JPH0645500B2 - Manufacturing method of honeycomb ceramics - Google Patents
Manufacturing method of honeycomb ceramicsInfo
- Publication number
- JPH0645500B2 JPH0645500B2 JP1172232A JP17223289A JPH0645500B2 JP H0645500 B2 JPH0645500 B2 JP H0645500B2 JP 1172232 A JP1172232 A JP 1172232A JP 17223289 A JP17223289 A JP 17223289A JP H0645500 B2 JPH0645500 B2 JP H0645500B2
- Authority
- JP
- Japan
- Prior art keywords
- honeycomb
- binder
- honeycomb structure
- hot water
- shape
- 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 - Lifetime
Links
- 239000000919 ceramic Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000011230 binding agent Substances 0.000 claims description 35
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 13
- 239000001263 FEMA 3042 Substances 0.000 claims description 13
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 13
- 239000000499 gel Substances 0.000 claims description 13
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 13
- 229940033123 tannic acid Drugs 0.000 claims description 13
- 235000015523 tannic acid Nutrition 0.000 claims description 13
- 229920002258 tannic acid Polymers 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 5
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- 238000001125 extrusion Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007602 hot air drying Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CUOSYYRDANYHTL-UHFFFAOYSA-N 1,4-dioctoxy-1,4-dioxobutane-2-sulfonic acid;sodium Chemical compound [Na].CCCCCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCCCC CUOSYYRDANYHTL-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は寸法精度に優れたハニカム状セラミックスを生
産性よく製造する方法に関し、本発明によって得られる
ハニカム状セラミックスは触媒担体用基体あるいはその
他一般構造材としても使用される。TECHNICAL FIELD The present invention relates to a method for producing a honeycomb-shaped ceramic having excellent dimensional accuracy with high productivity. The honeycomb-shaped ceramic obtained by the present invention is a catalyst carrier substrate or other general structural material. Also used as.
従来の技術 従来、触媒担体用基体としては一般に押出成形法から得
たハニカム状セラミックスが広く用いられており、この
製造方法は、一般にセラミックス粉末に適当量の成形助
剤と水とを加え、混練し、押出成形後、乾燥、焼成工程
を経て得るものであった。2. Description of the Related Art Conventionally, honeycomb ceramics obtained by an extrusion molding method have been widely used as a substrate for a catalyst carrier. This manufacturing method generally involves adding an appropriate amount of a molding aid and water to a ceramic powder and kneading the mixture. Then, after extrusion molding, it was obtained through a drying and firing process.
従来の製造方法では押出成形後、風乾、熱風乾燥するの
が一般的であった。そのために必要条件として、セラミ
ックス粉末としてすべり性に優れたものを選び、混練後
の成形材料にはできるだけ添加する水分量を減らし堅め
で調合する様努めてきた。In the conventional manufacturing method, air-drying and hot-air drying are generally performed after extrusion molding. Therefore, as a necessary condition, we have tried to select a ceramic powder having excellent slipperiness and to mix it with the molding material after kneading with as little water content as possible.
しかし、現実には押出成形後の風乾、熱風乾燥中に発生
するある程度の型くずれ、あるいは内部クラックの発生
は仕方のないことと考えられてきた。However, in reality, it has been considered that there is no choice but to cause a certain amount of mold deformation or internal cracks that occur during air drying after extrusion and hot air drying.
発明が解決しようとする課題 したがって、このような従来の製造方法では、ハニカム
状セラミックスに優れた寸法精度を保証するのは困難で
あり、歩留りも悪く、そのために生産コスト低減を図る
のも困難であった。Therefore, in such a conventional manufacturing method, it is difficult to ensure excellent dimensional accuracy of the honeycomb-shaped ceramics, the yield is also poor, and thus it is difficult to reduce the production cost. there were.
課題を解決するための手段 本発明は、原料となる無機材料粉末に、ある温度以上に
なるとゲル化する性質を有する結合剤を添加し、ハニカ
ム状に押出成形した後、タンニン酸またはタンニン酸と
界面活性剤とを含み前記結合剤がゲル化する温度以上の
熱水中に浸漬し、ハニカム構造体を保形させ、その後、
乾燥、焼成することを特徴とする。Means for Solving the Problems The present invention is, to an inorganic material powder as a raw material, a binder having a property of gelling at a certain temperature or higher is added, and after extrusion molding into a honeycomb shape, with tannic acid or tannic acid. The binder containing a surfactant is immersed in hot water at a temperature of gelling or higher to retain the shape of the honeycomb structure, and thereafter,
It is characterized by being dried and baked.
