JP7104492B2 - Magnetic refrigeration work material - Google Patents
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本発明は、磁気熱量効果を発現する磁気冷凍作業物質に関する。 The present invention relates to a magnetic refrigeration working substance that exhibits a magnetic calorific value effect.
Ｌａ（ＦｅＳｉ）１３系磁気冷凍作業物質は、比較的、エントロピー変化量ΔＳが大きく、磁気ヒートポンプ用材料として期待されている。Ｌａ（ＦｅＳｉ）１３系材料のキュリー温度を制御する手法としては、水素吸蔵による制御と元素の置換による制御とが知られている。例えば、特許文献１では、セリウム、マンガンにより元素を複合的に置換する技術が提案されている。
The La (FeSi) 13 -based magnetic refrigeration work material has a relatively large entropy change amount ΔS, and is expected as a material for a magnetic heat pump. As a method for controlling the Curie temperature of the La (FeSi) 13 -based material, control by hydrogen storage and control by element substitution are known. For example,
０℃近傍にキュリー温度を設定したい場合、特許文献１の技術では、ΔＳが大きく減少してしまうという問題があった。
本開示は、磁気冷凍作業物質の磁気エントロピー変化量の減少を抑制する技術を提供する。
When it is desired to set the Curie temperature in the vicinity of 0 ° C., the technique of
The present disclosure provides a technique for suppressing a decrease in the amount of change in magnetic entropy of a magnetic refrigeration work substance.
本開示の第１の態様は、Ｌａ１－ｘＣｅｘ（Ｆｅ１－ｙ－ｚＭｎｙＳｉｚ）１３Ｈｎで示される磁気冷凍作業物質であって、ｎ≧１．５であり、Ｌａ、Ｃｅ、Ｍｎ、及びＳｉの組成ムラを示す３σが１％以下である、磁気冷凍作業物質である。 The first aspect of the present disclosure is a magnetic refrigeration working material represented by La 1-x Cex (Fe 1-yz Mn y Si z ) 13 H n , where n ≧ 1.5 and La. , Ce, Mn, and Si, which is a magnetic refrigeration work substance having 3σ of 1% or less, which indicates uneven composition.
このような構成によれば、セリウムやマンガンにより元素を置換してキュリー温度を調整した場合であっても、磁気熱量効果による磁気エントロピー変化量が減少してしまうこと抑制することができる。また水素の吸蔵量を高めることで磁気熱量効果の経時劣化を抑制することができる。 According to such a configuration, even when the Curie temperature is adjusted by substituting the elements with cerium or manganese, it is possible to suppress the decrease in the amount of change in magnetic entropy due to the magnetic calorific value effect. Further, by increasing the occluded amount of hydrogen, it is possible to suppress the deterioration of the magnetic calorific value effect with time.
［１－１．実施形態］
以下、本開示の磁気冷凍作業物質について説明する。
本開示の磁気冷凍作業物質は、ＮａＺｎ１３結晶構造であるＬａ１－ｘＣｅｘ（Ｆｅ１－ｙ－ｚＭｎｙＳｉｚ）１３Ｈｎで示される磁気冷凍作業物質である。
[1-1. Embodiment]
Hereinafter, the magnetic refrigeration working substance of the present disclosure will be described.
The magnetic refrigeration work substance of the present disclosure is a magnetic refrigeration work substance represented by La 1-x Cex (Fe 1-yz Mn y Siz ) 13 Hn having a NaZn 13 crystal structure.
この磁気冷凍作業物質は、ＬａＦｅＳｉ系の磁気冷凍作業物質のＬａ、Ｆｅの一部をＣｅ、Ｍｎにて置換した構成とすることでキュリー温度（以下、単にＴｃとも記載する）を変化させることができる。キュリー温度とは、磁気冷凍作業物質においては磁気熱量効果を発現する温度である。また水素を吸蔵させることでもキュリー温度を変化させることができる。 This magnetic refrigeration work substance can change the Curie temperature (hereinafter, also simply referred to as Tc) by having a structure in which a part of La and Fe of the LaFeSi-based magnetic refrigeration work substance is replaced with Ce and Mn. can. The Curie temperature is a temperature at which a magnetic calorific value effect is exhibited in a magnetic refrigeration work substance. The Curie temperature can also be changed by occluding hydrogen.
