JP2728273B2 - Manufacturing method of porous ceramics - Google Patents
Manufacturing method of porous ceramicsInfo
- Publication number
- JP2728273B2 JP2728273B2 JP63271986A JP27198688A JP2728273B2 JP 2728273 B2 JP2728273 B2 JP 2728273B2 JP 63271986 A JP63271986 A JP 63271986A JP 27198688 A JP27198688 A JP 27198688A JP 2728273 B2 JP2728273 B2 JP 2728273B2
- Authority
- JP
- Japan
- Prior art keywords
- cured product
- weight
- pores
- water
- ceramic powder
- 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
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- 238000000034 method Methods 0.000 claims description 21
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- 238000010304 firing Methods 0.000 claims description 11
- 238000007717 redox polymerization reaction Methods 0.000 claims description 6
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- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 5
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
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- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 claims description 3
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- NNNLYDWXTKOQQX-UHFFFAOYSA-N 1,1-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OC(CC)(OC(=O)C=C)OC(=O)C=C NNNLYDWXTKOQQX-UHFFFAOYSA-N 0.000 description 1
- PWVUXRBUUYZMKM-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOCCO PWVUXRBUUYZMKM-UHFFFAOYSA-N 0.000 description 1
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Separation Of Gases By Adsorption (AREA)
- Filtering Materials (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はフィルター、吸着材、触媒担体、耐火断熱
材、吸音材、建材などとして有用なセラミックス多孔体
の新規な製造法に関する。The present invention relates to a novel method for producing a porous ceramic body useful as a filter, an adsorbent, a catalyst carrier, a fireproof heat insulating material, a sound absorbing material, a building material, and the like.
セラミックス多孔体は耐熱性、化学的安定性、耐摩耗
性、電気絶縁性などセラミックスがもっている特性と細
孔に起因する特性により優れた機能及び特徴を有してお
り、その製造法についても種々の方法が提案されてい
る。Porous ceramics have excellent functions and characteristics due to the properties possessed by ceramics such as heat resistance, chemical stability, abrasion resistance, electric insulation, and the properties caused by pores. A method has been proposed.
多孔化の代表的な方法として、粒子径のそろったセラ
ミックス粉末と有機バインダーとのグリーンを常圧で焼
結させたり、セラミックス粉末を粘土、ガラス質フラッ
クスなどの結合剤で結合させる方法がある。これらの方
法においては、主として粉末と粉末との間に存在する空
隙が気孔となるので、気孔の形状はくさび形であり、気
孔率についても一般的には30〜50%かそれ以下であり、
気孔率を大きくすることができない欠点がある。また、
気孔率や気孔の大きさは粉末の大きさや粉末の粒度分布
に大きく依存するため、所望の多孔体を得るには粉末の
大きさや形状を厳密に調整しなければならないなどの問
題がある。As a typical method of making porous, there are a method of sintering green of ceramic powder having a uniform particle diameter and an organic binder under normal pressure, and a method of bonding ceramic powder with a binder such as clay or vitreous flux. In these methods, voids existing mainly between the powders become pores, so that the shape of the pores is wedge-shaped, and the porosity is generally 30 to 50% or less,
There is a disadvantage that the porosity cannot be increased. Also,
Since the porosity and the size of the pores greatly depend on the size of the powder and the particle size distribution of the powder, there is a problem that the size and shape of the powder must be strictly adjusted to obtain a desired porous body.
他の方法として、セラミックス粉末と有機バインダー
と澱粉、木粉、もみがら粉、ワックス、合成樹脂、カー
ボンなどの可燃性物質、熱分解性物質の粉末との混合物
より得られるグリーンを焼成する方法がある。この方法
では、気孔は主として可燃性物質、熱分解性物質などの
粉末が除去されて形成されるので、気孔径はこれらの粉
末の大きさに依存する。一般にこれらの材料は粒度の調
整が困難で、微細な粉末が得られ難いとか、粉末の大き
さをそろえるのに多大の労力を要するとか、灰分が不純
物として入る恐れがあるなどの問題がある。この点を改
良する方法としてセラミックス粉末と有機バインダーと
水溶性粒状物質などからなるグリーンを水中にて抽出処
理した後焼成する方法(特開昭59−83972号)がある
が、この方法にも水溶性物質の粒子径を小さくしたり、
粒度を調整するのが困難であるとか、抽出操作がめんど
うであるなどの問題がある。As another method, there is a method of firing a green obtained from a mixture of a powder of a combustible substance such as a ceramic powder, an organic binder, a starch, a wood powder, a rice flour, a wax, a synthetic resin, carbon, and a pyrolytic substance. is there. In this method, the pores are formed mainly by removing powders of a combustible substance, a thermally decomposable substance, and the like, and thus the pore diameter depends on the size of these powders. In general, these materials have problems in that it is difficult to adjust the particle size, that it is difficult to obtain a fine powder, that a great deal of work is required to make the powder size uniform, and that ash may enter as impurities. As a method for improving this point, there is a method of extracting a green consisting of ceramic powder, an organic binder, and a water-soluble particulate substance in water, followed by baking (Japanese Patent Laid-Open No. 59-83972). Reducing the particle size of the active substance,
There are problems that it is difficult to adjust the particle size and that the extraction operation is troublesome.
