JPH05343748A - Manufacture of fesi2 sintered material - Google Patents
Manufacture of fesi2 sintered materialInfo
- Publication number
- JPH05343748A JPH05343748A JP4174809A JP17480992A JPH05343748A JP H05343748 A JPH05343748 A JP H05343748A JP 4174809 A JP4174809 A JP 4174809A JP 17480992 A JP17480992 A JP 17480992A JP H05343748 A JPH05343748 A JP H05343748A
- Authority
- JP
- Japan
- Prior art keywords
- fesi
- powder
- sintered body
- degreasing
- pvb
- 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- Withdrawn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
Landscapes
- Ceramic Products (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は例えば熱を電気に直接変
換する熱電変換素子に用いられるシート状のＦｅＳｉ2
焼結体の製造方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a sheet-like FeSi 2 used for a thermoelectric conversion element for directly converting heat into electricity.
The present invention relates to a method for manufacturing a sintered body.
【０００２】[0002]
【従来の技術】一般に、有機バインダ、例えばＰＶＢ
（ポリビニールブチラール）の脱脂方法としては、以下
のような方法がある。例えばＰＶＢを混合した粉末が酸
化物系の場合、これを空気中、６００℃で完全に脱脂す
る。また、非酸化物の粉末の場合、例えばＡｌＮまたは
金属電極を含む場合、Ｎ2ガスまたはＡｒガス中、５０
０℃で脱脂する。しかし、完全には脱脂されないので、
残留成分の除去が必要である。そこで、この残留成分の
除去は、Ｎ2＋Ｈ2＋Ｈ2Ｏの混合ガス中で、１０００℃
以上での脱脂が必要である。Generally, organic binders such as PVB are used.
The degreasing method of (polyvinyl butyral) includes the following methods. For example, when the powder mixed with PVB is an oxide type, it is completely degreased in air at 600 ° C. Further, in the case of non-oxide powder, for example, in the case of including AlN or a metal electrode, in N 2 gas or Ar gas, 50
Degrease at 0 ° C. However, since it is not completely degreased,
Removal of residual components is required. Therefore, the removal of this residual component is performed at 1000 ° C. in a mixed gas of N 2 + H 2 + H 2 O.
The above degreasing is necessary.
【０００３】ところで、熱電変換素子として使用される
ＦｅＳｉ2のシート状焼結体は、従来、以下の方法によ
り製造されている。すなわち、ＦｅＳｉ2粉末に、バイ
ンダ（ＰＶＢ等）、可塑剤（ＢＰＢＧ等）、溶剤（トル
エン等）を混練し、脱泡後、ドクタブレード泡等により
シート状に成形する。そして、このシート状の成形体の
脱脂を行う。この脱脂を、上記と同様の条件、例えば空
気中で６００℃の加熱により行うと、焼結後のＦｅＳｉ
2焼結体の密度が低いものであった。また、例えばＮ2ガ
スまたはＡｒガス中で５００℃の温度に加熱して脱脂す
ると、脱脂が完全に行われないため、残留する樹脂成分
を除去する必要がある。そこで、このシート状の成形体
を、さらに、Ｎ2＋Ｈ2＋Ｈ2Ｏの混合ガス中で、１００
０℃以上での脱脂を行うこととなる。By the way, the sheet-like sintered body of FeSi 2 used as a thermoelectric conversion element has been conventionally manufactured by the following method. That is, the FeSi 2 powder is kneaded with a binder (PVB or the like), a plasticizer (BPBG or the like), a solvent (toluene or the like), defoamed, and then formed into a sheet by a doctor blade foam or the like. Then, the sheet-shaped molded body is degreased. If this degreasing is performed under the same conditions as above, for example, by heating in air at 600 ° C., FeSi after sintering
2 The density of the sintered body was low. Further, if degreasing is performed by heating to a temperature of 500 ° C. in N 2 gas or Ar gas, for example, degreasing is not completely performed, and therefore it is necessary to remove the residual resin component. Then, the sheet-shaped molded body is further treated with 100% in a mixed gas of N 2 + H 2 + H 2 O.
Degreasing is performed at 0 ° C or higher.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、このよ
うな従来のシート状のＦｅＳｉ2焼結体の製造方法にあ
っては、いずれの脱脂方法を採用してもＦｅＳｉ2のシ
ート状焼結体の密度が小さいという課題があった。例え
ば、脱脂条件が、空気中、６００℃では、ＦｅＳｉ2粉
末の酸化が進み、焼結密度が上がらない。また、Ｎ2ガ
ス中またはＡｒガス中の脱脂では、有機樹脂の残留成分
のため、焼結密度が上がらない。さらに、Ｎ2＋Ｈ2＋Ｈ
2Ｏのガス中、１０００℃の条件では、ＦｅＳｉ2焼結体
の緻密化が阻害され、焼結密度が上がらない。これは、
１０００℃以下でＦｅＳｉ2焼結体についてその緻密化
が始まるためである。このようにＦｅＳｉ2焼結体の密
度が低い場合（相対密度が９０％以下）、その焼結体の
耐酸化性が劣るという課題があった。However, in such a conventional method for producing a sheet-like FeSi 2 sintered body, whichever degreasing method is adopted, the FeSi 2 sheet-like sintered body is produced. There was a problem of low density. For example, when the degreasing condition is 600 ° C. in air, the FeSi 2 powder is oxidized and the sintered density is not increased. Further, degreasing in N 2 gas or Ar gas does not increase the sintered density because of the residual components of the organic resin. Furthermore, N 2 + H 2 + H
Under the condition of 1000 ° C. in the gas of 2 O, the densification of the FeSi 2 sintered body is hindered and the sintered density does not increase. this is,
This is because the densification of the FeSi 2 sintered body starts at 1000 ° C. or less. As described above, when the density of the FeSi 2 sintered body is low (relative density is 90% or less), there is a problem that the oxidation resistance of the sintered body is poor.
