JPH012379A - Method for manufacturing thermoelectric elements - Google Patents
Method for manufacturing thermoelectric elementsInfo
- Publication number
- JPH012379A JPH012379A JP62-156645A JP15664587A JPH012379A JP H012379 A JPH012379 A JP H012379A JP 15664587 A JP15664587 A JP 15664587A JP H012379 A JPH012379 A JP H012379A
- Authority
- JP
- Japan
- Prior art keywords
- metal alloy
- thermoelectric element
- manufacturing
- powder
- thermoelectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は熱電特性に考れた全屈合金熱電素子の製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a fully bending alloy thermoelectric element in consideration of thermoelectric properties.
［従来の技術］
ゼーベック効果を応用して熱電発電を行なわせる熱電素
子は種々の分野において実用化か期待されている。[Prior Art] Thermoelectric elements that generate thermoelectric power by applying the Seebeck effect are expected to be put to practical use in various fields.
金属合金からなる熱電素子の実用化を妨げる要因の一つ
として、熱起電力か低いという問題かある。One of the factors hindering the practical application of thermoelectric elements made of metal alloys is the problem of low thermoelectromotive force.
このため、熱起電力の高い熱電素子を得るため種々の製
造方法か開発されており、その代表的な方法として、（
イ）金属合金の粉末を合成し、（ロ）これをプレス成形
して所定の形状を有する成形体とし、（ハ）次いて、こ
の成形体を焼結して熱電素子とする製造方法がある。For this reason, various manufacturing methods have been developed to obtain thermoelectric elements with high thermoelectromotive force, and the representative method is (
There is a manufacturing method in which a) metal alloy powder is synthesized, (b) this is press-molded to form a molded body with a predetermined shape, and (c) this molded body is then sintered to form a thermoelectric element. .
［解決すべき問題点］
しかし、従来の製造方法によって製造した金属合金の熱
電素子の熱起電力は、通常、１ ｍＶ／に程度てあり、
種々の分野て熱電素子を利用するには低くすぎるもので
あった。[Problems to be solved] However, the thermoelectromotive force of metal alloy thermoelectric elements manufactured by conventional manufacturing methods is usually about 1 mV/,
It was too low to utilize thermoelectric elements in various fields.
また、従来の製造方法（特に、機械的に金属合金を粉砕
する粉末冶金法）によって製造した金属合金の熱電素子
は、熱電素子間におけるばらつきか±５０％程度と非常
に大きく、信頼性に欠けるものであった。In addition, metal alloy thermoelectric elements manufactured by conventional manufacturing methods (particularly powder metallurgy methods that mechanically crush metal alloys) have extremely large variations of about ±50% between thermoelectric elements and lack reliability. It was something.
本発明は上記の問題点にかんがみてなされたもので、高
い熱起電力を得ることかてきるとともに、ばらつきか小
さく信頼性の高い８電素子を製造てきるようにしだ熱電
素子の製造方法の提供を目的とする。The present invention has been made in view of the above-mentioned problems, and provides a method for manufacturing a thermoelectric element that can obtain a high thermoelectromotive force and also manufacture a highly reliable 8-electron element with small variations. For the purpose of providing.
［問題点の解決手段］
本発明者は上記目的を達成するため鋭意検討した結果、
成形体を焼結した後、さらに大気中において熱処理を行
なうことにより上記目的を達成てきることを見出し１本
発明に到達した。[Means for solving the problem] As a result of intensive studies to achieve the above object, the inventor has found that
The inventors have discovered that the above object can be achieved by further performing heat treatment in the atmosphere after sintering the compact, and have thus arrived at the present invention.
すなわち、本発明は、 仁金属合金の粉末を製造し、これを合成する工程。That is, the present invention The process of manufacturing and synthesizing powdered metal alloys.
口０合成した粉末金属合金をプレスして所定の形状とす
る工程。Process of pressing the synthesized powder metal alloy into a predetermined shape.
ハ、所定の形状に成形した金属合金成形体を焼結する工
程。C. A step of sintering the metal alloy compact formed into a predetermined shape.
