JPH10215006A - Manufacture of thermoelectric conversion material - Google Patents
Manufacture of thermoelectric conversion materialInfo
- Publication number
- JPH10215006A JPH10215006A JP9016938A JP1693897A JPH10215006A JP H10215006 A JPH10215006 A JP H10215006A JP 9016938 A JP9016938 A JP 9016938A JP 1693897 A JP1693897 A JP 1693897A JP H10215006 A JPH10215006 A JP H10215006A
- Authority
- JP
- Japan
- Prior art keywords
- thermoelectric conversion
- oxygen
- carbon
- powder
- raw material
- 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.)
- Granted
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 81
- 239000001301 oxygen Substances 0.000 claims abstract description 81
- 239000000843 powder Substances 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002994 raw material Substances 0.000 claims abstract description 61
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 229910052797 bismuth Inorganic materials 0.000 claims description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 12
- 230000002093 peripheral effect Effects 0.000 claims description 12
- 229910052714 tellurium Inorganic materials 0.000 claims description 12
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007789 gas Substances 0.000 abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910017629 Sb2Te3 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- KWQLUUQBTAXYCB-UHFFFAOYSA-K antimony(3+);triiodide Chemical compound I[Sb](I)I KWQLUUQBTAXYCB-UHFFFAOYSA-K 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- -1 that is Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ビスマス及びテル
ルを主成分とした熱電変換材料の製造方法に関するもの
である。The present invention relates to a method for producing a thermoelectric conversion material containing bismuth and tellurium as main components.
【０００２】[0002]
【従来の技術】従来、この種の熱電変換材料の製造方法
として、次に説明する従来例が存在する。ビスマス（以
下Ｂｉ）及びテルル（以下Ｔｅ）を主成分とし、他にＳ
ｅ、Ｓｂ及びハロゲン化合物などを添加剤とする成分元
素粉末を混合し石英管などに封入する。次いで、その成
分元素粉末を加熱溶融し反応させた後、一方向凝固させ
て単結晶鋳塊を製造して、その単結晶鋳塊から任意のサ
イズの熱電変換材料を切り出す。2. Description of the Related Art Conventionally, as a method for producing this kind of thermoelectric conversion material, there is a conventional example described below. Bismuth (hereafter Bi) and tellurium (hereafter Te) are the main components.
e, Sb, and component element powders containing additives such as halogen compounds are mixed and sealed in a quartz tube or the like. Next, the component element powder is heated and melted and reacted, and then unidirectionally solidified to produce a single crystal ingot, and a thermoelectric conversion material of an arbitrary size is cut out from the single crystal ingot.
【０００３】また、別の従来例を次に説明する。上述し
た単結晶鋳塊を微粉化することによって熱電変換原料粉
末を形成する微粉化工程と、その熱電変換原料粉末を押
し出し成形して成形体を形成する成形工程と、その成形
体を加熱して焼結する燒結工程とを有している。[0003] Another conventional example will be described below. A pulverizing step of forming a thermoelectric conversion raw material powder by pulverizing the above-mentioned single crystal ingot, a forming step of extruding the thermoelectric conversion raw material powder to form a formed body, and heating the formed body And a sintering step for sintering.
【０００４】ここで、単結晶鋳塊を微粉化して熱電変換
原料粉末を作成するとき、または熱電変換原料粉末間に
酸素が含有された成形体を燒結するとき、熱電変換原料
粉末はＢｉＴｅ系化合物が酸素と結合し酸化されて導電
性を失い、つまり比抵抗値が増大し後述する熱電変換材
料の性能指数Ｚが低下する。したがって、酸化を阻止す
る措置がとられ、微粉化された熱電変換原料粉末があら
かじめ水素ガスなどの還元性ガスで還元される。あるい
は、微粉化、成形、及び燒結が不活性雰囲気中、又は水
素ガスや一酸化炭素の還元性ガス雰囲気中で行われる。[0004] Here, when a single crystal ingot is pulverized to prepare a thermoelectric conversion raw material powder, or when a compact containing oxygen is sintered between the thermoelectric conversion raw material powders, the thermoelectric conversion raw material powder is made of a BiTe-based compound. Is combined with oxygen and oxidized to lose conductivity, that is, the specific resistance increases, and the performance index Z of the thermoelectric conversion material described later decreases. Therefore, measures are taken to prevent oxidation, and the finely divided thermoelectric conversion raw material powder is reduced in advance with a reducing gas such as hydrogen gas. Alternatively, pulverization, molding, and sintering are performed in an inert atmosphere or in a reducing gas atmosphere of hydrogen gas or carbon monoxide.
【０００５】ここで、熱電変換材料の性能を評価する尺
度として、性能指数が一般に用いられる。その性能指数
（Ｚ値）はその材料が有するパラメータによって以下の
式で表される。[0005] Here, a performance index is generally used as a scale for evaluating the performance of a thermoelectric conversion material. The figure of merit (Z value) is represented by the following equation according to the parameters of the material.
【０００６】Ｚ＝α＊α／（ρκ） ここで、αは熱電能、ρは比抵抗値、及びκは熱伝導率
である。本式に示すように、比抵抗値ρが増大すると性
能指数Ｚが低下する。Z = α * α / (ρκ) where α is thermoelectric power, ρ is specific resistance, and κ is thermal conductivity. As shown in this equation, as the specific resistance value ρ increases, the figure of merit Z decreases.
