JP2011523771A - 熱交換器用の連続気泡多孔性成型物 - Google Patents
熱交換器用の連続気泡多孔性成型物 Download PDFInfo
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Abstract
(1)一般式(I)の化合物
(AyBy-1)2+δCwDxEz (I)
式中、
Aは、Mn又はCoであり、
Bは、Fe、Cr、又はNiであり、
CとDとEは、CとDとEのうち少なくとも2つ異なり、濃度がゼロでなく、P、B、Se、Ge、Ga、Si、Sn、N、As、およびSbから選ばれ、CとDとEの少なくとも一つがGe又はSiであり、
δは、−0.1〜0.1の範囲の数字であり、
w、x、y、zは、0〜1の範囲の数字である(ただし、w+x+z=1);
【選択図】なし
Description
(AyBy-1)2+δCwDxEz (I)
式中、
Aは、Mn又はCoであり、
Bは、Fe、Cr、又はNiであり、
CとDとEは、CとDとEのうち少なくとも2つ異なり、濃度がゼロでなく、P、B、Se、Ge、Ga、Si、Sn、N、As、およびSbから選ばれ、CとDとEの少なくとも一つがGe又はSiであり、
δは、−0.1〜0.1の範囲の数字であり、
w、x、y、zは、0〜1の範囲の数字である(ただし、w+x+z=1);
(2)一般式(II)及び/又は(III)及び/又は(IV)のLa及びFe系化合物
La(FexAl1-x)13HyまたはLa/FexSi1-x)13Hy (II)
式中、
xは0.7〜0.95の数字であり;
yは、0〜3の数字である;
La(FexAlyCoz)13またはLa(FexSiyCoz)13 (III)
式中、
xは0.7〜0.95の数字であり;
yは、0〜3の数字である;
zは0.005〜0.5の数字である;
LaMnxFe2-XGe (IV)
式中
xは1.7〜1.95の数字である;
(3)MnTP型のホイスラー合金(式中、Tは遷移金属で、Pはは原子中の電子数e/aが7〜8.5の範囲にあるp−ドープ金属である)。
(4)一般式(V)のGdとSi系化合物
Gd5(SixGe1-x)4 (V)
式中、xは、0.2〜1の番号である;
(5)Fe2P系化合物類、
(6)ペロブスカイト型の亜マンガン酸塩、
(7)一般式(VI)と(VII)の希土類元素含有化合物
Tb5(Si4-xGex) (VI)
式中、x=0、1、2、3、4、
XTiGe (VII)
式中、X=Dy、Ho、Tm、
(8)一般式(VIII)と(IX)のMnとSbあるいはAs系の化合物、
Mn2-xZxSb (VIII)
Mn2ZxSb1-x (IX)
式中、
Zは、Cr、Cu、Zn、Co、V、As、Geであり、
xは、0.01〜0.5である、
なお、ZがAsでない場合は、Sbは、Asで置き換えられてもよい。
Gd5(SixGe1-x)4
式中、xは0.2〜1の数字である、
例えば、Gd5(Si0.5Ge0.5)4、Gd5(Si0.425Ge0.575)4、Gd5(Si0.45Ge0.55)4、Gd5(Si0.365Ge0.635)4、Gd5(Si0.3Ge0.7)4、Gd5(Si0.25Ge0.75)4である。
a)所望の金属系材料に相当する量の化学元素及び/又は合金を、固相及び/又は液相で反応させる工程と、
b)適当なら工程a)の反応生成物を固体に変換する工程と、
c)工程a)またはb)の固体を焼結及び/又は熱処理する工程と、
d)工程c)からの焼結及び/又は熱処理後の固体を少なくとも100K/sの冷却速度で急冷する工程。
プレスしたMnFePGe試料を含む真空石英アンプルを1100℃で10時間維持して、この粉末を焼結させた。この焼結物を650℃で60時間熱処理して均質化させた。炉中でゆっくりと室温まで冷却するのでなく、試料を直ちに室温の水中で急冷した。この水中での急冷で、試料表面が一定程度酸化した。外側の酸化被膜を希酸で洗い流した。XRDパターンは、すべての試料が、Fe2P型の構造で結晶化していることを示した。
Mn1.1Fe0.9P0.81Ge0.19、Mn1.1Fe0.9P0.78Ge0.22、Mn1.1Fe0.9P0.75Ge0.25、およびMn1.2Fe0.8P0.81Ge0.19.。これらの試料の熱ヒステリシスの観測値は、順に7K、5K、2K、3Kである。徐冷された試料では熱ヒステリシスが10Kより大きく、この試料と比べると、熱ヒステリシスは大幅に低下している。
MnFeP(GeSb)の溶融紡糸
WO 2004/068512とJ. Appl.Phys. 99、08 Q107 (2006)に記載のように、ボールミル中で高エネルギーを注入して、固相反応法によりまず、多結晶MnFeP(Ge,Sb)合金を製造した。この材料をノズルを有する石英管に入れた。試験槽を10-2mbarにまで脱気し、高純度アルゴンガスで満たした。試料高周波で溶融し、回転銅ドラムを収めた試験槽ヘの差圧によりノズルから吹付けさせた。銅ホイールの表面速度は調整可能で、約105K/sの冷却速度が達成された。次いで、巻き取ったリボンを900℃で1時間熱処理した。
Claims (10)
- 熱交換器用の連続気泡多孔性成型物であって、次の化合物から選ばれる熱磁気材料を含む成型物。
(1)一般式(I)の化合物
(AyBy-1)2+δCwDxEz (I)
式中、
Aは、Mn又はCoであり、
Bは、Fe、Cr、又はNiであり、
