JPH09214007A - Manufacturing method of thermoelectric material - Google Patents
Manufacturing method of thermoelectric materialInfo
- Publication number
- JPH09214007A JPH09214007A JP8019537A JP1953796A JPH09214007A JP H09214007 A JPH09214007 A JP H09214007A JP 8019537 A JP8019537 A JP 8019537A JP 1953796 A JP1953796 A JP 1953796A JP H09214007 A JPH09214007 A JP H09214007A
- Authority
- JP
- Japan
- Prior art keywords
- thermoelectric
- sintered product
- pressing
- temperature
- crystallization
- 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.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000003825 pressing Methods 0.000 claims abstract description 17
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 11
- 238000001816 cooling Methods 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910002909 Bi-Te Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、熱電材料の製造方法に
関し、より具体的には、ホットプレスによる粉末焼結法
の改善に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thermoelectric material, and more particularly to improvement of a powder sintering method by hot pressing.
【０００２】[0002]
【従来の技術】ビスマス、テルル等の金属間化合物半導
体である熱電材料は、従来から熱電冷却や熱電発電素子
の材料として広く使用されている。熱電材料で得られる
最適の熱電効率は、その材料の熱電性能指数によって決
まる。この性能指数は、次の式により表わされる。 Ｚ＝α2／ρκ (1／K) ・・・ ここで、αはゼーベック係数(V／K)、ρは電気抵抗(Ω・
m)、及びκは熱伝導率(W／m・K)である。この性能指数Ｚ
が大きいほど熱電効率は大きくなるため、熱電材料は大
きな性能指数を有するべきである。ところで、性能指数
は、熱電材料を構成する元素の種類や量だけでなく、熱
電材料の製造方法にも左右される。2. Description of the Related Art Thermoelectric materials, which are intermetallic compound semiconductors such as bismuth and tellurium, have been widely used as materials for thermoelectric cooling and thermoelectric power generation elements. The optimum thermoelectric efficiency obtained with a thermoelectric material depends on the thermoelectric figure of merit of the material. This figure of merit is represented by the following equation. Z = α 2 / ρκ (1 / K) ・ ・ ・ where α is Seebeck coefficient (V / K) and ρ is electrical resistance (Ω ・
m) and κ are thermal conductivity (W / m · K). This figure of merit Z
The greater the value, the greater the thermoelectric efficiency, so the thermoelectric material should have a large figure of merit. By the way, the figure of merit depends not only on the type and amount of the elements constituting the thermoelectric material but also on the manufacturing method of the thermoelectric material.
【０００３】熱電材料を製造する方法の１つとして、ホ
ットプレスによる焼結法がある。この焼結法は、所定量
の成分元素粉末を混合溶解し徐冷することにより得たイ
ンゴットを粉砕した粉末、又は各成分元素粉末を所定量
混ぜ合わせた混合粉末を、ホットプレス装置のプレス型
に入れて昇温し、同時に加圧して焼結するものである。
ホットプレスによる焼結は、熱電素子材料の種類等によ
って異なるが、一般的には、約２００〜４５０kg/cm2の
圧力、結晶化可能な温度(材料系にもよるが、例えば約
３５０〜６００oC)の条件で、約２０分以上の時間をか
けて行なわれている。このホットプレス焼結法では、溶
製法と異なり、結晶方位がランダムになって、強度的に
弱い面は殆んど形成されないから、成形加工での歩留り
低下が生じないという利点を有する。As one of the methods for producing a thermoelectric material, there is a sintering method by hot pressing. In this sintering method, a powder obtained by crushing an ingot obtained by mixing and melting a predetermined amount of component element powder and gradually cooling it, or a mixed powder obtained by mixing a predetermined amount of each component element powder is pressed by a hot press machine. The temperature is increased by placing it in a furnace, and simultaneously pressurizing and sintering.
Sintering by hot pressing varies depending on the type of thermoelectric element material, etc., but in general, a pressure of about 200 to 450 kg / cm 2 and a temperature at which crystallization is possible (depending on the material system, for example, about 350 to 600 kg). o C), it takes about 20 minutes or more. Unlike the melting method, this hot press sintering method has an advantage that the crystal orientation becomes random and almost no weak surface is formed, so that the yield in molding does not decrease.
