JPH0347751B2 - - Google Patents
Info
- Publication number
- JPH0347751B2 JPH0347751B2 JP62156646A JP15664687A JPH0347751B2 JP H0347751 B2 JPH0347751 B2 JP H0347751B2 JP 62156646 A JP62156646 A JP 62156646A JP 15664687 A JP15664687 A JP 15664687A JP H0347751 B2 JPH0347751 B2 JP H0347751B2
- Authority
- JP
- Japan
- Prior art keywords
- adamantane
- metal alloy
- thermoelectric element
- mixture
- 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.)
- Expired
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 25
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 6
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
- 229910019001 CoSi Inorganic materials 0.000 description 1
- 229910019974 CrSi Inorganic materials 0.000 description 1
- 229910005329 FeSi 2 Inorganic materials 0.000 description 1
- 229910017639 MgSi Inorganic materials 0.000 description 1
- 229910017028 MnSi Inorganic materials 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910007657 ZnSb Inorganic materials 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 235000019685 rice crackers Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、熱電特性に優れた金属合金熱電素子
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a metal alloy thermoelectric element having excellent thermoelectric properties.
［従来の技術］
ゼーベツ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が期待さ
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、熱起電力が低いという問題があ
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
種々の改良のなされた熱電素子が開発されてい
る。このうち、金属合金からなる熱電素子におい
ても、金属合金の材料、含有率、粉末の粒子径を
変えたり、あるいは製造手順、条件を変えたりし
て種々の改良が行なわれている。 For this reason, various improved thermoelectric elements have been developed in order to obtain thermoelectric elements with high thermoelectromotive force. Among these, various improvements have been made in thermoelectric elements made of metal alloys by changing the material of the metal alloy, the content, the particle size of the powder, or by changing the manufacturing procedure and conditions.
そして、金属合金からなる熱電素子は、素子を
微細かつ均一な多孔質の焼結体とすることにより
熱起電力を高くできることが判明した。 It has also been found that the thermoelectromotive force of a thermoelectric element made of a metal alloy can be increased by forming the element into a fine and uniform porous sintered body.
［解決すべき問題点］
しかしながら、微細かつ均一な多数の孔を有す
る多孔質の焼結体で熱電素子を構成することは難
しかつた。すなわち、微細な孔を均一に作ること
ができないため、高い熱起電力を得ることができ
ないとともに、製品の均質化を図れることができ
ず、金属合金による熱電素子は実用化段階には至
つていないかつた。[Problems to be Solved] However, it has been difficult to construct a thermoelectric element using a porous sintered body having a large number of fine and uniform pores. In other words, since it is not possible to make fine holes uniformly, it is not possible to obtain a high thermoelectromotive force and it is not possible to achieve homogeneity of the product, and thermoelectric elements made of metal alloys have not reached the stage of practical use. I didn't have it.
本発明は上記の問題点にかんでみてなされたも
ので、高い熱起電力を得ることができるととも
に、製品の均質化を可能として素子間のばらつき
のない熱電素子の提供を目的とする。 The present invention has been made in view of the above-mentioned problems, and aims to provide a thermoelectric element that can obtain a high thermoelectromotive force, enables homogenization of the product, and has no variation between elements.
［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、金属合金の粉末にアダマンタンもしくは
アダマンタン／トリメチレンノルボルナン混合物
を混合添加し、その後焼結を行なつて熱電素子を
製造することにより、上記目的が達成できること
を見出し本発明に到達した。[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the inventor of the present invention mixed and added adamantane or an adamantane/trimethylene norbornane mixture to a metal alloy powder, and then sintered the mixture to form a thermoelectric element. The present inventors have discovered that the above object can be achieved by manufacturing the product, and have thus arrived at the present invention.
すなわち、本発明の熱電素子の製造方法は、金
属合金の粉末にアダマンタンもしくはアダマンタ
ン／トリメチレンノルボルナン混合物を添加して
プレス成形し、その後焼結を行なつて製造した方
法としてある。そして、好ましくは、焼成を、焼
結工程と熱処理工程の二段工程とする方法として
いる。 That is, the method for manufacturing a thermoelectric element of the present invention is a method in which adamantane or an adamantane/trimethylene norbornane mixture is added to metal alloy powder, press-molded, and then sintered. Preferably, the firing is a two-stage process of a sintering process and a heat treatment process.
