more, and particularly preferably 20 Jg -1 or more.
前記エントロピー変化量及びエンタルピー変化量は、他の類似結晶構造を有するペロブスカイト型酸化物（例えば、ＹＦｅＯ３、Ｓｍ０．６５Ｎｄ０．３５ＮｉＯ３、Ｌａ０．８Ａｇ０．２ＭｎＯ３）及び従来の磁気熱量効果材料（例えば、Ｇｄ５ＳｉＧｅ２）に比べて著しく大きく、本発明により高効率な熱量効果材料を提供できる。 The amount of change in entropy and the amount of change in enthalpy are perovskite-type oxides having other similar crystal structures (for example, YFeO 3 , Sm 0.65 Nd 0.35 NiO 3 , La 0.8 Ag 0.2 MnO 3 ) and It is remarkably larger than the conventional magnetic calorific value effect material (for example, Gd 5 SiGe 2 ), and the present invention can provide a highly efficient calorific value effect material.
示差走査熱量測定は、公知の装置を用いて、例えば、昇温速度又は降温速度を１０Ｋ／分とする条件で行うことができる。 The differential scanning calorimetry can be performed using a known device, for example, under the condition that the heating rate or the temperature decreasing rate is 10 K / min.
本発明の熱量効果材料は、体積変化により転移が生じる温度範囲において、発熱又は吸熱を生じる材料であることが好ましい。体積変化は、体積の増加（膨張）であってもよく、体積の減少（収縮）であってもよい。体積の変化は、温度変化に対して不連続又は急激であることが好ましい。 The calorific value effect material of the present invention is preferably a material that generates heat or endothermic in a temperature range in which a transition occurs due to a change in volume. The volume change may be an increase in volume (expansion) or a decrease in volume (contraction). The change in volume is preferably discontinuous or abrupt with respect to the temperature change.
体積変化により転移が生じる温度範囲とは、温度変化に伴って体積が急激に変化（又は不連続的に変化）する範囲をいい、具体的には、例えば、温度が１０Ｋ変化するとき体積が０．１％以上変化する範囲である。体積変化により転移が生じる温度範囲は、Ａ’の種類などにもよるが、通常、１７０Ｋ〜４５０Ｋ（好ましくは１９０Ｋ〜４５０Ｋ）であり、例えば、Ａ’がＬａである場合は３９０Ｋ〜４１０Ｋ、Ａ’がＰｒである場合は３１０Ｋ〜３４０Ｋ、Ａ’がＮｄである場合は２８０Ｋ〜３３０Ｋ、Ａ’がＳｍである場合は２６０Ｋ〜３００Ｋ、Ａ’がＧｄである場合は２５０Ｋ〜２７０Ｋ、Ａ’がＣａである場合は１７０Ｋ〜２２０Ｋであることが好ましい。本発明では、好ましくは体積変化に伴って発熱又は吸熱が生じる。 The temperature range in which a transition occurs due to a volume change is a range in which the volume changes abruptly (or discontinuously) with the temperature change. Specifically, for example, when the temperature changes by 10 K, the volume changes to 0. It is a range that changes by 1% or more. The temperature range in which the transition occurs due to the volume change depends on the type of A', but is usually 170K to 450K (preferably 190K to 450K). For example, when A'is La, 390K to 410K, A. When'is Pr, 310K to 340K, when A'is Nd, 280K to 330K, when A'is Sm, 260K to 300K, when A'is Gd, 250K to 270K, A'is In the case of Ca, it is preferably 170K to 220K. In the present invention, heat generation or endothermic heat is preferably generated as the volume changes.
体積は、例えば、公知のＸ線回折装置を用いて、結晶の格子定数を測定することにより算出することができる。 The volume can be calculated, for example, by measuring the lattice constant of the crystal using a known X-ray diffractometer.
