JPS5956781A - Thermo electric genetration material - Google Patents
Thermo electric genetration materialInfo
- Publication number
- JPS5956781A JPS5956781A JP57166025A JP16602582A JPS5956781A JP S5956781 A JPS5956781 A JP S5956781A JP 57166025 A JP57166025 A JP 57166025A JP 16602582 A JP16602582 A JP 16602582A JP S5956781 A JPS5956781 A JP S5956781A
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- JP
- Japan
- Prior art keywords
- atom
- boron
- thermoelectric
- content
- thermal
- Prior art date
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は熱発電材料に関するものであり、更に詳しくは
熱衝撃九対して優れた特性を持っ鉄けい化物の熱発電材
料に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoelectric material, and more particularly to an iron silicide thermoelectric material having excellent properties against thermal shock.
熱を電気に直接変換する熱発電素子は、基本的には高温
接合部と低温接合部、およびｐ型熱発市相料（半導体）
の分枝とｎ型熱発′１）℃材料（半導体）の分枝とから
構成されている。Thermoelectric power generation elements that directly convert heat into electricity basically consist of a high-temperature junction, a low-temperature junction, and a p-type thermogenic phase material (semiconductor).
It consists of a branch of n-type heat generating '1) °C material (semiconductor).
そして、高温接合部は一般にはｐ型とｎ型熱発？比材料
の分枝の一端を金属板で接合して構成されているが、熱
発電材料が鉄けい化物の場合には、耐熱性を劣化させな
いようにするため、ｐ型とｎ型の熱発電材料の分枝端を
直接接合させたｐ −ｎ接合になっている。低温接合部
はｐ型熱発亀材料とｎ型熱発゛成材料の各分枝端に導線
が接続されている。And do high-temperature junctions generally generate p-type and n-type heat? It is constructed by joining one end of a branch of a specific material with a metal plate, but when the thermoelectric power generation material is iron silicide, in order to prevent deterioration of heat resistance, p-type and n-type thermoelectric generation It is a p-n junction in which the branched ends of the materials are directly joined. In the low-temperature junction, conductive wires are connected to each branch end of the p-type thermoforming material and the n-type thermoforming material.
高温接合部（ｐ−ｎ接合）が熱源、例えばガスあるいは
石油炎で加熱、または高温物質と接触により加熱される
と、高温接合部と低温接合部との間に温度差が生じ、低
温接合部の２つの熱発電材料分枝端に接続された導線か
ら熱起電カン１出ずことができる。When a hot joint (p-n junction) is heated by a heat source, such as a gas or oil flame, or by contact with a hot substance, a temperature difference is created between the hot and cold joints, and the cold joint A thermovoltaic can can be produced from a conductive wire connected to the two thermovoltaic material branch ends of the thermovoltaic material.
この熱起心力は一般の金属熱電対より数十倍大きいので
各種ガス器具の安全弁用小型電源、またこれらを数対組
合せてガスまたは石油を熱源とするコードレス温風暖房
機の電源などに利用できる。This thermal centripetal force is several tens of times larger than that of general metal thermocouples, so it can be used as a small power source for safety valves in various gas appliances, or as a power source for cordless hot air heaters that use gas or oil as a heat source by combining several pairs of these. .
このような熱発電素子を１覗源として使用（２ていると
き、水滴などの冷却物質が高温接合部に付着すると熱衝
撃によって破損される。従って、熱電１材料は耐熱性に
加えて熱衝９＄注に優れていることが要求される。When such a thermoelectric element is used as a source (1), if a cooling substance such as a water droplet adheres to the high-temperature joint, it will be damaged by thermal shock. It is required to be excellent at $9 notes.
遷移金、ｊ７ｉけい化・吻は耐熱性であり、高温の大気
中で利用できる熱発成材料である。これらのうち、特に
鉄けい化物Ｆ’ｅＳｉ２は大きな熱起電力が得られる点
で優れた熱電１に材料である（本発明者による特許第９
３０７３３号）。しかしながら、鉄げい化物は熱衝撃性
が悪く、例えば、一端が９００℃に加熱された状態で水
中に投入すると−１１」で破壊される欠点があった。Transition gold, J7i silicide, is a thermogenic material that is heat resistant and can be used in high temperature atmospheres. Among these, iron silicide F'eSi2 is an excellent thermoelectric material 1 in that it can generate a large thermoelectromotive force (Patent No. 9 by the present inventor).
No. 30733). However, iron hydrides have poor thermal shock resistance, and have the disadvantage that, for example, if one end is heated to 900° C. and thrown into water, it will break at -11''.
本発明のＬ１的は前記の欠点を解消し、鉄けい化物の熱
電特性を劣化させることなく、熱衝撃性を改善した熱発
電利料を提供するにある。The first objective of the present invention is to eliminate the above-mentioned drawbacks and to provide a thermal power generation material with improved thermal shock resistance without deteriorating the thermoelectric properties of iron silicide.
