JPH0227779A - Manufacture of thermoelectric element - Google Patents
Manufacture of thermoelectric elementInfo
- Publication number
- JPH0227779A JPH0227779A JP63177796A JP17779688A JPH0227779A JP H0227779 A JPH0227779 A JP H0227779A JP 63177796 A JP63177796 A JP 63177796A JP 17779688 A JP17779688 A JP 17779688A JP H0227779 A JPH0227779 A JP H0227779A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- thermoelectric element
- metal
- particle size
- thermoelectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 23
- 238000000465 moulding Methods 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 9
- 239000011882 ultra-fine particle Substances 0.000 abstract description 23
- 238000002156 mixing Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- -1 silicide compound Chemical class 0.000 abstract description 2
- 229910021332 silicide Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- BFMKFCLXZSUVPI-UHFFFAOYSA-N ethyl but-3-enoate Chemical compound CCOC(=O)CC=C BFMKFCLXZSUVPI-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005933 Ge—P Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、熱電素子の製造法に関し、詳しくは原料であ
る金属、金属合金もしくはセラミックスの粒径を制御す
ることにより、熱電特性の優れた熱電素子（熱電変換素
子）を効率よく製造する方法に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for manufacturing a thermoelectric element, and more specifically, the present invention relates to a method for manufacturing a thermoelectric element, and more specifically, a method for manufacturing a thermoelectric element that has excellent thermoelectric properties by controlling the particle size of a metal, metal alloy, or ceramic that is a raw material. The present invention relates to a method for efficiently manufacturing a thermoelectric element (thermoelectric conversion element).
〔従来の技術及び発明が解決しようとする課題〕近年、
ゼーベック効果を利用して熱電発電を行わせる熱電素子
は、種々の分野において実用化が期待されており、この
熱電素子を製造する方法として各種の手段が提案されて
いる。代表的な方法としては、機械的に粉砕された金属
、金属合金もしくはセラミックスの粉末を原料として、
これをプレス等により圧縮して成形し、焼結させた後に
熱処理を行い、所定の形状の熱電素子とする製造方法が
挙げられる。[Problems to be solved by conventional techniques and inventions] In recent years,
Thermoelectric elements that generate thermoelectric power using the Seebeck effect are expected to be put to practical use in various fields, and various means have been proposed as methods for manufacturing these thermoelectric elements. A typical method is to use mechanically crushed metal, metal alloy, or ceramic powder as a raw material.
An example of a manufacturing method is to compress and mold this using a press or the like, sinter it, and then heat treat it to produce a thermoelectric element in a predetermined shape.
しかしながら、この従来の製造方法で得られる熱電素子
の熱起電力は、未だ充分なものではなく、より熱起電力
の優れた熱電素子の開発が望まれている。However, the thermoelectromotive force of the thermoelectric element obtained by this conventional manufacturing method is still not sufficient, and there is a desire to develop a thermoelectric element with even better thermoelectromotive force.
さらに、上記粉末の粒径が大きく、不定形粒子であるた
め、成形後の焼結密度が向上しないことや、粒界制御が
困難である等の問題もあった。Furthermore, since the above-mentioned powder has a large particle size and is an amorphous particle, there are also problems such as not improving the sintered density after molding and difficulty in grain boundary control.
そこで本発明者らは、熱起電力や熱伝導度等の熱雷特性
に優れた熱電素子を開発すべく研究を重ねた。Therefore, the present inventors conducted repeated research in order to develop a thermoelectric element with excellent thermal lightning characteristics such as thermoelectromotive force and thermal conductivity.
その結果、熱電素子の原料として粒径の異なる金属、金
属合金もしくはセラミックスの粉末を混合して用いるこ
とにより、得られる熱電素子の熱電特性が向上すること
を見出した。As a result, it has been found that by mixing powders of metals, metal alloys, or ceramics with different particle sizes as raw materials for thermoelectric elements, the thermoelectric properties of the resulting thermoelectric elements are improved.
本発明はかかる知見に基いて完成したものである。The present invention was completed based on this knowledge.