上述した一般式で表されるように、Ｌａの一部はＣｅにて置換することができる。またＦｅの一部はＭｎにて置換することができる。上述した一般式におけるｘ、ｙ及びｚは、以下に示す範囲であるときに、磁気冷凍作業物質が良好な磁気熱量効果を発現する。
０≦ｘ≦０．３５
０≦ｙ≦０．０３
０．０５≦ｚ≦０．２
但し、上記ｘ及びｙの少なくとも一方は０ではない。
As expressed by the general formula described above, a part of La can be replaced with Ce. Further, a part of Fe can be replaced with Mn. When x, y and z in the above general formula are in the range shown below, the magnetic refrigeration working substance exhibits a good magnetic calorific value effect.
0 ≦ x ≦ 0.35
0 ≦ y ≦ 0.03
0.05 ≤ z ≤ 0.2
However, at least one of the above x and y is not 0.
なお、ｘ及びｙを以下の範囲とすることで、大きな磁気エントロピー変化量（以下、単にΔＳとも記載する）を有しつつＴｃを０℃に近づけることができる。
０．１５≦ｘ≦０．３５
０．０１≦ｙ≦０．０３
またｚについても、好ましくは以下の範囲である。
０．０８≦ｚ≦０．１４
また上述したように、水素吸蔵量を変化させることでＴｃを変化させることができる。なお、吸蔵される水素量が少ない場合、経時劣化によりΔＳのピークが低下してしまうおそれがあるため、経時劣化を抑制するために、
ｎ≧１．５
とすることが望ましい。
By setting x and y in the following ranges, Tc can be brought close to 0 ° C. while having a large amount of change in magnetic entropy (hereinafter, also simply referred to as ΔS).
0.15 ≤ x ≤ 0.35
0.01 ≤ y ≤ 0.03
Further, z is also preferably in the following range.
0.08 ≤ z ≤ 0.14
Further, as described above, Tc can be changed by changing the hydrogen storage amount. If the amount of hydrogen occluded is small, the peak of ΔS may decrease due to deterioration over time.
n ≧ 1.5
Is desirable.
本開示の磁気冷凍作業物質は、例えば、次のようにして製造することができる。
単体元素の粉末またはバルクを所定の割合で調合して混合した磁気冷凍作業物質の粉末原料を用いて、溶融急冷法によりインゴットを作製する。このインゴットを、真空中で１２００℃、１０日間熱処理することでＮａＺｎ１３結晶構造とする。その後、インゴットを適当な形状に切り出す。切り出した材料片を、水素雰囲気の熱処理炉に投入してヒータにより２７０℃に加熱し、材料片に水素を吸収させる。このようにして、磁気冷凍作業物質の試験片を製造する。
The magnetic refrigeration working substance of the present disclosure can be produced, for example, as follows.
An ingot is prepared by a melt quenching method using a powder raw material of a magnetic refrigeration work substance in which a powder or bulk of a simple substance element is mixed in a predetermined ratio and mixed. This ingot is heat-treated in vacuum at 1200 ° C. for 10 days to obtain a NaZn 13 crystal structure. After that, the ingot is cut into an appropriate shape. The cut out material piece is put into a heat treatment furnace having a hydrogen atmosphere and heated to 270 ° C. by a heater so that the material piece absorbs hydrogen. In this way, a test piece of a magnetic refrigeration work substance is produced.