【０００４】ところで、前記式から理解されるよう
に、熱電材料の性能指数は、電気抵抗と熱伝導率を小さ
くすることにより大きくすることができるが、一般的
に、電気抵抗の小さい物質、つまり電気電導度の大きい
物質は、熱伝導率も大きい性質があり、電気電導度と熱
伝導率とは互いに相関関係を有している。これは、電気
エネルギーのキャリヤである電子とホールが熱エネルギ
ーも運ぶためである。しかし、半導体中では、熱エネル
ギーの多くはフォノンによって運ばれるため、フォノン
を移動し難くすることにより、電気抵抗値に影響を与え
ることなく、熱伝導率だけを下げて、熱電素子材料の性
能指数を上げることが可能である。即ち、フォノンは電
子やホールとは異なり、結晶粒界で動き難くなるため、
結晶粒界を多くすることにより、熱伝導率だけを小さく
することができる。By the way, as can be understood from the above equation, the figure of merit of a thermoelectric material can be increased by decreasing the electric resistance and the thermal conductivity, but in general, a substance having a small electric resistance, that is, A substance having high electric conductivity also has a property of high thermal conductivity, and the electric conductivity and the thermal conductivity have a correlation with each other. This is because electrons and holes, which are carriers of electric energy, also carry thermal energy. However, in semiconductors, most of the thermal energy is carried by phonons, so by making it difficult for phonons to move, the thermal conductivity is lowered without affecting the electrical resistance value, and the figure of merit of thermoelectric element materials is reduced. It is possible to raise. That is, phonons, unlike electrons and holes, are hard to move at grain boundaries,
By increasing the number of crystal grain boundaries, only the thermal conductivity can be reduced.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、ホッ
トプレスによる熱電材料の製造方法において、熱伝導率
を小さくすることにより、熱電性能指数を大きくするこ
とである。SUMMARY OF THE INVENTION An object of the present invention is to increase the thermoelectric figure of merit by reducing the thermal conductivity in the method for producing a thermoelectric material by hot pressing.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に、本発明の熱電材料の製造方法においては、ホットプ
レスによる焼結を、結晶化可能な温度にて、３分以内の
短い時間内でホットプレスを行なって焼結品を作製し、
プレス後直ちに、焼結品を少なくとも結晶化の進まない
温度まで強制冷却するようにしたものである。プレス後
は、直ちに焼結品を金型から取り外し、例えば送風機に
より焼結品の強制空冷を行なう。なお、焼結品の強制冷
却方法はこれに限定されるものでなく、常温の厚肉金属
板の上に載置して金属の高熱伝導率を利用して冷却する
ことも可能である。In order to achieve the above object, in the method for producing a thermoelectric material of the present invention, sintering by hot pressing is performed at a temperature at which crystallization is possible within a short time of 3 minutes or less. Hot press to make a sintered product,
Immediately after pressing, the sintered product is forcibly cooled at least to a temperature at which crystallization does not proceed. Immediately after pressing, the sintered product is removed from the mold, and the sintered product is forcedly cooled by, for example, a blower. The method for forcibly cooling the sintered product is not limited to this, and it is also possible to place it on a thick metal plate at room temperature and cool it by utilizing the high thermal conductivity of the metal.
【０００７】特にＢｉ−Ｔｅ系の熱電素子材料では、プ
レス時間が長くなると、結晶化が進んで結晶粒が大きく
成長するため、熱伝導率が大きくなる。本発明では、結
晶粒の成長を抑制するために、プレス時間を３分以内の
短い時間に限定すると共に、プレス後の焼結品を、結晶
化の進まない温度(例えば、Ｂｉ−Ｔｅ−Ｓｅの３元系
ｎ型熱電素子の場合、約３５０℃)まで急速冷却するよ
うにしたから、焼結品の結晶粒は小さく、熱伝導率は小
さくなる。この結果、性能指数の大きな熱電素子材料を
得ることができる。Particularly in a Bi-Te type thermoelectric element material, when the pressing time becomes long, crystallization progresses and crystal grains grow large, so that the thermal conductivity becomes large. In the present invention, in order to suppress the growth of crystal grains, the pressing time is limited to a short time within 3 minutes, and the sintered product after pressing is subjected to a temperature at which crystallization does not proceed (for example, Bi-Te-Se). In the case of the ternary n-type thermoelectric element of (3), rapid cooling was performed to about 350 ° C., so the crystal grains of the sintered product are small and the thermal conductivity is small. As a result, a thermoelectric element material having a large figure of merit can be obtained.