すなわち本発明は、原料である金属、金属合金もしくは
セラミックスの粉末を成形し、次いで焼結させて熱電素
子を製造するにあたり、原料として、平均粒径１００〜
３０００人の粉末と、平均粒径１〜５μｍの粉末とを混
合した金属、金属合金もしくはセラミックスの混合粉末
を用いることを特徴とする熱電素子の製造法を提供すも
のである。That is, in the present invention, when producing a thermoelectric element by molding and then sintering a powder of metal, metal alloy, or ceramic as a raw material, the average particle size of the raw material is 100 to 100.
The present invention provides a method for manufacturing a thermoelectric element characterized by using a mixed powder of metal, metal alloy, or ceramics, which is a mixture of powder of 3,000 particles and powder with an average particle size of 1 to 5 μm.
上記熱電素子の原料となる金属、金属合金もしくはセラ
ミックスの種類としては、従来から熱電素子の材料とし
て用いられている各種のものを用いることができる。代
表的なものとしては、Ｆｅ５ｉｚ、ＦｅＳｉｚ−Ｃｏ−
Ｍｎ−Ｃｒ。As for the metal, metal alloy, or ceramic used as the raw material for the thermoelectric element, various kinds of materials that have been conventionally used as materials for thermoelectric elements can be used. Typical examples include Fe5iz, FeSiz-Co-
Mn-Cr.
５ｉ−Ｇｅ−ＧａＰ、５１−Ｇｅ−Ｍｇ、５ｉ−Ｇｅ−
Ｂ。5i-Ge-GaP, 51-Ge-Mg, 5i-Ge-
B.
５ｉ−Ｇｅ−Ｐ、ＳｉＣ等を挙げることができ、特にＦ
ｅｌ−ｘＭｎＸＳｉｚ（ｘ＝ｏ〜ｏ、１５）＋Ｆｅ１−
ｙＣｏｙＳｉ２（ｙ＝０〜０．０１）等のシリサイド化
合物が好ましい。5i-Ge-P, SiC, etc., especially F
el-xMnXSiz(x=o~o, 15)+Fe1-
Silicide compounds such as yCoySi2 (y=0 to 0.01) are preferred.
本発明においては、これらの金属、金属合金もしくはセ
ラミックスとして、平均粒径が１００〜３０００人、好
ましくは、５００〜２０００人の超微粒子状の粉末（以
下、単に超微粒子という）と、平均粒径が１〜５μｍ、
好ましくは２〜３μｍの粉末（以下、単に粉末という）
の二種類が用いられる。In the present invention, as these metals, metal alloys, or ceramics, ultrafine powder with an average particle size of 100 to 3000 particles, preferably 500 to 2000 particles (hereinafter simply referred to as ultrafine particles), and is 1 to 5 μm,
Preferably a powder of 2 to 3 μm (hereinafter simply referred to as powder)
Two types are used:
上記金属、金属合金もしくはセラミックスを超微粒子と
するには、各種方法があるが、従来から用いられている
プラズマ法を用いることができる。There are various methods for making the metal, metal alloy, or ceramic into ultrafine particles, and a conventional plasma method can be used.
このプラズマ法としては、高周波プラズマ法あるいはア
ークプラズマジェット法、ハイブリットプラズマ法等を
用いることができ、これらの方法によって、上記各種の
金属合金もしくはセラミックスの合成と同時に、これら
の超微粒子を容易に得ることができる。As this plasma method, a high frequency plasma method, an arc plasma jet method, a hybrid plasma method, etc. can be used, and by these methods, these ultrafine particles can be easily obtained at the same time as the synthesis of the various metal alloys or ceramics mentioned above. be able to.
一方、金属、金属合金もしくはセラミックスを粉末とす
るには、アトマイズ法、液体急冷法、ジェットミル、ボ
ールミル、スタンプミル等の従来からの一般的に行われ
ている機械的粉砕により行うことができる。On the other hand, metals, metal alloys, or ceramics can be made into powder by conventional mechanical pulverization such as an atomization method, a liquid quenching method, a jet mill, a ball mill, or a stamp mill.
