JP2506502B2 - Method for manufacturing ceramic porous body - Google Patents
Method for manufacturing ceramic porous bodyInfo
- Publication number
- JP2506502B2 JP2506502B2 JP2333097A JP33309790A JP2506502B2 JP 2506502 B2 JP2506502 B2 JP 2506502B2 JP 2333097 A JP2333097 A JP 2333097A JP 33309790 A JP33309790 A JP 33309790A JP 2506502 B2 JP2506502 B2 JP 2506502B2
- Authority
- JP
- Japan
- Prior art keywords
- porous body
- ceramic
- ceramic porous
- slurry
- cross
- 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.)
- Expired - Fee Related
Links
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明なフィルター、断熱材、触媒担体、ヒータなど
に使用されるセラミック多孔体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a method for producing a ceramic porous body used for a filter, a heat insulating material, a catalyst carrier, a heater and the like.
従来、セラミック多孔体は、以下のような方法により
製造されていた。Conventionally, a ceramic porous body has been manufactured by the following method.
粒子径を制御した粒子を充填して焼結し、充填空隙を
気孔とすることによりセラミック多孔体を製造する方
法。A method for producing a ceramic porous body by filling particles having a controlled particle size, sintering the particles, and forming pores in the filled voids.
開気孔を有する多孔質樹脂（フォーム）にセラミック
スラリーを付着させ、乾燥させた後、脱脂・焼結するこ
とによりセラミック多孔体を製造する方法。A method for producing a ceramic porous body by depositing a ceramic slurry on a porous resin (foam) having open pores, drying, and degreasing and sintering.
多孔質樹脂（フォーム）のプレポリマー中にセラミッ
ク及び発泡剤を混合し、これを発泡させた状態で硬化
し、脱脂・焼結することによりセラミック多孔体を製造
する方法。A method for producing a ceramic porous body by mixing a ceramic and a foaming agent in a prepolymer of a porous resin (foam), curing the foamed state, degreasing and sintering the mixture.
セラミックスラリー又はセラミック微粒子と、粒子径
が制御された昇華性、可燃性又は溶解性の物質からなる
粒子とを混合し、成形した後、昇華性、可燃性又は溶解
性の物質を除去し、焼結することによりセラミック多孔
体を製造する方法。Ceramic slurry or ceramic fine particles are mixed with particles consisting of a sublimable, flammable or soluble substance having a controlled particle size, and after molding, the sublimable, flammable or soluble substance is removed and baked. A method for producing a ceramic porous body by binding.
セラミックスララーを泡立て発泡させ、これを脱水し
てスラリーの流動性を失わせた後、乾燥し、焼結するこ
とによりセラミック多孔体を製造する方法。A method for producing a ceramic porous body by bubbling and expanding a ceramics laler, dehydrating this to lose the fluidity of the slurry, and then drying and sintering.
前述した方法には、それぞれ以下のような欠点があ
る。Each of the above methods has the following drawbacks.
の方法では気孔率の高いセラミック多孔体を得るこ
とができない。It is not possible to obtain a ceramic porous body having a high porosity by the above method.
の方法では、高気孔率のセラミック多孔体を得るこ
とができる。しかし、樹脂の燃失時に発生するガスによ
り、セラミック骨格部分にクラックが発生しやすく、高
強度のセラミック多孔質体を得ることができない。ま
た、多孔質樹脂にセラミックスラリーを含浸させ、余分
なスラリーを除去する必要があるため、多孔質樹脂の気
孔径がある程度大きいことが要求され、気孔径の小さい
セラミック多孔体を得ることができない。According to the method (1), a ceramic porous body having a high porosity can be obtained. However, cracks easily occur in the ceramic skeleton portion due to the gas generated when the resin burns out, and a high-strength ceramic porous body cannot be obtained. Further, since it is necessary to impregnate the porous resin with the ceramic slurry and remove the excess slurry, it is required that the pore diameter of the porous resin be large to some extent, and a ceramic porous body having a small pore diameter cannot be obtained.
の方法では、高強度のセラミック多孔体を得ること
ができる。しかし、成形体中に多量の含有される樹脂を
脱脂する条件が制限され、特に閉気孔を有するセラミッ
ク多孔体を製造することが困難である。According to the method (1), a high-strength ceramic porous body can be obtained. However, the conditions for degreasing a large amount of resin contained in the molded body are limited, and it is particularly difficult to manufacture a ceramic porous body having closed pores.
