JPH104218A - Porous structure thermoelectric element and manufacture thereof - Google Patents
Porous structure thermoelectric element and manufacture thereofInfo
- Publication number
- JPH104218A JPH104218A JP8154163A JP15416396A JPH104218A JP H104218 A JPH104218 A JP H104218A JP 8154163 A JP8154163 A JP 8154163A JP 15416396 A JP15416396 A JP 15416396A JP H104218 A JPH104218 A JP H104218A
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- Japan
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- type
- fesi
- phase
- porous
- thermoelectric element
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポーラス構造熱電
素子及びその製造方法に係り、特に、ＦｅＳｉ2 を用い
たポーラス構造熱電素子及びその製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoelectric element having a porous structure and a method for manufacturing the same, and more particularly, to a thermoelectric element having a porous structure using FeSi 2 and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】通気性のあるポーラス構造素子体中に可
燃性ガスを流し込み、その可燃性ガスの出口（下流）側
のポーラス構造素子体表面において燃焼させる。これに
よって、可燃性ガスの燃焼部（下流側）は、火炎によっ
て高温になる。通常は、高温側から低温側への熱伝搬に
よって温度勾配が形成されるが、この場合、熱伝搬とは
逆の方に低温のガスが常に供給されているため熱伝搬は
起こらず、可燃性ガスの入口（上流）側と可燃性ガスの
出口（下流）側との温度差は通常のバルク体（塊）より
も大きくなるという理論が提案されている。この現象を
熱電発電に応用することで発電効率を向上させる方法が
行われている（特開平７−２２１３５３号公報など）。2. Description of the Related Art A combustible gas is poured into a porous structure element having air permeability, and is burned on the surface of the porous structure element at the outlet (downstream) side of the combustible gas. As a result, the combustion portion (downstream side) of the combustible gas becomes hot due to the flame. Normally, a temperature gradient is formed by heat propagation from the high-temperature side to the low-temperature side.In this case, heat propagation does not occur because the low-temperature gas is always supplied in the opposite direction to the heat propagation, and flammable A theory has been proposed that the temperature difference between the gas inlet (upstream) side and the combustible gas outlet (downstream) side is larger than that of a normal bulk body (lumps). A method of improving the power generation efficiency by applying this phenomenon to thermoelectric power generation has been performed (Japanese Patent Application Laid-Open No. Hei 7-221353).
【０００３】現有する熱電材料中、このポーラス燃焼に
最適な材料として、高温大気中で安定なＦｅＳｉ2 が挙
げられる。ＦｅＳｉ2 を用いたポーラス構造熱電素子の
作製方法として、球状粉末を焼結する方法がある。[0003] Among the existing thermoelectric materials, the most suitable material for the porous combustion is FeSi 2 which is stable in a high-temperature atmosphere. As a method of manufacturing a porous thermoelectric element using FeSi 2 , there is a method of sintering a spherical powder.
【０００４】この時、温度差によって発電した電力を取
り出すべくＦｅＳｉ2 ポーラス構造素子体に電極を取り
付けて（接合して）いるが、この電極は集電効果のある
低抵抗な材料であることは勿論のこと、可燃性ガスを通
気させるべく多孔質の構造を有していることが必要であ
る。また、電極材料として、ＦｅＳｉ2 と熱膨張係数が
同じ材料がベストであることは言うまでもないが、熱膨
張係数が完全に同一な材料はなく、熱膨張係数が同程度
のステンレス（例えば、ＳＵＳ３０４）などを用いてい
る。At this time, an electrode is attached (joined) to the FeSi 2 porous structure element to take out the electric power generated by the temperature difference, but this electrode is a low-resistance material having a current collecting effect. Needless to say, it is necessary to have a porous structure to allow a combustible gas to pass therethrough. Needless to say, as the electrode material, a material having the same thermal expansion coefficient as FeSi 2 is the best, but there is no material having a completely identical thermal expansion coefficient, and stainless steel having the same thermal expansion coefficient (for example, SUS304) And so on.
【０００５】ステンレスをＦｅＳｉ2 ポーラス構造素子
体の電極として用いる場合、熱膨張係数の違いによる応
力を緩和すべくメッシュ状にしている。[0005] When stainless steel is used as the electrode of the FeSi 2 porous structure element, the mesh is formed in order to reduce the stress due to the difference in thermal expansion coefficient.
【０００６】メッシュ状電極の概観を図３に示す。FIG. 3 shows an overview of the mesh electrode.
【０００７】図３に示すように、メッシュ状の電極２４
は、線材２４ａ，２４ｂを直交させて編込んでなるもの
であり、直交する線材２４ａと線材２４ｂとは接触して
いるだけである。このため、メッシュ状の電極２４を用
いた場合、電極２４自体の内部抵抗が大きくなり、低出
力化する。[0007] As shown in FIG.
Is made by weaving the wires 24a and 24b perpendicularly, and the wires 24a and 24b which are perpendicular to each other are only in contact with each other. For this reason, when the mesh-shaped electrode 24 is used, the internal resistance of the electrode 24 itself increases, and the output is reduced.