なお、熱処理温度、熱処理時間、雰囲気圧力など、製造方法は上述した内容に限定されず公知の様々な方法を用いることができる。
以下に、具体的な実施例を説明する。
The production method such as heat treatment temperature, heat treatment time, and atmospheric pressure is not limited to the above-mentioned contents, and various known methods can be used.
Specific examples will be described below.
［１－２．実施例］
＜実施例の磁気冷凍作業物質の組成＞
原料の割合を変更して、以下の３つの磁気冷凍作業物質の試験片を作製した。なお、インゴットを切り出して形成した試験片は、３ｍｍ×１ｍｍ×０．５ｍｍの短冊状体とした。
実施例１：Ｌａ０．８Ｃｅ０．２（Ｆｅ０．８７Ｍｎ０．０２Ｓｉ０．１１）１３－Ｈ１．５
実施例２：Ｌａ０．７Ｃｅ０．３（Ｆｅ０．８７Ｍｎ０．０２Ｓｉ０．１１）１３－Ｈ１．５
実施例３：Ｌａ０．７Ｃｅ０．３（Ｆｅ０．８６Ｍｎ０．０２５Ｓｉ０．１１５）１３－Ｈ１．５
上記実施例１～３の組成比は一般的な組成分析法で求めることができる。一般的な組成分析法とは、例えば、電子線プローブマイクロ分析（即ちＥＰＭＡ）やＸ線蛍光分析（即ちＸＲＦ）で求めることができる。水素の吸蔵量は水素化後の重量変化より見積もった。
[1-2. Example]
<Composition of Magnetic Refrigeration Working Material of Examples>
By changing the ratio of raw materials, test pieces of the following three magnetic refrigeration working substances were prepared. The test piece formed by cutting out the ingot was a strip of 3 mm × 1 mm × 0.5 mm.
Example 1: La 0.8 Ce 0.2 (Fe 0.87 Mn 0.02 Si 0.11 ) 13 -H 1.5
Example 2: La 0.7 Ce 0.3 (Fe 0.87 Mn 0.02 Si 0.11 ) 13 -H 1.5
Example 3: La 0.7 Ce 0.3 (Fe 0.86 Mn 0.025 Si 0.115 ) 13 -H 1.5
The composition ratios of Examples 1 to 3 can be obtained by a general composition analysis method. The general composition analysis method can be obtained by, for example, electron probe microanalysis (that is, EPMA) or X-ray fluorescence analysis (that is, XRF). The occlusal amount of hydrogen was estimated from the weight change after hydrogenation.
＜組成ムラの見積もり＞
集束イオンビーム（即ち、ＦＩＢ）加工により、実施例２に示す磁気冷凍作業物質の試験片を１００ｎｍ程度にまで薄片化し、走査透過電子顕微鏡（即ち、ＳＴＥＭ）に付属のエネルギー分散型Ｘ線分光分析装置（即ち、ＥＤＸ）を用いて組成分析を行い、組成ムラを見積もった。
<Estimation of composition unevenness>
By focusing ion beam (that is, FIB) processing, the test piece of the magnetic refrigeration work substance shown in Example 2 is sliced to about 100 nm, and the energy dispersive X-ray spectroscopic analysis attached to the scanning transmission electron microscope (that is, STEM) is performed. Composition analysis was performed using an apparatus (that is, EDX), and composition unevenness was estimated.
ＳＴＥＭ－ＥＤＸの測定条件として、加速電圧３００ｋＶ、倍率１０万倍とし、ビーム径１００ｐｍの電子線を用いて積算時間３０秒間として点分析を行った。測定点として、２μｍ角の視野に対し、それぞれ２００ｎｍ以上離れた複数の点について上記の分析を行った。 As the measurement conditions of STEM-EDX, an acceleration voltage of 300 kV, a magnification of 100,000 times, and an electron beam having a beam diameter of 100 pm were used to perform point analysis with an integration time of 30 seconds. As measurement points, the above analysis was performed on a plurality of points separated by 200 nm or more with respect to a field of view of 2 μm square.