【０００８】[0008]
【発明の実施の形態】本発明の熱電材料として、例え
ば、Ｂｉ、Ｔｅ、Ｓｅ及びＳｂからなる群から選択され
る３種又は４種の元素からなる構成を示すことができ
る。所望成分の元素を化学量論的に秤量し、これらを石
英管等に封入し、溶融し、冷却し、これにより得られた
インゴットを粉砕し、原料粉末を得る。或は、所望成分
の元素を化学量論的に秤量し、これを高エネルギー型ボ
ールミル又は転動ボールミルの中で粉砕混合したものを
原料粉末とすることもできる。BEST MODE FOR CARRYING OUT THE INVENTION As the thermoelectric material of the present invention, for example, a structure composed of three or four elements selected from the group consisting of Bi, Te, Se and Sb can be shown. The elements of the desired components are stoichiometrically weighed, sealed in a quartz tube or the like, melted and cooled, and the ingot thus obtained is crushed to obtain a raw material powder. Alternatively, the raw material powder can be obtained by weighing the elements of the desired components stoichiometrically and pulverizing and mixing them in a high energy type ball mill or a rolling ball mill.
【０００９】前記構成の原料粉末は、ホットプレスで加
圧焼結する。ホットプレスでの加圧焼結は、結晶化可能
な４００〜５５０℃の温度で、３分以内の短い時間内で
行なう。プレス時間を３分以内に規定するのは、結晶粒
の成長をできるだけ抑制するためである。短時間の加圧
焼結で十分緻密な焼結体を得るために、圧力は１０００
kg/cm2以上の高圧にする必要がある。なお、プレス時間
を短縮して緻密な焼結体を得るために、圧力は金型等の
強度面に支障をきたさない範囲内でより高圧にすること
が好ましく、２０００kg/cm2以上がより望ましく、３０
００kg/cm2以上がさらに望ましい。プレス時間の下限
は、一般的には、緻密な焼結体を得るのに必要な時間と
して設定されるもので、原料粉末の種類、プレス温度、
プレス圧力等の条件により異なるが、一般的には約２０
秒以上の時間が選択されが、緻密な焼結体を得られる限
り、約２０秒よりも短い時間に設定できることは勿論で
ある。ホットプレスは、真空中、又はＡｒガス、窒素ガ
ス等の不活性ガス雰囲気、又はＨ2、ＣＯ等の還元性ガ
スを含んだ雰囲気の中で行なうことが好ましいが、これ
に限定されることはなく、高圧条件で短時間で焼結が完
了するから、大気雰囲気下で行なっても所望の効果を得
ることができる。The raw material powder having the above structure is pressure-sintered by hot pressing. The pressure sintering by hot pressing is performed at a temperature of 400 to 550 ° C. at which crystallization is possible and within a short time of 3 minutes or less. The pressing time is defined within 3 minutes in order to suppress the growth of crystal grains as much as possible. In order to obtain a sufficiently dense sintered body by pressure sintering for a short time, the pressure is 1000
It is necessary to have a high pressure of kg / cm 2 or more. In order to shorten the pressing time and obtain a dense sintered body, the pressure is preferably higher within the range that does not hinder the strength of the mold or the like, and more preferably 2000 kg / cm 2 or more. , 30
00 kg / cm 2 or more is more desirable. The lower limit of the pressing time is generally set as the time required to obtain a dense sintered body, the type of raw material powder, the pressing temperature,
It depends on the conditions such as press pressure, but generally about 20
Although a time of more than a second is selected, it goes without saying that a time shorter than about 20 seconds can be set as long as a dense sintered body can be obtained. The hot pressing is preferably performed in a vacuum, an atmosphere of an inert gas such as Ar gas or nitrogen gas, or an atmosphere containing a reducing gas such as H 2 or CO, but is not limited thereto. Since the sintering is completed under a high pressure condition in a short time, the desired effect can be obtained even in the atmosphere.