本発明の熱量効果材料は、磁気転移が生じる温度範囲において、発熱又は吸熱を生じる材料であることが好ましい。磁気転移とは、常磁性から強磁性（又は反強磁性又はフェリ磁性）へと変化すること、或いは、強磁性（又は反強磁性又はフェリ磁性）から常磁性へと変化することをいう。磁気転移において、磁化率（磁化）の変化は、温度変化に対して不連続又は急激であることが好ましい。 The calorific value effect material of the present invention is preferably a material that generates heat or endothermic in a temperature range in which magnetic transition occurs. The magnetic transition means a change from paramagnetism to ferromagnetism (or antiferromagnetism or ferromagnetism), or a change from ferromagnetism (or antiferromagnetism or ferromagnetism) to paramagnetism. In the magnetic transition, the change in magnetic susceptibility (magnetization) is preferably discontinuous or abrupt with respect to the temperature change.
磁気転移が生じる温度範囲は、Ａ’の種類などにもよるが、通常、１７０Ｋ〜４５０Ｋ（好ましくは１９０Ｋ〜４５０Ｋ）であり、例えば、Ａ’がＬａである場合は３９０Ｋ〜４１０Ｋ、Ａ’がＰｒである場合は３１０Ｋ〜３４０Ｋ、Ａ’がＮｄである場合は２８０Ｋ〜３３０Ｋ、Ａ’がＳｍである場合は２６０Ｋ〜３００Ｋ、Ａ’がＧｄである場合は２５０Ｋ〜２７０Ｋ、Ａ’がＣａである場合は１７０Ｋ〜２２０Ｋであることが好ましい。本発明では、好ましくは磁気転移に伴って発熱又は吸熱が生じる。 The temperature range in which the magnetic transition occurs depends on the type of A'and the like, but is usually 170K to 450K (preferably 190K to 450K). For example, when A'is La, 390K to 410K and A'are When Pr is 310K to 340K, when A'is Nd, 280K to 330K, when A'is Sm, 260K to 300K, when A'is Gd, 250K to 270K, and A'is Ca. In some cases, it is preferably 170K to 220K. In the present invention, heat generation or endotherm is preferably generated with the magnetic transition.
本発明の熱量効果材料は、電気伝導性変化により転移が生じる温度範囲において、発熱又は吸熱を生じる材料であることが好ましい。電気伝導性の変化は、温度変化に対して不連続又は急激であることが好ましい。 The calorific value effect material of the present invention is preferably a material that generates heat or endothermic in a temperature range in which a transition occurs due to a change in electrical conductivity. The change in electrical conductivity is preferably discontinuous or abrupt with respect to temperature changes.
電気伝導性変化により転移が生じる温度範囲とは、例えば、温度変化に伴って電気抵抗が急激に変化（又は不連続的に変化）する範囲である。電気伝導性変化により転移が生じる温度範囲は、Ａ’の種類などにもよるが、通常、１７０Ｋ〜４５０Ｋ（好ましくは１９０Ｋ〜４５０Ｋ）であり、例えば、Ａ’がＬａである場合は３９０Ｋ〜４１０Ｋ、Ａ’がＰｒである場合は３１０Ｋ〜３４０Ｋ、Ａ’がＮｄである場合は２８０Ｋ〜３３０Ｋ、Ａ’がＳｍである場合は２６０Ｋ〜３００Ｋ、Ａ’がＧｄである場合は２５０Ｋ〜２７０Ｋ、Ａ’がＣａである場合は１７０Ｋ〜２２０Ｋであることが好ましい。本発明では、好ましくは電気伝導性変化に伴って発熱又は吸熱が生じる。 The temperature range in which a transition occurs due to a change in electrical conductivity is, for example, a range in which the electrical resistance changes abruptly (or discontinuously) with the change in temperature. The temperature range in which the transition occurs due to the change in electrical conductivity depends on the type of A', but is usually 170K to 450K (preferably 190K to 450K). For example, when A'is La, it is 390K to 410K. , 310K to 340K when A'is Pr, 280K to 330K when A'is Nd, 260K to 300K when A'is Sm, 250K to 270K when A'is Gd, A When'is Ca, it is preferably 170K to 220K. In the present invention, heat generation or endothermic heat is preferably generated with a change in electrical conductivity.
電気抵抗は、汎用の４端子法により測定することができる。 The electrical resistance can be measured by a general-purpose four-terminal method.
