JP5608949B2 - n型熱電変換性能を有する金属材料 - Google Patents
n型熱電変換性能を有する金属材料 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims description 45
- 239000007769 metal material Substances 0.000 title claims description 36
- 239000000463 material Substances 0.000 claims description 32
- 229910045601 alloy Inorganic materials 0.000 claims description 24
- 239000000956 alloy Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000010248 power generation Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019018 Mg 2 Si Inorganic materials 0.000 description 1
- 229910017028 MnSi Inorganic materials 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- UPIXZLGONUBZLK-UHFFFAOYSA-N platinum Chemical compound [Pt].[Pt] UPIXZLGONUBZLK-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- B22F9/00—Making metallic powder or suspensions thereof
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- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
- C22C27/025—Alloys based on vanadium, niobium, or tantalum alloys based on vanadium
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- C22C27/06—Alloys based on chromium
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- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
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- C22C9/10—Alloys based on copper with silicon as the next major constituent
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/854—Thermoelectric active materials comprising inorganic compositions comprising only metals
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Description
1. 組成式:Mn3-xM1 xSiyAlzM2 a (式中、M1は、Ti、V、Cr、Fe、Co、Ni、及びCuからなる群から選ばれる少なくとも一種の元素であり、M2は、B、P、Sn、及びBiからなる群から選ばれる少なくとも一種の元素であり、0≦x≦3.0、3.5≦y≦4.5、2.5≦z≦3.5、0<a≦1である)で表され、25℃以上の温度で負のゼーベック係数を有する合金からなる金属材料。
2. 組成式:Mn 3-x M 1 x Si y Al z M 2 a において、aの値が0.2≦a≦1である、上記項1に記載の金属材料。
3. 上記項1又は2に記載の金属材料又はその焼結体からなるn型熱電変換材料。
4. 上記項3に記載のn型熱電変換材料を含む熱電変換モジュール。
本発明の金属材料は、組成式:Mn3-xM1 xSiyAlzM2 a (式中、M1は、Ti、V、Cr、Fe、Co、Ni、及びCuからなる群から選ばれる少なくとも一種の元素であり、M2は、B、P、Sn、及びBiからなる群から選ばれる少なくとも一種の元素であり、0≦x≦3.0、3.5≦y≦4.5、2.5≦z≦3.5、0<a≦1である)で表されるものである。
Mn源としてマンガン(Mn)、Si源としてシリコン(Si)及びAl源としてアルミニウム(Al)を用い、Mn:Si:Al(元素比)=3.0:4.0:3.0となるように原料物質を配合した後、アーク熔解法によりアルゴン雰囲気中で原料を熔融させ、融液を十分に混合した後、室温まで冷却して上記した原料金属成分からなる合金を得た。
原料の種類又は配合割合を変える以外は実施例1と同様の工程により、下記表1に示す組成の焼結成型体を作製した。各原料としては、それぞれの金属単体を用いた。
実施例1〜37で得られた各焼結成型体について、下記の方法でゼーベック係数、電位抵抗率、熱伝導度、及び無次元性能指数を求めた。
試料を断面が3〜5mm角、長さが3〜8mm程度の矩形に成型し、Rタイプ(白金−白金・ロジウム)熱電対を銀ペーストで両端面に接続した。試料を管状電気炉に入れ、100〜700℃に加熱し、熱電対を設けた片面にエアポンプを用い室温の空気を当てることで温度差を付け、試料両端面で発生した熱起電力を熱電対の白金線を用い測定した。熱起電力と両端面の温度差によりゼーベック係数を算出した。
試料を断面が3〜5mm角、長さが3〜8mm程度の矩形に成型し、銀ペーストと白金線を用い両端面に電流端子、側面に電圧端子を設け、直流四端子法により測定した。
試料を幅約5mm、長さ約8mm、厚さ約1.5mmに成型し、レーザーフラッシュ法により熱拡散率と比熱を測定した。これらの数値とアルキメデス法により測定した密度をかけ合わせることで熱伝導度を算出した。
Claims (4)
- 組成式:Mn3-xM1 xSiyAlzM2 a (式中、M1は、Ti、V、Cr、Fe、Co、Ni、及びCuからなる群から選ばれる少なくとも一種の元素であり、M2は、B、P、Sn、及びBiからなる群から選ばれる少なくとも一種の元素であり、0≦x≦3.0、3.5≦y≦4.5、2.5≦z≦3.5、0<a≦1である)で表され、25℃以上の温度で負のゼーベック係数を有する合金からなる金属材料。
- 組成式:Mn 3-x M 1 x Si y Al z M 2 a において、aの値が0.2≦a≦1である、請求項1に記載の金属材料。
- 請求項1又は2に記載の金属材料又はその焼結体からなるn型熱電変換材料。
- 請求項3に記載のn型熱電変換材料を含む熱電変換モジュール。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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JP2010272204A JP5608949B2 (ja) | 2010-12-07 | 2010-12-07 | n型熱電変換性能を有する金属材料 |