の方法では、気孔径分布の均一なセラミック多孔体
を得ることができる。しかし、昇華性、可燃性又は溶解
性の物質が灰分などの不純物として残留しやすい。この
ため、例えばセラミック多孔質を高温で使用した場合、
不純物がガス発生の原因となったりする問題がある。ま
た、これらの物質を用いることは、コストアップにつな
がる。According to the method (1), it is possible to obtain a ceramic porous body having a uniform pore size distribution. However, sublimable, flammable, or soluble substances tend to remain as impurities such as ash. Therefore, for example, when using ceramic porous at high temperature,
There is a problem that impurities cause gas generation. Moreover, using these substances leads to an increase in cost.
の方法では、泡状スラリーを乾燥し脱水して泡組織
を固定する際に、脱水が表面から徐々に進行し、その間
に内部の泡組織は成長して泡径が大きくなるため、これ
を焼結して得られるセラミック多孔体は気孔径にばらつ
きが生じやすいという問題がある。In this method, when the foam slurry is dried and dehydrated to fix the foam structure, dehydration gradually progresses from the surface, and the foam structure inside grows and the bubble diameter becomes large during that time. The ceramic porous body obtained by binding has a problem that the pore diameter tends to vary.
本発明は前記問題点を解決するためになされたもので
あり、閉気孔、開気孔にかかわらず、気孔径を範囲が広
く、気孔径分布が均一であり、かつ高強度のセラミック
多孔体を容易かつ安価に製造することができる方法を提
供することを目的とする。The present invention has been made to solve the above-mentioned problems, and regardless of whether the pores are closed pores or open pores, a wide range of pore diameters, a uniform pore diameter distribution, and a high-strength ceramic porous body can be easily formed. And it aims at providing the method which can be manufactured at low cost.
本発明のセラミック多孔体の製造方法は、セラミック
粉末及び架橋重合によって硬化し得る有機物質を溶媒に
分散又は溶解させたセラミックスラリーに調製する工程
と、このセラミックスラリーに架橋剤を添加し、攪拌し
て発泡させた状態で成形・硬化させる工程と、この成形
体を乾燥し、焼結させることを特徴とするものである。The method for producing a ceramic porous body of the present invention comprises a step of preparing a ceramic slurry in which a ceramic powder and an organic substance curable by cross-linking polymerization are dispersed or dissolved in a solvent, and a cross-linking agent is added to the ceramic slurry and stirred. And a step of molding and curing in a foamed state, and drying and sintering this molded body.
本発明方法においては、まず溶媒にセラミック粉末及
び架橋重合により硬化し得る有機物質を分散又は溶解さ
せてセラミックスラリーを調製する。このセラミックス
ラリーには、バインダー、分散型、解膠剤、整泡剤、整
泡助剤、増粘剤などを添加してもよい。架橋重合により
硬化し得る有機物質としては、多官能性のポリマーが挙
げられる。多官能性のポリマーはバインダーとしても機
能する。In the method of the present invention, a ceramic slurry is prepared by first dispersing or dissolving a ceramic powder and an organic substance that can be cured by cross-linking polymerization in a solvent. A binder, a dispersion type, a peptizer, a foam stabilizer, a foam stabilizer, a thickener and the like may be added to the ceramic slurry. Examples of organic substances that can be cured by cross-linking polymerization include polyfunctional polymers. The polyfunctional polymer also functions as a binder.
次に、得られたセラミックスラリーに架橋剤を添加
し、機械的に攪拌して発泡させた状態で成形し、架橋重
合反応により前記有機物質をゲル化させて硬化させる。
セラミックスラリーに架橋剤を添加し機械的に攪拌して
発泡させたものを型に流し込んでも成形してもよいし、
一定容積の型（閉系）内で気相と共存させた状態でセラ
ミックスラリーを攪拌して成形してもよい。この際、攪
拌強度を調整することにより、泡状スラリーの気泡径を
制御することができる。泡立てられた直後の泡状スラリ
ーの気泡径は均一である。この状態で泡状スラリーの全
体にわたって架橋重合反応が進行してゲル化が起こるの
で、泡の成長が抑制され、硬化後の成形体の気孔径も均
一である。また、多官能性のポリマー及び硬化剤の種類
と添加率、反応温度、pHなどを調整して架橋重合反応の
速度を制御することにより、気孔を閉気孔にも開気孔に
もすることができる。Next, a cross-linking agent is added to the obtained ceramic slurry, and the mixture is mechanically stirred to be foamed, and the organic substance is gelled and cured by a cross-linking polymerization reaction.