【０００５】そこで、発明者は、酸素を０．５容量％以
上含む雰囲気で脱脂を行うと、ＰＶＢが完全に分解脱脂
する温度まで昇温しなくても、脱脂後に真空中または水
素中で焼結することにより、ＦｅＳｉ2焼結体の緻密化
が始まる温度以下で、ＰＶＢが分解され、ＦｅＳｉ2の
焼結を阻害しないことを見い出した。Therefore, the inventor, when performing degreasing in an atmosphere containing 0.5% by volume or more of oxygen, burns in vacuum or in hydrogen after degreasing without heating up to a temperature at which PVB is completely decomposed and degreased. It was found that, by binding, PVB is decomposed below the temperature at which the densification of the FeSi 2 sintered body starts and does not hinder the sintering of FeSi 2 .
【０００６】そこで、本発明は、有機バインダの脱脂に
際して焼結体の焼結密度を低下させることなく、その耐
酸化性を高めたＦｅＳｉ2焼結体の製造方法を提供する
ことを、その目的としている。[0006] Therefore, an object of the present invention is to provide a method for producing a FeSi 2 sintered body whose oxidation resistance is improved without decreasing the sintered density of the sintered body when degreasing the organic binder. I am trying.
【０００７】[0007]
【課題を解決するための手段】本発明の請求項１に係る
ＦｅＳｉ2焼結体の製造方法にあっては、ＦｅＳｉ2の粉
末に有機樹脂系バインダを混合してスラリーを形成し、
このスラリーを焼成することにより、ＦｅＳｉ2焼結体
を成形するＦｅＳｉ2焼結体の製造方法において、酸素
を０．５容量％以上含む雰囲気中で、３００℃以上でか
つＦｅＳｉ2粉末の酸化増量が１ｗｔ％以下であるよう
な温度で脱脂し、その後、真空中で、または、水素雰囲
気中で、１１５０〜１１９０℃で焼結するＦｅＳｉ2焼
結体の製造方法である。In a method for producing a FeSi 2 sintered body according to claim 1 of the present invention, a powder of FeSi 2 is mixed with an organic resin binder to form a slurry,
By firing the slurry, in the production method of the FeSi 2 sintered body forming the FeSi 2 sintered body in an atmosphere containing oxygen of 0.5 vol% or more, at 300 ° C. or higher and FeSi 2 oxide powder bulking there was degreased at a temperature such that less 1 wt%, then, in a vacuum or in a hydrogen atmosphere, a method for producing a FeSi 2 sintered body sintered at from 1,150 to 1,190 ° C..
【０００８】より具体的には、本発明に係るＦｅＳｉ2
焼結体の製造方法は、ＦｅＳｉ2粉末をＰＶＢと混練
し、例えばドクタブレード法によりシート状に成形した
後、ＦｅＳｉ2粉末を酸化させることなくＰＶＢを除去
する。例えば空気中で、３５０℃にて１時間、または、
１容量％のＯ2を含むＡｒガス雰囲気中で、６００℃に
て１時間の脱脂を行う。その後、このシート状成形体
を、１０-2Ｔｏｒｒ以下の真空中、または、水素中で、
１１５０℃にて焼結する。さらに、大気中でこれを７８
０℃〜８５０℃に５０時間程度保持して、アニールする
ものである。換言すると、ＦｅＳｉ2粉末の酸化増量が
１重量％以下となるように脱脂をコントロールするもの
である。この酸化増量が１重量％を超えると、焼結体の
密度が９０％未満となるものである。また、Ｏ2量が
０．５容量％以下となると、その後の焼結工程にあっ
て、ＰＶＢが分解されなくなるものである。More specifically, FeSi 2 according to the present invention
In the method for manufacturing the sintered body, FeSi 2 powder is kneaded with PVB, and the powder is shaped into a sheet by, for example, a doctor blade method, and then PVB is removed without oxidizing the FeSi 2 powder. For example, in air at 350 ° C for 1 hour, or
Degreasing is performed at 600 ° C. for 1 hour in an Ar gas atmosphere containing 1% by volume of O 2 . Then, the sheet-shaped molded body was subjected to a vacuum of 10 -2 Torr or less, or in hydrogen,
Sinter at 1150 ° C. In addition, 78
Annealing is performed by holding at 0 ° C. to 850 ° C. for about 50 hours. In other words, the degreasing is controlled so that the weight gain of oxidation of the FeSi 2 powder is 1% by weight or less. If the amount of increase in oxidation exceeds 1% by weight, the density of the sintered body will be less than 90%. Further, when the amount of O 2 is 0.5% by volume or less, PVB is not decomposed in the subsequent sintering process.