急激な加熱冷却にも耐える特性を有するものとなし得る
こと、および熱電１に子を摺成するｐ型ｖ３眠材料とし
て、更にこれに、Ｆｅより価電子が１飼少ないマンガン
元素周期表系列、またＳｌより価電子が１飼少ないアル
ミニウム元素周期表系列の元素から選ばれた１種または
２種以上をドープ材として陰ませ、ｎ型発１料として、
Ｆｅより価電子が１個多いコバルト元素周期表系列、ま
たＳ＋より価電子が１個多いＳｌ）元素周期表系列の元
素から選ばれた１種または２種以上をドープ材として作
ませた合金または固溶体からなる熱電ｒｔ材料は前記と
同様な！特性を有することを知見し得、この知見に基づ
いて本発明を完成した。It can be made into a material that can withstand rapid heating and cooling, and can be used as a p-type V3 material that forms a thermoelectric element. In addition, one or more elements selected from the elements of the periodic table of aluminum elements, which have one less valence electron than Sl, are used as a doping material, and as an n-type emitting material,
An alloy made with one or more elements selected as a dopant from the elements in the periodic table series of elements such as cobalt, which has one valence electron more than Fe, and Sl, which has one valence electron more than S+, in the periodic table series. The thermoelectric rt material consisting of a solid solution is similar to the above! The present invention was completed based on this knowledge.
１扶けい化物Ｆｅ Ｓ ＋ ２中にボロンの含有量を変
化させて得られた熱発成材料の熱起電力、熱衝撃性を示
すと第１表の通りである。Table 1 shows the thermoelectromotive force and thermal shock properties of thermogenerating materials obtained by varying the boron content in silicide Fe S + 2.
なお、熱起電力は温度差７５０℃で行い、破壊までの投
入回数は、一端または全体を９００℃に加熱した状態か
ら水中に投入したときの破第１表
壊に至るまでの投入回数を示す。また熱電市材料は実施
例１と同様にして作った。The thermoelectromotive force was measured at a temperature difference of 750°C, and the number of injections until failure indicates the number of injections until the first surface failure occurs when one end or the entire body is heated to 900°C and is placed in water. . Further, the thermoelectric city material was made in the same manner as in Example 1.
この第１表に示す結果から分かるように、ボロン元素の
含有量が０．３０原子条より熱衝撃性が優れ、その含有
量が増加すると共に増加するが、４．６原子係を超える
と熱％Ｍｉ撃性が低下すると共に熱電力も低下Ｖる。従
って、ボロン元素の潔有喰は０．３〜４．６原子係の範
囲であることが必砦である。As can be seen from the results shown in Table 1, the thermal shock resistance is better when the content of boron element is 0.30 atoms, and increases as the content increases, but when it exceeds 4.6 atoms, As the %Mi impactivity decreases, the thermal power also decreases. Therefore, it is essential that the value of the boron element is in the range of 0.3 to 4.6 atoms.
なお、ボロンな０．３〜４．６原子係を含んだ鉄けい化
物を大気中で９００ ℃で２００時間加熱した。場合に
おける重積増加は（１，８ｆ！ｑｃｙｎ２以下であり、
耐熱性も優れた性質を有していた。Note that an iron silicide containing 0.3 to 4.6 atoms of boron was heated in the air at 900°C for 200 hours. The intussusception increase in the case is less than (1,8f!qcyn2,
It also had excellent heat resistance.
また、鉄叶い化物にボロンの含有り七を変化さセルト共
ニ、マンガン、アルミニウム、コバルト、アンチモンの
ドープをき有させた場合の熱起電力と熱衝撃性の試験結
果は第２表の通りである。Table 2 shows the thermoelectromotive force and thermal shock test results when the iron alloy is doped with boron, manganese, aluminum, cobalt, and antimony. It is.
第２表
なお、熱蔵″屯力は温度差８００℃で行い、破壊までの
投入回数は、一端を９００℃に加熱した状聾から水中に
投入したときの破壊に至るまでの投入回数を示す。また
熱電改利料は実施例２、実施βＩＪ３と同様にして作っ
た。In Table 2, thermal storage capacity was measured at a temperature difference of 800°C, and the number of injections until destruction indicates the number of injections until destruction when one end was heated to 900°C and placed in water. .The thermoelectric conversion charge was made in the same manner as in Example 2 and Example βIJ3.
この第２表に示す結果から分かるように、ドープ材を加
えてもボロン含有酸が０．３原子係より熱％％ Ｑ’ｉ
性が優れ、熱起電力も低下することがない。As can be seen from the results shown in Table 2, even with the addition of the dopant, the boron-containing acid has a heat %% Q'i of 0.3 atom.