本発明の製造法では、上記熱電素子の原料となる金属、
金属合金もしくはセラミックスの超微粒子と粉末とを混
合した後に成形を行う。In the manufacturing method of the present invention, a metal serving as a raw material for the thermoelectric element,
After mixing ultrafine metal alloy or ceramic particles and powder, molding is performed.
超微粒子と粉末との混合割合は、特に制限はないが、一
般には粉末９７〜５０重量％、超微粒子３〜５０重量％
、好ましくは粉末９５〜６０重量％、超微粒子５〜４０
重量％の範囲で選定する。The mixing ratio of ultrafine particles and powder is not particularly limited, but generally powder is 97 to 50% by weight and ultrafine particles is 3 to 50% by weight.
, preferably 95-60% by weight of powder, 5-40% of ultrafine particles
Select within the weight% range.
この混合割合は、原料の種類やそれぞれの粒径あるいは
成形圧力や成形形状等により適宜最適な範囲で選定すれ
ばよい。This mixing ratio may be appropriately selected within an optimal range depending on the type of raw materials, their respective particle sizes, molding pressure, molding shape, etc.
超微粒子と粉末との混合は、各種方法で行うことができ
るが、物理的な撹拌では充分に混合させことが困難であ
るため、分散剤やバインダー、超音波等を用いて両者を
充分に混合することが好ましい。例えば、両者をボール
ミル等の撹拌装置で適当に混合させた後に、この混合粉
をポリビニルアルコール、エチルビニルアセテート、ス
テアリン酸、コロイド状パラフィン（油脂）、パラホル
ムアルデヒド等の水溶液中に分散させてゲル・ゾル状と
し、超音波をかけながら加熱して水分を蒸発させ、顆粒
状に造粒することによって、超微粒子と粉末とを充分な
じませることができる。Ultrafine particles and powder can be mixed using various methods, but it is difficult to mix them sufficiently with physical stirring, so it is necessary to mix them thoroughly using a dispersant, binder, ultrasound, etc. It is preferable to do so. For example, after properly mixing the two with a stirring device such as a ball mill, this mixed powder is dispersed in an aqueous solution of polyvinyl alcohol, ethyl vinyl acetate, stearic acid, colloidal paraffin (oil), paraformaldehyde, etc. to form a gel. The ultrafine particles and powder can be sufficiently blended by forming the material into a sol, heating it while applying ultrasonic waves to evaporate moisture, and granulating it into granules.
このように超微粒子と粉末とを混合させることにより、
成形時に粉末の各粒子間に生じる僅かな隙間に超微粒子
が充填されることとなり、粒界あるいは粒成長を制御す
ることができる。その結果、焼結密度が増加するととも
に隙間が低減するので、緻密な焼結体を得ることができ
、熱伝導度が低下して、得られる熱電素子の熱電特性を
向上させることができる。By mixing ultrafine particles and powder in this way,
Ultrafine particles are filled into the small gaps created between each particle of powder during compaction, making it possible to control grain boundaries or grain growth. As a result, the sintered density increases and the gaps decrease, so a dense sintered body can be obtained, the thermal conductivity decreases, and the thermoelectric properties of the resulting thermoelectric element can be improved.
本発明の製造法では、上記の如く超微粒子と粉末とを混
合した混合粉末に対して、以下の通常の手法により成形
、焼結、さらには熱処理を必要に応じて行えばよい。In the manufacturing method of the present invention, the mixed powder obtained by mixing ultrafine particles and powder as described above may be subjected to molding, sintering, and further heat treatment as necessary by the following conventional methods.
即ち、この成形工程、焼結工程あるいはその後の熱処理
工程は、従来の熱電素子の製造法における各工程と同様
に行うことができる。That is, the molding step, the sintering step, or the subsequent heat treatment step can be performed in the same manner as each step in the conventional thermoelectric element manufacturing method.
例えば成形は、プレス成形機を使用して数百ｋｇ乃至数
ｔ／ｃ−の圧力で圧縮することにより行うことができる
。また焼結は、得られた成形体を８００〜１５００°Ｃ
の高温に数時間加熱することにより行うことができる。For example, the molding can be performed by compressing using a press molding machine at a pressure of several hundred kg to several tons/c-. In addition, sintering is performed at a temperature of 800 to 1500°C.