このような製造方法によれば、微細かつ均一な
多孔質状の熱電素子を得ることができる。 According to such a manufacturing method, a fine and uniform porous thermoelectric element can be obtained.
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
ツク図であり、１は金属合金粉末の合成工程、２
は金属合金粉末とアダマンタン等の添加材を混合
する混合工程、３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、４は成
形体を真空中において焼結する焼結工程、５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 step of metal alloy powder, 2
3 is a mixing process in which metal alloy powder is mixed with additives such as adamantane; 3 is a press forming process in which the synthesized powder metal alloy is formed into a predetermined shaped compact; 4 is a sintering process in which the compact is sintered in a vacuum , 5 is a heat treatment step in which the sintered compact is heat treated in the atmosphere.
本発明な製造方法で製造される金属合金の熱電
素子においては、Bi2Te3，Sb2Te3，Bi2Se3，
Sb2Se3，ZnSb，ZnTe，25Bi2Te3＋75Sb2Te3，
70Bi2Te3＋30Bi2Se3，PbTe，PbSe、Bi（Si・
Sb2），Bi2（Ge・Se）3，CrSi2，MnSi1173、FeSi2，
CoSi，Ge3Si017，GdSe1149，Cu1197Ag0103
Se110045，ｘ−AlB12，β−Ｂ，MgSi1173，SiGe，
またはSi，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, Bi 2 Te 3 , Sb 2 Te 3 , Bi 2 Se 3 ,
Sb 2 Se 3 , ZnSb, ZnTe, 25Bi 2 Te 3 +75Sb 2 Te 3 ,
70Bi 2 Te 3 +30Bi 2 Se 3 , PbTe, PbSe, Bi(Si・
Sb 2 ), Bi 2 (Ge・Se) 3 , CrSi 2 , MnSi 1173 , FeSi 2 ,
CoSi, Ge 3 Si 017 , GdSe 1149 , Cu 1197 Ag 0103
Se 110045 , x-AlB 12 , β-B, MgSi 1173 , SiGe,
Or use an alloy containing Si or Te.
合金工程においては、上述した金属合金を機械
的に粉砕したり、プラズマ法によつて微粒子化す
ることによつ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 alloying process, metal alloy powder is obtained by mechanically pulverizing the metal alloy described above or by making it into fine particles using a plasma method (in the present invention, the term "powder" including fine particles is used). ).
このうち、プラズマ法によつて500nｍ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 nm or less are synthesized in the gas phase by a plasma method, the thermoelectric properties 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エツト法等を採用する
ことが好ましい。 As the plasma method, it is preferable to employ a high frequency plasma method, an arc plasma jet method, or the like.
混合工程２においては、合成工程１で合成した
金属合金粉末とアダマンタンあるいはアダマンタ
ン／トリメチレンノルボルナン（以下、TMNと
いう）混合物をヘンシエルミキサ等によつて撹拌
混合する。これにより、金属合金粉末中にアダマ
ンタンあるいはアダマンタン／TMN混合物を添
加する。なお、混合工程２において使用する混合
機としては、粉末材の混合を行なえるものであれ
ば特に限定されず、上述のヘンシエルミキサのほ
か、らいかい機等の混合機を用いることもでき
る。また、添加材としてアダマンタンあるいはア
ダマンタン／TMN混合物を用いると、焼成時の
抜けがよく、焼成時における添加材の残量が少な
く良好な多孔質状焼成体を形成できる。 In the mixing step 2, the metal alloy powder synthesized in the synthesis step 1 and the adamantane or adamantane/trimethylene norbornane (hereinafter referred to as TMN) mixture are stirred and mixed using a Henschel mixer or the like. This adds adamantane or an adamantane/TMN mixture into the metal alloy powder. The mixer used in the mixing step 2 is not particularly limited as long as it can mix the powder materials, and in addition to the above-mentioned Henschel mixer, a mixer such as a rice cracker can also be used. Furthermore, when adamantane or an adamantane/TMN mixture is used as the additive, a good porous fired body can be formed with good release during firing and a small amount of the additive remaining during firing.