ここでいう組成ムラとは、磁気冷凍作業物質を構成する元素組成の空間的均一性の程度ということができ、さらに言い換えると、磁気冷凍作業物質における部分ごとの元素組成のバラツキの程度ということができる。 The composition unevenness referred to here can be said to be the degree of spatial uniformity of the elemental composition constituting the magnetic refrigeration work substance, and in other words, the degree of variation in the elemental composition of each part of the magnetic refrigeration work substance. can.
求められた複数の原子組成比を元素ごとに統計解析を行い、標準偏差σを求めた。その値の三倍の値３σを材料の組成ムラとした。ＳＴＥＭ－ＥＤＸは日本電子株式会社製 ＪＥＭ－ＡＲＭ３００Ｆを使用した。 The obtained atomic composition ratios were statistically analyzed for each element, and the standard deviation σ was obtained. A value of 3σ, which is three times that value, was defined as material composition unevenness. As STEM-EDX, JEM-ARM300F manufactured by JEOL Ltd. was used.
ここで、組成ムラの測定は、同一の試験片について異なる２つの視野で行った。表１には視野１での異なる６箇所の原子組成比の測定結果を示す。また表２には視野２での異なる４箇所の原子組成比の測定結果を示す。また、表１，２から算出される各元素の組成ムラの３σを表３に示す。値はいずれも原子パーセント［ａｔ．％］である。
Here, the measurement of the composition unevenness was carried out for the same test piece from two different visual fields. Table 1 shows the measurement results of the atomic composition ratios at 6 different locations in the
＜ΔＳｍの測定＞
ΔＳｍは、外部磁場Ｈ印加時と無磁場状態の材料の重量当たりの磁気エントロピーの差である。この値が大きいほど磁気冷凍作業物質として優れているといえる。ΔＳｍは以下のマクスウェルの式を用いて求めることができる。下記式において、Ｍは磁化、Ｔは温度である。Ｍの測定にはカンタムデザイン社製Versalabを用いた。磁場の印加方向は切り出したインゴットの長手方向とした。
<Measurement of ΔSm>
ΔSm is the difference in magnetic entropy per weight of the material when the external magnetic field H is applied and in the non-magnetic field state. It can be said that the larger this value is, the more excellent the magnetic refrigeration work substance is. ΔSm can be calculated using Maxwell's equations below. In the following formula, M is magnetization and T is temperature. Versalab manufactured by Quantum Design Co., Ltd. was used for the measurement of M. The direction of application of the magnetic field was the longitudinal direction of the cut out ingot.
図１のグラフに示される、実施例１～３の３つの試験片の上記マクスウェルの式により見積もられるΔＳｍの温度依存性において、－ΔＳｍが急激に立ち上がり始める部分をＴｃとした。図１のグラフからは、実施例１ではＴｃ＝６．０℃、実施例２ではＴｃ＝－１．５℃、実施例３ではＴｃ＝－１６．６℃と判断できる。
In the temperature dependence of ΔSm estimated by Maxwell's equations for the three test pieces of Examples 1 to 3 shown in the graph of FIG. 1, the portion where −ΔSm suddenly starts to rise was defined as Tc. From the graph of FIG. 1, it can be determined that Tc = 6.0 ° C. in Example 1, Tc = −1.5 ° C. in Example 2, and Tc = −16.6 ° C. in Example 3.