This can be done by heating to a high temperature for several hours.
さらに熱処理は、必要に応じて成形、焼結後の成形体を
５００〜１０００°Ｃの温度で数時間加熱することによ
り行なわれる。これらの処理は、原料となる金属、金属
合金もしくはセラミックスの種類や形状等により最適な
条件に設定して行うものであり、特に限定されるもので
はない。Further, heat treatment is carried out, if necessary, by heating the molded body after molding and sintering at a temperature of 500 to 1000°C for several hours. These treatments are performed under optimal conditions depending on the type and shape of the metal, metal alloy, or ceramic used as the raw material, and are not particularly limited.
次に、本発明を実施例および比較例に基いてさらに詳し
く説明する。Next, the present invention will be explained in more detail based on Examples and Comparative Examples.
実施例１
まず原料としてのＦｅｏ、ｑｚＭｎｏ、ｏｓＳｉｚ、ｏ
ｏを、高周波によるプラズマ法により平均粒径が約５０
０人の超微粒子に形成するとともに、所定量のＦｅ。Example 1 First, Feo, qzMno, osSiz, o as raw materials
o with an average particle size of about 50 by plasma method using high frequency.
0 ultrafine particles and a predetermined amount of Fe.
Ｓｔ及びドーパントとしてのＭｎの単体を高周波で溶解
させた後に徐冷し、得られたインゴットをスライスし、
次いでスタンプミルで粉砕して平均粒径を２〜３μｍと
した不定形粒子（粉末）を製造（溶製粉末冶金法）、こ
れを超微粒子２０重量％。St and Mn as a dopant are dissolved by high frequency, then slowly cooled, and the resulting ingot is sliced.
Next, amorphous particles (powder) with an average particle size of 2 to 3 μm were produced by crushing with a stamp mill (smelting powder metallurgy method), and 20% by weight of these were ultrafine particles.
粉末８０重量％の割合で混合した。The powder was mixed at a ratio of 80% by weight.
この混合は、ボールミルを用いて４００ ｒｐｍで１時
間予備混合し、得られた混合粉末に１重量％のＰＶＡ（
ポリビニルアルコール、分子１１５００以下）を水溶液
として添加してゾル・ゲル状とした。This mixture was premixed using a ball mill at 400 rpm for 1 hour, and 1% by weight of PVA (
Polyvinyl alcohol (molecular 11,500 or less) was added as an aqueous solution to form a sol/gel.
これに超音波をかけながら加熱して、水分を１０〜２０
ｗｔ％、平均粒径０．５＋ｎｍの顆粒に造粒した。Heat this while applying ultrasonic waves to reduce the moisture by 10 to 20%.
It was granulated into granules with wt% and average particle size of 0.5+nm.
さらに、この顆粒状の混合粉末をプレス成形機で２Ｌ／
ｃ＋１の圧力で成形し、これを真空中で１１５０°Ｃで
３時間加熱焼結し、さらに８００°Ｃで３０時間処理を
行い熱電素子を製造し、この熱電素子の熱電特性を測定
した。その結果を表１に示す。Furthermore, this granular mixed powder was processed into a press molding machine at 2L/
It was molded at a pressure of c+1, heated and sintered in vacuum at 1150°C for 3 hours, and further treated at 800°C for 30 hours to produce a thermoelectric element, and the thermoelectric properties of this thermoelectric element were measured. The results are shown in Table 1.
比較例１
原料として実施例１と同じ手段で製造した平均粒径が２
〜３ｕｍの粉末のみを用いた以外は、実施例１と同様の
操作を行って熱電素子を製造し、同様に熱電特性を測定
した。その結果を同様に表１に示す。Comparative Example 1 An average particle size of 2 was produced using the same method as in Example 1 as a raw material.
A thermoelectric element was manufactured in the same manner as in Example 1, except that only powder of ~3 um was used, and the thermoelectric properties were measured in the same manner. The results are also shown in Table 1.