CN201180059099.7A CN103262272B (zh) | 2010-12-07 | 2011-12-01 | 具有n型热电转换性能的金属材料 |
PCT/JP2011/077852 WO2012077578A1 (ja) | 2010-12-07 | 2011-12-01 | n型熱電変換性能を有する金属材料 |
US13/992,501 US20130256608A1 (en) | 2010-12-07 | 2011-12-01 | METAL MATERIAL HAVING n-TYPE THERMOELECTRIC CONVERSION CAPABILITY |
DE112011104153.5T DE112011104153B4 (de) | 2010-12-07 | 2011-12-01 | Thermoelektrisches Wandlermaterial vom n-Typ umfassend ein Metallmaterial oder einen Sinterkörper daraus |
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JP2010272204A JP5608949B2 (ja) | 2010-12-07 | 2010-12-07 | n型熱電変換性能を有する金属材料 |
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JP5608949B2 true JP5608949B2 (ja) | 2014-10-22 |
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JP (1) | JP5608949B2 (ja) |
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JP5949347B2 (ja) * | 2012-09-04 | 2016-07-06 | 国立研究開発法人産業技術総合研究所 | n型熱電変換性能を有する金属材料 |
CN106170875A (zh) * | 2013-12-05 | 2016-11-30 | 罗伯特·博世有限公司 | 用于热电能量转换的材料 |
DE102014227033A1 (de) * | 2014-12-30 | 2016-06-30 | Siemens Aktiengesellschaft | Thermoelement und Verfahren zum Aufbringen eines solchen |
US20230157174A1 (en) | 2020-01-31 | 2023-05-18 | National Institute Of Advanced Industrial Science And Technology | Thermoelectric conversion module |
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US3684584A (en) * | 1971-03-15 | 1972-08-15 | Driver Co Wilbur B | Thermocouple extension wire |
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JP3424180B2 (ja) * | 1993-02-23 | 2003-07-07 | 独立行政法人物質・材料研究機構 | P型熱発電材料 |
JP3055419B2 (ja) * | 1994-12-27 | 2000-06-26 | ヤマハ株式会社 | 熱電材料及びその製造方法 |
JP3055418B2 (ja) * | 1994-12-27 | 2000-06-26 | ヤマハ株式会社 | 熱電材料及びその製造方法 |
JP2004006206A (ja) * | 2001-09-28 | 2004-01-08 | Toshiba Corp | 非水電解質電池用負極材料、負極、非水電解質電池及び非水電解質電池用負極材料の製造方法 |
KR100435180B1 (ko) | 2001-09-28 | 2004-06-11 | 가부시끼가이샤 도시바 | 비수전해질 전지용 음극 재료, 음극, 비수전해질 전지 및비수전해질 전지용 음극 재료의 제조 방법 |
US6987650B2 (en) * | 2003-05-22 | 2006-01-17 | Headway Technologies, Inc. | Device with thermoelectric cooling |
ATE527699T1 (de) * | 2004-07-01 | 2011-10-15 | Universal Entertainment Corp | Thermoelektrisches wandlermodul |
JP4888685B2 (ja) * | 2005-08-05 | 2012-02-29 | 株式会社豊田中央研究所 | 熱電材料及びその製造方法 |
JP4745183B2 (ja) * | 2006-09-29 | 2011-08-10 | 株式会社東芝 | 熱電変換材料とそれを用いた熱電変換モジュール |
JP5281308B2 (ja) * | 2008-03-24 | 2013-09-04 | 株式会社豊田中央研究所 | 熱電材料及びその製造方法 |
JP5352860B2 (ja) * | 2009-09-03 | 2013-11-27 | 株式会社豊田中央研究所 | 熱電材料及びその製造方法 |
-
2010
- 2010-12-07 JP JP2010272204A patent/JP5608949B2/ja active Active
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2011
- 2011-12-01 DE DE112011104153.5T patent/DE112011104153B4/de not_active Expired - Fee Related
- 2011-12-01 CN CN201180059099.7A patent/CN103262272B/zh not_active Expired - Fee Related
- 2011-12-01 WO PCT/JP2011/077852 patent/WO2012077578A1/ja active Application Filing
- 2011-12-01 US US13/992,501 patent/US20130256608A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
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CN103262272B (zh) | 2016-04-13 |
CN103262272A (zh) | 2013-08-21 |
US20130256608A1 (en) | 2013-10-03 |
DE112011104153T5 (de) | 2013-10-10 |
WO2012077578A1 (ja) | 2012-06-14 |
JP2012124243A (ja) | 2012-06-28 |
DE112011104153B4 (de) | 2019-05-09 |
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