二、焼結した金属合金成形体を大気中において熱処理す
る工程。2. A step of heat treating the sintered metal alloy compact in the atmosphere.
によって熱電素子を製造する方法としである。そして、
好ましくは、二における大気中の熱処理をＳＯＯ〜１０
００℃、特に好ましくは７００〜９００℃で行なうよう
にしている。This is a method for manufacturing a thermoelectric element. and,
Preferably, the heat treatment in the atmosphere in step 2 is performed at SOO~10
The temperature is preferably 700 to 900°C.
以下、本発明の内容を詳細に説明する。Hereinafter, the content of the present invention will be explained in detail.
第１図は本発明製造方法を説明するためのブロック図て
あり、１は金属合金粉末の合成工程、２は合成した粉末
金属合金を所定形状の成形体に成形するプレス成形工程
、３は成形体を真空中において焼結する焼結工程、４は
焼結した成形体を大気中において熱処理する熱処理工程
である。FIG. 1 is a block diagram for explaining the manufacturing method of the present invention, in which 1 is a synthesis process of metal alloy powder, 2 is a press forming process for forming the synthesized powder metal alloy into a compact of a predetermined shape, and 3 is a forming process. 4 is a sintering step in which the body is sintered in a vacuum; and 4 is a heat treatment step in which the sintered compact is heat-treated in the atmosphere.
本発明製造方法て製造される金属合金の熱電素子におい
ては、 Ｂｉ２Ｔｅ３，５ｂａＴｅ：＋、ＢＩ２Ｓｅ：
＋、５ｂ２Ｓｅ１＋Ｚｎ５ｂ、ＺｎＴｅ、２５ＢｉａＴ
ｅ：＋”７！＋Ｓｂ２Ｔｅ３，７０Ｂｉ、Ｔｅ、＋：１
ＯＢｉ、Ｓｅｚ、ＰｂＴｅ、Ｐｂ５ｅ、Ｂｉ（Ｓｉ−３
ｂ２） 、Ｂｉｚ（Ｇｅ−９ｅ）３゜Ｃｒ５ｉｚ、
ＭｎＳｉ＋、ｔ：＋＋Ｆｅ５ｉａ、ＣｏＳｉ、Ｇｅ、５
ｉｏ７＋ＧｄＳｅ＋、 ４’ｌ＋Ｃｕ１９ｙＡｇｏ、
ｏ３ｓｅ＋、 ００４ＳＩ Ｘ−＾１８．２゜β−Ｂ、
ＭｇＳｉ、ＭｇＳｉ＋、ｙｆｆ、５ｉＧｅ、またはＳ
ｉ 、 Ｔｅを含有する合金を用いる。In the metal alloy thermoelectric element manufactured by the manufacturing method of the present invention, Bi2Te3,5baTe:+, BI2Se:
+, 5b2Se1+Zn5b, ZnTe, 25BiaT
e:+”7!+Sb2Te3,70Bi,Te,+:1
OBi, Sez, PbTe, Pb5e, Bi(Si-3
b2), Biz(Ge-9e)3°Cr5iz,
MnSi+,t:++Fe5ia,CoSi,Ge,5
io7+GdSe+, 4'l+Cu19yAgo,
o3se+, 004SI X-^18.2゜β-B,
MgSi, MgSi+, yff, 5iGe, or S
i, an alloy containing Te is used.
合成工程ｌにおいては、上述した金属合金を機械的に粉
砕したり、プラズマ法によって微粒子化することによっ
て金属合金の粉末を得ている（本発明においては、微粒
子を含めて粉末と称す）。In the synthesis step 1, a metal alloy powder is obtained by mechanically pulverizing the above-mentioned metal alloy or making it into fine particles using a plasma method (in the present invention, the metal alloy is referred to as a powder including fine particles).
このうち、プラズマ法によって５００ｎｗ以下の微粒子
を気相中にて合成したものを用いると、製造された熱電
素子の熱電特性を、さらに向上させることができる。Among these, if particles of 500 nw or less are synthesized in the gas phase by a plasma method, the thermoelectric characteristics of the manufactured thermoelectric element can be further improved.