実施例２
原料としてＦ ｅｏ、 ＊ｔＭｎｏ、 ｏ：＋ Ｓ ｉ
ｔ、 ｏｏを用い、超微粒子、粉末共に実施例１と同様
の手順で得たものを実施例１と同様の混合、成形、焼結
、熱処理操作を行って熱電素子を製造し、同様に熱電特
性を測定した。その結果を同様に表１に示す。Example 2 Feo, *tMno, o:+S i as raw materials
Using ultrafine particles and powder obtained in the same manner as in Example 1, a thermoelectric element was manufactured by performing the same mixing, molding, sintering, and heat treatment operations as in Example 1. Characteristics were measured. The results are also shown in Table 1.
比較例２
実施例２において、原料として粉末のみを用いた以外は
実施例２と同様の操作を行って熱電素子を製造し、同様
に熱電特性を測定した。その結果を同様に表１に示す。Comparative Example 2 In Example 2, a thermoelectric element was manufactured in the same manner as in Example 2 except that only powder was used as the raw material, and the thermoelectric properties were measured in the same manner. The results are also shown in Table 1.
実施例３
原料としてＳｉＣを用い、これを高周波によるプラズマ
法により平均粒径を２０００人の超微粒子としたものと
、既知の方法により製造された平均粒径２〜３μｍの不
定形の粉末としたものを、超微粒子２５重量％、粉末７
５重量％の割合で混合した。Example 3 Using SiC as a raw material, it was made into ultrafine particles with an average particle size of 2000 particles by a plasma method using high frequency, and an irregularly shaped powder with an average particle size of 2 to 3 μm manufactured by a known method. 25% by weight of ultrafine particles, powder 7
They were mixed at a ratio of 5% by weight.
この混合は、ボールミルを用いて２０ Ｏｒｐｍで２時
間予備混合し、得られた混合粉末に５重量％のＥＶＡ（
エチルビニルアセテート）を水溶液として添加してゾル
・ゲル状とした。This mixture was premixed for 2 hours at 20 Orpm using a ball mill, and 5% by weight of EVA (
Ethyl vinyl acetate) was added as an aqueous solution to form a sol/gel.
これに超音波をかけながら加熱して、水分を５〜１５ｗ
ｔ％、平均粒径０．５ｍｍの顆粒に造粒した。Heat this while applying ultrasonic waves to remove 5 to 15w of moisture.
t%, and granulated into granules with an average particle size of 0.5 mm.
さらに、この顆粒状の混合粉末をプレス成形機で５．４
ｔ／ｃ＋１の圧力にて成形し、これを真空中で１９００
°Ｃ，１００時間焼結処理を行い、熱電素子を製造した
。Furthermore, this granular mixed powder was molded into a press molding machine with 5.4
Molded at a pressure of t/c+1 and then heated at 1900 m
A thermoelectric element was manufactured by performing sintering treatment at °C for 100 hours.
この熱電素子の熱電特性を測定した結果を表１に示す。Table 1 shows the results of measuring the thermoelectric properties of this thermoelectric element.
比較例３
実施例３において、原料として粉末のみを用いた以外は
、実施例３と同様の操作を行って熱電素子を製造し、同
様に熱電特性を測定した。その結果を同様に表１に示す
。Comparative Example 3 In Example 3, a thermoelectric element was manufactured in the same manner as in Example 3, except that only powder was used as the raw material, and the thermoelectric properties were measured in the same manner. The results are also shown in Table 1.
実施例４
原料として５ｉＧｅを用い、超微粒子、粉末共に実施例
３と同様の半順で得たものを、実施例３と同様に混合、
成形した後１１００°Ｃで１００時間焼結処理を行って
熱電素子を製造し、同様に熱電特性を測定した。その結
果を同様に表１に示す。Example 4 Using 5iGe as a raw material, ultrafine particles and powder were obtained in the same half-order as in Example 3, and mixed in the same manner as in Example 3.
After molding, a thermoelectric element was manufactured by performing a sintering treatment at 1100°C for 100 hours, and its thermoelectric properties were similarly measured. The results are also shown in Table 1.