【０００８】敢えて直交する線材２４ａと線材２４ｂと
を溶接した場合、電極２４自体の内部抵抗は小さくなる
が、縦横への伸縮性がなくなり、応力緩和ができなくな
ると共に、ＦｅＳｉ2 ポーラス構造素子体との接合もで
きなくなる。[0008] When the wires 24a and 24b, which are orthogonal to each other, are welded, the internal resistance of the electrode 24 itself is reduced, but the stretchability in the vertical and horizontal directions is lost, so that the stress cannot be relaxed and the FeSi 2 porous structure element is not formed. Cannot be joined.
【０００９】メッシュ状の電極２４とＦｅＳｉ2 ポーラ
ス構造素子体とを接合する場合、その接触が点接触であ
ると共に、異種材料の接合であるため、その接合部の抵
抗は大きくなってしまう。すなわち、ＦｅＳｉ2 ポーラ
ス構造熱電素子の本来の出力が得られていなかった。When the mesh electrode 24 is joined to the FeSi 2 porous structure element, the contact is a point contact and the joining is made of different materials, so that the resistance of the joint becomes large. That is, the original output of the FeSi 2 porous thermoelectric element was not obtained.
【００１０】[0010]
【発明が解決しようとする課題】ここで、ＦｅＳｉ2 ポ
ーラス構造熱電素子においては、α−ＦｅＳｉ2 からな
る電極部とβ−ＦｅＳｉ2 からなる素子部とを一体に形
成したものがある。このＦｅＳｉ2 ポーラス構造熱電素
子の場合、素子部と電極部との組成が同じであるため、
熱膨張係数も当然同じとなり、接合部における応力は発
生しない。BRIEF Problems to be Solved] Here, in the FeSi 2 porous structure thermoelectric elements, there is integrally formed with an element portion consisting of the electrode portion and the beta-FeSi 2 consisting of alpha-FeSi 2. In the case of this FeSi 2 porous structure thermoelectric element, since the composition of the element part and the electrode part is the same,
Naturally, the coefficient of thermal expansion is the same, and no stress occurs at the joint.
【００１１】また、電極部と素子部とを一体に形成して
あるため、接合部における電極部と素子部との接触は、
ほぼ面接触に近く、接合部における抵抗も小さくなる。
すなわち、メッシュ状の電極を用いたＦｅＳｉ2 ポーラ
ス構造熱電素子における問題点が解消され、ＦｅＳｉ2
ポーラス構造熱電素子の本来の出力を得ることができる
はずである。Further, since the electrode portion and the element portion are integrally formed, the contact between the electrode portion and the element portion at the joint portion is
It is almost close to surface contact, and the resistance at the junction is also small.
That is, the problem in the FeSi 2 porous structure thermoelectric element using the mesh electrode is solved, and the FeSi 2
The original output of the porous thermoelectric element should be able to be obtained.
【００１２】従来のＦｅＳｉ2 ポーラス構造熱電素子の
概観を図４に示す。FIG. 4 shows an outline of a conventional FeSi 2 porous thermoelectric element.
【００１３】図４に示すように、従来のＦｅＳｉ2 ポー
ラス構造熱電素子１１は、円板状部１１ａと横断面ほぼ
半円形状の一対の脚部１１ｂ、１１ｃとで構成される。As shown in FIG. 4, the conventional thermoelectric element 11 having a porous structure of FeSi 2 has a disc-shaped portion 11a and a pair of legs 11b and 11c having a substantially semicircular cross section.
【００１４】円板状部１１ａおよび脚部１１ｂ、１１ｃ
は、ｐｎ型素子部１２で構成されており、脚部１１ｂお
よび脚部１１ｃの下端部には、ｐ型電極部１４、ｎ型電
極部１５がそれぞれ形成されている。ｐｎ型素子部１２
は、ｐ型素子部１２ａとｎ型素子部１２ｂとで構成さ
れ、ｐｎ接合部１３を介して接合されている。Disc-shaped part 11a and legs 11b, 11c
Is composed of a pn-type element portion 12, and a p-type electrode portion 14 and an n-type electrode portion 15 are formed at lower ends of the leg portions 11b and 11c, respectively. pn type element section 12
Is composed of a p-type element section 12a and an n-type element section 12b, and is joined via a pn junction section 13.
【００１５】従来のＦｅＳｉ2 ポーラス構造熱電素子の
製造方法のチャート図を図５に示す。FIG. 5 is a chart showing a method for manufacturing a conventional thermoelectric element having a porous structure of FeSi 2 .
【００１６】図５に示すように、ＦｅＳｉ2 ポーラス構
造熱電素子１１を作製するための原料粉末はα−ＦｅＳ
ｉ2 粉末であり、α−ＦｅＳｉ2 粉末を型内に充填した
後に圧縮成形してなるα−ＦｅＳｉ2 ポーラス体を焼結
し、ポーラス焼結体を作製する。このポーラス焼結体を
ＦｅＳｉ2 ポーラス構造熱電素子１１とするためには、
α−ＦｅＳｉ2 からなる素子形成部をβ−ＦｅＳｉ2 に
相変態させねばならない。このため、ポーラス構造の焼
結体に熱処理（例えば、大気中、８５０℃）を施してい
る。As shown in FIG. 5, the raw material powder for producing the FeSi 2 porous structure thermoelectric element 11 is α-FeS
An α-FeSi 2 porous body, which is an i 2 powder and is formed by filling an α-FeSi 2 powder into a mold and then compression molding, is sintered to produce a porous sintered body. In order to make this porous sintered body a FeSi 2 porous thermoelectric element 11,
The element forming portion made of α-FeSi 2 must be transformed into β-FeSi 2 . For this reason, the sintered body having the porous structure is subjected to heat treatment (for example, at 850 ° C. in the air).