本発明の熱量効果材料は、構成元素ＡとＢとの間で電荷の移動、又はＢの電荷の分離が生じることにより、発熱又は吸熱を生じる材料であることが好ましい。 The calorific value effect material of the present invention is preferably a material that generates heat or endothermic due to the transfer of electric charges between the constituent elements A and B or the separation of the electric charges of B.
例えば、ＬｎＣｕ３Ｆｅ４Ｏ１２の場合、約１２０℃以上では、Ｂサイトにおいて高い酸化状態のＦｅ３．７５＋イオンであるが、約１２０℃以下では、ＡサイトのＣｕ２＋イオンとの間で電荷移動が生じる。この電荷移動は、下記式：
３Ｃｕ２＋＋４Ｆｅ３．７５＋→３Ｃｕ３＋＋４Ｆｅ３＋
で表すことができる。
For example, in the case of LnCu 3 Fe 4 O 12 , at about 120 ° C. or higher, the Fe 3.75 + ion is in a highly oxidized state at the B site, but at about 120 ° C. or lower, the charge is charged with the Cu 2+ ion at the A site. Movement occurs. This charge transfer is expressed by the following equation:
3Cu 2+ + 4Fe 3.75+ → 3Cu 3+ + 4Fe 3+
Can be represented by.
また、ＣａＣｕ３Ｆｅ４Ｏ１２の場合、約−６０℃以上では、ＢサイトにおいてＦｅ４＋イオンであるが、約−６０℃以下では、Ｆｅ４＋イオンの電荷分離が生じる。この電荷分離は、下記式：
４Ｆｅ４＋→２Ｆｅ３＋＋２Ｆｅ５＋
で表すことができる。
Further, in the case of CaCu 3 Fe 4 O 12 , at about −60 ° C. or higher, Fe 4+ ions are formed at the B site, but at about −60 ° C. or lower, charge separation of Fe 4+ ions occurs. This charge separation is based on the following formula:
4Fe 4+ → 2Fe 3+ + 2Fe 5+
Can be represented by.
本発明の熱量効果材料では、好ましくは、構成元素ＡとＢとの間での電荷移動、又はＢの電荷分離に起因して発熱又は吸熱を生じる。 In the calorific value effect material of the present invention, heat generation or endothermic heat is preferably generated due to charge transfer between the constituent elements A and B, or charge separation of B.
構成元素ＡとＢとの間での電荷移動、及びＢの電荷分離が生じているか否かは、例えば、メスバウアー分光法により確認することができる。 Whether or not charge transfer between the constituent elements A and B and charge separation of B have occurred can be confirmed by, for example, Mössbauer spectroscopy.
本発明の熱量効果材料は、高効率な熱量効果材料であり、熱量効果材料自体の体積、熱量効果材料周囲の圧力、熱量効果材料周囲の温度、熱量効果材料周囲の磁場、熱量効果材料に加えられる電圧、熱量効果材料に加えられる電流、熱量効果材料自体の電気抵抗などを変化させることにより、非常に大きな発熱又は吸熱を生じる材料であるから、例えば、冷却装置などに好適に利用することができる。 The calorific value effect material of the present invention is a highly efficient calorie effect material, and in addition to the volume of the calorie effect material itself, the pressure around the calorie effect material, the temperature around the calorie effect material, the magnetic field around the calorie effect material, and the calorie effect material. Since it is a material that generates extremely large heat generation or endothermic by changing the voltage, the current applied to the calorific value effect material, the electrical resistance of the calorie effect material itself, etc., it can be suitably used for, for example, a cooling device. it can.
＜冷却装置＞
本発明の冷却装置は、前記熱量効果材料を用いた冷却装置である。冷却装置は、前記熱量効果材料の熱量効果（例えば、体積、磁場、電圧、又は電流などの変化による発熱及び吸熱）を利用した冷却が可能である限り、構造は特に限定されない。
<Cooling device>
The cooling device of the present invention is a cooling device using the calorific value effect material. The structure of the cooling device is not particularly limited as long as it can be cooled by utilizing the calorific effect of the calorific effect material (for example, heat generation and endothermic heat due to changes in volume, magnetic field, voltage, current, etc.).