比較例４
実施例４において、原料として粉末のみを用いた以外は
、実施例４と同様の操作を行って熱電素子を製造し、同
様に熱電特性を測定した。その結果を同様に表１に示す
。Comparative Example 4 A thermoelectric element was manufactured in the same manner as in Example 4, except that only powder was used as the raw material, and the thermoelectric properties were measured in the same manner. The results are also shown in Table 1.
実施例５
原料としてＢ、Ｃを用い、これを高周波によるプラズマ
法により平均粒径を１１００Ａの超微粒子としたものと
、既知の方法により製造された平均粒径を２〜４μｍの
不定形の粉末としたものを、超微粒子１０重量％、粉末
９０重量％の割合で混合した。Example 5 Using B and C as raw materials, ultrafine particles with an average particle size of 1100A were made by high frequency plasma method, and irregularly shaped powder with an average particle size of 2 to 4 μm manufactured by a known method. These were mixed in a ratio of 10% by weight of ultrafine particles and 90% by weight of powder.
この混合は、ボールミルを用いて３００ ｒｐｍで２時
間予備混合し、得られた混合粉末に１．０重量％のＰＶ
Ａを水溶液として添加してゾル・ゲル状とした。This mixture was premixed using a ball mill at 300 rpm for 2 hours, and 1.0% by weight of PV was added to the resulting mixed powder.
A was added as an aqueous solution to form a sol/gel.
これに超音波をかけながら加熱して、水分を１０重量％
、平均粒径０．３〜０．４順の顆粒に造粒した。Heat this while applying ultrasound to reduce the water content to 10% by weight.
, and granulated into granules with an average particle size of 0.3 to 0.4.
さらに、この顆粒状の混合粉末をプレス成形機で６ ｔ
／ ｃｄの圧力で成形し、これを真空中で１４００°
Ｃで５０時間焼結処理を行い、熱電素子を製造した。Furthermore, this granular mixed powder was molded into 6 tons using a press molding machine.
/ cd pressure and then heated at 1400° in vacuum.
A thermoelectric element was manufactured by performing sintering treatment at C for 50 hours.
この熱電素子の熱電特性を測定した結果を表１に示す。Table 1 shows the results of measuring the thermoelectric properties of this thermoelectric element.
比較例５
実施例５において、原料として粉末のみを用いた以外は
、実施例５と同様の操作を行って熱電素子を製造し、同
様に熱電特性を測定した。その結果を同様に表１に示す
。Comparative Example 5 A thermoelectric element was manufactured in the same manner as in Example 5, except that only powder was used as the raw material, and the thermoelectric properties were measured in the same manner. The results are also shown in Table 1.
実施例６
実施例１において、混合割合を超微粒子５重量％、粉末
９５！を量％とした以外は、実施例１と同様の操作を行
って熱電素子を製造し、同様に熱電特性を測定した。そ
の結果を同様に表１に示す。Example 6 In Example 1, the mixing ratio was 5% by weight of ultrafine particles and 95% of powder! A thermoelectric element was manufactured by performing the same operation as in Example 1, except that the amount was expressed as %, and the thermoelectric properties were measured in the same manner. The results are also shown in Table 1.
実施例７
実施例１において、混合割合を超微粒子９１重量％、粉
末９重量％とじた以外は、実施例１と同様の操作を行っ
て熱電素子を製造し、同様に熱電特性を測定した。その
結果を同様に表１に示す。Example 7 A thermoelectric element was manufactured in the same manner as in Example 1, except that the mixing ratio was 91% by weight of ultrafine particles and 9% by weight of powder, and the thermoelectric properties were measured in the same manner. The results are also shown in Table 1.
（以下余白）
［発明の効果］
上述の如く、本発明の製造法によれば、原料として平均
粒径が１００〜３０００人の超微粒子状の粉末と、粒径
が１〜５μｍの粉末とを混合してなる金属、金属合金も
しくはセラミックスの混合粉末を用いることにより、得
られる熱電素子の熱電特性の向上を図ることができる。(The following is a blank space) [Effects of the invention] As described above, according to the production method of the present invention, ultrafine powder with an average particle size of 100 to 3000 particles and powder with a particle size of 1 to 5 μm are used as raw materials. By using a mixed powder of metals, metal alloys, or ceramics, it is possible to improve the thermoelectric properties of the resulting thermoelectric element.