【００１０】[0010]
【実施例】標準的なｎ型熱電素子である(Ｂｉ2Ｔｅ3)
0.85(Ｂｉ2Ｓｅ3)0.15の組成となるように、Ｂｉ、Ｔｅ
及びＳｅの元素粉末を化学量論的に秤量し、これらをボ
ールミルの中で粉砕混合し、平均粒径約５μmの原料粉
末を得た。原料粉末を、プレス用金型の中に充填し、予
め５５０℃に加熱してある金型加熱炉に入れ、５００℃
になった時に３０００kg/cm2の圧力で焼結した後、焼結
品を金型から速やかに取り出し、金属作業台の上に載せ
て送風機により強制冷却し、熱電材料を作製した。な
お、ホットプレスは大気雰囲気中で行ない、ホットプレ
スのプレス時間と、得られた熱電材料の密度比、ホール
移動度及び物性値を表１に示す。表１中、供試No.１は
プレス時間が短い比較例、供試No.２〜No.４は本発明の
実施例、供試No.５はプレス時間が本発明の規定より長
い比較例である。EXAMPLE A standard n-type thermoelectric element (Bi 2 Te 3 ).
Bi, Te so that the composition is 0.85 (Bi 2 Se 3 ) 0.15.
And Se elemental powders were stoichiometrically weighed and pulverized and mixed in a ball mill to obtain a raw material powder having an average particle size of about 5 μm. The raw material powder is filled in a press die and placed in a die heating furnace which has been preheated to 550 ° C. to 500 ° C.
Then, after sintering at a pressure of 3000 kg / cm 2 , the sintered product was quickly taken out of the mold, placed on a metal workbench, and forcibly cooled by a blower to prepare a thermoelectric material. The hot pressing was carried out in the atmosphere, and the pressing time of the hot pressing, the density ratio, the hole mobility and the physical property values of the obtained thermoelectric material are shown in Table 1. In Table 1, sample No. 1 is a comparative example with a short press time, sample Nos. 2 to 4 are examples of the present invention, and sample No. 5 is a comparative example with a press time longer than the regulation of the present invention. Is.
【００１１】[0011]
【表１】 [Table 1]
【００１２】No.１の比較例は、密度比が８９.６％と低
く、十分に焼結が進んでいないことを示している。これ
に対し、No.２〜No.５は、密度比が約９９％以上と高
く、十分緻密な焼結体であるといえる。なお、密度比と
は、完全緻密体の密度に対する成形品の密度の比を表わ
すもので、焼結品の密度はアルキメデス法により測定し
た。The comparative example of No. 1 has a low density ratio of 89.6%, indicating that sintering has not progressed sufficiently. On the other hand, No. 2 to No. 5 have a high density ratio of about 99% or more, and can be said to be sufficiently dense sintered bodies. The density ratio represents the ratio of the density of the molded product to the density of the perfect dense body, and the density of the sintered product was measured by the Archimedes method.
【００１３】ホール移動度をみると、No.１の比較例
は、No.２〜No.５と比べて値が小さく、.熱電性能に劣
ることを示している。ホール移動度とは、単位電圧・時
間当たりに電子又はホールが移動する距離を表わす指標
で、熱電性能と相関関係があり、ホール移動度が大きい
ほど、熱電性能がすぐれることを示している。即ち、N
o.１は、No.２〜No.５と比べて結晶化温度以上でのプレ
ス時間が極端に短いため、結晶化が十分に進んでいない
ものと推察される。Regarding the hole mobility, the comparative example of No. 1 has a smaller value than No. 2 to No. 5, indicating that the thermoelectric performance is inferior. The hole mobility is an index representing the distance traveled by an electron or hole per unit voltage / time, and has a correlation with the thermoelectric performance. The higher the hole mobility, the better the thermoelectric performance. That is, N
In No. 1 to No. 2, since the pressing time at the crystallization temperature or more is extremely shorter than No. 2 to No. 5, it is presumed that the crystallization is not sufficiently advanced.