【０００７】[0007]
【発明が解決しようとする課題】上記した別の従来例の
熱電変換材料の製造方法では、微粉化工程、成形工程及
び燒結工程を経て、生産性が高く、線状の熱電変換材料
を容易に製造することができる。In the above-mentioned conventional method for producing a thermoelectric conversion material, a high productivity and a linear thermoelectric conversion material can be easily obtained through a pulverization step, a forming step and a sintering step. Can be manufactured.
【０００８】しかしながら、熱電変換原料粉末と、すな
わちＢｉＴｅ系化合物と結合した酸素を、還元性ガスで
もって十分に還元することが困難であって、性能指数の
向上に限界があった。また、不活性雰囲気を維持するた
めの装置が高価であること、大量に消費されるガスのラ
ンニングコストが高いこと、水素ガスや一酸化炭素ガス
などの還元性ガスが爆発危険性や毒性を含んでいるこ
と、といった問題も生じていた。However, it is difficult to sufficiently reduce the thermoelectric conversion raw material powder, that is, the oxygen combined with the BiTe-based compound, with a reducing gas, and there is a limit in improving the performance index. In addition, the equipment for maintaining the inert atmosphere is expensive, the running cost of gas consumed in large quantities is high, and reducing gases such as hydrogen gas and carbon monoxide gas contain explosion hazard and toxicity. There was also the problem of being out.
【０００９】本発明は、上記事由に鑑みてなしたもの
で、その目的とするところは、熱電変換原料粉末と結合
した酸素を、又は粉末間の酸素を還元性ガスを使用する
ことなく燒結工程で十分に除去して、性能指数を向上で
きる熱電変換材料の製造方法を提供することにある。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sintering process in which oxygen combined with thermoelectric conversion raw material powder or oxygen between powders is used without using a reducing gas. The present invention provides a method for producing a thermoelectric conversion material that can be sufficiently removed by the method described above to improve the figure of merit.
【００１０】[0010]
【課題を解決するための手段】上記した課題を解決する
ために、請求項１記載の熱電変換材料の製造方法は、少
なくともビスマス及びテルルの元素を含有した熱電変換
原料粉末を加圧成形して成形体を形成する成形工程と、
成形体を加熱して焼結する燒結工程とを有した熱電変換
材料の製造方法において、前記成形工程は、前記熱電変
換原料粉末と結合した酸素、又はその粉末間の酸素を燒
結工程で除去する除去手段が設けられた構成にしてあ
る。According to a first aspect of the present invention, there is provided a method for producing a thermoelectric conversion material, comprising: forming a thermoelectric conversion raw material powder containing at least bismuth and tellurium elements under pressure; A molding step of forming a molded body,
A sintering step of heating and sintering the formed body, wherein the forming step removes oxygen combined with the thermoelectric conversion raw material powder or oxygen between the powders in the sintering step. The configuration is such that a removing means is provided.
【００１１】請求項２記載の熱電変換材料の製造方法
は、請求項１記載の製造方法において、前記除去手段
は、前記酸素と反応する炭素でもって形成された構成に
してある。According to a second aspect of the present invention, there is provided a method for producing a thermoelectric conversion material, wherein the removing means is formed of carbon which reacts with the oxygen.
【００１２】請求項３記載の熱電変換材料の製造方法
は、請求項２記載の製造方法において、前記除去手段
は、前記熱電変換原料粉末とともに混合され成形された
０．１乃至０．５重量％の炭素粉末でもって形成された
構成にしてある。According to a third aspect of the present invention, there is provided a method for producing a thermoelectric conversion material according to the second aspect, wherein the removing means comprises 0.1 to 0.5% by weight mixed and molded with the thermoelectric conversion raw material powder. Of carbon powder.
【００１３】請求項４記載の熱電変換材料の製造方法
は、請求項２記載の製造方法において、前記成形工程
は、前記熱電変換原料粉末が内部に密閉充填された長尺
状の金属ビュレットを押し出して加圧成形するものであ
って、前記除去手段は金属ビュレットの内周壁に設けら
れた炭素層でもって形成された構成にしてある。According to a fourth aspect of the present invention, in the manufacturing method of the second aspect, the molding step includes extruding a long metal buret in which the thermoelectric conversion raw material powder is hermetically sealed. And the pressure removing means, wherein the removing means is formed of a carbon layer provided on the inner peripheral wall of the metal buret.
【００１４】請求項５記載の熱電変換材料の製造方法
は、請求項４記載の製造方法において、前記成形工程
は、前記金属ビュレットの長手方向に対する直交方向へ
沿って別の炭素層が複数設けられるとともに、前記除去
手段は前記炭素層及び別の炭素層でもって形成された構
成にしてある。According to a fifth aspect of the present invention, in the manufacturing method of the fourth aspect, in the forming step, a plurality of different carbon layers are provided along a direction perpendicular to a longitudinal direction of the metal buret. At the same time, the removing means is formed of the carbon layer and another carbon layer.
【００１５】[0015]
【発明の実施の形態】本発明の第１実施形態を図１及び
図２に基づいて以下に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment of the present invention will be described below with reference to FIGS.
