JPH03129782A - Manufacture of thermoelectric element - Google Patents
Manufacture of thermoelectric elementInfo
- Publication number
- JPH03129782A JPH03129782A JP2109802A JP10980290A JPH03129782A JP H03129782 A JPH03129782 A JP H03129782A JP 2109802 A JP2109802 A JP 2109802A JP 10980290 A JP10980290 A JP 10980290A JP H03129782 A JPH03129782 A JP H03129782A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- iron silicide
- type iron
- hot press
- thermoelectric element
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000000843 powder Substances 0.000 claims abstract description 117
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 162
- 229910052742 iron Inorganic materials 0.000 claims description 81
- 229910021332 silicide Inorganic materials 0.000 claims description 81
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 80
- 238000000034 method Methods 0.000 claims description 18
- 238000007731 hot pressing Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 2
- 230000035939 shock Effects 0.000 abstract description 10
- 238000005452 bending Methods 0.000 abstract description 7
- 238000005192 partition Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000012733 comparative method Methods 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229910005331 FeSi2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、様々な熱源を利用して直接発電を行うこと
のできる鉄ケイ化物を主成分とした熱電素子の製造方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method of manufacturing a thermoelectric element mainly composed of iron silicide, which can directly generate electricity using various heat sources.
一般に、鉄ケイ化物を主成分とする熱電素子は、第４図
に示されるように、Ｍｎ添加のｐ型鉄ケイ化物１とＣｏ
添加のｎ型鉄ケイ化物２をｐｎ接合部３にて接合し、そ
れ以外の部分が空隙４からなるＵ字構造となっているこ
とが知られている。Generally, thermoelectric elements mainly composed of iron silicide are made of p-type iron silicide 1 with Mn added and Co as shown in FIG.
It is known that the added n-type iron silicide 2 is joined at a pn junction 3, and the other part has a U-shaped structure consisting of voids 4.
かかるＵ字構造を有する熱電素子は、
（１）ｐ型鉄ケイ化物粉末とｎ型鉄ケイ化物粉末をＵ宇
金型に充填し、プレス成形してＵ字形圧粉体とし、この
Ｕ￥形圧粉体を焼結する方法、（２〉ｐ型鉄ケイ化物粉
末およびｎ型鉄ケイ化物粉末にそれぞれ溶剤を混合して
得られた混練物を圧延して、それぞれｐ型鉄ケイ化物シ
ートおよびｎ型鉄ケイ化物シートを作製し、これらｐ型
鉄ケイ化物シートおよびｎ型鉄ケイ化物シートの接合部
を残して、慎成時に昇華、蒸発してしまう樟脳紙、不織
布、Ｈ機物等からなる隔離シートを上記ｐ型鉄ケイ化物
シートおよびｎ型鉄ケイ化物シートの間に挾み込んで積
層体を作製し、この積層体を焼成する方法（特開昭５８
−１５２２８２号公報参照）、により製造されることが
知られている。A thermoelectric element having such a U-shaped structure is produced by: (1) P-type iron silicide powder and n-type iron silicide powder are filled into a U mold, press-molded to form a U-shaped green compact, and this U-shaped powder body is formed. A method of sintering a green compact (2> A kneaded product obtained by mixing a solvent with a p-type iron silicide powder and an n-type iron silicide powder, respectively, is rolled to form a p-type iron silicide sheet and a p-type iron silicide sheet, respectively. An n-type iron silicide sheet is made, and the bonded parts of the p-type iron silicide sheet and the n-type iron silicide sheet are left in place, and the material is made from camphor paper, nonwoven fabric, H-type material, etc., which sublimes and evaporates during fabrication. A method of sandwiching an isolation sheet of
-152282)).
さらに、上記隔離シートの代りに、ホルステライト、酸
化アルミニウム５．酸化マグネシウム、あるいは酸化ジ
ルコニウムなどの絶縁物インサートを上記ｐ型鉄ケイ化
物シートおよびｎ型鉄ケイ化物シートの接合部を残して
挾み込んだ積層体を作製し、この積層体を焼成すること
により第３図に示されるようなｐ型鉄ケイ化物１、ｎ型
鉄ケイ化物２および絶縁層５からなる熱電素子を製造す
る方法も知られている（同上公報参照）。Furthermore, instead of the above isolation sheet, holsterite, aluminum oxide5. By producing a laminate in which an insulating insert such as magnesium oxide or zirconium oxide is sandwiched between the p-type iron silicide sheet and the n-type iron silicide sheet, leaving the bonded portion, and firing this laminate. A method for manufacturing a thermoelectric element consisting of a p-type iron silicide 1, an n-type iron silicide 2, and an insulating layer 5 as shown in FIG. 3 is also known (see the above publication).