可燃性発泡体にセラミックス粉末スラリーを含浸して
付着させた後焼成する方法(特開昭55−24585号)で
は、得られた多孔体がいわゆる骨格構造となっているの
で気孔率が大きいという特長を有している反面、強度が
弱いとか気孔径の大きいものしか得られないなどの問題
点を有している。その他、発泡剤により気孔を形成させ
る方法(特開昭60−195073号)があるが、気孔径の調節
が困難であるなどの問題がある。The method of impregnating a combustible foam with a ceramic powder slurry and adhering it, followed by firing (JP-A-55-24585), has the advantage that the resulting porous body has a so-called skeletal structure and therefore has a high porosity. On the other hand, it has problems such as low strength and a large pore size. In addition, there is a method of forming pores with a foaming agent (JP-A-60-195073), but there is a problem that it is difficult to adjust the pore diameter.
本発明者らは、先に、上述のごとき問題点のない新規
な製造方法として、セラミックス粉末、重合性不飽和化
合物、乳化剤、水を混合して油中水型エマルジョンとな
し、次いで該逆エマルジョンを硬化後乾燥した後焼成す
る方法を提案した(特願昭62−104829号)。The present inventors have previously proposed a novel production method having no problems as described above, by mixing a ceramic powder, a polymerizable unsaturated compound, an emulsifier, and water to form a water-in-oil emulsion, and then forming the inverse emulsion. After curing, drying and baking were proposed (Japanese Patent Application No. 62-104829).
本発明はさらに上述のごとき問題点のない新規な多孔
体の製造方法に係わり、その目的は気孔径が小さく、そ
の気孔が連続気孔であってしかもセラミックス全体にむ
らなく分布しており、加えて、容易に気孔率を広い範囲
で調節できるセラミックス多孔体の製造法を得ることに
ある。The present invention further relates to a method for producing a novel porous body having no problems as described above, the purpose of which is to have a small pore diameter, the pores are continuous pores, and are evenly distributed throughout the ceramics. Another object of the present invention is to provide a method for producing a porous ceramic body in which the porosity can be easily adjusted in a wide range.
本発明者らはかかる現状に鑑み、鋭意検討を重ねた結
果、重合性不飽和化合物を油層とする油中水型エマルジ
ョンにセラミックス粉末を混合分散して得られた該逆エ
マルジョンの硬化物の焼成によっても本発明の目的を達
成できるという知見を得、本発明を完成するに到った。In view of the present situation, the present inventors have made intensive studies and as a result, calcined a cured product of the inverse emulsion obtained by mixing and dispersing ceramic powder in a water-in-oil emulsion having a polymerizable unsaturated compound as an oil layer. It has been found that the object of the present invention can be achieved also by this method, and the present invention has been completed.
即ち、本発明は重合性不飽和化合物、乳化剤、水から
なる油中水型エマルジョンにセラミックス粉末を混合し
てセラミックス粉末を含む油中水型エマルジョンとな
し、次いで該逆エマルジョン中の重合性不飽和化合物を
ラジカル重合またはレドックス重合させることによって
得られた硬化物を乾燥した後焼成することを特徴とする
セラミックス多孔体の製造法に関する。That is, the present invention provides a water-in-oil emulsion containing a ceramic powder by mixing ceramic powder with a water-in-oil emulsion comprising a polymerizable unsaturated compound, an emulsifier, and water, and then polymerizing the unsaturated polymer in the inverse emulsion. The present invention relates to a method for producing a porous ceramic body, characterized in that a cured product obtained by subjecting a compound to radical polymerization or redox polymerization is dried and then fired.
本発明中、重合性不飽和化合物は逆エマルジョンの油
層として作用し、さらに重合後は油層中に分散されてい
るセラミックス粉末のバインダーとしても作用するとい
う特徴を有している。水は小滴となって油層中にむらな
く分散している。重合後この水を蒸発させるとその部分
が気孔となり、従って硬化物は多孔質となる。この多孔
質硬化物を通常の方法で焼成すると、水が蒸発して形成
された気孔がセラミックス中に残存して多孔質のセラミ
ックスとなるのである。In the present invention, the polymerizable unsaturated compound is characterized in that it acts as an oil layer of the inverse emulsion and, after polymerization, also acts as a binder for the ceramic powder dispersed in the oil layer. Water is evenly dispersed in the oil layer as droplets. When this water is evaporated after the polymerization, the portion becomes pores, and thus the cured product becomes porous. When the porous cured product is fired by a usual method, pores formed by evaporating water remain in the ceramic and become porous ceramic.