【００１７】しかしながら、従来のポーラス構造熱電素
子１１の製造方法においては、α−ＦｅＳｉ2 粉末を圧
縮成形後、焼結固化して形成したα−ＦｅＳｉ2 ポーラ
ス焼結体をα相からβ相へと相変態させるための熱処理
に大変長い時間（例えば、５０ｈｒ）を必要とした。However, in the conventional method for manufacturing the porous thermoelectric element 11, the α-FeSi 2 porous sintered body formed by compression-molding the α-FeSi 2 powder and then sintering and solidifying is converted from the α phase to the β phase. A very long time (for example, 50 hours) was required for the heat treatment for phase transformation.
【００１８】また、その際に、α−ＦｅＳｉ2 からなる
電極形成部もβ−ＦｅＳｉ2 に同時に相変態されるた
め、α−ＦｅＳｉ2 からなる電極部１４、１５とβ−Ｆ
ｅＳｉ2 からなる素子部１２とを一体に形成する場合に
おいては、α−ＦｅＳｉ2 からなる素子形成部をβ−Ｆ
ｅＳｉ2 に相変態させる際に同時に相変態されたβ−Ｆ
ｅＳｉ2 からなる電極形成部に、再度熱処理を加えて、
α−ＦｅＳｉ2 に再変態させる方法がとられている。Further, at that time, alpha-FeSi 2 made of the electrode forming portion for also simultaneously phase transformation beta-FeSi 2, the electrode portion 14, 15 made of α-FeSi 2 β-F
In the case where the element portion 12 made of eSi 2 is integrally formed, the element formation portion made of α-FeSi 2 is formed as β-F
β-F phase-transformed simultaneously with phase transformation to eSi 2
Heat treatment is again applied to the electrode forming portion made of eSi 2 ,
A method of retransforming into α-FeSi 2 has been adopted.
【００１９】すなわち、元々はα−ＦｅＳｉ2 からなる
電極形成部をβ−ＦｅＳｉ2 に変態させ、再度、α−Ｆ
ｅＳｉ2 に変態させるという非効率的な工程を経てポー
ラス構造熱電素子を作製していた。[0019] That is, originally to transform the electrode forming portion consisting of alpha-FeSi 2 in beta-FeSi 2, again, alpha-F
A porous thermoelectric element has been manufactured through an inefficient process of transforming into eSi 2 .
【００２０】そこで本発明は、上記課題を解決し、β相
化のための熱処理時間が短く、かつ、製造工程が簡易な
ポーラス構造熱電素子及びその製造方法を提供すること
にある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a porous thermoelectric element having a short heat treatment time for β phase formation and a simple manufacturing process, and a method for manufacturing the same.
【００２１】[0021]
【課題を解決するための手段】上記課題を解決するため
に請求項１の発明は、β−ＦｅＳｉ2 相のｐｎ型素子部
と、α−ＦｅＳｉ2 相のｐ型とｎ型の電極部とを備えた
ポーラス構造熱電素子において、ｐ型とｎ型に調整した
α−ＦｅＳｉ2 に相変態促進材をそれぞれ添加してｐｎ
型素子形成部を形成し、そのｐｎ型素子形成部の直上
に、ｐ型とｎ型に調整したα−ＦｅＳｉ2 で電極形成部
をそれぞれ形成し、その後、焼結固化すると共に、上記
ｐｎ型素子形成部のみをα相からβ相に相変態するため
の熱処理を施したものである。In order to solve the above-mentioned problems, the invention of claim 1 comprises a pn-type element portion of β-FeSi 2 phase, and a p-type and n-type electrode portion of α-FeSi 2 phase. In the porous thermoelectric element having the above structure, the phase transformation accelerating material is added to the α-FeSi 2 adjusted to the p-type and the n-type, respectively.
Forming a mold element forming part, forming an electrode forming part with α-FeSi 2 adjusted to p-type and n-type immediately above the pn-type element forming part, and then sintering and solidifying the pn-type element forming part. The heat treatment for transforming only the element formation portion from the α phase to the β phase is performed.
【００２２】請求項２の発明は、β−ＦｅＳｉ2 相のｐ
ｎ型素子部と、α−ＦｅＳｉ2 相のｐ型とｎ型の電極部
とを備えたポーラス構造熱電素子の製造方法において、
ｐ型とｎ型に調整したα−ＦｅＳｉ2 に相変態促進材を
それぞれ添加してｐｎ型素子形成部を形成し、そのｐｎ
型素子形成部の直上に、ｐ型とｎ型に調整したα−Ｆｅ
Ｓｉ2 で電極形成部をそれぞれ形成し、その後、焼結固
化すると共に、上記ｐｎ型素子形成部のみをα相からβ
相に相変態するための熱処理を施すようにしたものであ
る。The invention according to claim 2 is characterized in that the β-FeSi 2 phase
In a method of manufacturing a porous thermoelectric element having an n-type element portion and α-FeSi 2 phase p-type and n-type electrode portions,
A phase transformation accelerating material is added to each of α-FeSi 2 adjusted to p-type and n-type to form a pn-type element forming portion,
Immediately above the mold element formation part, α-Fe adjusted to p-type and n-type
Each of the electrode forming portions is formed of Si 2 , and then sintered and solidified, and only the pn-type element forming portion is changed from the α phase to the β phase.