【００１６】先ず、微粉化工程において、それぞれ純度
が９９．９９９％以上で、全体に対して８０重量％のＢ
ｉ2Ｔｅ3、及び２０重量％のＳｂ2Ｔｅ3に、ＳｂＩ3か
らなる添加剤を約０．０９重量％添加し、パイレックス
ガラス管（図示せず）内に真空封入する。そして、溶解
したのち一方向凝固し、導電型がＮ型の半導体である単
結晶鋳塊を作成し、その単結晶鋳塊をボールミルで平均
粒径５０μｍとなるまで粉砕して、熱電変換原料粉末１
を形成する。First, in the pulverization step, the purity of each is 99.999% or more, and 80% by weight of B
About 0.09% by weight of an additive consisting of SbI3 is added to i2Te3 and 20% by weight of Sb2Te3, and the mixture is vacuum-sealed in a Pyrex glass tube (not shown). Then, after melting, the solid is unidirectionally solidified to form a single crystal ingot having a semiconductor of an N-type conductivity, and the single crystal ingot is pulverized by a ball mill until the average particle diameter becomes 50 μm, and the thermoelectric conversion raw material powder is obtained. 1
To form
【００１７】次いで、混合工程において、炭素粉末２が
カーボンブラックにより、粒径１０乃至５０μｍの粉末
状に形成され、全体の粉体重量に対して０．１重量％に
なるよう、熱電変換原料粉末１に添加混合される。金属
ビュレット３は、アルミニウム合金により、直径６７ｍ
ｍ、長さ２７５ｍｍの有底円筒状で長尺状に形成され、
直径２３ｍｍで長さ２００ｍｍの有底穴が設けられ、熱
電変換原料粉末１及び炭素粉末２がその有底穴に充填さ
れる。Next, in the mixing step, the carbon powder 2 is formed into a powder having a particle size of 10 to 50 μm with carbon black, and the thermoelectric conversion raw material powder is adjusted to 0.1% by weight with respect to the total powder weight. Add to 1 and mix. The metal buret 3 is made of aluminum alloy and has a diameter of 67 m.
m, is formed in a cylindrical shape with a bottom and a length of 275 mm in length,
A bottomed hole having a diameter of 23 mm and a length of 200 mm is provided, and the bottomed hole is filled with the thermoelectric conversion raw material powder 1 and the carbon powder 2.
【００１８】次いで、成形工程において、金属ビュレッ
ト３を密閉し熱電変換原料粉末１及び炭素粉末２を内部
に密閉充填し、４００℃に加熱し金属ビュレット３のア
ルミニウム合金に適度な軟性を持たせ、８００ＭＰａの
圧力で直接押し出し法により押し出して、線形状に加圧
成形されたＢｉＴｅ系の成形体４を形成する。Next, in the forming step, the metal buret 3 is sealed, the thermoelectric conversion raw material powder 1 and the carbon powder 2 are hermetically filled therein, and heated to 400 ° C. to give the aluminum alloy of the metal buret 3 a moderate softness. Extrusion is performed by a direct extrusion method at a pressure of 800 MPa to form a BiTe-based molded body 4 that is linearly molded under pressure.
【００１９】次いで、燒結工程において、金属ビュレッ
ト３の両端部を切削により取り除き、アルミニウム外周
部３１を残した状態で、成形体４を６００℃で２４時
間、不活性雰囲気中で加熱して焼結する。室温まで冷却
した後、アルミニウム外周部３１を切削により取り除
き、内部の成形体４を取り出して熱電変換材料を得た。Next, in the sintering step, the molded body 4 is heated at 600 ° C. for 24 hours in an inert atmosphere and sintered in a state where the both ends of the metal buret 3 are removed by cutting and the aluminum outer peripheral portion 31 is left. I do. After cooling to room temperature, the aluminum outer peripheral portion 31 was removed by cutting, and the internal molded body 4 was taken out to obtain a thermoelectric conversion material.
【００２０】ここで、成形体４に分散した炭素粉末２が
近傍のＢｉＴｅ系化合物の酸化体中の酸素、すなわち熱
電変換原料粉末１と結合した酸素と、及び熱電変換原料
粉末１間の空隙に存在する酸素とそれぞれ反応して、そ
の酸素を二酸化炭素として除去する。つまり、炭素粉末
２が酸素の除去手段を形成する。詳述すると、炭素粉末
２がまず近傍の酸素と反応して一酸化炭素を発生し、そ
の一酸化炭素が成形体４中に拡散して浸透し、さらに酸
素と反応して二酸化炭素を生成し、熱電変換原料粉末１
と結合した酸素、又は成形体４中の酸素を除去する。ま
た、酸素と反応した炭素粉末２が二酸化炭素ガスになっ
て、そこに空隙を生じるので、成形体４の熱伝導率が低
くなる。Here, the carbon powder 2 dispersed in the compact 4 contains oxygen in the neighboring BiTe-based compound oxidant, that is, oxygen combined with the thermoelectric conversion raw material powder 1, and voids between the thermoelectric conversion raw material powder 1. Each reacts with the oxygen present and removes the oxygen as carbon dioxide. That is, the carbon powder 2 forms a means for removing oxygen. More specifically, the carbon powder 2 first reacts with oxygen in the vicinity to generate carbon monoxide, and the carbon monoxide diffuses and penetrates into the compact 4 and further reacts with oxygen to generate carbon dioxide. , Thermoelectric conversion raw material powder 1
And the oxygen in the compact 4 is removed. In addition, since the carbon powder 2 that has reacted with oxygen becomes carbon dioxide gas and produces voids therein, the thermal conductivity of the molded body 4 decreases.