CとDとEは、CとDとEのうち少なくとも2つ異なり、濃度がゼロでなく、P、B、Se、Ge、Ga、Si、Sn、N、As、およびSbから選ばれ、CとDとEの少なくとも一つがGe又はSiであり、
δは、−0.1〜0.1の範囲の数字であり、
w、x、y、zは、0〜1の範囲の数字である(ただし、w+x+z=1);
(2)一般式(II)及び/又は(III)及び/又は(IV)のLa及びFe系化合物
La(FexAl1-x)13HyまたはLa/FexSi1-x)13Hy (II)
式中、
xは0.7〜0.95の数字であり;
yは、0〜3の数字である;
La(FexAlyCoz)13またはLa(FexSiyCoz)13 (III)
式中
xは0.7〜0.95の数字であり;
yは0.05〜1−xの数字であり;
zは0.005〜0.5の数字である;
LaMnxFe2-xGe (IV)
式中
xは1.7〜1.95の数字である;
(3)MnTP型のホイスラー合金(式中、Tは遷移金属で、Pはは原子中の電子数e/aが7〜8.5の範囲にあるp−ドープ金属である)、
(4)一般式(V)のGdとSi系化合物
Gd5(SixGe1-x)4 (V)
式中、xは、0.2〜1の番号である;
(5)Fe2P系化合物類、
(6)ペロブスカイト型の亜マンガン酸塩、
(7)一般式(VI)と(VII)の希土類元素含有化合物、
Tb5(Si4-xGex) (VI)
式中、x=0、1、2、3、4、
XTiGe (VII)
式中、X=Dy、Ho、Tm、
(8)一般式(VIII)と(IX)のMnとSbあるいはAs系の化合物、
Mn2-xZxSb (VIII)
Mn2ZxSb1-x (IX)
式中、
Zは、Cr、Cu、Zn、Co、V、As、Geであり、
xは、0.01〜0.5である、
なお、ZがAsでない場合は、Sbは、Asで置き換えられてもよい。 - 前記熱磁気材料が、少なくとも、MnとFeとPと、必要ならSbに加え、さらにGe、Si、As、FeとSi、GeとAs、SiとAs、あるいはGeとSiとAsを含む一般式(I)の4元化合物から選ばれる請求項1に記載の成型物。
- その気孔率が5〜95%である請求項1または2に記載の成型物。
- その気孔率が30〜95%である請求項1〜3のいずれか一項に記載の成型物。
- 連続気泡発泡体の形で存在する請求項1〜4のいずれか一項に記載の成型物。
- スラブ状、ハニカム状、モノリス状または持体上に被膜の状態で存在する請求項1〜5のいずれか一項に記載の成型物。
- 熱磁気材料の粉末を成型することからなる請求項1〜6のいずれか一項に記載の成型物の製造方法であって、その際に、粉末の粒子が結合して連続気泡多孔性構造を形成する方法。
- 熱磁気材料の粉末が、プレスにより、適当なら熱処理と共にプレスにより、焼結プロセスにより、あるいは発泡体成形プロセスにより処理される請求項7に記載の方法。
- 前記熱磁気材料をポリマーバインダー中に導入し、得られる熱可塑性成形材料を成型し、該バインダーを除去し、得られる緑色成型物を焼結する、あるいは前記熱磁気材料の粉末をポリマーバインダーで被覆し、適当なら熱処理とともにプレスにより成型する請求項7に記載の方法。
- 請求項1〜6のいずれか一項に記載の成型物の、冷蔵庫、空気調和単位、ヒートポンプまたは発電量中での熱の直接変換での利用。
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PCT/EP2009/055023 WO2009133048A1 (de) | 2008-04-28 | 2009-04-27 | Offenzelliger, poröser formkörper für wärmetauscher |
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JP2015149464A (ja) * | 2014-02-05 | 2015-08-20 | 株式会社三徳 | 磁気冷凍デバイスおよび磁気冷凍システム |
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Also Published As
Publication number | Publication date |
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EP2274750B1 (de) | 2016-06-15 |
AU2009242215A1 (en) | 2009-11-05 |
CN102077303A (zh) | 2011-05-25 |
WO2009133048A1 (de) | 2009-11-05 |
JP5713889B2 (ja) | 2015-05-07 |
CN102077303B (zh) | 2015-04-08 |
US9343209B2 (en) | 2016-05-17 |
KR20110014612A (ko) | 2011-02-11 |
KR101558019B1 (ko) | 2015-10-06 |
US20110042608A1 (en) | 2011-02-24 |
TW201003024A (en) | 2010-01-16 |
EP2274750A1 (de) | 2011-01-19 |
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