しかしながら、第４図に示されるＵ字構造を有する熱電
素子は、第４図のＡ矢印方向に力が加わった場合、非常
に弱く、特に応答性を上げるために肉厚を２〜３開程度
に薄くすると、指先の力でも簡単に折れてしまい、素子
組立て作業上あるいは使用上の大きな障害となっていた
。また、このＵ字構造を有する熱電素子をガスコンロな
どの台所用家電製品に組込んで使用する際には、使用中
に水がかかるなどによる熱衝撃が与えられることがある
が、このような熱衝撃にも上記熱電素子は比較的弱く、
強いものでも１０回程度の熱衝撃を受けることによりク
ラックが発生した。However, the thermoelectric element having the U-shaped structure shown in Fig. 4 is very weak when force is applied in the direction of arrow A in Fig. 4, and the wall thickness is reduced by 2 to 3 degrees in order to increase the response. If they were made too thin, they would easily break even with the force of a fingertip, creating a major obstacle in device assembly and use. In addition, when a thermoelectric element with this U-shaped structure is incorporated into a kitchen appliance such as a gas stove, it may be subjected to thermal shock due to splashing water during use; The above thermoelectric element is relatively weak against shock,
Even a strong one would crack after being subjected to about 10 thermal shocks.
さらに、ＴＳ３図に示される上記ｐ型鉄ケイ化物シート
およびｎ型鉄ケイ化物シートの間に絶縁層を有する従来
の熱電素子は、焼結温度が低いために上記絶縁層の強度
が十分でなく、焼結中のシートと絶縁層の収縮串の差な
どから層間剥離が／ｌ＝、じ、健全な熱電素子を得るこ
とは困難であった。Furthermore, in the conventional thermoelectric element shown in Figure TS3, which has an insulating layer between the p-type iron silicide sheet and the n-type iron silicide sheet, the strength of the insulating layer is insufficient due to the low sintering temperature. However, it was difficult to obtain a sound thermoelectric element due to the difference in shrinkage between the sheet and the insulating layer during sintering, which caused delamination between the layers.
そこで、本発明者等は、ｐ型鉄ケイ化物およびｎ型鉄ケ
イ化物を接合してなる強度および耐熱衝撃性の優れた熱
電素子を製造すべく研究を行った結果、
ｐ型鉄ケイ化物とｎ型鉄ケイ化物の間に高強度の絶縁層
を介在させることにより強度の優れた熱電素子を製造す
ることができ、上記高強度の絶縁層はホットプレス法に
より得ることができるという知見を得たのである。Therefore, the present inventors conducted research to manufacture a thermoelectric element with excellent strength and thermal shock resistance by joining p-type iron silicide and n-type iron silicide, and found that p-type iron silicide and n-type iron silicide We obtained the knowledge that a thermoelectric element with excellent strength can be manufactured by interposing a high-strength insulating layer between n-type iron silicides, and that the above-mentioned high-strength insulating layer can be obtained by hot pressing. It was.
この発明は、かかる知見にもとづいてなされたものであ
って、
ホットプレス用モールドに、ｐ型鉄ケイ化物粉末または
ｎ型鉄ケイ化物粉末を充填した後、その上に絶縁性酸化
物粉末または上記絶縁性酸化物粉末を含むシートを上記
充填されたｐ型鉄ケイ化物粉末またはｎ型鉄ケイ化物粉
末の少なくとも一部は覆わないように充填または載置し
、さらに、その上に全体を覆うように上記充填したｐ型
鉄ケイ化物粉末またはｎ型鉄ケイ化物粉末と電導型の異
なる鉄ケイ化物粉末を充填し、ホットプレスによって成
形焼結させ、その後、大気中で熱処理する熱Ｔ４素子の
製造方法に特徴を有するものである。This invention was made based on this knowledge, and after filling a hot press mold with p-type iron silicide powder or n-type iron silicide powder, the insulating oxide powder or the above-mentioned A sheet containing an insulating oxide powder is filled or placed so as not to cover at least a part of the filled p-type iron silicide powder or n-type iron silicide powder, and further, a sheet containing an insulating oxide powder is filled or placed on top of the filled p-type iron silicide powder or n-type iron silicide powder so as to cover the whole. Manufacturing of a thermal T4 element by filling the above-mentioned filled p-type iron silicide powder or n-type iron silicide powder with iron silicide powder having a different conductivity type, shaping and sintering by hot pressing, and then heat-treating in the atmosphere. This method is unique.