また、－ΔＳｍの最大値の半分の値を有する温度幅を－ΔＳｍの半値全幅とした。この値が大きい材料ほど、広い温度範囲にわたって高い磁気熱量効果を発揮できるため好ましい材料であるといえる。磁気冷凍作業物質としては、ΔＳが大きく、半値全幅が大きな材料が望ましいが、実施例１～３の磁気冷凍作業物質は、同等のＴｃを有するこれまでの材料に比べて優れた特性を有している。例えば、特表２０１５－５１７０２３号公報に記載される磁気熱量素子ではＴｃ＝０℃のとき－ΔＳm＝７Ｊ／ｋｇ・Ｋであるのに対し、本開示に実施例ではＴｃ＝－１．５℃のとき－ΔＳm＝１６Ｊ／ｋｇ・Ｋである。 Further, the temperature width having a half value of the maximum value of −ΔSm was defined as the full width at half maximum of −ΔSm. It can be said that a material having a larger value is a preferable material because a higher magnetic calorific value effect can be exhibited over a wide temperature range. As the magnetic refrigeration work substance, a material having a large ΔS and a large full width at half maximum is desirable, but the magnetic refrigeration work substances of Examples 1 to 3 have excellent properties as compared with the conventional materials having the same Tc. ing. For example, in the magnetic calorific device described in Japanese Patent Application Laid-Open No. 2015-517023, when Tc = 0 ° C., −ΔSm = 7J / kg · K, whereas in the present disclosure, Tc = −1.5 ° C. When −ΔSm = 16J / kg · K.
＜Ｍ－Ｈカーブ特性＞
図２～４に示される実施例１～３の磁気冷凍作業物質のＭ－Ｈカーブから明らかなように、外部磁場Ｈを大きくしていった時にＭが急激に上昇した。このような磁気冷凍作業物質は、比較的小さな磁場でも大きな熱量を取り出すことができるため、冷凍システムを構成する上で都合がよい。
<MH curve characteristics>
As is clear from the MH curves of the magnetic refrigeration working substances of Examples 1 to 3 shown in FIGS. 2 to 4, M increased sharply as the external magnetic field H was increased. Since such a magnetic refrigeration work substance can extract a large amount of heat even with a relatively small magnetic field, it is convenient for constructing a refrigeration system.
＜磁化の温度依存性の経時変化＞
図５、図６に示されるグラフは、試験片に水素化処理を施した直後と、約１５日間、Ｔｃ付近で保管した後と、の磁化の温度依存性を測定したものである。仮に経時劣化が生じていた場合、グラフの波形が大きく変化するが、保管前後での差異は非常に小さい。即ち、実施例１～３の磁気冷凍作業物質は経時劣化が抑制されていることを示している。
<Temperature-dependent change in magnetization over time>
The graphs shown in FIGS. 5 and 6 measure the temperature dependence of the magnetization immediately after the test piece was hydrogenated and after being stored in the vicinity of Tc for about 15 days. If deterioration over time occurs, the waveform of the graph changes significantly, but the difference before and after storage is very small. That is, it is shown that the magnetic refrigeration working substances of Examples 1 to 3 are suppressed from deteriorating with time.
＜半値全幅の比較＞
図７、図８に示されるグラフは、ΔＳｍの半値と半値全幅が外部磁場の大きさによりどのように変化するかを示したグラフである。比較的小さな磁場、例えば１テスラでも高いΔＳｍを有していることがわかる。半値全幅は、Ｃｅ、Ｍｎにより置換された、実施例１～３の構成の方が、比較例として示すＣｅ、Ｍｎに置換されていない構成のものよりも大きいため、優れているといえる。
<Comparison of full width at half maximum>
The graphs shown in FIGS. 7 and 8 are graphs showing how the full width at half maximum and the full width at half maximum of ΔSm change depending on the magnitude of the external magnetic field. It can be seen that even a relatively small magnetic field, for example, 1 Tesla, has a high ΔSm. It can be said that the full width at half maximum is superior because the configurations of Examples 1 to 3 substituted with Ce and Mn are larger than those not substituted with Ce and Mn shown as Comparative Examples.