また、結合剤はメチルセルロース、ヒドロキシプロピル
セルロース、ヒドロキシプロピルメチルセルロースより
なる群から選ばれたものとすることができる。Further, the binder may be selected from the group consisting of methyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose.
また、ハニカム構造体がＳｉＯ２ ８０〜９２ｗｔ％、
Ａｌ２Ｃ３ ５〜１８ｗｔ％、ＴｉＯ２ ２〜６ｗｔ
％、Ｋ２Ｏ ０．４〜１．５ｗｔ％の組成を有するもの
とすることができる。In addition, the honeycomb structure has a SiO 2 content of 80 to 92 wt%,
Al 2 C 3 5~18wt%, TiO 2 2~6wt
%, K 2 O 0.4 to 1.5 wt%.
作 用 結合剤がゲル化する温度以上にした熱水中に、成形した
ハニカム構造体を直ちに浸漬すると、結合剤はゲル化
し、ハニカム構造体に充分な保形性を維持できるだけの
機械的強度が発現し、型くずれ等の問題を回避できるよ
うになる。しかし、その後熱水から引上げたハニカム構
造体を均一かつ迅速に乾燥しなければ、構造体が冷却
し、ゲル化した結合剤が再溶融してき、成形直後よりも
機械的強度がなくなってくる。そのため折角熱水中で寸
法精度よく保形させたハニカム構造体もその後の製造工
程中に型くずれを起こしてしまう。したがって、誘電加
熱方法等でハニカム構造体は均一かつ迅速に乾燥してや
らなければならなかった。そのため設備費用がかさみ、
生産工程等に課題を有していた。Immediate immersion of the formed honeycomb structure in hot water at a temperature above the gelation temperature of the binder causes the binder to gel, and the honeycomb structure has sufficient mechanical strength to maintain shape retention. It becomes possible to avoid problems such as loss of shape. However, unless the honeycomb structure pulled up from the hot water is dried uniformly and quickly thereafter, the structure cools and the gelled binder remelts, resulting in less mechanical strength than immediately after molding. As a result, the honeycomb structure that has been maintained in shape with high dimensional accuracy in hot water also loses its shape during the subsequent manufacturing process. Therefore, it is necessary to dry the honeycomb structure uniformly and quickly by the dielectric heating method or the like. Therefore, the equipment cost is high,
There was a problem in the production process.
本発明では熱水中に浸漬し、結合剤をゲル化させるとと
もに、結合剤をタンニン酸で不溶化させる。それによ
り、保形されたハニカム構造体が次の乾燥工程に移るま
でに冷却されても、機械的強度は損なわれない。また、
乾燥工程も簡単な熱風乾燥方法で充分型くずれ等の問題
を回避できる。In the present invention, the binder is gelled by being immersed in hot water, and the binder is insolubilized with tannic acid. As a result, the mechanical strength is not impaired even when the shape-retained honeycomb structure is cooled before the next drying step. Also,
A simple hot air drying method can be used for the drying process to avoid problems such as mold collapse.
さらに、本発明では熱水中にタンニン酸とともに界面活
性剤を添加するとハニカム構造体の型くずれ防止に効果
的である。たとえば、ハニカム構造体の開口率が小さか
ったり、長さが長かったりすると、結合剤をゲル化させ
るのに時間を要してしまい、ハニカム構造体の格子に歪
み、型くずれ等を発生させてしまう原因になり易い。し
たがって、この結合剤のゲル化、不溶化を促進させるた
め界面活性剤を添加すると、ハニカム構造体と水との湿
潤性、浸透性が改善される。その結果、ハニカム構造体
を熱水中に投入すると瞬時に含水し、結合剤のゲル化、
不溶化速度を速めることができ、ハニカム構造体の保形
性を向上させることができる。その結果、寸法精度に優
れたハニカム状セラミックスを得ることができる。Furthermore, in the present invention, adding a surfactant together with tannic acid to hot water is effective in preventing the honeycomb structure from losing its shape. For example, when the aperture ratio of the honeycomb structure is small or the length is long, it takes time for the binder to gel, and the lattice of the honeycomb structure may be distorted or deformed. It is easy to become. Therefore, when a surfactant is added to promote gelation and insolubilization of the binder, the wettability and the permeability of the honeycomb structure and water are improved. As a result, when the honeycomb structure is put into hot water, it immediately contains water and gels the binder,
The insolubilization rate can be increased, and the shape retention of the honeycomb structure can be improved. As a result, it is possible to obtain a honeycomb ceramic having excellent dimensional accuracy.