【００２１】炭素粉末２は、全体の粉体重量に対して
０．１乃至０．５重量％が適正範囲であり、０．１重量
％未満では、熱電変換原料粉末１と結合した酸素、又は
成形体４中の酸素を燒結工程で除去する除去能力が低く
なり、また、０．５重量％を越えると空隙が多くなって
材料強度が劣化する。The carbon powder 2 has a proper range of 0.1 to 0.5% by weight based on the total powder weight, and if less than 0.1% by weight, oxygen combined with the thermoelectric conversion raw material powder 1 or The ability to remove oxygen in the compact 4 in the sintering step is reduced, and if it exceeds 0.5% by weight, voids are increased and the material strength is reduced.
【００２２】燒結された成形体４は、酸素含有率及び比
抵抗値が測定される。ここで、酸素含有率はパーキンエ
ルマー社製全自動元素分析装置２４００IIＣＨＮＳ／Ｏ
型を用いて測定し、また比抵抗値は山崎精機研究所製Ｙ
ＭＲ３型を用いて、線状の成形体４の長手方向へ沿って
通電することによって測定した。測定結果は、酸素含有
率が０．０２３重量％、比抵抗値が１．２μΩｍであっ
た。また、熱電変換原料粉末１の酸素含有率は０．１１
重量％であった。The sintered compact 4 is measured for oxygen content and specific resistance. Here, the oxygen content was measured by a PerkinElmer full-automatic element analyzer 2400IICHNS / O.
Is measured using a mold.
The measurement was performed by applying an electric current along the longitudinal direction of the linear molded body 4 using the MR3 type. As a result of the measurement, the oxygen content was 0.023% by weight, and the specific resistance was 1.2 μΩm. The oxygen content of the thermoelectric conversion raw material powder 1 was 0.11.
% By weight.
【００２３】比較例を図９及び図１０に基づいて以下に
説明する。比較例では、炭素粉末２を混合せずに熱電変
換原料粉末１を加圧成形して成形体４を形成し、アルミ
ニウム外周部３１を切削し、水素雰囲気中で焼結した以
外は第１実施形態と同一である。得られた熱電変換材料
の測定結果は、酸素含有率が０．０２６重量％、比抵抗
値が１．２μΩｍであった。酸素含有率は熱電変換原料
粉末１よりも低く、酸素の除去が行われているものの、
第１実施形態と比較すると高い。すなわち、第１実施形
態における酸素含有率は、比較例よりも低く良好な値で
あって、熱電変換原料粉末１と結合した酸素、及び成形
体４中の酸素が十分に除去されていることがわかる。A comparative example will be described below with reference to FIGS. 9 and 10. In the comparative example, the thermoelectric conversion raw material powder 1 was press-formed without mixing the carbon powder 2 to form a compact 4, and the aluminum outer peripheral portion 31 was cut and sintered in a hydrogen atmosphere. Same as the form. As a result of the measurement of the obtained thermoelectric conversion material, the oxygen content was 0.026% by weight, and the specific resistance was 1.2 μΩm. Although the oxygen content is lower than that of the thermoelectric conversion raw material powder 1 and oxygen is removed,
This is higher than the first embodiment. That is, the oxygen content in the first embodiment is lower than that of the comparative example and is a good value, and the oxygen combined with the thermoelectric conversion raw material powder 1 and the oxygen in the compact 4 are sufficiently removed. Recognize.
【００２４】かかる第１実施形態の熱電変換材料の製造
方法にあっては、上記したように、熱電変換原料粉末１
と結合した酸素、及びその熱電変換原料粉末１間の酸素
を除去する除去手段が成形工程に設けられたから、成形
工程につづく焼結工程で、除去手段が酸化したビスマス
及びテルルの酸素を除去し還元して、及び粉末間の酸素
が除去されるのでビスマス及びテルルの新規酸化を阻止
して、従来のように爆発危険性のある還元性ガスを使用
することなく、比抵抗値を減少せしめ性能指数を向上し
た熱電変換材料を安定して製造することができる。In the method of manufacturing a thermoelectric conversion material according to the first embodiment, as described above, the thermoelectric conversion raw material powder 1 is used.
In the forming step, a removing means for removing oxygen combined with oxygen and the oxygen between the thermoelectric conversion raw material powders 1 is provided. In the sintering step following the forming step, the removing means removes oxidized bismuth and oxygen of tellurium. Reduction and removal of oxygen between powders prevent new oxidation of bismuth and tellurium, and reduce specific resistance without using explosive reducing gas as in the past. A thermoelectric conversion material with an improved index can be stably manufactured.
【００２５】また、除去手段が炭素でもって形成された
から、炭素がビスマス及びテルルと結合した酸素と反応
し還元して、及び熱電変換原料粉末１間の酸素と反応し
て、炭素が比較的安価な原料であるので、コスト的に有
利な熱電変換材料を製造することができる。Further, since the removing means is formed of carbon, carbon reacts with oxygen bonded to bismuth and tellurium to reduce and reacts with oxygen between the thermoelectric conversion raw material powders 1 so that carbon is relatively inexpensive. Since it is a raw material, it is possible to produce a thermoelectric conversion material that is advantageous in cost.