一実施態様において、冷却装置は、
断熱容器と、前記断熱容器内に配置され、前記熱量効果材料（ここでは、作業物質ともいう。）が充填された充填室であって、その内部を熱交換媒体（冷媒ともいう。）が通過可能な充填室と、
前記充填室への圧力、磁場、電圧、又は電流の印加及び除去を繰り返す手段と、
前記充填室への圧力、磁場、電圧、又は電流が印加されたとき、前記熱量効果材料の温熱により昇温した熱交換媒体を熱交換する第１の熱交換器と、
前記充填室への圧力、磁場、電圧、又は電流が除去されたとき、前記熱量効果材料の冷熱により降温した熱交換媒体を熱交換する第２の熱交換器とを備える。
In one embodiment, the cooling device
A heat insulating container and a filling chamber arranged in the heat insulating container and filled with the calorific value effect material (hereinafter, also referred to as a working substance), through which a heat exchange medium (also referred to as a refrigerant) passes. With possible filling chambers
A means for repeatedly applying and removing pressure, magnetic field, voltage, or current to the filling chamber, and
A first heat exchanger that exchanges heat with a heat exchange medium that has been heated by the heat of the calorific value effect material when a pressure, magnetic field, voltage, or current is applied to the filling chamber.
It is provided with a second heat exchanger that exchanges heat with a heat exchange medium whose temperature has been lowered by the cold heat of the calorific value effect material when the pressure, magnetic field, voltage, or current to the filling chamber is removed.
前記充填室への圧力、磁場、電圧、又は電流の印加及び除去を繰り返す手段は、例えば、
前記充填室への圧力、磁場、電圧、又は電流を発生させる発生手段と、
前記充填室への接近及び離反を繰り返すように前記発生手段を移動（例：往復又は回転）させる移動手段と
を備えていてもよい。
The means for repeatedly applying and removing pressure, magnetic field, voltage, or current to the filling chamber is, for example,
A generating means for generating a pressure, a magnetic field, a voltage, or an electric current to the filling chamber, and
It may be provided with a moving means for moving (eg, reciprocating or rotating) the generating means so as to repeatedly approach and separate from the filling chamber.
或いは、前記充填室への圧力、磁場、電圧、又は電流の印加及び除去を繰り返す手段は、例えば、
前記充填室を回転可能に支持する回転ディスクと、
前記回転ディスクの回転方向の一部の領域（以下、領域Ａという。）において、前記充填室への圧力、磁場、電場、又は電流を発生させる発生手段と、
前記回転ディスクを回転させて、前記充填室を領域Ａ内及び領域Ａ外に交互に位置させる回転駆動手段と
を備えていてもよい。
Alternatively, a means for repeatedly applying and removing pressure, magnetic field, voltage, or current to the filling chamber is, for example,
A rotating disc that rotatably supports the filling chamber,
A generating means for generating a pressure, a magnetic field, an electric field, or an electric current to the filling chamber in a part of the rotation direction of the rotating disk (hereinafter referred to as a region A).
A rotary driving means for rotating the rotary disk to alternately position the filling chamber in the region A and outside the region A may be provided.
本発明の冷却装置は、具体的には、図１１に示される磁気冷却装置であってもよい。
磁気冷却装置１は、
断熱容器２と、
断熱容器２内の上部に配置され、冷媒Ｃを含有する冷媒槽３と、
それぞれ冷媒槽３の下部に流路４１及び４２を介して接続され、断熱容器２の内周面に互いに対向して配置され、粒子状の磁気熱量効果材料Ｍが充填された複数の充填室５ａ、５ｂと、
充填室に磁場を発生させる磁場発生手段６ａ、６ｂと、
磁場発生手段６ａ、６ｂを回転可能に支持する回転ディスク７ａ、７ｂと、
回転ディスク７ａ、７ｂを、回転軸８１を中心に回転させる回転駆動手段８と、
断熱容器２外に配置され、それぞれの上部が流路４５及び４６を介して冷媒槽３の上部に接続され、それぞれの下部が流路４３及び４４を介して充填室５ａ及び５ｂに接続される熱交換器９ａ、９ｂと
を備えている。
Specifically, the cooling device of the present invention may be the magnetic cooling device shown in FIG.