上記熱電素子の製造において、ホットプレスを採用した
理由は、次の通りである。The reason why hot pressing was adopted in manufacturing the above thermoelectric element is as follows.
一般に、絶縁性酸化物粉末の焼結温度は１３００℃以上
であり、高強度の絶縁層を有する熱電素子を得るために
は１３００℃以上の高温度で焼結しなければならない。Generally, the sintering temperature of insulating oxide powder is 1300° C. or higher, and in order to obtain a thermoelectric element having a high-strength insulating layer, sintering must be performed at a high temperature of 1300° C. or higher.
ところが鉄ケイ化物の融点は１２２０℃であるから、鉄
ケイ化物粉末と絶縁性酸化物粉末との積層体を上記１３
００℃以上の温度で焼結すると上記鉄ケイ化物粉末は溶
融してしまうことになる。However, since the melting point of iron silicide is 1220°C, the laminate of iron silicide powder and insulating oxide powder is
If sintered at a temperature of 00° C. or higher, the iron silicide powder will melt.
したがって、上記鉄ケイ化物が溶融しない低温度で高強
度の絶縁層を得、さらに層間の接合強度を高めるために
は、高圧を付与したホットプレスを採用することがどう
しても必要となるのである。Therefore, in order to obtain a high-strength insulating layer at a low temperature at which the iron silicide does not melt, and to further increase the bonding strength between layers, it is absolutely necessary to employ a hot press that applies high pressure.
上記ホットプレスを用いて鉄ケイ化物粉末の焼結体に挾
まれた高強度の絶縁層を有する熱電素子を得るためには
、非酸化性雰囲気中、温度：９００〜１１００℃で行う
のが好ましい。In order to obtain a thermoelectric element having a high-strength insulating layer sandwiched between sintered bodies of iron silicide powder using the hot press described above, it is preferable to conduct the hot press at a temperature of 900 to 1100°C in a non-oxidizing atmosphere. .
この発明で用いる絶縁性酸化物粉末は、公知のフォルス
テライト粉末、酸化アルミニウム粉末、酸化マグネシウ
ム粉末、酸化ジルコニウム粉末などを用いてもよいが、
ＳｉＯ２ ：４０．０〜４７．０％、
Ａｆ１２０３７１．５〜３４０％
を含有し、残りがＭｇＯおよび不可避不純物からなる組
成（以上、重量％）を有するＭｇＯ７ｉ合粉末を用いる
のが最も好ましい。このＭｇＯ１合粉末は、複合粉末で
あるために焼結温度が低く、このＭｇＯ１合粉末をホッ
トプレスして得られた絶縁層は、強度および絶縁性に優
れ、上記ホットプレス後の熱処理によって生成するβ−
ＦｅＳｉ２との間に層間剥離がなく十分な圧縮応力を付
与し、鉄ケイ化物の耐熱衝撃性を大幅に向上させること
ができる。上記ホットプレス後の熱処理は、大気中、温
度ニア００〜８００℃に１００〜２００１１＝’７間保
持することにより高ゼーベック係数をもつβ−Ｆ ｅ
Ｓ Ｌ ２相を析出させることができる。The insulating oxide powder used in this invention may be known forsterite powder, aluminum oxide powder, magnesium oxide powder, zirconium oxide powder, etc., but SiO2: 40.0 to 47.0%, Af120371.5 It is most preferable to use an MgO7i composite powder having a composition (wt%) containing ~340% of MgO and the remainder consisting of MgO and unavoidable impurities. Since this MgO1 composite powder is a composite powder, the sintering temperature is low, and the insulating layer obtained by hot pressing this MgO1 composite powder has excellent strength and insulation properties, and is produced by the heat treatment after the hot pressing. β-
There is no delamination between the iron silicide and FeSi2, sufficient compressive stress can be applied, and the thermal shock resistance of iron silicide can be greatly improved. The heat treatment after the above hot pressing is carried out in the air at a temperature of near 00 to 800°C for a period of 100 to 20011='7 to obtain β-F e with a high Seebeck coefficient.