The ceramic slurry may be added with a cross-linking agent, mechanically stirred and foamed, or poured into a mold or molded,
The ceramic slurry may be stirred and molded in a mold (closed system) having a constant volume while coexisting with the gas phase. At this time, the bubble diameter of the foamy slurry can be controlled by adjusting the stirring strength. Immediately after foaming, the foam slurry has a uniform cell diameter. In this state, the cross-linking polymerization reaction proceeds throughout the foam slurry to cause gelation, so that the growth of bubbles is suppressed and the pore size of the cured molded product is uniform. In addition, the pores can be closed or open by controlling the rate of the cross-linking polymerization reaction by adjusting the kind and addition rate of the polyfunctional polymer and the curing agent, the reaction temperature, the pH, and the like. .
更に、成形体を乾燥して溶媒を除去し、脱脂した後、
焼結することにより、気孔径が均一に高強度のセラミッ
ク多孔体を製造することができる。Furthermore, after drying the molded body to remove the solvent and degreasing,
By sintering, it is possible to manufacture a high-strength ceramic porous body having a uniform pore size.
以下、本発明の実施例を説明する。 Examples of the present invention will be described below.
実施例１ 平均粒径1.0μｍのアルミナ100部、イオン交換水40
部、架橋重合可能なポリマーとしてポリビニルアルコー
ル（PVA）５部、及び解膠剤としてポリアクリル酸アン
モニウム１部をポットミルにて一昼夜混合してスラリー
を調製した。このスラリーに、増粘剤としてメチルセル
ロース１部、及び架橋剤としてグルタルアルデヒド1.25
部（PVAに対して25wt％）を添加し、攪拌機を用いて攪
拌し、泡立てた。更に、このスラリーに、架橋触媒とし
て塩酸をpHが1.2となるように添加し、充分に攪拌した
後、型に流し込んだ。この結果、架橋重合が進行し、約
１時間後には離型可能となった。成形体を乾燥した後、
焼結してセラミック多孔体を得た。Example 1 100 parts of alumina having an average particle size of 1.0 μm, ion-exchanged water 40
Parts, 5 parts of polyvinyl alcohol (PVA) as a cross-linkable polymer, and 1 part of ammonium polyacrylate as a deflocculant were mixed in a pot mill overnight to prepare a slurry. To this slurry, 1 part of methyl cellulose as a thickener and 1.25 glutaraldehyde as a cross-linking agent
Parts (25 wt% with respect to PVA) were added, and the mixture was stirred using a stirrer and foamed. Further, hydrochloric acid as a crosslinking catalyst was added to this slurry so as to have a pH of 1.2, sufficiently stirred, and then poured into a mold. As a result, the cross-linking polymerization proceeded, and the mold release was possible after about 1 hour. After drying the molded body,
It sintered and the ceramic porous body was obtained.
得られたセラミック多孔体は、気孔率65％、かさ密度
1.4g/cm3、平均気孔径200μｍであった。また、ほぼ全
ての気孔が開気孔となっていた。The obtained ceramic porous body has a porosity of 65% and a bulk density.
The average pore size was 1.4 g / cm 3 , and the average pore size was 200 μm. In addition, almost all the pores were open pores.
実施例２ 平均粒径1.0μｍのカルシア安定化ジルコニア100部、
イオン交換水30部、架橋重合可能なポリマーとしてイソ
バン−110（クラレ製）３部、及び解膠剤としてポリア
クリル酸アンモニウム１部をポットミルにて一昼夜混合
てスラリーを調製した。このスラリーに、増粘剤として
メチルセルロース１部、及び整泡剤としてステアリン酸
アンモニウム１部を添加し、攪拌機を用いて攪拌し、泡
立てた。更に、このスラリーに、架橋剤としてＢ−１
（クラレ製）0.3部（イソバン−110に対して10wt％）を
添加し、充分に攪拌した後、型に流し込んだ。この結
果、架橋重合が進行し、約５時間後に離型可能となっ
た。成形体を乾燥した後、空気中、1700℃で２時間焼結
してセラミック多孔体を得た。Example 2 100 parts of calcia-stabilized zirconia having an average particle size of 1.0 μm,
A slurry was prepared by mixing 30 parts of ion-exchanged water, 3 parts of Isovan-110 (manufactured by Kuraray) as a crosslinkable polymer, and 1 part of ammonium polyacrylate as a deflocculant in a pot mill overnight. To this slurry, 1 part of methyl cellulose as a thickening agent and 1 part of ammonium stearate as a foam stabilizer were added, and the mixture was stirred with a stirrer to generate a foam. Further, B-1 was added to this slurry as a crosslinking agent.