The magnetic cooling device 1
Insulation container 2 and
A refrigerant tank 3 arranged in the upper part of the heat insulating container 2 and containing the refrigerant C,
A plurality of filling chambers 5a connected to the lower part of the refrigerant tank 3 via the flow paths 41 and 42, arranged opposite to each other on the inner peripheral surface of the heat insulating container 2, and filled with the particulate magnetic heat effect material M. 5b and
Magnetic field generating means 6a and 6b that generate a magnetic field in the filling chamber,
Rotating disks 7a, 7b that rotatably support the magnetic field generating means 6a, 6b, and
Rotational driving means 8 for rotating the rotating disks 7a and 7b around the rotating shaft 81, and
Arranged outside the heat insulating container 2, the upper part thereof is connected to the upper part of the refrigerant tank 3 via the flow paths 45 and 46, and the lower part thereof is connected to the filling chambers 5a and 5b via the flow paths 43 and 44. It is equipped with heat exchangers 9a and 9b.
この例では、磁場発生手段６ａ、６ｂは永久磁石であり、回転ディスク７ａ、７ｂは磁気ヨークであり、回転駆動手段８はモーターであるが、これらに限定されない。 In this example, the magnetic field generating means 6a and 6b are permanent magnets, the rotating disks 7a and 7b are magnetic yokes, and the rotating driving means 8 is a motor, but the present invention is not limited thereto.
回転駆動手段８により回転ディスク７ａ、７ｂを回転させることにより、磁場発生手段６ａ、６ｂの間に充填室５ａが位置したとき、充填室５ａに磁場が印加され、充填室５ａ内の磁気熱量効果材料Ｍは発熱し、冷媒槽３から充填室５ａに流入した冷媒Ｃは、前記磁気熱量効果材料Ｍの温熱により昇温し、昇温した冷媒Ｃは熱交換器９ａで排熱され、再び冷媒槽３に流入する。これに対して、充填室５ｂは磁場発生手段６ａ、６ｂの間に位置せず、充填室５ｂへの磁場は除去されているため、充填室５ｂ内の磁気熱量効果材料Ｍは吸熱し、冷媒槽３から充填室５ｂに流入した冷媒Ｃは、前記磁気熱量効果材料Ｍの冷熱により降温し、降温した冷媒Ｃは熱交換器９ｂで吸熱され、再び冷媒槽３に流入する。このようなサイクルを繰り返すことにより、高効率な冷却効果を得ることができる。 By rotating the rotating disks 7a and 7b by the rotation driving means 8, when the filling chamber 5a is located between the magnetic field generating means 6a and 6b, a magnetic field is applied to the filling chamber 5a and the magnetic heat effect in the filling chamber 5a. The material M generates heat, the refrigerant C flowing into the filling chamber 5a from the refrigerant tank 3 is heated by the heat of the magnetic heat effect material M, the heated refrigerant C is exhausted by the heat exchanger 9a, and the refrigerant C is exhausted again. It flows into the tank 3. On the other hand, since the filling chamber 5b is not located between the magnetic field generating means 6a and 6b and the magnetic field to the filling chamber 5b is removed, the magnetic calorific value effect material M in the filling chamber 5b absorbs heat and is a refrigerant. The refrigerant C that has flowed into the filling chamber 5b from the tank 3 is cooled by the cold heat of the magnetic heat quantity effect material M, and the cooled refrigerant C is absorbed by the heat exchanger 9b and flows into the refrigerant tank 3 again. By repeating such a cycle, a highly efficient cooling effect can be obtained.
上記で説明した冷却装置の構造は、本発明の趣旨を逸脱しない限りにおいて、種々の変更（追加、修正、改良、削除など）が可能であり、変更された態様も本発明に包含される。 The structure of the cooling device described above can be variously modified (added, modified, improved, deleted, etc.) as long as it does not deviate from the gist of the present invention, and the modified aspects are also included in the present invention.