【００２６】また、除去手段が熱電変換原料粉末１とと
もに混合され成形された炭素粉末２でもって形成され、
かつ炭素の組成範囲が０．１乃至０．５重量％で適正範
囲に選択されたたから、成形体４中に分散した炭素粉末
２が燒結工程で酸素と反応し除去されて空隙を生じ、そ
の空隙が成形体４の熱伝導率を低下せしめて、熱電変換
材料の性能指数をさらに向上することができる。Further, the removing means is formed by the carbon powder 2 mixed and molded with the thermoelectric conversion raw material powder 1,
In addition, since the composition range of carbon was selected to be an appropriate range of 0.1 to 0.5% by weight, the carbon powder 2 dispersed in the compact 4 reacts with oxygen in the sintering step and is removed to form voids. The voids lower the thermal conductivity of the molded body 4 and can further improve the figure of merit of the thermoelectric conversion material.
【００２７】なお、第１実施形態では、酸素と反応する
炭素粉末２をカーボンブラックとしたが、グラファイト
又は活性炭でもよく限定されない。In the first embodiment, the carbon powder 2 which reacts with oxygen is carbon black. However, graphite or activated carbon is not limited.
【００２８】また、第１実施形態では、燒結工程で酸素
を除去する除去手段を炭素でもって形成したが、ビスマ
ス及びテルルよりも酸素と親和力が強くそのビスマス及
びテルルと結合した酸素を還元する元素でもって、除去
手段を形成してもよく限定されない。Further, in the first embodiment, the removing means for removing oxygen in the sintering step is formed by using carbon. However, an element which has a higher affinity for oxygen than bismuth and tellurium and reduces oxygen combined with bismuth and tellurium is used. Thus, the removing means may be formed without limitation.
【００２９】また、第１実施形態では、炭素粉末２が熱
電変換原料粉末１と結合した酸素、及びその粉末間の酸
素の両方を燒結工程で除去したが、いづれか一方を除去
してもよく限定されない。Further, in the first embodiment, both the oxygen combined with the thermoelectric conversion raw material powder 1 and the oxygen between the carbon powder 2 are removed in the sintering step, but either one may be removed. Not done.
【００３０】本発明の第２実施形態を図３乃び図４に基
づいて以下に説明する。なお、第２実施形態では第１実
施形態と異なる製造方法について述べることとし、第１
実施形態と実質的に同一機能を有する部材については、
同一符号を付して説明を省略する。A second embodiment of the present invention will be described below with reference to FIGS. In the second embodiment, a manufacturing method different from that of the first embodiment will be described.
For members having substantially the same function as the embodiment,
The same reference numerals are given and the description is omitted.
【００３１】成形工程において、炭素粉末２を混合せず
に熱電変換原料粉末１のみを加圧成形して成形体４を形
成する。炭素層２１は、グラファイトにより、厚さが
１．５ｍｍに形成され、金属ビュレット３の内周壁に設
けられて除去手段を形成する。成形工程において、熱電
変換原料粉末１が充填された金属ビュレット３を押し出
して加圧成形し、外周部に炭素層２１を被覆した成形体
４を形成する。その成形体４を焼結した後、アルミニウ
ム外周部３１と炭素層２１とを取り除いて熱電変換材料
を得る。In the compacting step, only the thermoelectric conversion raw material powder 1 is compacted without mixing the carbon powder 2 to form a compact 4. The carbon layer 21 is formed of graphite to a thickness of 1.5 mm, and is provided on the inner peripheral wall of the metal buret 3 to form a removing unit. In the forming step, the metal burette 3 filled with the thermoelectric conversion raw material powder 1 is extruded and pressed to form a formed body 4 having an outer peripheral portion covered with a carbon layer 21. After sintering the molded body 4, the aluminum outer peripheral portion 31 and the carbon layer 21 are removed to obtain a thermoelectric conversion material.
【００３２】得られた熱電変換材料の測定結果は、酸素
含有率が０．０１２重量％、比抵抗値が１．１μΩｍで
あった。酸素含有率及び比抵抗値は、いづれも比較例よ
りも低く良好な値であって、熱電変換原料粉末１と結合
した酸素、及び成形体４中の酸素が十分に除去されてい
ることがわかる。As a result of the measurement of the obtained thermoelectric conversion material, the oxygen content was 0.012% by weight and the specific resistance was 1.1 μΩm. The oxygen content and the specific resistance were both lower than the comparative example and were good values, indicating that oxygen combined with the thermoelectric conversion raw material powder 1 and oxygen in the compact 4 were sufficiently removed. .
【００３３】かかる第２実施形態の熱電変換材料の製造
方法にあっては、上記したように、除去手段が金属ビュ
レット３の内周壁に設けられた炭素層２１で形成された
から、炭素層２１が酸素を成形体４の外周部から順次除
去して、成形体４が空隙を生じることなく焼結されて、
熱電変換材料の強度を向上することができる。In the method for manufacturing a thermoelectric conversion material according to the second embodiment, since the removing means is formed by the carbon layer 21 provided on the inner peripheral wall of the metal burette 3 as described above, the carbon layer 21 Oxygen is sequentially removed from the outer peripheral portion of the molded body 4 so that the molded body 4 is sintered without forming a void,
The strength of the thermoelectric conversion material can be improved.
