JP5713889B2 - 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/015—Metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1028—Controlled cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B21/00—Machines, plants or systems, using electric or magnetic effects
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/058—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IVa elements, e.g. Gd2Fe14C
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/02—Magnetic
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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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- Hard Magnetic Materials (AREA)
Description
(AyB 1−y )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 (12)
- 熱交換器用の、気孔率が30〜95%であり、以下の化合物から選ばれる熱磁気材料を含む連続気泡多孔性の成型物の製造方法であって、
(1)一般式(I)の化合物
(AyB1−y)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つは異なり、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);
(3)MnTP型のホイスラー合金(式中、Tは遷移金属で、P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して、該ポリマーバインダーが粒子上のシェルとして残り、
前記ポリマーバインダーは、ポリビニルピロリドン、ビニルピロリドン−スチレンコポリマー、ビニルピロリドン−酢酸ビニルコポリマー、ポリエチレン、ポリプロピレン、ポリスチレン、ポリアミド、ポリウレタン、ポリエステル、ポリエーテル、ポリスルホン、ポリエーテルケトン、ポリカーボネート、ポリエステル樹脂、エポキシ樹脂、ポリメタクリル酸メチル、ポリエチレンテレフタレート、ポリイミド、フェノールホルムアルデヒド樹脂、不飽和ポリエステル樹脂からなる群より選択されることを特徴とする製造方法。
- 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、Ge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に記載の方法。
- 前記成型物が連続気泡発泡体の形で存在する請求項1または2に記載の方法。
- 前記成型物がスラブ状、ハニカム状、モノリス状または基体上に被膜の状態で存在する請求項1〜3のいずれか一項に記載の方法。
- 前記熱磁気材料が、噴霧塗布によりバインダーで被覆される請求項1〜4の何れか1項に記載の製造方法。
- 前記熱磁気材料が、流動床噴霧塗布法によりバインダーで被覆される請求項1〜5の何れか1項に記載の製造方法。
- 前記ポリマーバインダーにより被覆された熱磁気材料が、金型に入れられ、熱及び/又は圧力で処理される請求項1〜6の何れか1項に記載の製造方法。
- 60〜95%の気孔率を有する連続気泡多孔性の成型物を製造する請求項1〜7の何れか1項に記載の製造方法。
- 30〜60%の気孔率を有する連続気泡多孔性の成型物を製造する請求項1〜7の何れか1項に記載の製造方法。
- 開放気孔の比率が、気孔体積の少なくとも30%である請求項1〜9の何れか1項に記載の製造方法。
- 開放気孔の比率が、気孔体積の少なくとも60%である請求項1〜10の何れか1項に記載の製造方法。
- 開放気孔の比率が、気孔体積の少なくとも80%である請求項1〜11の何れか1項に記載の製造方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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EP08155255 | 2008-04-28 | ||
EP08155255.6 | 2008-04-28 | ||
PCT/EP2009/055023 WO2009133048A1 (de) | 2008-04-28 | 2009-04-27 | Offenzelliger, poröser formkörper für wärmetauscher |
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JP2011523771A JP2011523771A (ja) | 2011-08-18 |
JP2011523771A5 JP2011523771A5 (ja) | 2013-08-29 |
JP5713889B2 true JP5713889B2 (ja) | 2015-05-07 |
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JP2011505531A Expired - Fee Related JP5713889B2 (ja) | 2008-04-28 | 2009-04-27 | 熱交換器用の連続気泡多孔性成型物 |
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US (1) | US9343209B2 (ja) |
EP (1) | EP2274750B1 (ja) |
JP (1) | JP5713889B2 (ja) |
KR (1) | KR101558019B1 (ja) |
CN (1) | CN102077303B (ja) |
AU (1) | AU2009242215A1 (ja) |
TW (1) | TW201003024A (ja) |
WO (1) | WO2009133048A1 (ja) |
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2009
- 2009-04-23 TW TW098113511A patent/TW201003024A/zh unknown
- 2009-04-27 JP JP2011505531A patent/JP5713889B2/ja not_active Expired - Fee Related
- 2009-04-27 US US12/990,107 patent/US9343209B2/en not_active Expired - Fee Related
- 2009-04-27 KR KR1020107026640A patent/KR101558019B1/ko active IP Right Grant
- 2009-04-27 WO PCT/EP2009/055023 patent/WO2009133048A1/de active Application Filing
- 2009-04-27 CN CN200980124576.6A patent/CN102077303B/zh not_active Expired - Fee Related
- 2009-04-27 EP EP09738092.7A patent/EP2274750B1/de not_active Not-in-force
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US11951544B2 (en) | 2016-10-14 | 2024-04-09 | Lg Chem, Ltd. | Method for manufacturing metal alloy foam |
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KR20110014612A (ko) | 2011-02-11 |
JP2011523771A (ja) | 2011-08-18 |
CN102077303B (zh) | 2015-04-08 |
US9343209B2 (en) | 2016-05-17 |
KR101558019B1 (ko) | 2015-10-06 |
EP2274750B1 (de) | 2016-06-15 |
EP2274750A1 (de) | 2011-01-19 |
CN102077303A (zh) | 2011-05-25 |
WO2009133048A1 (de) | 2009-11-05 |
TW201003024A (en) | 2010-01-16 |
AU2009242215A1 (en) | 2009-11-05 |
US20110042608A1 (en) | 2011-02-24 |
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