冷却装置に用いられる熱交換媒体（冷媒）としては、特に制限されず、例えば、水、アルコール（エタノールなど）、水とアルコール（エタノールなど）との混合溶液、空気、水素、ヘリウム、ネオンが挙げられる。 The heat exchange medium (refrigerant) used in the cooling device is not particularly limited, and examples thereof include water, alcohol (ethanol, etc.), a mixed solution of water and alcohol (ethanol, etc.), air, hydrogen, helium, and neon. Be done.
以下、本発明を実施例により詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
（実施例１〜５）
国際公開第２０１０／１０１１５３の実施例に準じて、ＰｒＣｕ３Ｆｅ４Ｏ１２、ＮｄＣｕ３Ｆｅ４Ｏ１２、ＳｍＣｕ３Ｆｅ４Ｏ１２、ＧｄＣｕ３Ｆｅ４Ｏ１２、及びＴｂＣｕ３Ｆｅ４Ｏ１２を製造した。
(Examples 1 to 5)
Manufacture of PrCu 3 Fe 4 O 12 , NdCu 3 Fe 4 O 12 , SmCu 3 Fe 4 O 12 , GdCu 3 Fe 4 O 12 , and TbCu 3 Fe 4 O 12 according to the examples of International Publication No. 2010/101153. did.
（実施例６）
Journal of Physics D: Applied Physics 48 (2015) 504006のExperimentsに準じて、ＣａＣｕ３Ｆｅ４Ｏ１２を製造した。
(Example 6)
CaCu 3 Fe 4 O 12 was produced according to the Experiments of Journal of Physics D: Applied Physics 48 (2015) 504006.
（１）示差走査熱量測定
実施例に示す材料について、汎用の示差走査熱量測定装置（NETZSCH社製 DSC3500 Sirius）を用い、以下の条件で測定した。
温度範囲：−１２５℃（１４８Ｋ）〜７８℃（３５１Ｋ）
昇温速度：１０℃（１０Ｋ）／分
(1) Differential scanning calorimetry The material shown in the examples was measured under the following conditions using a general-purpose differential scanning calorimetry device (DSC3500 Sirius manufactured by NETZSCH).
Temperature range: -125 ° C (148K) to 78 ° C (351K)
Heating rate: 10 ° C (10K) / min
エントロピー変化量は、以下の計算式を用いて算出した。
結果を図１〜図４並びに表１に示す。
※２：Journal of Solid State Chemistry 120 (1995) 157-163からの値
※３：Journal of Magnetism and Magnetic Materials 222 (2000) 110-114からの値
※４：Applied Physics Letters 101 (2012) 071906からの値
The results are shown in FIGS. 1 to 4 and Table 1.
* 2 : Value from Journal of Solid State Chemistry 120 (1995) 157-163
* 3 : Value from Journal of Magnetism and Magnetic Materials 222 (2000) 110-114
* 4 : Value from Applied Physics Letters 101 (2012) 071906
実施例２〜４及び６のペロブスカイト型酸化物は、比較例１〜３のペロブスカイト型酸化物及び比較例４の従来の磁気熱量効果材料よりもエントロピー変化量又エンタルピー変化量が著しく大きいことが分かる。また、図１〜図４に示すように、実施例２〜４及び６のペロブスカイト型酸化物の発熱ピークの半値幅は３０Ｋ以下であった。 It can be seen that the perovskite-type oxides of Examples 2 to 4 and 6 have a significantly larger entropy change amount and enthalpy change amount than the perovskite-type oxides of Comparative Examples 1 to 3 and the conventional magnetic calorific value effect material of Comparative Example 4. .. Further, as shown in FIGS. 1 to 4, the half width of the exothermic peak of the perovskite-type oxides of Examples 2 to 4 and 6 was 30 K or less.