［１－３．効果］
以上詳述したように、本開示の磁気冷凍作業物質は、Ｌａ，Ｃｅ，Ｆｅ，Ｍｎ，Ｓｉのそれぞれについて、組成ムラを示す３σをいずれも１ａｔ．％以下とすることで、高いΔＳを有するものとなった。特に、実施例１，２の磁気冷凍作業物質は、キュリー温度が－１２～１０℃の範囲であり、かつ励磁磁場が１テスラの場合にエントロピー変化量が１０Ｊ／ｋｇ・Ｋ以上であるため、磁気熱量効果に優れ、０℃近傍での冷凍システム構築に都合のよい、優れた磁気冷凍作業物質であると言える。なお本開示の磁気冷凍作業物質は、実施例３に示されるように、Ｃｅ，Ｍｎの置換量を変化させてＴｃを変化させても、優れた磁気熱量効果を奏する。
[1-3. effect]
As described in detail above, the magnetic refrigeration working substance of the present disclosure has 1 at. By setting it to% or less, it has a high ΔS. In particular, the magnetic refrigeration working substances of Examples 1 and 2 have an entropy change amount of 10 J / kg · K or more when the curry temperature is in the range of −12 to 10 ° C. and the exciting magnetic field is 1 Tesla. It can be said that it is an excellent magnetic refrigeration work substance that has an excellent magnetic calorific value effect and is convenient for constructing a refrigeration system near 0 ° C. As shown in Example 3, the magnetic refrigeration working substance of the present disclosure exhibits an excellent magnetic calorific value effect even if the substitution amount of Ce and Mn is changed to change Tc.
特表２０１５－５１７０２３号公報に記載される磁気熱量素子は、０℃近傍において本開示の実施例のような高い-ΔＳｍを示していない。この理由は、組成ムラが大きく材料均一性が低いためであると推測できる。 The magnetic calorific value device described in JP-A-2015-517023 does not show a high −ΔSm as in the examples of the present disclosure in the vicinity of 0 ° C. It can be inferred that the reason for this is that the composition unevenness is large and the material uniformity is low.
なお上記実施例では、Ｌａ，Ｃｅ，Ｆｅ，Ｍｎ，Ｓｉの全てについて、３σを１ａｔ．％以下とした結果、上述した優れた磁気冷凍作業物質を製造することができた。しかしながら、本願の発明者らは、更なる試験により、Ｆｅについては、組成ムラが大きくても磁気冷凍作業物質のΔＳ、半値全幅に与える影響が小さいという知見を得た。よって、Ｆｅについては、３σが１ａｔ．％を超えていてもよい。 In the above embodiment, 3σ is set to 1 at. For all of La, Ce, Fe, Mn, and Si. As a result of% or less, the above-mentioned excellent magnetic refrigeration working substance could be produced. However, the inventors of the present application have obtained from further tests that Fe has a small effect on ΔS and the full width at half maximum of the magnetic refrigeration working substance even if the composition unevenness is large. Therefore, for Fe, 3σ is 1 at. It may exceed%.
また、Ｌａについては、組成ムラの３σを０．４５ａｔ．％以下とすることで、より優れた磁気冷凍作業物質とすることができる。
また、Ｃｅについては、組成ムラの３σを０．５０ａｔ．％以下とすることで、より優れた磁気冷凍作業物質とすることができる。
For La, the composition unevenness of 3σ was set to 0.45 at. By setting the content to% or less, a more excellent magnetic refrigeration working substance can be obtained.
For Ce, the composition unevenness of 3σ was set to 0.50 at. By setting the content to% or less, a more excellent magnetic refrigeration working substance can be obtained.
また、Ｍｎについては、組成ムラの３σを０．４０ａｔ．％以下とすることで、より優れた磁気冷凍作業物質とすることができる。
また、Ｓｉについては、組成ムラの３σを０．６０ａｔ．％以下とすることで、より優れた磁気冷凍作業物質とすることができる。
Regarding Mn, the composition unevenness of 3σ was set to 0.40 at. By setting the content to% or less, a more excellent magnetic refrigeration working substance can be obtained.