本発明におけるセラミックス粉末としては、アルミ
ナ、ジルコニア、マグネシア、酸化亜鉛、酸化錫、酸化
鉄、酸化チタン、スピネル、水酸化アルミニウム、水酸
化マグネシウム、水酸化カルシウム、炭酸バリウム、炭
化珪素、窒化珪素、窒化アルミニウムなどが好適である
が、焼結性があって逆エマルジョンの著しい相分離をも
たらさないものであればこれらに限定されるものではな
い。また、これらは適宜混合されて用いられてもよい
し、これらの粉末に酸化イットリウム、酸化セリウム、
酸化リチウム、ホウ酸塩、珪酸塩などの焼結助剤やガラ
ス質フラックスなどの結合剤、その他着色剤などを加え
てもよい。Examples of the ceramic powder in the present invention include alumina, zirconia, magnesia, zinc oxide, tin oxide, iron oxide, titanium oxide, spinel, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium carbonate, silicon carbide, silicon nitride, and nitride. Aluminum and the like are preferred, but are not limited thereto as long as they have sinterability and do not cause significant phase separation of the inverse emulsion. Further, these may be used by being appropriately mixed, and yttrium oxide, cerium oxide,
Sintering aids such as lithium oxide, borate and silicate, binders such as vitreous flux, and other coloring agents may be added.
重合性不飽和化合物としてはラジカル重合またはレド
ックス重合しうるものであってしかも逆エマルジョンを
生成しうるものであればよく、その代表的なものとして
スチレン、α−メチルスチレン、ジビニルベンゼンなど
のスチレン類、メチルメタクリレート、エチルメタクリ
レート、ブチルメタクリレート、エチレングリコールジ
メタクリレート、トリメチロールプロパントリメタクリ
レートなどのメタクリル酸エステルやメタクリル酸、メ
チルアクリレート、エチルアクリレート、ブチルアクリ
レート、2−エチルヘキシルアクリレート、エチレング
リコールジアクリレート、トリメチロールプロパントリ
アクリレートなどのアクリル酸エステルやアクリル酸、
酢酸ビニルエステル、ビニルピリジン類、ジアリルフタ
レート、アクリロニトリル、無水マレイン酸、不飽和ポ
リエステル類などがあげられる。これらは単独もしくは
適宜組み合わせて用いられる。As the polymerizable unsaturated compound, any compound capable of undergoing radical polymerization or redox polymerization and capable of forming an inverse emulsion may be used. Typical examples thereof include styrenes such as styrene, α-methylstyrene, and divinylbenzene. Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ethylene glycol diacrylate, trimethylol Acrylic esters and acrylic acid such as propane triacrylate,
Examples include vinyl acetate, vinyl pyridines, diallyl phthalate, acrylonitrile, maleic anhydride, unsaturated polyesters and the like. These are used alone or in appropriate combination.
乳化剤としてはソルビタントリステアレート、ソルビ
タンモノステアレート、ソルビタンセスキオレート、ソ
ルビタンモノオレート、ソルビタンモノパルミテート、
ソルビタンモノラウレートなどのソルビタンの高級脂肪
酸エステル、グリセロールステアレート、ポリグリセロ
ールオレートなどグリセロールあるいはポリグリセロー
ルの高級脂肪酸エステル、ジエチレングリコールステア
レート、ジエチレングリコールオレート、ポリオキシエ
チレンオレートなどポリエチレングリコールの高級脂肪
酸エステル、ポリオキシエチレンオレイルエーテル、ポ
リオキシエチレンドデシルフェニルエーテル、ポリオキ
シエチレンノニルフェニルエーテルなどの非イオン性界
面活性剤、平均分子量が1,000〜10,000のポリプロピレ
ングリコール、ポリブチレングリコールなどのボリアル
キレングリコールと無水コハク酸、無水マレイン酸、ヘ
キサヒドロ無水フタル酸などの二塩基酸無水物との付加
物で、末端にカルボキシル基を有するポリアルキレング
リコール誘導体のカルシウムまたはマグネシウム中和
物、アルキレングリコール類と二塩基酸からなる末端に
カルボキシル基を有するポリエステルオリゴマーのカル
シウムまたはマグネシウム、アミン中和物などがあげら
れるが、逆エマルジョンを生成する作用を有するもので
あればこれらの乳化剤に限定されない。これらのうち、
ソルビタントリステアレート、ソルビタンモノステアレ
ート、ソルビタンセスキオレート、ソルビタンモノオレ
ート、ソルビタンモノパルミテートなどは特に好まし
い。また、これらの乳化剤は単独で用いてもよいし、望
ましい作用効果を得るために二種以上混合して用いても
よい。As emulsifiers, sorbitan tristearate, sorbitan monostearate, sorbitan sesquiolate, sorbitan monooleate, sorbitan monopalmitate,
Higher fatty acid esters of sorbitan such as sorbitan monolaurate, higher fatty acid esters of glycerol or polyglycerol such as glycerol stearate and polyglycerol, higher fatty acid esters of polyethylene glycol such as diethylene glycol stearate, diethylene glycol oleate and polyoxyethylene oleate, polyoxy Nonionic surfactants such as ethylene oleyl ether, polyoxyethylene dodecyl phenyl ether, and polyoxyethylene nonyl phenyl ether; polyalkylene glycols such as polypropylene glycol and polybutylene glycol having an average molecular weight of 1,000 to 10,000 and succinic anhydride; An adduct with a dibasic acid anhydride such as maleic acid or hexahydrophthalic anhydride. Neutralized calcium or magnesium of a polyalkylene glycol derivative having a hydroxyl group, calcium or magnesium of a polyester oligomer having a carboxyl group at the end comprising an alkylene glycol and a dibasic acid, neutralized with an amine, and the like. It is not limited to these emulsifiers as long as they have an action of producing the emulsifier. Of these,
Sorbitan tristearate, sorbitan monostearate, sorbitan sesquiolate, sorbitan monooleate, sorbitan monopalmitate and the like are particularly preferred. Further, these emulsifiers may be used alone or in combination of two or more in order to obtain a desired effect.