（２）試料同定、構造評価、格子体積の計算
実施例に示す材料について、室温での放射光Ｘ線回折測定で単相試料であることを確認した。その後、１０℃（１０Ｋ）毎に温度を変えてＸ線回折データを取得して、各温度での結晶構造変化を測定した。試料体積は、結晶構造解析で得られた格子定数を用いて算出した。
(2) Sample identification, structure evaluation, calculation of lattice volume The material shown in the examples was confirmed to be a single-phase sample by synchrotron radiation X-ray diffraction measurement at room temperature. After that, the temperature was changed every 10 ° C. (10K) to acquire X-ray diffraction data, and the change in crystal structure at each temperature was measured. The sample volume was calculated using the lattice constant obtained by crystal structure analysis.
結果を図５及び図６並びに表２に示す。
実施例１〜５のペロブスカイト型酸化物は、体積変化により転移が生じる温度範囲から、体積変化に伴って発熱又は吸熱を生じさせる材料となることが判明した。 The perovskite-type oxides of Examples 1 to 5 were found to be materials that generate heat or endothermic with the volume change from the temperature range in which the transition occurs due to the volume change.
（３）磁化率測定
実施例に示す材料の磁化率を、１℃（１Ｋ）毎に温度を変えて、磁力計（クウォンタムデザイン社製「ＰＰＭＳ」）を用いて測定した。
(3) Magnetic susceptibility measurement The magnetic susceptibility of the material shown in the examples was measured using a magnetometer (“PPMS” manufactured by Quantum Design Co., Ltd.) at different temperatures in 1 ° C. (1K) increments.
結果を図７及び図８並びに表３に示す。
実施例１〜６のペロブスカイト型酸化物は、磁気転移が生じる温度範囲から、磁気転移に伴って発熱又は吸熱を生じさせる材料となることが判明した。 From the temperature range in which the magnetic transition occurs, the perovskite-type oxides of Examples 1 to 6 have been found to be materials that generate heat or endothermic with the magnetic transition.
（４）電気抵抗測定
実施例に示す材料の電気抵抗を、汎用の４プローブ法により測定した。具体的には、１０℃（１０Ｋ）毎に温度を変えて、物理特性測定装置（クウォンタムデザイン社製「ＭＰＭＳ」）を用いて行った。
(4) Electrical resistance measurement The electrical resistance of the material shown in the examples was measured by a general-purpose 4-probe method. Specifically, the temperature was changed every 10 ° C. (10K), and the measurement was performed using a physical characteristic measuring device (“MPMS” manufactured by Quantum Design Co., Ltd.).
結果を図９及び図１０並びに表４に示す。
実施例２及び６のペロブスカイト型酸化物は、電気抵抗変化により転移が生じる温度範囲から、電気抵抗変化に伴って発熱又は吸熱を生じさせる材料となることが判明した。 The perovskite-type oxides of Examples 2 and 6 were found to be materials that generate heat or endothermic with the change in electrical resistance from the temperature range in which the transition occurs due to the change in electrical resistance.
以上のとおり、ＬｎＣｕ３Ｆｅ４Ｏ１２の比熱を測定したところ、巨大な潜熱が発生することが明らかになった（図１〜４）。この比熱測定により見積もられるエントロピー変化量は、他のペロブスカイト型酸化物（ＹＦｅＯ３、Ｓｍ０．６５Ｎｄ０．３５ＮｉＯ３、Ｌａ０．８Ａｇ０．２ＭｎＯ３）や従来の磁気熱量効果材料（Ｇｄ５ＳｉＧｅ２）での値よりはるかに大きなものである。このような大きなエントロピー変化を利用した高効率な磁気熱量効果材料となる。 As described above, when the specific heat of LnCu 3 Fe 4 O 12 was measured, it was clarified that a huge latent heat was generated (FIGS. 1 to 4). The amount of change in entropy estimated by this specific heat measurement is other perovskite-type oxides (YFeO 3 , Sm 0.65 Nd 0.35 NiO 3 , La 0.8 Ag 0.2 MnO 3 ) and conventional magnetic heat capacity effect materials. It is much larger than the value at (Gd 5 SiGe 2). It is a highly efficient magnetic calorific value effect material that utilizes such a large entropy change.