It has excellent properties and the thermoelectromotive force does not decrease.
この表ではマンガン、アルミニウム、コバルト、アンチ
モンを代表例としてあげたが、ｐ型熱電屯材料としては
、Ｍｎの周期表系列のＴｃ１Ｒｅ、アルミニウムの周期
表系列のＣ，Ｇａ５Ｔｎ。In this table, manganese, aluminum, cobalt, and antimony are listed as representative examples, but p-type thermoelectric materials include Tc1Re in the periodic table series of Mn, C, and Ga5Tn in the periodic table series of aluminum.
ＴＩを、ｎ型熱電取材料としては、ＣＯの周期表系列の
Ｒｈ、Ｉｒ、Ｓｂの周期表系列のＮ、 Ｐ、 Ａｓ、Ｂ
ｉもそれぞれ同様なドープ材効果が得られる。TI is used as an n-type thermoelectric collection material such as Rh in the periodic table series of CO, Ir, N in the periodic table series of Sb, P, As, B.
A similar dopant effect can be obtained for i as well.
本発明の熱発電材料は、一般の鋳造法によって円柱や角
柱などの簡単な形状のものを得ることができるが、鋳造
法では鋳造孔（ピンホールや気泡）のない複雑な形状の
ものを得ることは極めて困難である。従ってこのような
ものを作るには粉末冶金法により製造することが好まし
い。以下の実施例は粉末冶金法で行ったものを示す。The thermoelectric power generation material of the present invention can be obtained in simple shapes such as cylinders and prisms by general casting methods, but complex shapes without casting holes (pinholes and bubbles) can be obtained by casting methods. This is extremely difficult. Therefore, it is preferable to manufacture such a product by a powder metallurgy method. The following examples were carried out by powder metallurgy.
実施例１゜
鉄、ボロン、金属シリコンをＩ” ｌ−１Ｂ Ｘ Ｓ
Ｉ ２．１の組成になるように秤量し、この混合物を高
周波炉を用いて溶解し、鉄製金型に鋳込んでＢを０．３
〜５．５７原子矛含有する鉄ゆい化物合金を作った。こ
の各合金をスタンプミルとボールミルを用いて粒径約２
μｍの粉末にした。Example 1゜Iron, boron, and metal silicon
Weigh the mixture so that it has a composition of I 2.1, melt this mixture using a high frequency furnace, and cast it into an iron mold to make B 0.3.
An iron halide alloy containing ~5.57 atoms was made. Each of these alloys was processed using a stamp mill and a ball mill to obtain particles with a particle size of approximately 2 mm.
It was made into a μm-sized powder.
この粉末に結合剤（硝脳、ポリビニールアルコール、バ
ラフィン等）を適址混合した後、冷間ブレスを行って長
方形の粉末成形体とした。After a binder (nitrate, polyvinyl alcohol, paraffin, etc.) was appropriately mixed into this powder, it was cold pressed to form a rectangular powder compact.
この成形体を真空中１１７０〜１１８０℃で３時間焼結
し、引続いて８００℃で９５時間熱処理して熱発電材料
（３ｘ ３ ｘ ３０ ｗ＆ ）を得た。This molded body was sintered in vacuum at 1170-1180°C for 3 hours, and then heat treated at 800°C for 95 hours to obtain a thermoelectric material (3 x 3 x 30 w&).
この熱発電材料の熱起電力、熱衝撃性は、第１表に示す
通りのものであった。The thermoelectromotive force and thermal shock properties of this thermoelectric power generation material were as shown in Table 1.
実施例２゜
実施例１で得られたＢ含有ｉｏ、３０原子チと２．５原
子係の各粉末に、Ｆｅより価電子が１何歩ないＭｒ＋を
３，３原子係、Ｂ含有量２．００原子係の粉末に、Ｓｌ
より価［Ｅ子が１何歩ないＡＩを２．００原子チ、Ｂ含
有量２．５０原子チの粉末にＭｎ１．７Ｊα子チとＡＩ
ｌ、００原子俤の組成のものとし、これらを実施例１と
同様な焼結および熱処理した。Example 2゜Into each of the B-containing io powders obtained in Example 1, with a concentration of 30 atoms and a concentration of 2.5 atoms, Mr+, which has 1 step less valence electrons than Fe, was added to the powders containing 3.3 atoms and a B content of 2. .00 atomic powder, Sl
[Mn1.7Jα and AI are added to a powder with a B content of 2.50 atoms and 2.00 atoms of AI, which has an E content of 1 step.
The composition was sintered and heat treated in the same manner as in Example 1.