【００３４】本発明の第３実施形態を図５及び図６に基
づいて以下に説明する。なお、第３実施形態では第２実
施形態と異なる製造方法について述べることとし、第２
実施形態と実質的に同一機能を有する部材については、
同一符号を付して説明を省略する。A third embodiment of the present invention will be described below with reference to FIGS. In the third embodiment, a manufacturing method different from that of the second embodiment will be described.
For members having substantially the same function as the embodiment,
The same reference numerals are given and the description is omitted.
【００３５】成形工程において、別の炭素層２２は、グ
ラファイトにより、厚さが３ｍｍで外径が金属ビュレッ
ト３の内径と同一で板状に形成され、金属ビュレット３
の長手方向に対する直交方向へ沿って複数設けられる。
すなわち、熱電変換原料粉末５０ｇに対して１枚の割合
で交互に充填されて、熱電変換原料粉末１を直交方向へ
貫通し、炭素層２１とともに除去手段を形成する。In the forming step, another carbon layer 22 is formed of graphite into a plate shape having a thickness of 3 mm and an outer diameter equal to the inner diameter of the metal burette 3.
Are provided in a direction orthogonal to the longitudinal direction of the plurality.
That is, the powder is alternately filled at a rate of 50 g of the thermoelectric conversion raw material powder, penetrates the thermoelectric conversion raw material powder 1 in the orthogonal direction, and forms a removing unit together with the carbon layer 21.
【００３６】得られた熱電変換材料の測定結果は、酸素
含有率が０．００７重量％、比抵抗値が０．８μΩｍで
あった。酸素含有率及び比抵抗値は、いづれも比較例よ
りも大幅に低く良好な値であって、熱電変換原料粉末１
と結合した酸素、及び成形体４中の酸素が十分に除去さ
れていることがわかる。As a result of the measurement of the obtained thermoelectric conversion material, the oxygen content was 0.007% by weight and the specific resistance was 0.8 μΩm. The oxygen content and the specific resistance were all significantly lower than those of the comparative example and were good values.
It can be seen that the oxygen combined with and the oxygen in the compact 4 were sufficiently removed.
【００３７】かかる第３実施形態の熱電変換材料の製造
方法にあっては、上記したように、除去手段が炭素層２
１及び複数の別の炭素層２２でもって形成されたから、
別の炭素層２２が金属ビュレット３の長手方向に対する
直交方向へ沿って設けられ、すなわち充填された熱電変
換原料粉末１を貫通して、成形体４の内部に位置した酸
素を除去することができる。In the method for manufacturing a thermoelectric conversion material according to the third embodiment, as described above, the removing means is used for removing the carbon layer 2.
Since it was formed with one and a plurality of different carbon layers 22,
Another carbon layer 22 is provided along the direction perpendicular to the longitudinal direction of the metal burette 3, that is, it can penetrate the filled thermoelectric conversion raw material powder 1 to remove oxygen located inside the molded body 4. .
【００３８】本発明の第４実施形態を図７及び図８に基
づいて以下に説明する。なお、第３実施形態では第１実
施形態と異なる機能について述べることとし、第１実施
形態と実質的に同一機能を有する部材については、同一
符号を付して説明を省略する。A fourth embodiment of the present invention will be described below with reference to FIGS. In the third embodiment, functions different from those in the first embodiment will be described, and members having substantially the same functions as those in the first embodiment will be denoted by the same reference numerals and description thereof will be omitted.
【００３９】成形工程において、炭素粉末２を混合せず
に熱電変換原料粉末１のみを加圧成形して成形体４を形
成する。また、グラファイトからなる別の炭素層２２
は、板状で厚さが３ｍｍで外径が金属ビュレット３の内
径と同一に形成され、金属ビュレット３の長手方向に対
する直交方向へ沿って複数設けられる。すなわち、熱電
変換原料粉末５０ｇに対して１枚の割合で交互に充填さ
れて、熱電変換原料粉末１を直交方向へ貫通して、除去
手段を形成する。In the molding step, only the thermoelectric conversion raw material powder 1 is molded under pressure without mixing the carbon powder 2 to form a molded body 4. Further, another carbon layer 22 made of graphite is used.
The metal buret 3 is formed in a plate shape, the thickness is 3 mm, and the outer diameter is formed to be the same as the inner diameter of the metal buret 3. That is, the powder is alternately filled at a rate of one sheet per 50 g of the thermoelectric conversion raw material powder, penetrates the thermoelectric conversion raw material powder 1 in the orthogonal direction, and forms a removing means.
【００４０】得られた熱電変換材料の測定結果は、酸素
含有率が０．０１重量％、比抵抗値が０．９μΩｍであ
った。酸素含有率及び比抵抗値は、いづれも比較例より
も低く良好な値であって、熱電変換原料粉末１と結合し
た酸素、及び成形体４中の酸素が十分に除去されている
ことがわかる。As a result of the measurement of the obtained thermoelectric conversion material, the oxygen content was 0.01% by weight and the specific resistance was 0.9 μΩm. The oxygen content and the specific resistance were both lower than the comparative example and were good values, indicating that oxygen combined with the thermoelectric conversion raw material powder 1 and oxygen in the compact 4 were sufficiently removed. .