【００１４】次に、熱伝導率をみると、No.５の比較例
は、No.１〜No.４と比べて値が大きく、結果として性能
指数が小さくなっている。この理由は、No.５は、No.１
〜No.４よりもプレス時間が遥かに長く、結晶粒の成長
がより進んだために、熱伝導率が大きくなったと推察さ
れる。Looking at the thermal conductivity, the comparative example of No. 5 has a larger value than No. 1 to No. 4, and as a result, the figure of merit is small. The reason is that No. 5 is No. 1
It is presumed that the thermal conductivity was high because the pressing time was much longer than in No. 4 and the growth of crystal grains was more advanced.
【００１５】[0015]
【発明の効果】本発明の製造方法によれば、従来のホッ
トプレスの処理時間に比べて、遥かに短い時間で高密度
の焼結品が得られ、焼結品はプレス後急速に冷却される
から、スループットが早く生産能率の向上を達成でき
る。しかも、短いプレス時間で焼結を完了するため、結
晶粒が小さく、結晶の方向依存性の殆んどない均質な熱
電素子材料が得られる。従って、その後の成形加工では
ダイスの方向を揃える必要もなく、組立て工程での作業
効率が向上する等、すぐれた効果を有するものである。
本発明は、ごみ焼却炉や工場廃熱による熱電発電、レジ
ャークーラーや簡易冷蔵庫での熱電冷却などに使用され
る熱電材料の製造方法としてその産業上の利用価値は大
きい。According to the manufacturing method of the present invention, a high density sintered product can be obtained in a much shorter time than the processing time of the conventional hot press, and the sintered product is cooled rapidly after pressing. Therefore, the throughput is fast and the production efficiency can be improved. Moreover, since the sintering is completed in a short pressing time, it is possible to obtain a homogeneous thermoelectric element material having a small crystal grain and almost no crystal direction dependency. Therefore, in the subsequent molding process, it is not necessary to align the dice directions, and the working efficiency in the assembling process is improved, which is an excellent effect.
INDUSTRIAL APPLICABILITY The present invention has a great industrial utility value as a method for producing a thermoelectric material used for thermoelectric power generation using a waste incinerator or waste heat from a factory, thermoelectric cooling in a leisure cooler or a simple refrigerator, and the like.
Claims (1)
圧焼結する熱電材料の製造方法において、結晶化可能な
温度にて、３分以内の時間内でホットプレスを行ない、
プレス後直ちに、焼結品を少なくとも結晶化の進まない
温度まで強制冷却することを特徴とする熱電材料の製造
方法。1. In a method for producing a thermoelectric material in which a raw material metal powder is pressure-sintered by hot pressing, hot pressing is performed at a crystallizable temperature within 3 minutes.
A method for producing a thermoelectric material, characterized in that, immediately after pressing, the sintered product is forcibly cooled at least to a temperature at which crystallization does not proceed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8019537A JPH09214007A (en) | 1996-02-06 | 1996-02-06 | Manufacturing method of thermoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8019537A JPH09214007A (en) | 1996-02-06 | 1996-02-06 | Manufacturing method of thermoelectric material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09214007A true JPH09214007A (en) | 1997-08-15 |
Family
ID=12002081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8019537A Withdrawn JPH09214007A (en) | 1996-02-06 | 1996-02-06 | Manufacturing method of thermoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09214007A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8035026B2 (en) | 2003-08-26 | 2011-10-11 | Kyocera Corporation | Thermoelectric material, thermoelectric element, thermoelectric module and methods for manufacturing the same |
-
1996
- 1996-02-06 JP JP8019537A patent/JPH09214007A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8035026B2 (en) | 2003-08-26 | 2011-10-11 | Kyocera Corporation | Thermoelectric material, thermoelectric element, thermoelectric module and methods for manufacturing the same |
| US8519256B2 (en) | 2003-08-26 | 2013-08-27 | Kyocera Corporation | Thermoelectric material, thermoelectric element, thermoelectric module and method for manufacturing the same |
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