For Si, the composition unevenness of 3σ was set to 0.60 at. By setting the content to% or less, a more excellent magnetic refrigeration working substance can be obtained.
Claims (8)
ｎ≧１．５であり、
Ｌａ、Ｃｅ、Ｍｎ、及びＳｉのそれぞれについて、組成ムラを示す３σが１ａｔ．％以下であり、
０≦ｘ≦０．３５、０≦ｙ≦０．０３、かつ、０．０５≦ｚ≦０．２であり、ｘ及びｙの少なくとも一方は０ではなく、
Ｆｅの組成ムラを示す３σが１ａｔ．％を超えており、
前記組成ムラとは、磁気冷凍作業物質を構成する元素組成の空間的均一性の程度である、磁気冷凍作業物質。 La 1-x Ce x (Fe 1-y-z Mn y Si z ) A magnetic refrigeration work substance represented by 13 Hn.
n ≧ 1.5
For each of La, Ce, Mn, and Si, 3σ indicating compositional unevenness is 1 at. % Or less
0 ≦ x ≦ 0.35, 0 ≦ y ≦ 0.03, and 0.05 ≦ z ≦ 0.2, and at least one of x and y is not 0.
3σ, which indicates uneven composition of Fe, is 1 at. Over%,
The composition unevenness is a degree of spatial uniformity of the elemental composition constituting the magnetic refrigeration work substance, which is a magnetic refrigeration work substance.
Ｌａ、Ｃｅ、Ｍｎ、及びＳｉのそれぞれについて、走査透過電子顕微鏡に付属のエネルギー分散型Ｘ線分光分析装置組成により分析される、組成ムラを示す３σが１ａｔ．％以下である、磁気冷凍作業物質。 The magnetic refrigeration work substance according to claim 1.
For each of La, Ce, Mn, and Si, 3σ indicating compositional unevenness, which is analyzed by the energy dispersive X-ray spectroscopic analyzer composition attached to the scanning transmission electron microscope, is 1 at. % Or less, magnetic refrigeration work material.
０．１５≦ｘ、かつ、０．０１≦ｙである、磁気冷凍作業物質。 The magnetic refrigeration working substance according to claim 1 or 2 .
A magnetic refrigeration work substance having 0.15 ≦ x and 0.01 ≦ y.
Ｌａの組成ムラを示す３σが０．４５ａｔ．％以下である、磁気冷凍作業物質。 The magnetic refrigeration working substance according to any one of claims 1 to 3 .
3σ indicating uneven composition of La is 0.45 at. % Or less, magnetic refrigeration work material.
Ｃｅの組成ムラを示す３σが０．５０ａｔ．％以下である、磁気冷凍作業物質。 The magnetic refrigeration working substance according to any one of claims 1 to 4 .
3σ indicating uneven composition of Ce is 0.50 at. % Or less, magnetic refrigeration work material.
Ｍｎの組成ムラを示す３σが０．４０ａｔ．％以下である、磁気冷凍作業物質。 The magnetic refrigeration working substance according to any one of claims 1 to 5 .
3σ indicating uneven composition of Mn is 0.40 at. % Or less, magnetic refrigeration work material.
Ｓｉの組成ムラを示す３σが０．６０ａｔ．％以下である、磁気冷凍作業物質。 The magnetic refrigeration working substance according to any one of claims 1 to 6 .
3σ indicating uneven composition of Si is 0.60 at. % Or less, magnetic refrigeration work material.
キュリー温度が－１２～１０℃の範囲であり、励磁磁場が１テスラの場合にエントロピー変化量が１０Ｊ／ｋｇ・Ｋ以上である、磁気冷凍作業物質。 The magnetic refrigeration working substance according to any one of claims 1 to 7 .
A magnetic refrigeration work substance having a Curie temperature in the range of -12 to 10 ° C. and an entropy change amount of 10 J / kg · K or more when the exciting magnetic field is 1 tesla.
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