【００４１】[0041]
【発明の効果】請求項１記載の熱電変換材料の製造方法
は、熱電変換原料粉末と結合した酸素、又はその熱電変
換原料粉末間の酸素を除去する除去手段が成形工程に設
けられたから、成形工程につづく焼結工程で、除去手段
が酸化したビスマス及びテルルの酸素を除去し還元し
て、又は粉末間の酸素が除去されるのでビスマス及びテ
ルルの新規酸化を阻止して、従来のように爆発危険性の
ある還元性ガスを使用することなく、比抵抗値を減少せ
しめ性能指数を向上した熱電変換材料を安定して製造す
ることができる。According to the method for producing a thermoelectric conversion material according to the first aspect of the present invention, the removing step for removing oxygen combined with the thermoelectric conversion raw material powder or oxygen between the thermoelectric conversion raw material powder is provided in the molding step. In the sintering step following the step, the removing means removes and reduces the oxygen of the oxidized bismuth and tellurium, or prevents the new oxidation of bismuth and tellurium as the oxygen between the powders is removed. A thermoelectric conversion material having a reduced specific resistance value and an improved figure of merit can be stably manufactured without using a reducing gas having a risk of explosion.
【００４２】請求項２記載の熱電変換材料の製造方法
は、請求項１記載の製造方法の効果に加えて、除去手段
が炭素でもって形成されたから、炭素がビスマス及びテ
ルルと結合した酸素と反応し還元して、又は熱電変換原
料粉末間の酸素と反応して、炭素が比較的安価な原料で
あるので、コスト的に有利な熱電変換材料を製造するこ
とができる。In the method for producing a thermoelectric conversion material according to the second aspect, in addition to the effect of the production method according to the first aspect, since the removing means is formed of carbon, the carbon reacts with oxygen bonded to bismuth and tellurium. Since carbon is a relatively inexpensive raw material by reducing and reducing or reacting with oxygen between thermoelectric conversion raw material powders, a thermoelectric conversion material which is advantageous in cost can be produced.
【００４３】請求項３記載の熱電変換材料の製造方法
は、請求項２記載の製造方法の効果に加えて、除去手段
が熱電変換原料粉末とともに混合され成形された炭素粉
末でもって形成され、かつ炭素の組成範囲が０．１乃至
０．５重量％で適正範囲に選択されたたから、成形体中
に分散した炭素粉末が燒結工程で酸素と反応し除去され
て空隙を生じ、その空隙が成形体の熱伝導率を低下せし
めて、熱電変換材料の性能指数をさらに向上することが
できる。According to a third aspect of the present invention, in addition to the effect of the second aspect, the removing means is formed of carbon powder mixed and molded with the thermoelectric conversion raw material powder, and Since the composition range of carbon was selected in an appropriate range from 0.1 to 0.5% by weight, the carbon powder dispersed in the molded body reacted with oxygen in the sintering step and was removed to form voids. By lowering the thermal conductivity of the body, the figure of merit of the thermoelectric conversion material can be further improved.
【００４４】請求項４記載の熱電変換材料の製造方法
は、請求項２記載の製造方法の効果に加えて、成形工程
が熱電変換原料粉末を充填した長尺状の金属ビュレット
を、押し出して成形するものであれば、除去手段が金属
ビュレットの内周壁に設けられた炭素層で形成されたか
ら、炭素層が酸素を成形体の外周部から順次除去して、
成形体が空隙を生じることなく焼結されて、熱電変換材
料の強度を向上することができる。According to a fourth aspect of the present invention, in addition to the effect of the second aspect, the molding step comprises extruding a long metal burette filled with the thermoelectric conversion raw material powder. If it does, since the removing means is formed of a carbon layer provided on the inner peripheral wall of the metal buret, the carbon layer sequentially removes oxygen from the outer peripheral portion of the molded body,
The molded body is sintered without generating voids, and the strength of the thermoelectric conversion material can be improved.
【００４５】請求項５記載の熱電変換材料の製造方法
は、請求項４記載の製造方法の効果に加えて、除去手段
が炭素層及び複数の別の炭素層でもって形成されたか
ら、別の炭素層が金属ビュレットの長手方向に対する直
交方向へ沿って設けられ、すなわち、充填された熱電変
換原料粉末を貫通して、成形体の内部にわたって酸素を
除去することができる。According to a fifth aspect of the present invention, in addition to the effect of the fourth aspect, the removing means is formed of a carbon layer and a plurality of other carbon layers. A layer is provided along a direction perpendicular to the longitudinal direction of the metal buret, that is, oxygen can be removed through the filled thermoelectric conversion raw material powder and throughout the inside of the molded body.
【図１】本発明の第１実施形態を示す熱電変換原料粉末
及び炭素粉末が充填された金属ビュレットの断面図であ
る。FIG. 1 is a cross-sectional view of a metal buret filled with a thermoelectric conversion raw material powder and a carbon powder according to a first embodiment of the present invention.
【図２】同上の焼結された成形体の断面図である。FIG. 2 is a cross-sectional view of the same sintered compact.