0.3 part (made by Kuraray Co., Ltd.) (10 wt% with respect to Isoban-110) was added, sufficiently stirred, and then poured into a mold. As a result, cross-linking polymerization proceeded, and the mold release became possible after about 5 hours. The molded body was dried and then sintered in air at 1700 ° C. for 2 hours to obtain a ceramic porous body.
得られたセラミック多孔体は、気孔率87％、かさ密度
0.8g/cm3、平均気孔径50μｍ、気孔の最大径70μｍであ
り、気孔径のばらつきが小さかった。また、ほぼ全ての
気孔が開気孔となっていた。The obtained ceramic porous body has a porosity of 87% and a bulk density.
The average pore diameter was 0.8 g / cm 3 , the maximum pore diameter was 70 μm, and the variation in pore diameter was small. In addition, almost all the pores were open pores.
以上詳述したように本発明の方法を用いれば、閉気
孔、開気孔にかかわらず、気孔径の範囲が広く、気孔径
分布が均一であり、かつ高強度のセラミック多孔体を容
易かつ安価に製造することができる。As described above in detail, by using the method of the present invention, regardless of whether the pores are closed or open, the range of pore diameter is wide, the pore diameter distribution is uniform, and a high-strength ceramic porous body can be easily and inexpensively produced. It can be manufactured.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 柴田 一朗 神奈川県秦野市曽屋30番地 東芝セラミ ックス株式会社中央研究所内 (72)発明者 岡本 賢一 神奈川県秦野市曽屋30番地 東芝セラミ ックス株式会社中央研究所内 (72)発明者 新妻 明子 神奈川県秦野市曽屋30番地 東芝セラミ ックス株式会社中央研究所内 (56)参考文献 特開 昭58−64255（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ichiro Shibata 30 Soya, Hadano City, Kanagawa Prefecture Central Research Laboratory, Toshiba Ceramics Co., Ltd. (72) Inventor Kenichi Okamoto 30 Soya, Hadano City, Kanagawa Prefecture Central Research In-house (72) Akiko Niitsuma 30 Soya, Hadano-shi, Kanagawa Central Research Laboratory, Toshiba Ceramics Co., Ltd. (56) Reference JP-A-58-64255 (JP, A)
Claims (1)
し得る有機物質を溶媒に分散又は溶解させたセラミック
スラリーに調製する工程と、このセラミックスラリーに
架橋剤を添加し、攪拌して発泡させた状態で成形・硬化
させる工程と、この成形体を乾燥し、焼結させることを
特徴とするセラミック多孔体の製造方法。1. A step of preparing a ceramic slurry in which a ceramic powder and an organic substance which can be cured by cross-linking polymerization are dispersed or dissolved in a solvent, and a step of adding a cross-linking agent to the ceramic slurry and stirring and foaming the mixture. A method for producing a ceramic porous body, comprising the steps of molding and curing, and drying and sintering this molded body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2333097A JP2506502B2 (en) | 1990-11-29 | 1990-11-29 | Method for manufacturing ceramic porous body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2333097A JP2506502B2 (en) | 1990-11-29 | 1990-11-29 | Method for manufacturing ceramic porous body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04202071A JPH04202071A (en) | 1992-07-22 |
| JP2506502B2 true JP2506502B2 (en) | 1996-06-12 |
Family
ID=18262246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2333097A Expired - Fee Related JP2506502B2 (en) | 1990-11-29 | 1990-11-29 | Method for manufacturing ceramic porous body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2506502B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8097203B2 (en) * | 2007-01-29 | 2012-01-17 | Corning Incorporated | Crosslinked green body articles and method of manufacturing porous ceramic articles therefrom |
| JP6530620B2 (en) * | 2014-03-28 | 2019-06-12 | 日本碍子株式会社 | Manufacturing method of membrane junction structure |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5864255A (en) * | 1981-10-08 | 1983-04-16 | カネボウ株式会社 | Manufacture of ceramic porous body |
-
1990
- 1990-11-29 JP JP2333097A patent/JP2506502B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04202071A (en) | 1992-07-22 |
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