Heat treatment for phase transformation into a phase is performed.
【００２３】請求項３の発明は、上記相変態促進材が、
Ｐｄ、Ｃｕ、Ａｕ、Ｒｕから選択される１種または２種
以上の混合体である請求項１または請求項２記載のポー
ラス構造熱電素子の製造方法である。According to a third aspect of the present invention, the phase transformation accelerating material is
3. The method for producing a porous thermoelectric element according to claim 1, wherein the porous thermoelectric element is one or a mixture of two or more kinds selected from Pd, Cu, Au, and Ru.
【００２４】請求項４の発明は、上記相変態促進材の添
加量が、０．５〜６ｗｔ％である請求項１乃至請求項３
記載のポーラス構造熱電素子の製造方法である。According to a fourth aspect of the present invention, the amount of the phase transformation accelerator added is 0.5 to 6% by weight.
It is a manufacturing method of the porous thermoelectric element of the description.
【００２５】上記数値範囲を限定した理由を以下に述べ
る。The reason for limiting the above numerical range will be described below.
【００２６】上記相変態促進材の添加量を０．５〜６ｗ
ｔ％と限定した理由は、相変態促進材の添加量が０．５
ｗｔ％より少ないと原料の成分純度のため測定上限界が
あるからであり、相変態促進材の添加量が６ｗｔ％より
多いと熱電素子の熱起電力が急激に減少するからであ
る。The addition amount of the above-mentioned phase transformation accelerator is 0.5 to 6 watts.
The reason for limiting to t% is that the amount of the phase transformation accelerator added is 0.5%.
If the amount is less than wt%, there is a limit in the measurement due to the purity of the components of the raw material, and if the amount of the phase transformation accelerating material is more than 6 wt%, the thermoelectromotive force of the thermoelectric element sharply decreases.
【００２７】以上の構成によれば、ｐ型とｎ型に調整し
たα−ＦｅＳｉ2 に相変態促進材をそれぞれ添加してｐ
ｎ型素子形成部を形成し、そのｐｎ型素子形成部の直上
に、ｐ型とｎ型に調整したα−ＦｅＳｉ2 で電極形成部
をそれぞれ形成し、その後、焼結固化すると共に、ｐｎ
型素子形成部のみをα相からβ相に相変態するための熱
処理を施すため、β相化のための熱処理時間が短く、か
つ、製造工程が簡易なポーラス構造熱電素子を得ること
ができる。According to the above-described structure, the p-type and n-type α-FeSi 2 are each added with a phase transformation accelerator to add
An n-type element forming part is formed, and an electrode forming part is formed directly above the pn-type element forming part with α-FeSi 2 adjusted to p-type and n-type.
Since heat treatment for transforming only the mold element forming portion from the α phase to the β phase is performed, a porous thermoelectric element having a short heat treatment time for the β phase and a simple manufacturing process can be obtained.
【００２８】[0028]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。Embodiments of the present invention will be described below.
【００２９】本発明のポーラス構造熱電素子の概観を図
１に示す。FIG. 1 shows an overview of the porous thermoelectric element of the present invention.
【００３０】図１に示すように、本発明のＦｅＳｉ2 ポ
ーラス構造熱電素子１は、円板状部１ａと、その円板状
部１ａから下方へ一体的に延出された横断面ほぼ半円形
状の一対の脚部１ｂ、１ｃとで構成される。そして、脚
部１ｂ、１ｃの間には、所定の幅を有してスリット状隙
間部が形成される。As shown in FIG. 1, a thermoelectric element 1 having a porous structure of FeSi 2 according to the present invention has a disk-shaped portion 1a and a substantially semicircular cross-section integrally extending downward from the disk-shaped portion 1a. It is composed of a pair of legs 1b and 1c having a shape. A slit-shaped gap having a predetermined width is formed between the legs 1b and 1c.
【００３１】円板状部１ａおよび脚部１ｂ、１ｃの大部
分は、ｐｎ型素子部２で構成されており、脚部１ｂの下
端部および脚部１ｃの下端部はｐ型電極部４、ｎ型電極
部５で構成されている。ｐｎ型素子部２は、ｐ型素子部
２ａとｎ型素子部２ｂとで構成され、ｐｎ接合部３を介
して接合されている。Most of the disc-shaped portion 1a and the legs 1b, 1c are constituted by a pn-type element portion 2, and the lower end of the leg 1b and the lower end of the leg 1c are formed by a p-type electrode portion 4, It is composed of an n-type electrode unit 5. The pn-type element section 2 includes a p-type element section 2a and an n-type element section 2b, and is joined via a pn junction section 3.
【００３２】ｐ型素子部２ａおよびｎ型素子部２ｂは、
ｐ型、ｎ型にそれぞれ調整されたα−ＦｅＳｉ2 球状粉
末に、Ｐｄ、Ｃｕ、Ａｕ、Ｒｕから選択される１種また
は２種以上の相変態促進材を添加してなる混合体で構成
される。また、ｐ型電極部４およびｎ型電極部５は、ｐ
型、ｎ型にそれぞれ調整されたα−ＦｅＳｉ2 球状粉末
で構成される。The p-type element section 2a and the n-type element section 2b
It is composed of a mixture of α-FeSi 2 spherical powders adjusted to p-type and n-type and one or more phase transformation accelerators selected from Pd, Cu, Au, and Ru added thereto. You. Further, the p-type electrode unit 4 and the n-type electrode unit 5
It is composed of α-FeSi 2 spherical powder adjusted to a type and an n-type, respectively.