プレス成形工程３においては、添加材を混合し
た粉末金属合金を0.5〜2ton／cm2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ではない。 In press forming step 3, the powdered metal alloy mixed with additives is compressed at a pressure of 0.5 to 2 ton/ cm2 ,
Press molding is performed to obtain 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４においては、プレス成形された成形
体を800〜1500℃、好ましくは1000〜1200℃の高
温で加熱して焼成する。このとき、添加材が昇華
され成形体中に多数の微細孔が形成される。プラ
ズマ法によつて得た微粒子状の金属合金成形体の
場合には、10-2Torrの真空中で、800〜1200℃の
加熱を４〜８時間行なう。焼結時の加熱温度が低
いと昇華不足、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 4, the press-formed compact is heated and fired at a high temperature of 800 to 1500°C, preferably 1000 to 1200°C. At this time, the additive material is sublimated and a large number of micropores are formed in the molded body. In the case of a particulate metal alloy compact obtained by the plasma method, heating is performed at 800 to 1200° C. for 4 to 8 hours in a vacuum of 10 −2 Torr. If the heating temperature during sintering is low, there will be insufficient sublimation and sintering, while if it is high, an oversintered state will result, and in either case, the element characteristics of the thermoelectric element will deteriorate.
熱処理工程５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 5, the sintered metal alloy molded body is heated at 500 to 1000°C, preferably 700 to 1000°C, in the atmosphere.
Heat treatment at a temperature of 900℃ for several hours. 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、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 described while comparing Examples of the present invention with Comparative Examples.
Γ実施例 １
プラズマ法により合成した鉄ケイ化物粉末100
ｇと、アダマンタン25ｇをヘンシエルミキサに入
れて３分間撹拌混合し、その後混合物を1ton／cm2
の圧力でプレス成形し、これを1100℃で６時間焼
結した。そしてその後、850℃で３時間熱処理を
行なつて熱電素子とした。（なお、焼結体の嵩比
重は2.1Kg／cm3、計算上の空隙率は50％であつ
た。）
この結果、第２図に示すように最高9.2ｍＶ／
Ｋ程度の熱起電力を得ることができた。Γ Example 1 Iron silicide powder synthesized by plasma method 100
g and 25 g of adamantane in a Henschel mixer, stir and mix for 3 minutes, then mix the mixture at 1 ton/cm 2
This was press-molded at a pressure of 1,100°C for 6 hours. Then, heat treatment was performed at 850°C for 3 hours to produce a thermoelectric element. (The bulk specific gravity of the sintered body was 2.1 Kg/cm 3 , and the calculated porosity was 50%.) As a result, as shown in Figure 2, the maximum
It was possible to obtain a thermoelectromotive force of about K.
Γ実施例 ２
実施例１におけるアダマンタン25ｇを、アダマ
ンタン：TMN＝２：８としたアダマンタン／
TMN混合物65ｇに代え、その他は実施例１と同
じ条件で熱電素子を製造した。（なお、焼結体の
嵩比重は1.2Kg／cm3、計算上の空隙率は70％であ
つた。）
この結果、第２図に示すように最高10ｍＶ／Ｋ
の熱起電力を得ることができた。ΓExample 2 25g of adamantane in Example 1 was converted into adamantane/TMN=2:8.
A thermoelectric element was manufactured under the same conditions as in Example 1 except that 65 g of the TMN mixture was used. (The bulk specific gravity of the sintered body was 1.2Kg/cm 3 and the calculated porosity was 70%.) As a result, as shown in Figure 2, the maximum
We were able to obtain a thermoelectromotive force of .