【０００９】また、化１は有機バインダとして用いられ
るＰＶＢ（ポリビニールブチラール）の化学構造を示し
ている。この場合、８４≦ｘ≦８８、９≦ｙ≦１３、０
≦ｚ≦５である。分子量は４５０００〜５５０００であ
る。また、ＦｅＳｉ2粉末に混入されるＰＶＢは５〜６
重量％、可塑剤は２〜６重量％、さらに溶剤を適当な粘
度を得るために加える。上記可塑剤としては、例えばＢ
ＰＢＧ（ブチルフタリルブチルグリコレート）、ＤＯ
Ｐ、ＤＢＰ等を加える。この混合したものをボールミル
等で混練し、脱泡して粘度を調整する。そして、これを
上記のようにドクターブレード法によりシート状に成形
するものである。Chemical formula 1 shows the chemical structure of PVB (polyvinyl butyral) used as an organic binder. In this case, 84 ≦ x ≦ 88, 9 ≦ y ≦ 13,0
≦ z ≦ 5. The molecular weight is 45,000-55,000. Further, PVB mixed in FeSi 2 powder is 5 to 6
% By weight, 2 to 6% by weight of plasticizer, and solvent is added to obtain a proper viscosity. Examples of the plasticizer include B
PBG (Butylphthalyl butyl glycolate), DO
Add P, DBP, etc. The mixture is kneaded with a ball mill or the like and defoamed to adjust the viscosity. Then, this is molded into a sheet by the doctor blade method as described above.
【００１０】[0010]
【実施例】以下、本発明の実施例を説明する。この脱脂
に使用されるＦｅＳｉ2の粉末粒径は１〜３０μｍと
し、この化合物粉末に焼結助剤、バインダ（ＰＶＢ）、
可塑剤（ＤＯＰ）、溶剤等を混入してスラリーを作製し
た。さらに、脱泡後、１００μｍの厚さにシート成形
し、以下の条件で脱脂を行ったものである。その結果を
表１に示す。EXAMPLES Examples of the present invention will be described below. The powder particle size of FeSi 2 used for this degreasing is set to 1 to 30 μm, and a sintering aid, a binder (PVB),
A slurry was prepared by mixing a plasticizer (DOP), a solvent and the like. Further, after defoaming, a sheet having a thickness of 100 μm was formed and degreased under the following conditions. The results are shown in Table 1.
【００１１】[0011]
【表１】 [Table 1]
【００１２】[0012]
【発明の効果】本発明によれば、密度が高いＦｅＳｉ2
焼結体を得ることができる。その結果、このＦｅＳｉ2
焼結体の耐酸化性が高まる。According to the present invention, FeSi 2 having a high density is obtained.
A sintered body can be obtained. As a result, this FeSi 2
The oxidation resistance of the sintered body is enhanced.
【化１】 [Chemical 1]
Claims (1)
してスラリーを形成し、このスラリーを焼成することに
より、ＦｅＳｉ2焼結体を成形するＦｅＳｉ2焼結体の製
造方法において、 酸素を０．５容量％以上含む雰囲気中で、３００℃以上
でかつＦｅＳｉ2粉末の酸化増量が１ｗｔ％以下である
ような温度で脱脂し、 その後、真空中で、または、水素雰囲気中で、１１５０
〜１１９０℃で焼結することを特徴とするＦｅＳｉ2焼
結体の製造方法。1. A by mixing an organic binder to powder of FeSi 2 to form a slurry, by firing the slurry, in the production method of the FeSi 2 sintered body forming the FeSi 2 sintered body, the oxygen 0 Degreasing is performed in an atmosphere containing 0.5 vol% or more at a temperature of 300 ° C. or higher and at a temperature such that the oxidation increase of the FeSi 2 powder is 1 wt% or less, and then, in vacuum or in a hydrogen atmosphere, 1150
A method for manufacturing a FeSi 2 sintered body, which comprises sintering at ˜1190 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4174809A JPH05343748A (en) | 1992-06-09 | 1992-06-09 | Manufacture of fesi2 sintered material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4174809A JPH05343748A (en) | 1992-06-09 | 1992-06-09 | Manufacture of fesi2 sintered material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05343748A true JPH05343748A (en) | 1993-12-24 |
Family
ID=15985049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4174809A Withdrawn JPH05343748A (en) | 1992-06-09 | 1992-06-09 | Manufacture of fesi2 sintered material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05343748A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005055338A (en) * | 2003-08-06 | 2005-03-03 | Hiroyasu Kido | Temperature sensor element and its manufacturing method |
-
1992
- 1992-06-09 JP JP4174809A patent/JPH05343748A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005055338A (en) * | 2003-08-06 | 2005-03-03 | Hiroyasu Kido | Temperature sensor element and its manufacturing method |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19990831 |