【００３３】ｐ型素子部２ａ、ｎ型素子部２ｂ、ｐ型電
極部４、およびｎ型電極部５を構成するα−ＦｅＳｉ2
球状粉末の粒径は特に限定しないが、１５０〜２５０μ
ｍの粒径のものが特に好ましい。Α-FeSi 2 constituting the p-type element section 2a, the n-type element section 2b, the p-type electrode section 4, and the n-type electrode section 5
Although the particle size of the spherical powder is not particularly limited,
Those having a particle size of m are particularly preferred.
【００３４】ｐ型素子部２ａおよびｎ型素子部２ｂに添
加される相変態促進材の添加量は、０．５〜６ｗｔ％が
望ましく、特に、２ｗｔ％が好ましい。The amount of the phase transformation accelerating material added to the p-type element portion 2a and the n-type element portion 2b is preferably 0.5 to 6% by weight, and particularly preferably 2% by weight.
【００３５】次に、本発明の製造方法を説明する。Next, the manufacturing method of the present invention will be described.
【００３６】本発明のポーラス構造熱電素子の製造方法
を図２に示す。FIG. 2 shows a method for manufacturing a porous thermoelectric element according to the present invention.
【００３７】図２に示すように、先ず、ポーラス構造熱
電素子の形状とニアネットシェイプの所定の型内に、ｐ
型素子部２ａおよびｎ型素子部２ｂを構成する原料粉末
として、ｐ型およびｎ型にそれぞれ調整されたα−Ｆｅ
Ｓｉ2 球状粉末（例えば、粒径が１５０〜２５０μｍ）
に、相変態促進材（例えば、２ｗｔ％のＰｄ）を添加し
てなる混合粉末を充填する。次に、その混合粉末の上
に、ｐ型電極部４およびｎ型電極部５を構成する原料粉
末として、ｐ型およびｎ型にそれぞれ調整されたα−Ｆ
ｅＳｉ2 球状粉末（例えば、粒径が１５０〜２５０μ
ｍ）を充填する。As shown in FIG. 2, first, the shape of the porous thermoelectric element and p
Α-Fe adjusted to p-type and n-type, respectively, as a raw material powder constituting the n-type element portion 2a and the n-type element portion 2b
Si 2 spherical powder (for example, particle size of 150 to 250 μm)
Is filled with a mixed powder obtained by adding a phase transformation accelerating material (for example, 2 wt% of Pd). Next, on the mixed powder, α-F adjusted to p-type and n-type, respectively, as a raw material powder constituting the p-type electrode portion 4 and the n-type electrode portion 5.
eSi 2 spherical powder (for example, having a particle size of 150 to 250 μm)
m).
【００３８】次に、それぞれの粉末が充填された型に圧
縮成形を施し、α−ＦｅＳｉ2 ポーラス体を作製する。
その後、そのα−ＦｅＳｉ2 ポーラス体に焼結（例え
ば、ＰＡＳ、ホットプレスなど）を施し、α−ＦｅＳｉ
2 ポーラス焼結体を作製する。Next, the mold filled with each powder is subjected to compression molding to produce an α-FeSi 2 porous body.
Thereafter, the α-FeSi 2 porous body is sintered (for example, PAS, hot press, etc.) to obtain α-FeSi 2
A two- porous sintered body is produced.
【００３９】α−ＦｅＳｉ2 ポーラス焼結体におけるｐ
型素子部２ａおよびｎ型素子部２ｂは、依然としてα相
であるため、β相化するための熱処理（例えば、大気
中、８５０℃、１ｈｒ）を施す。ここで、ｐ型素子部２
ａおよびｎ型素子部２ｂには、相変態促進材が添加され
ているため、この熱処理によって容易にβ相化するが、
ｐ型電極部４およびｎ型電極部５には、相変態促進材が
添加されていないため、この熱処理によってβ相化せず
α相のままである。P in the α-FeSi 2 porous sintered body
Since the mold element portion 2a and the n-type element portion 2b are still in the α phase, they are subjected to a heat treatment (for example, at 850 ° C., 1 hour in the air) for changing to the β phase. Here, the p-type element section 2
Since the phase transformation promoting material is added to the a and n-type element parts 2b, the β-phase is easily formed by this heat treatment.
Since the p-type electrode portion 4 and the n-type electrode portion 5 do not contain a phase transformation accelerating material, they remain in the α phase without being converted to the β phase by this heat treatment.
【００４０】すなわち、α−ＦｅＳｉ2 ポーラス焼結体
に一度の熱処理を施すだけで、ポーラス構造熱電素子の
素子部と電極部とを同時に形成することができる。この
ため、ポーラス構造熱電素子の製造工程が簡易になると
共に、熱処理時間も大幅に短縮され、低コストでポーラ
ス構造熱電素子を作製することができる。That is, the element portion and the electrode portion of the porous thermoelectric element can be formed simultaneously by performing only one heat treatment on the α-FeSi 2 porous sintered body. For this reason, the manufacturing process of the porous thermoelectric element is simplified, the heat treatment time is significantly reduced, and the porous thermoelectric element can be manufactured at low cost.