S L 2 phase can be precipitated.
また、従来と同様に、この発明においても、ｎ型鉄ケイ
化物粉末としてＣａｎ加鉄ケイ化物粉末を用い、ｐ型鉄
ケイ化物粉末としてＭｎｎ型鉄ケイ化物粉末用いること
ができる。Further, in the present invention as well as in the prior art, Can-rich iron silicide powder can be used as the n-type iron silicide powder, and Mnn-type iron silicide powder can be used as the p-type iron silicide powder.
この発明で上記ｎ型鉄ケイ化物粉末、ｐ型鉄ケイ化物粉
末および絶縁性酸化物粉末を用いて熱電素子を製造する
には、まず、第１−１図に示されるようなホットプレス
用モールド６を用意し、このホットプレス用モールドｂ
内に仕切り板７を立てたのち、第１−１図（ａ）に示さ
れるように、ｎ型鉄ケイ化物粉末を上記仕切り板７を境
界として厚さを変えて充填し、ｎ型鉄ケイ化物粉末薄層
２′およびｎ型鉄ケイ化物粉末厚層２″が形成されるよ
うに充填する。In order to manufacture a thermoelectric element using the above n-type iron silicide powder, p-type iron silicide powder and insulating oxide powder in this invention, first, a hot press mold as shown in FIG. 1-1 is used. 6, prepare this hot press mold B
After setting up the partition plate 7 inside the interior, as shown in FIG. Filling is performed so that a thin layer 2' of oxide powder and a thick layer 2'' of n-type iron silicide powder are formed.
上、？ｃ！ｎ型鉄ケイ化物粉末薄層２′の上には、さら
に第１−１図（ｂ）に示されるように、絶縁性酸化物粉
末層５′を充填したのち、仕切り板７を抜き取り、その
上に第１−１図（Ｃ）に示されるようにｐ型鉄ケイ化物
粉末層１′を全面を覆うように充填する。Up,? c! As shown in FIG. 1-1(b), an insulating oxide powder layer 5' is further filled on the n-type iron silicide powder thin layer 2', and then the partition plate 7 is removed. As shown in FIG. 1-1(C), a p-type iron silicide powder layer 1' is filled on top so as to cover the entire surface.
このようにして充填されたホットプレス用モールド５内
には粉末積層体が形成され、かかる粉末積層体をホット
プレスしてホットプレス体を作製し、上記ホットプレス
体を大気中で熱処理することにまり熱電素子を製造する
。A powder laminate is formed in the hot press mold 5 filled in this way, the powder laminate is hot pressed to produce a hot pressed body, and the hot pressed body is heat treated in the atmosphere. Manufacture thermoelectric elements.
また、絶縁性酸化物粉末を含むシートを用いて熱電素子
を製造するには、第１−２図（ａ）に示されるよるに、
ホットプレス用モールド６にｐ型鉄ケイ化物粉末層１′
を形威し、このｐ型鉄ケイ化物粉末層１′の上に第１−
２図（ｂ）に示されるように、ｐｎ接合部となる部分を
除いて絶縁性酸化物粉末を含むシート５′を載置する。In addition, in order to manufacture a thermoelectric element using a sheet containing insulating oxide powder, as shown in FIG. 1-2 (a),
P-type iron silicide powder layer 1' in hot press mold 6
on this p-type iron silicide powder layer 1'.
As shown in FIG. 2(b), a sheet 5' containing insulating oxide powder is placed except for the portion that will become the pn junction.
この絶縁性酸化物粉末を含むシート５″は、ドクターブ
レード法により作製するのが最も好ましいが、これに限
定されるものではない。、また、この絶縁性酸化物粉末
を含むシート５′は、厚さがｌａｍ以下であるのが好ま
しい。これ以上厚いとホットプレス時にホットプレス体
にクラックが入りやすいためである。The sheet 5'' containing this insulating oxide powder is most preferably produced by a doctor blade method, but is not limited thereto.Also, the sheet 5' containing this insulating oxide powder is produced by: It is preferable that the thickness is lam or less, because if it is thicker than this, cracks will easily occur in the hot-pressed body during hot-pressing.