次に製造方法について説明する。 Next, a manufacturing method will be described.
本発明においてはまず重合性不飽和化合物、乳化剤、
水を混合して逆エマルジョンを生成させ、次いで得られ
た逆エマルジョンにセラミックス粉末を混合する。逆エ
マルジョンを生成するためにはかい形、プロペラ形、タ
ービン形などの翼を持った撹拌機やコロイドミルなどの
混合機が用いられ、セラミックス粉末の混合にはボール
ミル、ペブルミル、コロイドミルなどの混合機、ニーダ
ー、ポニーミキサー、スクリュー押出機などの混練機を
用いることができるが、これに限定されるものではな
い。またセラミックス粉末を均一に分散させたり、気泡
をつくらないために必要ならば分散剤や消泡剤などを適
宜用いてもさしつかえない。In the present invention, first, a polymerizable unsaturated compound, an emulsifier,
Water is mixed to form an inverse emulsion, and then the resulting inverse emulsion is mixed with ceramic powder. A mixer such as a paddle-type, propeller-type, or turbine-type stirrer with a blade or a colloid mill is used to generate an inverse emulsion, and a ceramic powder is mixed with a ball mill, pebble mill, colloid mill, etc. A kneader such as a kneader, a kneader, a pony mixer, and a screw extruder can be used, but is not limited thereto. If necessary, a dispersing agent or an antifoaming agent may be appropriately used in order to uniformly disperse the ceramic powder or to prevent generation of bubbles.
本発明の方法では、逆エマルジョンを生成させる過程
においてセラミックス粉末が存在しないので粘度が低
く、乳化し易いため逆エマルジョンを生成するときの撹
拌に大きなエネルギーを要しない利点がある。さらに逆
エマルジョンの生成後セラミックス粉末を加えるので、
該粉末の分散の過程でエマルジョン粒子、即ち、水の小
滴が小さくなる効果がある。The method of the present invention has the advantage that the viscosity is low because no ceramic powder is present in the process of forming the inverse emulsion, and it is easy to emulsify, so that a large amount of energy is not required for stirring when the inverse emulsion is formed. In addition, ceramic powder is added after the formation of the inverse emulsion,
In the process of dispersing the powder, there is an effect that emulsion particles, that is, water droplets become small.
セラミックス粉末を含む逆エマルジョンの組成につい
ては、セラミックス粉末、重合性不飽和化合物、水が重
量比で100:10〜50:10〜300であるのが望ましい。水の比
率は硬化物や焼成して得られるセラミックスのかさ比重
と極めて密接に関係する。即ち、水の比率がおおきくな
るとかさ比重は小さくなり、気孔率は大きくなる。逆に
水の比率が小さいとかさ比重や強度は大きくなり、気孔
率は小さくなる。重合性不飽和化合物の比率は小さいほ
うが焼成し易く、また経済的にも好ましいが、一方、硬
化物の強度は小さくなり、逆エマルジョンの粘度が高く
なる傾向になる。Regarding the composition of the inverse emulsion containing the ceramic powder, the weight ratio of the ceramic powder, the polymerizable unsaturated compound and water is desirably 100: 10 to 50:10 to 300. The ratio of water is very closely related to the bulk specific gravity of a cured product or a ceramic obtained by firing. That is, as the ratio of water increases, the bulk specific gravity decreases and the porosity increases. Conversely, when the ratio of water is small, the bulk specific gravity and strength increase, and the porosity decreases. The smaller the ratio of the polymerizable unsaturated compound is, the easier the baking is and the more economically preferable. However, the strength of the cured product is reduced, and the viscosity of the inverse emulsion tends to increase.