【００４１】[0041]
（実施例１）ｐ型素子部の原料粉末として２ｗｔ％Ｐｄ
添加ｐ型α−ＦｅＳｉ2 （化学組成：Ｆｅ0.91Ｍｎ0.09
Ｓｉ2 ）粉末、ｎ型素子部の原料粉末として２ｗｔ％Ｐ
ｄ添加ｎ型α−ＦｅＳｉ2 （化学組成：Ｆｅ0.97Ｃｏ
0.03Ｓｉ2 ）粉末、ｐ型電極部の原料粉末としてｐ型α
−ＦｅＳｉ2 粉末、ｎ型電極部の原料粉末としてｎ型α
−ＦｅＳｉ2 粉末を用い、順次、所定の型内に充填した
後、圧縮成形を施す。(Example 1) 2 wt% Pd as raw material powder for p-type element portion
Added p-type α-FeSi 2 (chemical composition: Fe 0.91 Mn 0.09
Si 2 ) powder, 2 wt% P as raw material powder for n-type element part
d-added n-type α-FeSi 2 (chemical composition: Fe 0.97 Co
0.03 Si 2 ) powder, p-type α as raw material powder for p-type electrode part
-FeSi 2 powder, n-type α as raw material powder for n-type electrode part
-Compression molding is performed after sequentially filling a predetermined mold using FeSi 2 powder.
【００４２】粉末を圧縮成形してなるα−ＦｅＳｉ2 ポ
ーラス体を、ＰＡＳにて焼結を施し、α−ＦｅＳｉ2 ポ
ーラス焼結体を作製する。The α-FeSi 2 porous body obtained by compression-molding the powder is sintered by PAS to produce an α-FeSi 2 porous sintered body.
【００４３】α−ＦｅＳｉ2 ポーラス焼結体に、大気
中、８５０℃、１ｈｒの熱処理を施して、ポーラス構造
熱電素子における素子部をα相からβ相に相変態させ、
α−ＦｅＳｉ2 電極を有したβ−ＦｅＳｉ2 ポーラス構
造熱電素子を作製した。The α-FeSi 2 porous sintered body is subjected to a heat treatment at 850 ° C. for 1 hour in the air to transform the element portion of the porous thermoelectric element from α phase to β phase.
A β-FeSi 2 porous structure thermoelectric element having an α-FeSi 2 electrode was manufactured.
【００４４】この時、α−ＦｅＳｉ2 電極を有したβ−
ＦｅＳｉ2 ポーラス構造熱電素子における円板状部の直
径は２０ｍｍ、厚さは２ｍｍ、脚部の高さは２ｍｍ、お
よび電極部の厚さは２ｍｍである。At this time, the β-electrode having the α-FeSi 2 electrode
The diameter of the disc-shaped portion in the FeSi 2 porous structure thermoelectric element is 20 mm, the thickness is 2 mm, the height of the leg portion is 2 mm, and the thickness of the electrode portion is 2 mm.
【００４５】（比較例１）ｐ型素子部の原料粉末として
ｐ型α−ＦｅＳｉ2 （化学組成：Ｆｅ0.91Ｍｎ0.09Ｓｉ
2 ）粉末、ｎ型素子部の原料粉末としてｎ型α−ＦｅＳ
ｉ2 （化学組成：Ｆｅ0.97Ｃｏ0.03Ｓｉ2 ）粉末を用
い、所定の型内に充填した後、圧縮成形を施す。Comparative Example 1 p-type α-FeSi 2 (chemical composition: Fe 0.91 Mn 0.09 Si) was used as the raw material powder for the p-type element portion.
2 ) Powder, n-type α-FeS as raw material powder for n-type element part
After using i 2 (chemical composition: Fe 0.97 Co 0.03 Si 2 ) powder and filling it into a predetermined mold, compression molding is performed.
【００４６】粉末を圧縮成形してなるα−ＦｅＳｉ2 ポ
ーラス体を、ＰＡＳにて焼結を施し、α−ＦｅＳｉ2 ポ
ーラス焼結体を作製する。The α-FeSi 2 porous body obtained by compression molding the powder is sintered by PAS to produce an α-FeSi 2 porous sintered body.
【００４７】α−ＦｅＳｉ2 ポーラス焼結体に、大気
中、８５０℃、５０ｈｒの熱処理を施して、ポーラス構
造熱電素子における素子部をα相からβ相に相変態させ
ると共に、ｐ型とｎ型にそれぞれ調整したＳＵＳ３０４
からなるメッシュ状の電極をそれぞれの素子部に接合し
て、ステンレス電極を有したβ−ＦｅＳｉ2 ポーラス構
造熱電素子を作製した。The α-FeSi 2 porous sintered body is subjected to a heat treatment at 850 ° C. for 50 hours in the air to transform the element portion of the porous thermoelectric element from the α phase to the β phase. SUS304 adjusted to each
Were joined to the respective element parts to produce a β-FeSi 2 porous thermoelectric element having a stainless steel electrode.