Γ比較例
アダマンタンあるいはアダマンタン／TMN混
合物を添加しない鉄ケイ化物のみで、実施例１と
同じ条件で熱電素子を製造した。（なお、焼結体
の嵩比重は3.8Kg／cm3、計算上の空隙率は５％で
あつた。）
この結果、第２図に示すように最高1.5ｍＶ／
Ｋの熱起電力を得ることができた。Γ Comparative Example A thermoelectric element was manufactured under the same conditions as in Example 1 using only iron silicide without adding adamantane or an adamantane/TMN mixture. (The bulk specific gravity of the sintered body was 3.8 Kg/cm 3 , and the calculated porosity was 5%.) As a result, as shown in Figure 2, the maximum
We were able to obtain a thermoelectromotive force of K.
［発明の効果］
以上のように本発明によれば、アダマンタン等
の添加材を添加して焼成することにより、微細か
つ均一な孔からなる多孔質状の、熱電特性に優れ
た熱電素子を製造できるといつた効果がある。[Effects of the Invention] As described above, according to the present invention, by adding additives such as adamantane and firing, it is possible to manufacture a porous thermoelectric element having excellent thermoelectric properties and having fine and uniform pores. There is an effect that can be done.
第１図は本発明製造方法の実施手順を説明する
ためのブロツク図、第２図本発明製造方法によつ
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：混合工程、３：プレス成形
工程、４：焼結工程、５：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 diagram showing thermoelectric characteristics of a thermoelectric element obtained by the manufacturing method of the present invention and a comparative thermoelectric element. 1: Synthesis process, 2: Mixing process, 3: Press molding process, 4: Sintering process, 5: Heat treatment process.
Claims (1)
マンタン／トリメチレンノルボルナン混合物を添
加してプレス成形し、その後焼成を行なつて製造
することを特徴とした熱電素子の製造方法。 ２ 焼成を、焼結工程とその後の熱処理工程の二
段階の工程に分けて行なう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。[Scope of Claims] 1. A method for manufacturing a thermoelectric element, which comprises adding adamantane or an adamantane/trimethylene norbornane mixture to a metal alloy powder, press-molding the mixture, and then firing the mixture. 2. The method for manufacturing a thermoelectric element according to claim 1, wherein the firing is performed in two steps: a sintering step and a subsequent heat treatment step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62156646A JPS642380A (en) | 1987-06-25 | 1987-06-25 | Manufacture of thermoelectric element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62156646A JPS642380A (en) | 1987-06-25 | 1987-06-25 | Manufacture of thermoelectric element |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH012380A JPH012380A (en) | 1989-01-06 |
| JPS642380A JPS642380A (en) | 1989-01-06 |
| JPH0347751B2 true JPH0347751B2 (en) | 1991-07-22 |
Family
ID=15632208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62156646A Granted JPS642380A (en) | 1987-06-25 | 1987-06-25 | Manufacture of thermoelectric element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS642380A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69132779T2 (en) * | 1990-04-20 | 2002-07-11 | Matsushita Electric Industrial Co., Ltd. | Vacuum insulated thermoelectric semiconductors and thermoelectric devices using P and N type thermoelectric semiconductors |
| US20070240749A1 (en) * | 2004-03-22 | 2007-10-18 | Japan Science And Technology Agency | Porous Thermoelectric Material and Process for Producing the Same |
| JP4729013B2 (en) * | 2007-07-13 | 2011-07-20 | 古河電気工業株式会社 | Female terminal |
| AT508979A1 (en) * | 2009-10-23 | 2011-05-15 | Miba Sinter Austria Gmbh | METHOD FOR PRODUCING A THERMOELECTRIC ELEMENT |
| JP6411782B2 (en) * | 2013-08-07 | 2018-10-24 | 株式会社Ｎｔｔファシリティーズ | Method for manufacturing thermoelectric material |
| CN106956004B (en) * | 2017-02-23 | 2018-12-28 | 厦门理工学院 | High stability Zn4Sb3Thermoelectric composite material and preparation method thereof |
| CN107507909B (en) * | 2017-08-08 | 2020-02-14 | 武汉科技大学 | Porous P-type Bi2Te3Base thermoelectric material and preparation method thereof |
-
1987
- 1987-06-25 JP JP62156646A patent/JPS642380A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS642380A (en) | 1989-01-06 |
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