上記第１−２図（ｂ）に示されるように、ｐｎ接合部と
なる部分を除いて絶縁性酸化物粉末を含むシート５′を
載置したのち、その上に第１−２図（ｅ）に示されるよ
うにｎ型鉄ケイ化物粉末層２′を形成し、上記ホットプ
レス用モールド６内に粉末積層体が形成され、かかる粉
末積層体をホットプレスしてホットプレス体を作製する
。上記第１−２図に示される工程により作製された広幅
のホットプレス体を第２図に示す。第２図に示される幅
の広いホットプレス体９を切断線８で切断して複数個の
ホットプレス成形体１０を作製し、このホットプレス成
形体ＩＯを大気中で熱処理し、複数個の熱電素子を同時
に製造することもできる。As shown in FIG. 1-2(b) above, a sheet 5' containing insulating oxide powder is placed except for the portion that will become the pn junction, and then the sheet 5' containing insulating oxide powder is placed on top of the sheet 5' as shown in FIG. 1-2(e). ), an n-type iron silicide powder layer 2' is formed, a powder laminate is formed in the hot pressing mold 6, and the powder laminate is hot pressed to produce a hot pressed body. FIG. 2 shows a wide hot-pressed body produced by the steps shown in FIGS. 1-2 above. The wide hot press body 9 shown in FIG. 2 is cut along the cutting line 8 to produce a plurality of hot press bodies 10, and the hot press body IO is heat-treated in the atmosphere to form a plurality of thermoelectric bodies. It is also possible to manufacture the elements simultaneously.
上記絶縁性酸化物粉末を含むシート５′を用いて熱電素
子を製造すると、熱電素子の絶縁層の厚さを均一にする
ことができ、またシートの厚さを３３節することにより
絶縁層の厚さを制御することができる。When a thermoelectric element is manufactured using the sheet 5' containing the above-mentioned insulating oxide powder, the thickness of the insulating layer of the thermoelectric element can be made uniform. Thickness can be controlled.
なお、上記第１−１図および第１−２図（ａ〉。Note that FIG. 1-1 and FIG. 1-2 (a) above.
（ｂ）および（ｅ）における熱電素子の製造方法では、
まずｎ型鉄ケイ化物粉末を充填し、ついでｐ型鉄ケイ化
物粉末を充填したが、まずｐ型鉄ケイ化物粉末を充填し
、ついでｎ型鉄ケイ化物粉末を充填しても同じ効果が得
られることは勿論である。In the method for manufacturing a thermoelectric element in (b) and (e),
Although the n-type iron silicide powder was first filled and then the p-type iron silicide powder was filled, the same effect could be obtained by first filling the p-type iron silicide powder and then filling the n-type iron silicide powder. Of course, it can be done.
つぎに、この発明を実施例にもとづいて具体的に説明す
る。Next, the present invention will be specifically explained based on examples.
実施例 １
Ｆｅ１．９４ｃｏＯ，０８Ｓｉ２の組成を有し平均粒径
；２．３坤のｎ型鉄ケイ化物粉末、
Ｆｅ１．９０Ｍｎ０．１Ｏ８’２の組成を有し平均粒径
：３．２−のｐ型鉄ケイ化物粉末、
および平均粒径：３．５−をＨし、第１表に示される配
合組成をＨする絶縁性酸化物粉末を用意した。Example 1 An n-type iron silicide powder with a composition of Fe1.94coO,08Si2 and an average particle size of 2.3 Kn, an n-type iron silicide powder with a composition of Fe1.90Mn0.1O8'2 and an average particle size of 3.2- A p-type iron silicide powder and an insulating oxide powder having an average particle size of 3.5-H and a blending composition shown in Table 1 were prepared.
これら粉末を、上記第１−１図（ａ） 、（ｂ）および
（Ｃ）に示されるように、ホットプレス用モールド内に
充填し、粉末積層体を形成し、この粉末積層体を真空中
、第１表に示される条件でホットプレスしてホットプレ
ス体を作製し、このホットプレス体を幅：４ｍｎに切断
して複数個のホットプレス成形体を作製し、このホット
プレス成形体を大気中、第１表に示される条件で熱処理
し、本発明法１〜９および比較法１〜４により熱電素子
を製造した。These powders are filled into a hot press mold to form a powder laminate as shown in Figures 1-1 (a), (b) and (C) above, and this powder laminate is placed in a vacuum. A hot pressed body was produced by hot pressing under the conditions shown in Table 1, and this hot pressed body was cut into a width of 4 mm to produce a plurality of hot pressed bodies, and this hot pressed body was exposed to the atmosphere. Thermoelectric elements were manufactured by heat treatment under the conditions shown in Table 1, and by methods 1 to 9 of the present invention and comparative methods 1 to 4.