【００４８】この時、ステンレス電極を有したβ−Ｆｅ
Ｓｉ2 ポーラス構造熱電素子における円板状部の直径は
２０ｍｍ、厚さは２ｍｍ、脚部の高さは２ｍｍ、および
電極部の厚さは２ｍｍである。At this time, β-Fe having a stainless steel electrode
The diameter of the disc-shaped portion in the Si 2 porous structure thermoelectric element is 20 mm, the thickness is 2 mm, the height of the leg portion is 2 mm, and the thickness of the electrode portion is 2 mm.
【００４９】実施例１および比較例１におけるポーラス
構造熱電素子の熱電特性の測定結果を表１に示す。熱電
特性は、熱電素子の温度差が７００℃の時の値を評価し
た。Table 1 shows the measurement results of the thermoelectric characteristics of the porous thermoelectric elements in Example 1 and Comparative Example 1. As the thermoelectric characteristics, values when the temperature difference between the thermoelectric elements was 700 ° C. were evaluated.
【００５０】[0050]
【表１】 [Table 1]
【００５１】表１に示すように、熱電素子の温度差が７
００℃の時において、実施例１のポーラス構造熱電素子
は、０．３５Ｖの電圧が生じ、電力は２６（Ｗｍ／
ｍ2 ）を示した。これは、電極部にα−ＦｅＳｉ2 を用
いることにより、素子と電極部との間の良好な接合（低
接触抵抗、熱膨張率がほぼ等しいことによる低歪み）が
得られるためであり、これによって得られる電力が向上
する。As shown in Table 1, the temperature difference between the thermoelectric elements was 7
At a temperature of 00 ° C., the porous thermoelectric element of Example 1 generates a voltage of 0.35 V and the power is 26 (Wm /
m 2 ). This is because, by using α-FeSi 2 for the electrode portion, good junction (low contact resistance, low distortion due to almost equal thermal expansion coefficients) between the element and the electrode portion can be obtained. The resulting power is improved.
【００５２】これに対して、比較例１のポーラス構造熱
電素子は、電圧は０．３５Ｖが生じるものの、電力は１
９（Ｗｍ／ｍ2 ）に止まった。On the other hand, in the porous thermoelectric element of Comparative Example 1, although a voltage of 0.35 V was generated, the power was 1
It stopped at 9 (Wm / m 2 ).
【００５３】また、ＳＵＳ３０４メッシュなどの金属材
料をβ−ＦｅＳｉ2 ポーラス構造熱電素子の電極として
用いる場合、α−ＦｅＳｉ2 をβ相化する際の熱処理時
において、雰囲気を高真空下に保持しないと酸化劣化し
てしまう。これに対して、α−ＦｅＳｉ2 をβ−ＦｅＳ
ｉ2 ポーラス構造熱電素子の電極として用いる場合、大
気中で熱処理を施しても酸化劣化は生じない。すなわ
ち、雰囲気制御が不要で容易な熱処理となる。Further, when a metal material such as SUS304 mesh is used as an electrode of a β-FeSi 2 porous thermoelectric element, the atmosphere must be kept under a high vacuum during the heat treatment for converting α-FeSi 2 into β phase. It is oxidatively deteriorated. On the other hand, α-FeSi 2 is replaced with β-FeS
When used as an electrode for i 2 porous structure thermoelectric elements, there is no oxidative degradation by heat treatment in air. That is, the heat treatment can be easily performed without controlling the atmosphere.
【００５４】[0054]
【発明の効果】以上要するに本発明によれば、次のよう
な優れた効果を発揮する。In summary, according to the present invention, the following excellent effects are exhibited.
【００５５】（１） 素子部を構成するα−ＦｅＳｉ2
中に、相変態促進材を添加しているため、β相化のため
の熱処理時間の大幅な短縮を図ることができる。(1) α-FeSi 2 constituting the element section
Since the phase transformation accelerating material is added therein, the heat treatment time for β-phase conversion can be significantly reduced.
【００５６】（２） 素子部と電極部との組成が異なる
ため、１回の熱処理を施すことによってα相からβ相に
相変態する部分とそうでない部分とを形成することがで
きる。(2) Since the compositions of the element portion and the electrode portion are different, a portion that undergoes a phase transformation from the α phase to the β phase and a portion that does not are formed can be formed by performing a single heat treatment.
【００５７】（３） 製造工程が簡易になるため、低コ
ストでポーラス構造熱電素子を作製することができる。(3) Since the manufacturing process is simplified, a porous thermoelectric element can be manufactured at low cost.
【図１】本発明のポーラス構造熱電素子の概観を示す図
である。FIG. 1 is a view showing an overview of a porous thermoelectric element of the present invention.
【図２】本発明のポーラス構造熱電素子の製造方法のチ
ャート図である。FIG. 2 is a chart of a method for manufacturing a porous thermoelectric element of the present invention.
【図３】メッシュ状の電極の部分拡大図である。FIG. 3 is a partially enlarged view of a mesh electrode.
【図４】従来のポーラス構造熱電素子の概観を示す図で
ある。FIG. 4 is a diagram showing an overview of a conventional porous thermoelectric element.
【図５】従来のポーラス構造熱電素子の製造方法のチャ
ート図である。FIG. 5 is a chart of a conventional method for manufacturing a porous thermoelectric element.