さらに原料の全てを製造コストのかかるプラズマ法によ
る超微粒子としたものに比べて製造コストを低減するこ
とができ、熱電特性の優れた熱電素子を安価に提供する
ことが可能となる。Further, the manufacturing cost can be reduced compared to the case where all the raw materials are made into ultrafine particles by the plasma method, which is expensive to manufacture, and it becomes possible to provide a thermoelectric element with excellent thermoelectric properties at a low cost.
従って、本発明によって得られる熱電素子は、各種の分
野において幅広くかつ有効な利用が期待される。Therefore, the thermoelectric element obtained by the present invention is expected to be widely and effectively utilized in various fields.
特許出願人 出光石油化学株式会社 代理人 弁理士 大 谷 保Patent applicant: Idemitsu Petrochemical Co., Ltd. Agent: Patent Attorney Tamotsu Otani
Claims (2)
の粉末を成形し、次いで焼結させて熱電素子を製造する
にあたり、原料として、平均粒径１００〜３０００Åの
粉末と、平均粒径１〜５μｍの粉末とを混合した金属，
金属合金もしくはセラミックスの混合粉末を用いること
を特徴とする熱電素子の製造法。(1) When producing a thermoelectric element by molding and sintering raw material metal, metal alloy, or ceramic powder, the raw materials are powders with an average particle size of 100 to 3000 Å and powders with an average particle size of 1 to 5 μm. metal mixed with powder,
A method for manufacturing a thermoelectric element characterized by using a mixed powder of metal alloy or ceramics.
平均粒径１００〜３０００Åの粉末３〜５０重量％の割
合で混合してなる請求項１記載の製造法。(2) The manufacturing method according to claim 1, wherein 97 to 50% by weight of powder having an average particle size of 1 to 5 μm and 3 to 50% by weight of powder having an average particle size of 100 to 3000 Å are mixed.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63177796A JPH0227779A (en) | 1988-07-15 | 1988-07-15 | Manufacture of thermoelectric element |
| EP93114246A EP0583795A1 (en) | 1988-03-30 | 1989-03-18 | Method for producing thermoelectric elements |
| EP89104908A EP0335213A3 (en) | 1988-03-30 | 1989-03-18 | Method for producing thermoelectric elements |
| US07/327,592 US4992235A (en) | 1988-03-30 | 1989-03-23 | Method for producing thermoelectric elements |
| KR1019890004151A KR890015436A (en) | 1988-03-30 | 1989-03-30 | Manufacturing method of thermoelectric element |
| US07/619,339 US5069868A (en) | 1988-03-30 | 1990-11-29 | Method for producing thermoelectric elements |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63177796A JPH0227779A (en) | 1988-07-15 | 1988-07-15 | Manufacture of thermoelectric element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0227779A true JPH0227779A (en) | 1990-01-30 |
Family
ID=16037241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63177796A Pending JPH0227779A (en) | 1988-03-30 | 1988-07-15 | Manufacture of thermoelectric element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0227779A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010245089A (en) * | 2009-04-01 | 2010-10-28 | Swcc Showa Cable Systems Co Ltd | Method for manufacturing thermoelectric conversion element |
| JP2025030231A (en) * | 2023-08-23 | 2025-03-07 | 国立大学法人島根大学 | Thermoelectric material and method for producing thermoelectric material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6221750A (en) * | 1985-07-18 | 1987-01-30 | 株式会社日本触媒 | Manufacture of ceramic sintered body |
-
1988
- 1988-07-15 JP JP63177796A patent/JPH0227779A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6221750A (en) * | 1985-07-18 | 1987-01-30 | 株式会社日本触媒 | Manufacture of ceramic sintered body |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010245089A (en) * | 2009-04-01 | 2010-10-28 | Swcc Showa Cable Systems Co Ltd | Method for manufacturing thermoelectric conversion element |
| JP2025030231A (en) * | 2023-08-23 | 2025-03-07 | 国立大学法人島根大学 | Thermoelectric material and method for producing thermoelectric material |
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