さらに比較のために、従来法によりＵ字構造を有する熱
電素子を製造した。Furthermore, for comparison, a thermoelectric element having a U-shaped structure was manufactured using a conventional method.
上記本発明法１〜９、比較法１〜４および従来広により
得られた熱雷素子について、積層方向の曲げ強度を７１
）１定し、さらにｐｎ接合部をガス炎で約８００℃に加
熱したのち水中に投下し、クラックが発生するまで上記
加熱および水中投下を繰り返し、クラックが発生するま
での水中投下回数を測定し、これら測定結果を第１表に
示した。The bending strength in the stacking direction was 71 for the thermal lightning elements obtained by the above-mentioned methods 1 to 9 of the present invention, comparative methods 1 to 4, and conventional methods.
)1, then heat the pn junction to approximately 800°C with a gas flame, then drop it into water, repeat the above heating and dropping into water until cracks occur, and measure the number of drops until cracks occur. The results of these measurements are shown in Table 1.
実施例 ２
第２表に示される配合組成の絶縁性酸化物粉末を用意し
、これら絶縁性酸化物粉末に、ｆｆｌｆｆｉ％で、ア
り リ ル 樹 脂： １０％ジオクチルフタレ
ート：１％、
ポリエチレングリコール：３％、
ト ル エ ン 二 ６７％、
エ タ ノ − ル ：残部
からなる溶液を添加し、これをポリエチレンのボールミ
ルスポット、に入れ、直径：１０ｍｍのＺｒＯ。ボール
とともに２４特開混合を行った。Example 2 Insulating oxide powders having the composition shown in Table 2 were prepared, and fflffi% was added to these insulating oxide powders.
Resin: 10% Dioctyl phthalate: 1%, Polyethylene glycol: 3%, Toluene 67%,
Ethanol: Add the remaining solution and place it in a polyethylene ball mill spot with a ZrO diameter of 10 mm. 24 JP-A mixture was performed along with the ball.
上記混合終了後、Ｚ ｒ Ｏ２ボールのみを分離し、つ
いでアスピレータ−で脱泡後、ドクターブレード成形機
を用いて厚さ二０．５開の上記絶縁性酸化物粉末を含む
シートを作製した。After the above mixing was completed, only the ZrO2 balls were separated, and after degassing using an aspirator, a sheet containing the above insulating oxide powder having a thickness of 20.5 mm was produced using a doctor blade molding machine.
これらシートを実施例１で用意したｐ型鉄ケイ化物粉末
およびｎ型鉄ケイ化物粉末とともに第１−２図（ａ）か
ら第１−２図（ｅ）に示されるように上記シートをホッ
トプレス用モールドに装入し、第２表に示される条件で
ホットプレスしたのち熱処理し、本発明法ｌＯ〜１８お
よび比較法５〜８により熱電素子を製造した。These sheets were hot pressed together with the p-type iron silicide powder and n-type iron silicide powder prepared in Example 1 as shown in Figures 1-2(a) to 1-2(e). The thermoelectric elements were put into a mold, hot pressed under the conditions shown in Table 2, and then heat treated, and thermoelectric elements were manufactured by methods 10 to 18 of the present invention and comparative methods 5 to 8.
上記本発明法ｌＯ〜１８および比較法５〜８により得ら
れた熱電素子について、実施例１と同一の条件で積層方
向の曲げ強度およびクラックが発生するまでの水中投下
同数を測定し、これらの測定結果を第２表に示した。The thermoelectric elements obtained by the above-mentioned methods 10 to 18 of the present invention and comparative methods 5 to 8 were measured under the same conditions as in Example 1, and the bending strength in the lamination direction and the same number of times they were dropped into water until cracking occurred. The measurement results are shown in Table 2.