１ ポーラス構造熱電素子 １ａ 円板状部 １ｂ、１ｃ 脚部 ２ ｐｎ型素子部 ２ａ ｐ型素子部 ２ｂ ｎ型素子部 ３ ｐｎ接合部 ４ ｐ型電極部 ５ ｎ型電極部 DESCRIPTION OF SYMBOLS 1 Porous thermoelectric element 1a Disc-shaped part 1b, 1c Leg part 2 pn-type element part 2a p-type element part 2b n-type element part 3 pn junction part 4 p-type electrode part 5 n-type electrode part
Claims (4)
−ＦｅＳｉ2 相のｐ型とｎ型の電極部とを備えたポーラ
ス構造熱電素子において、ｐ型とｎ型に調整したα−Ｆ
ｅＳｉ2 に相変態促進材をそれぞれ添加してｐｎ型素子
形成部を形成し、そのｐｎ型素子形成部の直上に、ｐ型
とｎ型に調整したα−ＦｅＳｉ2 で電極形成部をそれぞ
れ形成し、その後、焼結固化すると共に、上記ｐｎ型素
子形成部のみをα相からβ相に相変態するための熱処理
を施したことを特徴とするポーラス構造熱電素子。A pn-type element portion of β-FeSi 2 phase;
In a porous thermoelectric element having p-type and n-type electrode portions of -FeSi 2 phase, α-F adjusted to p-type and n-type
A phase transformation accelerating material is added to each of eSi 2 to form a pn-type element forming portion, and an electrode forming portion is formed directly above the pn-type element forming portion with α-FeSi 2 adjusted to p-type and n-type. Then, the porous structure thermoelectric element is sintered and solidified and subjected to a heat treatment for transforming only the pn-type element forming portion from the α phase to the β phase.
−ＦｅＳｉ2 相のｐ型とｎ型の電極部とを備えたポーラ
ス構造熱電素子の製造方法において、ｐ型とｎ型に調整
したα−ＦｅＳｉ2 に相変態促進材をそれぞれ添加して
ｐｎ型素子形成部を形成し、そのｐｎ型素子形成部の直
上に、ｐ型とｎ型に調整したα−ＦｅＳｉ2 で電極形成
部をそれぞれ形成し、その後、焼結固化すると共に、上
記ｐｎ型素子形成部のみをα相からβ相に相変態するた
めの熱処理を施すようにしたことを特徴とするポーラス
構造熱電素子の製造方法。 2. A pn-type element portion of β-FeSi 2 phase,
In a method for manufacturing a porous thermoelectric element having p-type and n-type electrode portions of -FeSi 2 phase, a phase transformation accelerating material is added to α-FeSi 2 adjusted to p-type and n-type, respectively. An element formation portion is formed, and an electrode formation portion is formed directly above the pn type element formation portion with α-FeSi 2 adjusted to p-type and n-type, and then sintered and solidified. A method for manufacturing a porous thermoelectric element, wherein a heat treatment for transforming only a formation portion from an α phase to a β phase is performed.
ｕ、Ｒｕから選択される１種または２種以上の混合体で
ある請求項１または請求項２記載のポーラス構造熱電素
子の製造方法。3. The method according to claim 2, wherein the phase transformation promoting material is Pd, Cu, A
The method for producing a porous thermoelectric element according to claim 1, wherein the method is one or a mixture of two or more kinds selected from u and Ru.
６ｗｔ％である請求項１乃至請求項３記載のポーラス構
造熱電素子の製造方法。4. The addition amount of the phase transformation accelerator is 0.5 to 0.5.
4. The method for producing a porous thermoelectric element according to claim 1, wherein the content is 6 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8154163A JPH104218A (en) | 1996-06-14 | 1996-06-14 | Porous structure thermoelectric element and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8154163A JPH104218A (en) | 1996-06-14 | 1996-06-14 | Porous structure thermoelectric element and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH104218A true JPH104218A (en) | 1998-01-06 |
Family
ID=15578217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8154163A Pending JPH104218A (en) | 1996-06-14 | 1996-06-14 | Porous structure thermoelectric element and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH104218A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006253343A (en) * | 2005-03-10 | 2006-09-21 | National Institute Of Advanced Industrial & Technology | Thermoelectric element integrating electrode, and its manufacturing process |
| US7397609B2 (en) | 2005-11-29 | 2008-07-08 | Eastman Kodak Company | Imaging apparatus |
| JP2008305986A (en) * | 2007-06-07 | 2008-12-18 | Sumitomo Chemical Co Ltd | Thermoelectric conversion module |
-
1996
- 1996-06-14 JP JP8154163A patent/JPH104218A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006253343A (en) * | 2005-03-10 | 2006-09-21 | National Institute Of Advanced Industrial & Technology | Thermoelectric element integrating electrode, and its manufacturing process |
| JP4524383B2 (en) * | 2005-03-10 | 2010-08-18 | 独立行政法人産業技術総合研究所 | Thermoelectric element with integrated electrode and method for producing the same |
| US7397609B2 (en) | 2005-11-29 | 2008-07-08 | Eastman Kodak Company | Imaging apparatus |
| JP2008305986A (en) * | 2007-06-07 | 2008-12-18 | Sumitomo Chemical Co Ltd | Thermoelectric conversion module |
| EP2159854A1 (en) * | 2007-06-07 | 2010-03-03 | Sumitomo Chemical Company, Limited | Thermoelectric conversion module |
| EP2159854A4 (en) * | 2007-06-07 | 2011-12-07 | Sumitomo Chemical Co | Thermoelectric conversion module |
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