また、成形材料中に使用する結合剤にはセルロースエー
テル系のメチルセルロース、ヒドロキシプロピルセルロ
ース、ヒドロキシプロピルメチルセルロースよりなる群
から選ばれたものを使用すると押出成形の成形性、可塑
性にも効果を発揮しながら、本発明の目的とするゲル化
保形工程という点においても約６０〜９０℃という広い
範囲においてゲル化温度を選択でき、ゲル化させるため
の媒体としても水という安価なものを使用できるので生
産コスト低減にも有効である。When a binder selected from the group consisting of cellulose ether-based methyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose is used as the binder used in the molding material, the moldability and plasticity of extrusion molding can be effectively achieved. Also, in terms of the gelling and shape-retaining step which is the object of the present invention, the gelling temperature can be selected in a wide range of about 60 to 90 ° C., and an inexpensive medium such as water can be used as a medium for gelling. It is also effective for cost reduction.
ここで、ゲル化する結合剤とは、冷水には溶けて粘ちょ
うな溶液となるが、熱水には溶けずゲル化する性質を持
ったものである。たとえば、メトローズ６０ＳＨ−４０
００（信越化学工業、商品名）の場合、室温の水には溶
けるが、６０℃以上ではゲル化をおこす。これにより、
ハニカム構造体の保形性が維持される。Here, the binder that gels has a property of dissolving in cold water to form a viscous solution, but not in hot water and gelling. For example, Metroses 60SH-40
In the case of 00 (trade name of Shin-Etsu Chemical Co., Ltd.), it dissolves in water at room temperature, but gelation occurs at 60 ° C or higher. This allows
The shape retention of the honeycomb structure is maintained.
本発明で用いる無機材料粉末としては、シリカ、アルミ
ナ、チタニア、ジルコニア、カオリン、タルク、ムライ
ト、アルカリあるいはアルカリ土類のチタンン酸塩、コ
ージライト、炭化珪素、窒化珪素等を用いることができ
る。しかし、実用に際しては得られるセラミックスの機
械的強度、耐熱衝撃性等の観点から、ＳｉＯ２ ８０〜
９２ｗｔ％、Ａｌ２Ｃ３ ５〜１８ｗｔ％、ＴｉＯ２
２〜６ｗｔ％、Ｋ２Ｏ ０．４〜１．５ｗｔ％の組成を
有するものが優れている。As the inorganic material powder used in the present invention, silica, alumina, titania, zirconia, kaolin, talc, mullite, alkali or alkaline earth titanate, cordierite, silicon carbide, silicon nitride and the like can be used. However, in practical use, from the viewpoint of mechanical strength, thermal shock resistance, etc. of the obtained ceramics, SiO 2 80-
92wt%, Al 2 C 3 5~18wt %, TiO 2
Those having a composition of 2 to 6 wt% and K 2 O 0.4 to 1.5 wt% are excellent.
実施例 以下本発明の一実施例におけるハニカム状セラミックス
の製造方法について説明する。Example A method for manufacturing a honeycomb-shaped ceramic according to an example of the present invention will be described below.
（実施例１） 再水和性アルミナ １０重量部、溶融シリカ ８５重量
部、チタン酸カリウム ５重量部と結合剤としてメトロ
ーズ６０ＳＨ−４０００（信越化学工業、商品名） ７
重量部を混合し、その後適量の水と油脂とを加え湿式混
練した後、ハニカム状に押出成形し、１０５ｍｍφ、長
さ１００ｍｍ、セル密度３００セル／ｉｎ２（セルピッ
チ１．５ｍｍ、リブ厚０．２０ｍｍ）のハニカム構造体
を得た。その後、図に示す工程にもとづいて、タンニン
酸が５ｗｔ％含まれる９０℃の熱水中に６分間浸漬し、
結合剤（メトローズ６０ＳＨ−４０００）をゲル化し、
不溶化させた。(Example 1) 10 parts by weight of rehydratable alumina, 85 parts by weight of fused silica, 5 parts by weight of potassium titanate and METOLOSE 60SH-4000 as a binder (Shin-Etsu Chemical Co., Ltd., trade name) 7
After mixing parts by weight, and then adding an appropriate amount of water and fats and oils and wet-kneading the mixture, the mixture was extruded into a honeycomb shape, 105 mmφ, length 100 mm, cell density 300 cells / in 2 (cell pitch 1.5 mm, rib thickness 0. A 20 mm) honeycomb structure was obtained. Then, based on the steps shown in the figure, it is immersed for 6 minutes in 90 ° C. hot water containing 5 wt% of tannic acid,
Gel the binder (Metroze 60SH-4000),
Insolubilized.