乳化剤の添加量は重合性不飽和化合物100重量部に対
し5〜100重量部が適当である。不飽和ポリエステルオ
リゴマーの中和物を用いる場合は該中和剤は乳化剤とし
て作用すると同時に重合体中に組み込まれてバインダー
としても作用するので添加量が多くなっても特に問題は
ない。ただし、乳化剤と重合性不飽和化合物の合計量が
多くなり過ぎると焼成が困難になる。An appropriate amount of the emulsifier is 5 to 100 parts by weight based on 100 parts by weight of the polymerizable unsaturated compound. When a neutralized product of an unsaturated polyester oligomer is used, the neutralizing agent acts as an emulsifier and at the same time acts as a binder by being incorporated into the polymer, so that there is no particular problem even if the added amount is large. However, if the total amount of the emulsifier and the polymerizable unsaturated compound is too large, baking becomes difficult.
次いで逆エマルジョン中の重合性不飽和化合物をラジ
カル重合またはレドックス重合して硬化物を得ることが
できる。該重合は通常の重合開始剤、レドックス重合開
始剤を用いておこなう。その代表例として、過酸化水
素、過硫酸カリウム、過硫酸アンモニウム、過酸化ベン
ゾイル、過酸化ラウロイル、メチルエチルケトンパーオ
キサイド、t−ブチルヒドロパーオキサイドなどの過酸
化物系重合開始剤や、該過酸化物系重合開始剤と亜硫酸
水素ナトリウム、第1鉄塩、ジメチルアニリン、ナフテ
ン酸コバルト、スルフィン酸などの還元性物質との組合
せよりなるレドックス重合開始剤があげられる。重合開
始剤の使用量は重合性不飽和化合物100重量部に対し0.0
2〜5重量部が望ましい。Next, the polymerizable unsaturated compound in the inverse emulsion is subjected to radical polymerization or redox polymerization to obtain a cured product. The polymerization is carried out using a usual polymerization initiator and a redox polymerization initiator. Typical examples thereof include peroxide polymerization initiators such as hydrogen peroxide, potassium persulfate, ammonium persulfate, benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, and the like. Redox polymerization initiators comprising a combination of a polymerization initiator and a reducing substance such as sodium bisulfite, ferrous salt, dimethylaniline, cobalt naphthenate, sulfinic acid and the like can be mentioned. The amount of the polymerization initiator used is 0.0 with respect to 100 parts by weight of the polymerizable unsaturated compound.
2-5 parts by weight are desirable.
重合温度、重合時間は100℃以下で1〜48時間とする
のが好ましい。該重合条件についてはこれらに限定され
ないが、重合中の著しい水分の蒸発は避けるべきであ
る。The polymerization temperature and the polymerization time are preferably from 100 ° C. or lower to 1 to 48 hours. The polymerization conditions are not limited to these, but significant evaporation of water during polymerization should be avoided.
セラミックス粉末含有逆エマルジョンを重合して得ら
れた硬化物は系内に水がむらなく分散されており、これ
を乾燥して水を蒸発させる多孔質硬化物が得られる。乾
燥方法としては熱風乾燥、内部加熱乾燥、真空乾燥、凍
結乾燥などがある。A cured product obtained by polymerizing a ceramic powder-containing inverse emulsion has water uniformly dispersed in the system, and is dried to obtain a porous cured product in which water is evaporated. Drying methods include hot air drying, internal heating drying, vacuum drying, freeze drying and the like.
該多孔質硬化物を通常の方法で焼成すると、まず有機
物が酸化分解あるいは熱分解により除去され、次いでセ
ラミックス粉末の焼結かあるいは結合がおこってセラミ
ックス多孔体が得られる。焼成条件は1〜200℃/hrの昇
温速度で1000℃以上とするのが好ましい。焼成条件を決
める要因としてはセラミックス粉末の種類、粒度、その
他硬化物を構成している材料の種類及びそれらの組成
比、硬化物の大きさや形状、炉内雰囲気などであるが、
これらを勘案して最適になるよう適宜選定すればよい。
有機物の除去がおこる温度域ではクラックや変形を防ぐ
ため、昇温速度を小さくし、時間をかけて焼成するのが
好ましい。この際硬化物が架橋された構造となっている
と、この温度域での昇温速度を大きくすることができ、
それだけ焼成のためのエネルギーが少なくてよく有利で
ある。架橋は多官能性不飽和化合物を共重合させること
によりおこなうことができる。この多官能性不飽和化合
物としてはジビニルベンゼン、エチレングリコールジメ
タクリレート、トリメチロールプロパントリメタクリレ
ート、エチレングリコールジアクリレート、トリメチロ
ールプロパントリアクリレート、ジアリルフタレート、
不飽和ポリエステル類などがあげられる。When the porous cured product is fired by a usual method, organic substances are first removed by oxidative decomposition or thermal decomposition, and then ceramic powder is sintered or bonded to obtain a ceramic porous body. The firing conditions are preferably set to 1000 ° C. or higher at a temperature increase rate of 1 to 200 ° C./hr. Factors that determine the sintering conditions include the type of ceramic powder, particle size, the type of material constituting the cured product and their composition ratio, the size and shape of the cured product, the furnace atmosphere, and the like.