第１表の結果から、この発明の製造方法で作製された熱
電素子は、従来法により作製された９字構造の熱電素子
と比べて曲げ強度が格段に優れており、さらに、クラッ
ク発／−ｌ＝、までの水中投下回数の測定値により評価
した耐熱衝撃性についても従来の９字構造の熱電素子と
比べて格段に優れていることが明らかである。From the results in Table 1, it is clear that the thermoelectric element manufactured by the manufacturing method of the present invention has significantly superior bending strength compared to the thermoelectric element with a figure-9 structure manufactured by the conventional method. It is also clear that the thermal shock resistance evaluated by the measured value of the number of drops into water up to 1 is significantly superior to that of the conventional thermoelectric element having a 9-shaped structure.
しかしながら、比較例１〜４にみられるように、絶縁性
酸化物粉末の戊分組戊がこの発明の条件を外れたものは
曲げ強度および耐熱衝撃性が劣ることがわかる。However, as can be seen in Comparative Examples 1 to 4, it can be seen that insulating oxide powders whose composition is outside the conditions of the present invention have poor bending strength and thermal shock resistance.
また、第２表の結果から、絶縁性酸化物粉末をドクター
ブレード法によるシートとし、このシートをｎ型鉄ケイ
化物粉末とｐ型鉄ケイ化物粉末の間に挟んでホットプレ
スすることにより作製された熱電素子も同様に曲げ強度
および耐熱衝撃性が優れていることがわかる。In addition, from the results in Table 2, it was found that insulating oxide powder was made into a sheet by the doctor blade method, and this sheet was sandwiched between n-type iron silicide powder and p-type iron silicide powder and hot-pressed. It can be seen that the thermoelectric element also has excellent bending strength and thermal shock resistance.
したがっｔ、この発明の製造方法により得られた熱電素
子は曲げ強度および耐熱衝撃性が優れており、長期にわ
たって破損することがなく、信頼性および経済性ともに
高い熱電素子を提供することができる。Therefore, the thermoelectric element obtained by the manufacturing method of the present invention has excellent bending strength and thermal shock resistance, does not break over a long period of time, and can provide a thermoelectric element with high reliability and economic efficiency.
第１−１図は、この発明の製造方性によりホットプレス
用モールド内に各々の粉末を充填する工程を示す概略図
、
第１−２図は、この発明の製造方法によりホットプレス
用モールド内に粉末と絶縁性酸化物粉末を含むシートを
充填する工程を示す概略図、第２図は、この発明の製造
方法により作製された広輻のホットプレス体を示す斜視
図、第３図および第４図は、従来の熱雷素子を示す斜視
図である。
ｌａｐミル型鉄ケイ ２：ｎ型鉄ケイ化物３：ｐｎ
接合部 ４：空 隙
５：絶縁層
６：ホットプレス用モールド
７ 、 ＩＪ：切り板 ８：切断線法帖のホ
ットプレス体
ホットプレス成形体
：ｐｍ鉄ケイ化物粉末層
＝ｎ型鉄ケイ化物粉末薄層
：ｎ型鉄ケイ化物扮末厚層
：絶縁性酸化物粉末層
：絶縁性酸化物粉末を含むシー
ト
出
願
人
： 三菱金属株式会社
代
理
人
富
田
和
夫
外１名
２：ｎ型鉄ケイ化物
第
図Fig. 1-1 is a schematic diagram showing the process of filling each powder into a hot press mold according to the manufacturing method of the present invention, and Fig. 1-2 is a schematic diagram showing the process of filling each powder into a hot press mold according to the manufacturing method of the present invention. FIG. 2 is a schematic view showing the process of filling a sheet containing powder and insulating oxide powder into a sheet, FIG. FIG. 4 is a perspective view showing a conventional thermal lightning element. lap mill type iron silicide 2: n-type iron silicide 3: pn
Joint part 4: Air gap 5: Insulating layer 6: Hot press mold 7, IJ: Cutting plate 8: Hot press body of cutting line method Hot press molded body: pm iron silicide powder layer = n-type iron silicide powder thin Layer: N-type iron silicide layer Thick layer: Insulating oxide powder Layer: Sheet containing insulating oxide powder Applicant: Mitsubishi Metals Corporation Agent Kazuo Tomita and one other person 2: N-type iron silicide Diagram
Claims (5)
充填し、 上記充填されたｎ型鉄ケイ化物粉末の上に絶縁性酸化物
粉末を上記ｎ型鉄ケイ化物粉末の少くとも一部が被覆さ
れないように充填し、 さらに、その上に全体を覆うようにｐ型鉄ケイ化物粉末
を充填して、上記ホットプレス用モールド内に粉末積層
体を形成充填し、 ついで、上記粉末積層体をホットプレスしたのち、大気
中で熱処理することを特徴とする熱電素子の製造方法。(1) Fill a hot press mold with n-type iron silicide powder, and apply insulating oxide powder on top of the filled n-type iron silicide powder so that at least a portion of the n-type iron silicide powder Fill it so that it is not covered, and then fill it with p-type iron silicide powder so as to cover the whole, form and fill the powder laminate in the hot press mold, and then fill the powder laminate in the hot press mold. A method for manufacturing a thermoelectric element, which comprises hot pressing and then heat treatment in the atmosphere.