さらに重要な点は、ＬｎＣｕ３Ｆｅ４Ｏ１２の相転移では、磁気転移のみならず、電荷移動転移に伴う電気伝導性の変化とさらに結晶格子の変化に伴う体積変化が同時に起こるため、測定された大きな比熱変化が電圧や電流、圧力を加えることによる体積変形によっても取り出せる、つまりマルチ熱量効果となる。 More importantly, the phase transition of LnCu 3 Fe 4 O 12 is measured because not only the magnetic transition but also the change in electrical conductivity due to the charge transfer transition and the volume change due to the change in the crystal lattice occur at the same time. A large change in specific heat can also be taken out by volume deformation due to the application of voltage, current, or pressure, that is, a multi-calorific effect.
Claims (13)
Ａ’Ａ３Ｂ４Ｏ１２ （１）
（式中、
Ａ’は、Ｌａ、Ｂｉ、Ｙ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｃａ、Ｓｒ、Ｂａ、及びＰｂからなる群より選ばれる少なくとも一種の元素であり、
Ａは、Ｃｕ、Ｍｎ、Ｆｅ、Ｂｉ、及びＮｉからなる群より選ばれる少なくとも一種の元素であり、
Ｂは、Ｆｅ、Ｔｉ、Ｖ、Ｃｒ、Ｃｕ、Ｍｎ、Ｒｅ、Ｃｏ、Ｎｉ、Ｇｅ、Ｓｎ、Ｚｒ、及びＲｕからなる群より選ばれる少なくとも一種の元素である。）
で表されるペロブスカイト型酸化物を含有する熱量効果材料。 The following formula (1):
A'A 3 B 4 O 12 (1)
(During the ceremony,
A'is at least one selected from the group consisting of La, Bi, Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba, and Pb. Is an element of
A is at least one element selected from the group consisting of Cu, Mn, Fe, Bi, and Ni.
B is at least one element selected from the group consisting of Fe, Ti, V, Cr, Cu, Mn, Re, Co, Ni, Ge, Sn, Zr, and Ru. )
A calorific effect material containing a perovskite-type oxide represented by.
ＬｎＣｕ３Ｆｅ４Ｏ１２ （２）
（式中、Ｌｎは、Ｌａ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、又はＴｂである。）
ＣａＣｕ３Ｆｅ４Ｏ１２ （３）
で表される、請求項１〜９のいずれか一項に記載の熱量効果材料。 The perovskite-type oxide has the following formula (2) or (3):
LnCu 3 Fe 4 O 12 (2)
(In the formula, Ln is La, Pr, Nd, Sm, Eu, Gd, or Tb.)
CaCu 3 Fe 4 O 12 (3)
The calorific value effect material according to any one of claims 1 to 9, represented by.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398909A (en) * | 2021-06-08 | 2021-09-17 | 中国科学院物理研究所 | Perovskite material and preparation method and application thereof |
| WO2023002698A1 (en) * | 2021-07-20 | 2023-01-26 | 株式会社アイシン | Heat absorption/release system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0582254A (en) * | 1991-09-21 | 1993-04-02 | Zexel Corp | Heat generating method using electromagnetic wave and heating element |
| WO2010101153A1 (en) * | 2009-03-04 | 2010-09-10 | 国立大学法人京都大学 | A-site ordered perovskite-type oxide |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0582254A (en) * | 1991-09-21 | 1993-04-02 | Zexel Corp | Heat generating method using electromagnetic wave and heating element |
| WO2010101153A1 (en) * | 2009-03-04 | 2010-09-10 | 国立大学法人京都大学 | A-site ordered perovskite-type oxide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398909A (en) * | 2021-06-08 | 2021-09-17 | 中国科学院物理研究所 | Perovskite material and preparation method and application thereof |
| CN113398909B (en) * | 2021-06-08 | 2022-05-24 | 中国科学院物理研究所 | Perovskite material and preparation method and application thereof |
| WO2023002698A1 (en) * | 2021-07-20 | 2023-01-26 | 株式会社アイシン | Heat absorption/release system |
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