An appropriate selection may be made in consideration of these factors.
In a temperature range in which organic substances are removed, in order to prevent cracks and deformation, it is preferable that the heating rate is reduced and firing is performed over time. At this time, if the cured product has a crosslinked structure, the rate of temperature rise in this temperature range can be increased,
This is advantageous because less energy is required for firing. Crosslinking can be performed by copolymerizing a polyfunctional unsaturated compound. Examples of the polyfunctional unsaturated compound include divinylbenzene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate, diallyl phthalate,
And unsaturated polyesters.
本発明によって得られるセラミックス多孔体において
は、気孔はむらなく分布している。気孔の大きさは比較
的一定で、ほとんどが7〜8μm以下であるが、製造条
件によってはそれ以上の大きさのものが混在することも
ある。気孔の形状は概ね球状かまたは球状の気孔が複数
部分的に融合した形状となっているが、焼成前の硬化物
中の気孔がセラミックス粉末の大きさに比較してあまり
大きくない場合は、その形状は明確ではなくなる。焼成
によりセラミックス粉末は連続層となるが、一方、気孔
もほとんどが連続気孔となっている。In the ceramic porous body obtained according to the present invention, pores are uniformly distributed. The size of the pores is relatively constant, most of which is 7 to 8 μm or less, however, depending on the manufacturing conditions, pores having a larger size may be mixed. The shape of the pores is generally spherical or a shape in which a plurality of spherical pores are partially fused, but if the pores in the cured product before firing are not too large compared to the size of the ceramic powder, The shape becomes less clear. The ceramic powder becomes a continuous layer by firing, while the pores are mostly continuous pores.
実施例 1 スチレン21.6重量部とトリメチロールプロパントリメ
タクリレート2.4重量部、ソルビタンモノオレート6.0重
量部の混合液30重量部に0.15重量%過硫酸アンモニウム
水溶液100重量部を徐々に加えながら十字形撹拌翼で激
しく撹拌したところ逆エマルジョンが得られた。次に得
られた逆エマルジョン130重量部とアルミナ(AES−22
S、住友化学工業社製)100重量部をポールミルにて24時
間混合した。続いてこれを脱泡後型枠に流し込み、60℃
で24時間重合させた後型枠から取り出し、60℃で乾燥し
たところ多孔質硬化が得られた。さらに該硬化物を切削
して12.7mm×6.3mm×76.2mmの大きさとした。Example 1 100 parts by weight of a 0.15% by weight ammonium persulfate aqueous solution was gradually added to 30 parts by weight of a mixture of 21.6 parts by weight of styrene, 2.4 parts by weight of trimethylolpropane trimethacrylate, and 6.0 parts by weight of sorbitan monooleate with a cruciform stirring blade. Upon stirring, an inverse emulsion was obtained. Next, 130 parts by weight of the obtained inverse emulsion and alumina (AES-22
S, manufactured by Sumitomo Chemical Co., Ltd.) was mixed with a pole mill for 24 hours. Then, after defoaming, pour it into the mold,
After polymerization for 24 hours, the resin was taken out of the mold and dried at 60 ° C. to obtain a porous cured product. The cured product was further cut to a size of 12.7 mm × 6.3 mm × 76.2 mm.
次にこれを焼成すべく電気炉に入れ、空気中で昇温速
度50℃/hrで1450℃まで昇温し、5時間保持した後冷却
してセラミックス多孔体を得た。この多孔体にはクラッ
クや変形は見られなかった。Next, this was put into an electric furnace for firing, heated to 1450 ° C. in air at a rate of 50 ° C./hr, kept for 5 hours, and then cooled to obtain a porous ceramic body. No crack or deformation was observed in this porous body.
硬化物とセラミックスの割面を走査型電子顕微鏡で観
察したところ、硬化物には4〜5μm以下の球状の気孔
がむらなく分布していた。セラミックスにも概ね球状か
または球状の気孔が複数部分的に融合した形状のものと
がむらなく分布していた。硬化物とセラミックスの性状
を表1に示す。Observation of the cut surface of the cured product and the ceramics with a scanning electron microscope revealed that the cured product had spherical pores of 4 to 5 μm or less distributed uniformly. The ceramics also had a substantially spherical shape or a shape in which a plurality of spherical pores were partially fused, and were uniformly distributed. Table 1 shows the properties of the cured product and the ceramics.