酸化物粉末を含むシートを上記ｎ型鉄ケイ化物粉末の少
くとも一部が被覆されないように載置することを特徴と
する請求項１記載の熱電素子の製造方法。(2) A sheet containing an insulating oxide powder is placed on the filled n-type iron silicide powder so that at least a part of the n-type iron silicide powder is not covered. A method for manufacturing a thermoelectric element according to claim 1.
充填し、 上記充填されたｐ型鉄ケイ化物粉末の上に絶縁性酸化物
粉末を上記ｐ型鉄ケイ化物粉末の少くとも一部が被覆さ
れないように充填し、 さらに、その上に全体を覆うようにｎ型鉄ケイ化物粉末
を充填して、上記ホットプレス用モールド内に粉末積層
体を形成充填し、 ついで、上記粉末積層体をホットプレスしたのち、大気
中で熱処理することを特徴とする熱電素子の製造方法。(3) Fill a hot press mold with p-type iron silicide powder, and apply insulating oxide powder on top of the filled p-type iron silicide powder so that at least a portion of the p-type iron silicide powder Fill it so that it is not covered, and then fill it with n-type iron silicide powder so as to cover the whole, form and fill the powder laminate in the hot press mold, and then fill the powder laminate in the hot press mold. A method for manufacturing a thermoelectric element, which comprises hot pressing and then heat treatment in the atmosphere.
酸化物粉末を含むシートを上記ｐ型鉄ケイ化物粉末の少
くとも一部が被覆されないように載置することを特徴と
する請求項３記載の熱電素子の製造方法。(4) A sheet containing an insulating oxide powder is placed on the filled p-type iron silicide powder so that at least a part of the p-type iron silicide powder is not covered. A method for manufacturing a thermoelectric element according to claim 3.
成（以上、重量％）を有するＭｇＯ複合粉末であること
を特徴とする請求項１、２、３または４記載の熱電素子
の製造方法。(5) The above-mentioned insulating oxide powder contains SiO_2: 40.0 to 47.0%, Al_2O_3: 1.5 to 3%, and the remainder is MgO and unavoidable impurities (wt%). 5. The method for manufacturing a thermoelectric element according to claim 1, wherein the MgO composite powder has the following properties.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/550,879 US5009717A (en) | 1989-07-18 | 1990-07-11 | Thermoelectric element and method of manufacturing same |
| DE4022690A DE4022690A1 (en) | 1989-07-18 | 1990-07-17 | THERMOELECTRIC ELEMENT AND METHOD FOR PRODUCING THE SAME |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-185767 | 1989-07-18 | ||
| JP18576789 | 1989-07-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03129782A true JPH03129782A (en) | 1991-06-03 |
Family
ID=16176525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2109802A Pending JPH03129782A (en) | 1989-07-18 | 1990-04-25 | Manufacture of thermoelectric element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03129782A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995017020A1 (en) * | 1993-12-16 | 1995-06-22 | Mitsubishi Materials Corporation | Thermoelectric conversion element, thermoelectric conversion element array, and thermal displacement converter |
| JP2014090101A (en) * | 2012-10-30 | 2014-05-15 | Shigeyuki Tsurumi | Thermoelectric conversion element |
-
1990
- 1990-04-25 JP JP2109802A patent/JPH03129782A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995017020A1 (en) * | 1993-12-16 | 1995-06-22 | Mitsubishi Materials Corporation | Thermoelectric conversion element, thermoelectric conversion element array, and thermal displacement converter |
| JP2014090101A (en) * | 2012-10-30 | 2014-05-15 | Shigeyuki Tsurumi | Thermoelectric conversion element |
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