なお、焼成前の合金粉末は、ＦｅｌＭｎ、 ＡＩおよび
Ｓｉを溶成した丙、粉砕した金ル１粉末でもよい。Note that the alloy powder before firing may be a powder made of FeIMn, AI and Si melted, or a powder made of metal 1 which is pulverized.
このようにして得られた熱電ち、材料は、半導体のドー
グ材で予１１ｊｌＪされるように、上記ドープ材１原子
当りのアクセプターの成牛率がＢをドープ利とするドナ
ーの成牛率より太き（・ため、ｐ型熱電電材月となる。The thermoelectric material obtained in this way has a mating rate of the acceptor per atom of the doping material that is higher than that of the donor doped with B, as shown in the semiconductor Dog material. Because of its thickness, it becomes a p-type thermoelectric material.
この熱電［１も利料の熱起ｒｌｆ、カ、熱衝撃１コ］ミ
は第２表に示す辿り優れたものであった。The thermoelectric properties [1, 1, 1, 1, 1, 2, 1, 2] of thermal shock were excellent as shown in Table 2.
実施例３゜
実施１＋ｌ １で得［）れたＢ含付喰１．３原子係の粉
末に、ｌ、ｍ ｅよりＩ＋ｌＩｉ 成子が１個多いＣ０
Ｑ１．７原子チ、またＣｏ ］、Ｏ原子チおよびＳｂＯ
，８原子チを加えたものを、それぞれ実施例１と同様な
焼成および熱処理した。Example 3゜In the B-containing powder obtained in Example 1+l 1 with a concentration of 1.3 atoms, C0 has one more I+lIi Seiko than l and m e.
Q1.7 atoms, also Co ], O atoms and SbO
, 8 atoms of CH were added and subjected to firing and heat treatment in the same manner as in Example 1.
得られた熱電４材料は、や導体のドープ材で予測される
ようにｎ型熱電市（オ料となる。この熱起電力および熱
衝繋試、験の結果は、第２表に示す通り優れたものであ
った。The obtained thermoelectric material 4 becomes an n-type thermoelectric material (O material) as expected from a conductor doped material.The results of this thermoelectromotive force and thermal shock coupling test are shown in Table 2. It was excellent.
特許出願人 科学技術庁金爲材料技術研究所長手続補正
書
１１ｇ３和５８年 ３ 月 ７７ 日
特許庁長官 若杉和夫 殿
（特許庁審査官 ＃）
１ｊｌ’件ノｉ示１１ｆ’＋和５７年特訂願第１６１ｉ
０２５％２、発明の名称 熱発電材料
別紙
＋１） 明細書第６頁上から６行目［アンチモンのド
ープｊの次に１−材」を挿入する。Patent Applicant: Science and Technology Agency, Materials Technology Research Institute Director-General Procedural Amendment 11g3, March 77, 2010, Director General of the Patent Office, Mr. Kazuo Wakasugi (Patent Office Examiner #), 1jl' Matter No. 11f' + 11f' Special Edition, 2007 Petition No. 161i
025%2, Title of the invention Thermoelectric power generation material Attachment +1) Page 6 of the specification, line 6 from the top [insert 1-material after antimony dope j].
Claims (2)
元素を含有させた合金または固溶体からなる熱発心材料
。(1) A thermocentering material consisting of an alloy or solid solution of iron silicide containing 0.3 to 4.6 atoms of boron element.
ロン元素とマンガン、コバルト、アルミニウムおよびア
ンチモンの元素周期表系列から選ばれた１種または２種
以上の元素のドーグ材を含有させた合金または固溶体か
らなる熱発電材料。(2) Iron silicide '11 with 0.3 to 4.6) i% of boron element and one or more elements selected from the periodic table of elements of manganese, cobalt, aluminum and antimony. A thermoelectric power generation material consisting of an alloy or solid solution containing a material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57166025A JPS5956781A (en) | 1982-09-25 | 1982-09-25 | Thermo electric genetration material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57166025A JPS5956781A (en) | 1982-09-25 | 1982-09-25 | Thermo electric genetration material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5956781A true JPS5956781A (en) | 1984-04-02 |
| JPH021381B2 JPH021381B2 (en) | 1990-01-11 |
Family
ID=15823534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57166025A Granted JPS5956781A (en) | 1982-09-25 | 1982-09-25 | Thermo electric genetration material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5956781A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2708789A1 (en) * | 1993-08-04 | 1995-02-10 | Technova Inc | Thermoelectrical semiconductor material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0485145A (en) * | 1990-07-28 | 1992-03-18 | Toyoda Gosei Co Ltd | Box for automobile |
-
1982
- 1982-09-25 JP JP57166025A patent/JPS5956781A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2708789A1 (en) * | 1993-08-04 | 1995-02-10 | Technova Inc | Thermoelectrical semiconductor material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH021381B2 (en) | 1990-01-11 |
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