実施例 2 スチレン20重量部とソルビタンセスキオレート5重量
部の混合液25重量部に0.21重量%過硫酸アンモニウム水
溶液60重量部を徐々に加えながら十字形撹拌翼で激しく
撹拌したところ逆エマルジョンが得られた。次に得られ
た逆エマルジョン85重量部とアルミナ(AES−22S)100
重量部をボールミルにて48時間混合した。続いて脱泡後
型枠に流し込み60℃で24時間重合させた後型枠から取り
出し、60℃で乾燥したところ多孔質硬化物が得られた。Example 2 A reverse emulsion was obtained by vigorously stirring with a cross-shaped stirring blade while gradually adding 60 parts by weight of a 0.21% by weight aqueous solution of ammonium persulfate to 25 parts by weight of a mixture of 20 parts by weight of styrene and 5 parts by weight of sorbitan sesquiolate. . Next, 85 parts by weight of the obtained inverse emulsion and alumina (AES-22S) 100
Parts by weight were mixed in a ball mill for 48 hours. Subsequently, after defoaming, the mixture was poured into a mold, polymerized at 60 ° C. for 24 hours, taken out of the mold, and dried at 60 ° C. to obtain a porous cured product.
次に実施例1と同様に切削加工された硬化物を焼成す
べく電気炉に入れ、空気中で昇温速度5℃/hrで600℃ま
で昇温した後いったん放冷し、続いて昇温速度50℃/hr
で1450℃まで昇温し、5時間保持した後冷却してセラミ
ックス多孔体を得た。この多孔体にはクラックや変形は
見られなかった。Next, the cured product cut in the same manner as in Example 1 was placed in an electric furnace to be baked, heated to 600 ° C. at a heating rate of 5 ° C./hr in air, allowed to cool once, and then heated. Speed 50 ° C / hr
The temperature was raised to 1450 ° C., kept for 5 hours, and then cooled to obtain a porous ceramic body. No crack or deformation was observed in this porous body.
実施例1と同様に割面を観察したところ、硬化物には
2〜3μm以下の球状の気孔がむらなく分布していた。
セラミックスにも気孔はむらなく分布していた。硬化物
とセラミックスの性状を表1に示す。When the fracture surface was observed in the same manner as in Example 1, spherical pores of 2 to 3 μm or less were uniformly distributed in the cured product.
Pores were evenly distributed in the ceramics. Table 1 shows the properties of the cured product and the ceramics.
実施例 3 あらかじめ、分子量2053のポリプロピレングリコール
205.3重量部と無水マレイン酸9.8重量部を不活性ガス中
120℃で5時間反応させて得られた付加誘導体100重量部
を0.92重量部の酸化マグネシウムで中和して得られた中
和物(以下PPGMA(P−Mg)と略す)を合成した。Example 3 Polypropylene glycol having a molecular weight of 2053 in advance
205.3 parts by weight and 9.8 parts by weight of maleic anhydride in an inert gas
A neutralized product (hereinafter abbreviated as PPGMA (P-Mg)) obtained by neutralizing 100 parts by weight of the adduct obtained by reacting at 120 ° C. for 5 hours with 0.92 parts by weight of magnesium oxide was synthesized.
次にスチレン36.0重量部とトリメチロールプロパント
リメタクリレート4.0重量部とPPGMA(P−Mg)10.0重量
部の混合液50重量部に0.5重量%過硫酸アンモニウム水
溶液50重量部を徐々に加えながら十字形撹拌翼で激しく
撹拌したところ逆エマルジョンが得られた。次に得られ
た逆エマルジョン100重量部とアルミナ(AES−11、住友
化学工業社製)100重量部をボールミルにて40時間混合
した。以下実施例2と同様にして切削加工された硬化物
を得た。Next, 50 parts by weight of a mixture of 36.0 parts by weight of styrene, 4.0 parts by weight of trimethylolpropane trimethacrylate, and 10.0 parts by weight of PPGMA (P-Mg) were gradually added with 50 parts by weight of a 0.5% by weight aqueous solution of ammonium persulfate to form a cruciform stirring blade. After vigorous stirring, an inverse emulsion was obtained. Next, 100 parts by weight of the obtained inverse emulsion and 100 parts by weight of alumina (AES-11, manufactured by Sumitomo Chemical Co., Ltd.) were mixed in a ball mill for 40 hours. Thereafter, a hardened material cut and processed in the same manner as in Example 2 was obtained.
次に切削加工された硬化物を焼成すべく電気炉に入
れ、空気中で600℃まで昇温速度20℃/hrで昇温し、続い
て1350℃まで昇温速度50℃/hrで昇温し、5時間保持し
た後冷却してセラミックス多孔体を得た。この多孔体に
はクラックや変形は見られなかった。Next, the cut hardened material is put into an electric furnace to be fired, heated in air to 600 ° C at a heating rate of 20 ° C / hr, and then heated to 1350 ° C at a heating rate of 50 ° C / hr. After holding for 5 hours, the mixture was cooled to obtain a ceramic porous body. No crack or deformation was observed in this porous body.