なお、プラズマ法としては、高周波プラズマ法あるいは
アークプラズマジェット法等を採用することか好ましい
。As the plasma method, it is preferable to employ a high frequency plasma method, an arc plasma jet method, or the like.
プレス成形工程２に３いては、合成した粉末金属合金を
５００〜１０００ｋｇ／ｃ＋ｗ２の圧力で圧縮し、所定
形状の成形体となるようにプレス成形する。成形圧力は
、粉末金属合金が成形体として所定の形状を保持できる
程度の圧力であればよく、必ずしも上記成形圧力に限定
されるものてはない。In press forming steps 2 and 3, the synthesized powder metal alloy is compressed at a pressure of 500 to 1000 kg/c+w2 and press formed into a molded body of a predetermined shape. The compacting pressure may be a pressure that allows the powder metal alloy to maintain a predetermined shape as a compact, and is not necessarily limited to the above-mentioned compacting pressure.
焼結工程３においては、プレス成形された金属合金成形
体を８００〜１５００°Ｃ１好ましくは１０００〜１２
００℃の高温で加熱して結合する。プラズマ法によって
得た微粒子状の金属合金成形体の場合には、１Ｏ−２Ｔ
ｏｒｒの真空中て、 ８００〜ＩＺ００℃の加熱を２〜
５時間行なう。焼結時の加熱温度か低いと焼結不足とな
り、逆に高いと過焼結状態となり、いずれの場合も熱電
素子の素子特性低下につながる。In the sintering step 3, the press-formed metal alloy compact is heated to 800 to 1500°C, preferably 1000 to 12°C.
Bonding is performed by heating at a high temperature of 00°C. In the case of fine particle shaped metal alloy compacts obtained by plasma method, 1O-2T
Heating at 800~IZ00℃ in a vacuum of 2~
Do it for 5 hours. If the heating temperature during sintering is low, sintering will be insufficient, and if it is high, it will be oversintered, and in either case, the device characteristics of the thermoelectric element will deteriorate.
熱処理工程４においては、焼結した金属合金成形体を大
気中で５００〜１０００℃、好ましくは７００〜９００
℃の温度で数時間熱処理する。熱処理時における加熱温
度の設定も重要であり、低いと素子特性の向上を図れず
、高いと結晶形態が変化してしまい、やはり素子特性の
向上を図れない結果となる。In heat treatment step 4, the sintered metal alloy molded body is heated at 500 to 1000°C, preferably 700 to 900°C, in the atmosphere.
Heat treatment for several hours at a temperature of °C. Setting the heating temperature during heat treatment is also important; if it is too low, the device characteristics cannot be improved, and if it is too high, the crystal morphology changes, resulting in the inability to improve the device characteristics.
［実施例］
次に１本発明の実施例を比較例と比べつつ、本発明を具
体的に説明する。[Example] Next, the present invention will be specifically explained while comparing an example of the present invention with a comparative example.
Ｏ実施例
化合成工程１：プラズマ法により気相中で鉄ケイ化物微
粒子を合成。O Example synthesis step 1: Synthesize iron silicide fine particles in the gas phase by plasma method.
ロ、プレス成形工程２ ： １ ｔｏｎ／ｃ＋＊”の圧
力でプレス成形。B. Press molding step 2: Press molding at a pressure of 1 ton/c+*".
ハ、焼結工程３ ： １０””Ｔｏｒｒの真空中におい
て、１１００°Ｃの温度で６時間加熱して
焼結。C. Sintering step 3: Sintered by heating at a temperature of 1100° C. for 6 hours in a vacuum of 10”” Torr.
二、熱処理工程４：大気中において、 ８５０°Ｃの温
度で３時間加熱して熱処理。2. Heat treatment step 4: Heat treatment in the atmosphere at a temperature of 850°C for 3 hours.