【図３】本発明の第２実施形態を示す熱電変換原料粉末
が充填された金属ビュレットの断面図である。FIG. 3 is a cross-sectional view of a metal buret filled with thermoelectric conversion raw material powder according to a second embodiment of the present invention.
【図４】同上の焼結された成形体の断面図である。FIG. 4 is a cross-sectional view of the same sintered compact.
【図５】本発明の第３実施形態を示す熱電変換原料粉末
が充填された金属ビュレットの断面図である。FIG. 5 is a cross-sectional view of a metal buret filled with thermoelectric conversion raw material powder according to a third embodiment of the present invention.
【図６】同上の焼結された成形体の断面図である。FIG. 6 is a cross-sectional view of the same sintered compact.
【図７】本発明の第４実施形態を示す熱電変換原料粉末
が充填された金属ビュレットの断面図である。FIG. 7 is a cross-sectional view of a metal buret filled with thermoelectric conversion raw material powder according to a fourth embodiment of the present invention.
【図８】同上の焼結された成形体の断面図である。FIG. 8 is a sectional view of the sintered compact according to the first embodiment.
【図９】従来例を示す熱電変換原料粉末が充填された金
属ビュレットの断面図である。FIG. 9 is a cross-sectional view of a metal buret filled with thermoelectric conversion raw material powder, showing a conventional example.
【図１０】同上の焼結された成形体の断面図である。FIG. 10 is a cross-sectional view of the same sintered body.
１ 熱電変換原料粉末 ２ 炭素粉末（除去手段） ２１ 炭素層（除去手段） ２２ 別の炭素層（除去手段） ３ 金属ビュレット DESCRIPTION OF SYMBOLS 1 Thermoelectric conversion raw material powder 2 Carbon powder (removal means) 21 Carbon layer (removal means) 22 Another carbon layer (removal means) 3 Metal buret
Claims (5)
含有した熱電変換原料粉末を加圧成形して成形体を形成
する成形工程と、成形体を加熱して焼結する燒結工程と
を有した熱電変換材料の製造方法において、 前記成形工程は、前記熱電変換原料粉末と結合した酸
素、又はその粉末間の酸素を燒結工程で除去する除去手
段が設けられたことを特徴とする熱電変換材料の製造方
法。1. A thermoelectric conversion method comprising: a forming step of forming a compact by pressing a thermoelectric conversion raw material powder containing at least bismuth and tellurium elements; and a sintering step of heating and sintering the compact. In the method for producing a material, a method for producing the thermoelectric conversion material, further comprising: removing means for removing oxygen bonded to the thermoelectric conversion raw material powder or oxygen between the powder in the sintering step. .
素でもって形成されたことを特徴とする請求項１記載の
熱電変換材料の製造方法。2. The method for producing a thermoelectric conversion material according to claim 1, wherein said removing means is formed of carbon reacting with said oxygen.
とともに混合され成形された０．１乃至０．５重量％の
炭素粉末でもって形成されたことを特徴とする請求項２
記載の熱電変換材料の製造方法。3. The method according to claim 2, wherein the removing means is formed of 0.1 to 0.5% by weight of carbon powder mixed and molded with the thermoelectric conversion raw material powder.
A method for producing the thermoelectric conversion material according to the above.
が内部に密閉充填された長尺状の金属ビュレットを押し
出して加圧成形するものであって、前記除去手段は金属
ビュレットの内周壁に設けられた炭素層でもって形成さ
れたことを特徴とする請求項２記載の熱電変換材料の製
造方法。4. The molding step includes extruding a long metal burette in which the thermoelectric conversion raw material powder is hermetically sealed and press-molding the metal buret, and the removing means is provided on an inner peripheral wall of the metal buret. 3. The method for producing a thermoelectric conversion material according to claim 2, wherein the method is formed with the provided carbon layer.
長手方向に対する直交方向へ沿って別の炭素層が複数設
けられるとともに、前記除去手段は前記炭素層及び別の
炭素層でもって形成されたことを特徴とする請求項４記
載の熱電変換材料の製造方法。5. In the forming step, a plurality of different carbon layers are provided along a direction perpendicular to a longitudinal direction of the metal buret, and the removing unit is formed of the carbon layer and another carbon layer. The method for producing a thermoelectric conversion material according to claim 4, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01693897A JP3617229B2 (en) | 1997-01-30 | 1997-01-30 | Method for producing thermoelectric conversion material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01693897A JP3617229B2 (en) | 1997-01-30 | 1997-01-30 | Method for producing thermoelectric conversion material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10215006A true JPH10215006A (en) | 1998-08-11 |
| JP3617229B2 JP3617229B2 (en) | 2005-02-02 |
Family
ID=11930073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01693897A Expired - Fee Related JP3617229B2 (en) | 1997-01-30 | 1997-01-30 | Method for producing thermoelectric conversion material |
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| Country | Link |
|---|---|
| JP (1) | JP3617229B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100478391B1 (en) * | 1999-06-25 | 2005-03-23 | 마츠시다 덴코 가부시키가이샤 | Method of producing sintered body of material for thermoelectric element |
-
1997
- 1997-01-30 JP JP01693897A patent/JP3617229B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100478391B1 (en) * | 1999-06-25 | 2005-03-23 | 마츠시다 덴코 가부시키가이샤 | Method of producing sintered body of material for thermoelectric element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3617229B2 (en) | 2005-02-02 |
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