実施例1と同様に割面を観察したところ、硬化物には
1μm以下の気孔がむらなく分布していた。セラミック
スにも気孔はむらなく分布していた。硬化物とセラミッ
クスの性状を表1に示す。When the fractured surface was observed in the same manner as in Example 1, pores of 1 μm or less were uniformly distributed in the cured product. Pores were evenly distributed in the ceramics. Table 1 shows the properties of the cured product and the ceramics.
〔効果〕 本発明の製法はセラミックス粉末を含む逆エマルジョ
ンの硬化物を焼成する方法で、この方法においては気孔
は主として水が蒸発して形成された気孔によるものであ
る。そのため、気孔が全体にむらなく分布しているこ
と、気孔径が小さいこと、気孔の形状が概ね球状かまた
は球状の気孔が複数部分的に融合した形状となっている
こと、硬化物中の組成比を変えるだけで気孔率の大きい
ものから小さいものまで広い範囲で自由に調節できるこ
と、製造方法が容易であること、硬化物が切削加工でき
ることなどの特徴を有する。本発明はこれらに加えて、
あらかじめ重合性不飽和化合物、乳化剤、水により逆エ
マルジョンをつくるので、逆エマルジョンの生成が極め
て容易であること、逆エマルジョンの生成後セラミック
ス粉末を加えるので該粉末の分散中にエマルジョン中に
存している水の小滴の径がさらに小さくなり、硬化物や
セラミックス中の気孔も小さくなるなどの特徴を有し、
工業的にも有利な製造方法であり、かつ広く利用できる
ものである。 [Effects] The production method of the present invention is a method of firing a cured product of an inverse emulsion containing ceramic powder. In this method, pores are mainly formed by evaporation of water. Therefore, the pores are distributed evenly throughout the pores, the pore diameter is small, the shape of the pores is generally spherical or a shape in which a plurality of spherical pores are partially fused, the composition in the cured product It has the features that it can be freely adjusted in a wide range from a large porosity to a small porosity simply by changing the ratio, that the production method is easy, and that a cured product can be cut. The present invention, in addition to these,
Since an inverse emulsion is formed in advance with a polymerizable unsaturated compound, an emulsifier, and water, it is extremely easy to form an inverse emulsion.Because ceramic powder is added after the formation of an inverse emulsion, it is present in the emulsion during dispersion of the powder. It has the characteristics that the diameter of small water droplets is smaller and the pores in the cured product and ceramics are smaller,
It is an industrially advantageous production method and can be widely used.
本発明によって得られたセラミックス多孔体はその特
徴を生かし、フィルター、吸着材、触媒担体、耐火断熱
材、吸音材、建材等に有用である。The ceramic porous body obtained according to the present invention is useful for filters, adsorbents, catalyst carriers, heat-insulating materials, sound-absorbing materials, building materials, etc. by utilizing its features.
Claims (3)
油中水型エマルジョンにセラミックス粉末を混合してセ
ラミックス粉末を含む油中水型エマルジョンとなし、次
いで該逆エマルジョン中の重合性不飽和化合物をラジカ
ル重合またはレドックス重合させることによって得られ
た硬化物を乾燥した後焼成することを特徴とするセラミ
ックス多孔体の製造法。1. A water-in-oil emulsion comprising a polymerizable unsaturated compound, an emulsifier and water, mixed with a ceramic powder to form a water-in-oil emulsion containing the ceramic powder, and then the polymerizable unsaturated compound in the inverse emulsion. A method for producing a porous ceramic body, comprising drying a cured product obtained by subjecting a compound to radical polymerization or redox polymerization, followed by firing.
ルビタンモノステアレート、ソルビタンセスキオレー
ト、ソルビタンモノオレート、ソルビタンモノパルミテ
ートであることを特徴とする特許請求の範囲第1項記載
のセラミックス多孔体の製造法。2. The method according to claim 1, wherein the emulsifier is sorbitan tristearate, sorbitan monostearate, sorbitan sesquiolate, sorbitan monooleate, or sorbitan monopalmitate. Law.
されていることを特徴とする特許請求の範囲第1項また
は第2項記載のセラミックス多孔体の製造法。3. The method according to claim 1, wherein the cured product is cross-linked by a polyfunctional unsaturated compound.
Priority Applications (1)
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---|---|---|---|
JP63271986A JP2728273B2 (en) | 1988-10-29 | 1988-10-29 | Manufacturing method of porous ceramics |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63271986A JP2728273B2 (en) | 1988-10-29 | 1988-10-29 | Manufacturing method of porous ceramics |
Publications (2)
Publication Number | Publication Date |
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JPH02120285A JPH02120285A (en) | 1990-05-08 |
JP2728273B2 true JP2728273B2 (en) | 1998-03-18 |
Family
ID=17507556
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JP63271986A Expired - Fee Related JP2728273B2 (en) | 1988-10-29 | 1988-10-29 | Manufacturing method of porous ceramics |
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