上記工程を経て製造した結果、第２図に示すように高温
側での熱起電力が約７ ＠Ｖ／にと大巾に向上し、また
、ばらつきも±５％以内の熱電素子を得ることがてきた
。As a result of manufacturing through the above steps, as shown in Figure 2, the thermoelectromotive force on the high temperature side is greatly improved to about 7 @V/, and the variation is within ±5%. It's here.
Ｏ比 較 例１
化合成工程１．０．プレス成形工程２．ハ、焼結工程３
を実施例と同じ条件で行ない、熱処理工程を行なわない
で熱電素子を製造した結果、第２図に示すように約１．
５ｍＶ／にの熱起電力を発生した。O Comparison Example 1 Chemical synthesis process 1.0. Press molding process 2. C. Sintering process 3
As a result of manufacturing a thermoelectric element under the same conditions as in the example without performing the heat treatment process, as shown in FIG.
A thermoelectromotive force of 5 mV/m was generated.
また、熱電素子間のばらつきは±２０％であった。Furthermore, the variation between thermoelectric elements was ±20%.
Ｏ比 較 例２
金属合金を機械的に粉砕し、粉砕した粉末をプレスによ
って圧縮成形し、これを焼結する従来の粉末冶金法によ
って熱電素子を得た結果、第２図に示すように約０．Ｉ
５＋ｓＶ／にの熱起電力を発生した。Comparison Example 2 A thermoelectric element was obtained using the conventional powder metallurgy method of mechanically pulverizing a metal alloy, compressing the pulverized powder using a press, and sintering it. 0. I
A thermoelectromotive force of 5+sV/ was generated.
また、熱電素子間のばらつきは±５０％程度工程った。Further, the variation between thermoelectric elements was about ±50%.
［発明の効果］
以上のように本発明によれば、焼結工程後に、さらに熱
処理工程を施すことにより熱電特性に優れた熱電素子を
製造できるといった効果かある。[Effects of the Invention] As described above, according to the present invention, a thermoelectric element with excellent thermoelectric properties can be manufactured by further performing a heat treatment process after the sintering process.
第１図は本発明製造方法の実施手順を説明するためのブ
ロック図、第２図本発明製造方法によって得た熱電素子
と比較例熱電素子の熱電特性図を示す。
１：合成工程 ２ニブレス成形工程３：焼結工程
４：熱処理工程FIG. 1 is a block diagram for explaining the implementation procedure of the manufacturing method of the present invention, and FIG. 2 is a thermoelectric characteristic diagram of a thermoelectric element obtained by the manufacturing method of the present invention and a comparative thermoelectric element. 1: Synthesis process 2 Nibbles forming process 3: Sintering process
4: Heat treatment process
Claims (5)
の製造方法。 イ、金属合金の粉末を製造し、これを合成する工程。 ロ、合成した粉末金属合金をプレスして所定の形状とす
る工程。 ハ、所定の形状に成形した金属合金成形体を焼結する工
程。 ニ、焼結した金属合金成形体を大気中において熱処理し
、熱電素子を製造する工程。(1) A method for manufacturing a thermoelectric element characterized by comprising steps A to D. B. The process of producing metal alloy powder and synthesizing it. B. A process of pressing the synthesized powder metal alloy into a predetermined shape. C. A step of sintering the metal alloy compact formed into a predetermined shape. D. A step of heat-treating the sintered metal alloy compact in the atmosphere to produce a thermoelectric element.
３、Ｂｉ＿２Ｓｅ＿３、Ｓｂ＿２Ｓｅ＿３、ＺｎＳｂ、
ＺｎＴｅ、２５Ｂｉ＿２Ｔｅ＿３＾＋７５Ｓｂ＿２Ｔｅ
＿３、７０Ｂｉ＿２Ｔｅ＿３＾＋３０Ｂｉ＿２Ｓｅ＿３
、ＰｂＴｅ、ＰｂＳｅ、Ｂｉ（Ｓｉ・Ｓｂ＿２）、Ｂｉ
＿２（Ｇｅ・Ｓｅ）＿３、ＣｒＳｉ＿２、ＭｎＳｉ＿１
＿．＿７＿３、ＦｅＳｉ＿２、ＣｏＳｉ、Ｇｅ＿３Ｓｉ
ｏ＿７、ＧｄＳｅ＿１＿．＿４＿９、Ｃｕ＿１＿．＿９
＿７Ａｇ＿０＿．＿０＿３Ｓｅ＿１＿．＿０＿０＿４＿
５、χ−ＡＩＩＢ＿１＿２、β−Ｂ、ＭｇＳｉ、ＭｇＳ
ｉ＿１、＿７３、ＳｉＧｅ、またはＳｉ、Ｔｅを含有す
るものからなることを特徴とした特許請求の範囲第１項
記載の熱電素子の製造方法。(2) Metal alloy, Bi_2Te_3, Sb_2Te_
3, Bi_2Se_3, Sb_2Se_3, ZnSb,
ZnTe, 25Bi_2Te_3^+75Sb_2Te
_3, 70Bi_2Te_3^+30Bi_2Se_3
, PbTe, PbSe, Bi (Si・Sb_2), Bi
_2(Ge・Se)_3, CrSi_2, MnSi_1
＿． _7_3, FeSi_2, CoSi, Ge_3Si
o_7, GdSe_1_. _4_9, Cu_1_. ＿9
_7Ag_0_. _0_3Se_1_. ＿0＿0＿4＿
5, χ-AIIB_1_2, β-B, MgSi, MgS
The method for manufacturing a thermoelectric element according to claim 1, characterized in that the thermoelectric element is made of a material containing i_1, _73, SiGe, Si, or Te.
行なうことを特徴とした特許請求の範囲第１または２項
記載の熱電素子の製造方法。(3) The method for manufacturing a thermoelectric element according to claim 1 or 2, characterized in that the metal alloy molded body is heat-treated at 800 to 1500°C.
た特許請求の範囲第１、２または３項記載の熱電素子の
製造方法。(4) The method for manufacturing a thermoelectric element according to claim 1, 2 or 3, wherein the metal alloy powder is in the form of fine particles.
ことを特徴とした特許請求の範囲第４項記載の熱電素子
の製造方法。(5) The method for manufacturing a thermoelectric element according to claim 4, wherein the metal alloy fine particles are manufactured by a plasma method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62156645A JPS642379A (en) | 1987-06-25 | 1987-06-25 | Manufacture of thermoelectric element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62156645A JPS642379A (en) | 1987-06-25 | 1987-06-25 | Manufacture of thermoelectric element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH012379A true JPH012379A (en) | 1989-01-06 |
| JPS642379A JPS642379A (en) | 1989-01-06 |
Family
ID=15632188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62156645A Pending JPS642379A (en) | 1987-06-25 | 1987-06-25 | Manufacture of thermoelectric element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS642379A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2879152B2 (en) * | 1989-07-10 | 1999-04-05 | 工業技術院長 | Manufacturing method of thermoelectric material |
| JP2829415B2 (en) * | 1989-06-14 | 1998-11-25 | 株式会社小松製作所 | Thermoelectric semiconductor material and method of manufacturing the same |
| CN100452466C (en) * | 2003-09-12 | 2009-01-14 | 密歇根州州立大学托管委员会 | Thermoelectric material and its preparation method, thermoelectric element and method of generating electric current from thermal energy |
| US11063197B2 (en) | 2016-03-31 | 2021-07-13 | Sumitomo Chemical Company, Limited | Compound, thermoelectric conversion material, and method for producing compound |
| US11171277B2 (en) | 2016-03-31 | 2021-11-09 | Sumitomo Chemical Company, Limited | Compound and thermoelectric conversion material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS572584A (en) * | 1980-06-06 | 1982-01-07 | Tdk Corp | Thermoelectric element and manufacture thereof |
| JPS6287403A (en) * | 1985-10-14 | 1987-04-21 | Toyota Motor Corp | Production of electrically-conductive silicon nitride raw material powder |
-
1987
- 1987-06-25 JP JP62156645A patent/JPS642379A/en active Pending
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