この時、結合剤をゲル化、不溶化させるのに必要な所用
時間の目安としてはハニカム構造体を熱水中に浸漬し、
気泡がなくなってから、さらに３分間程度と判断した。At this time, gel the binder, as a measure of the time required to insolubilize, the honeycomb structure is immersed in hot water,
It was judged that the time was about 3 minutes after the air bubbles disappeared.
その後、ハニカム構造体を熱水から引上げ、エアーガン
（０．５ｋｇ／ｃｍ２）で、格子中に残留している余分
な水分を除去した。その後、１１０℃、２時間の熱処理
を行い、充分な乾燥が行われた後、ハニカム構造体を徐
々に１２００℃まで焼成し、１時間ホールドし、ハニカ
ム状セラミックスを得た。Then, the honeycomb structure was pulled up from the hot water, and the excess water remaining in the lattice was removed with an air gun (0.5 kg / cm 2 ). After that, heat treatment was performed at 110 ° C. for 2 hours, and after sufficient drying, the honeycomb structure was gradually fired to 1200 ° C. and held for 1 hour to obtain a honeycomb ceramic.
その結果、ハニカム状セラミックスには型くずれなく、
優れた寸法精度を維持させることができた。As a result, the honeycomb-shaped ceramics will not lose its shape,
It was possible to maintain excellent dimensional accuracy.
さらに、本実施例の場合にはタンニン酸５ｗｔ％の熱水
を使用したが、タンニン酸１ｗｔ％以上であれば効果が
確認された。Further, in the case of the present embodiment, hot water containing 5 wt% of tannic acid was used, but the effect was confirmed if the content of tannic acid was 1 wt% or more.
また、本実施例の場合には結合剤を５〜１０重量部添加
するのが好ましかった。その理由は、結合剤が５重量部
以下では熱水中でゲル化させても充分な機械的強度が得
られなく、１０重量部以上添加してもほとんど有意差は
なく、製造コストの点からも好ましくないためである。Further, in the case of this example, it was preferable to add 5 to 10 parts by weight of the binder. The reason is that if the amount of the binder is 5 parts by weight or less, sufficient mechanical strength cannot be obtained even if it is gelled in hot water, and even if it is added in an amount of 10 parts by weight or more, there is almost no difference, and from the viewpoint of manufacturing cost. Is also not preferable.
また、ハニカム構造体を浸漬する熱水の温度は結合剤の
有するゲル化温度によって異なるが、大体結合剤の有す
るゲル化温度よりも少なくても１０℃以上高温の熱水に
浸漬させないと充分な機械的強度の得られないことがわ
かった。Further, the temperature of hot water for immersing the honeycomb structure varies depending on the gelling temperature of the binder, but it is sufficient to immerse the honeycomb structure in hot water of 10 ° C. or higher even if it is lower than the gelling temperature of the binder. It was found that mechanical strength could not be obtained.
（比較例１） 実施例１と同様なハニカム構造体を押出成形で得た後、
１１０℃、２時間の熱処理を行い、充分な乾燥が行われ
た後、徐々に１２００℃まで焼成し、１時間ホールド
し、ハニカム状セラミックスを得た。(Comparative Example 1) After a honeycomb structure similar to that of Example 1 was obtained by extrusion molding,
After heat treatment at 110 ° C. for 2 hours and sufficient drying, it was gradually burned to 1200 ° C. and held for 1 hour to obtain a honeycomb ceramic.
その結果、ハニカム状セラミックスにはクラックが発生
するとともに、かなりの型くずれがあった。具体的に
は、乾燥時に自重で下部の径が少し大きくなっていた。
また、下部ハニカム格子にもよれが生じていた。As a result, cracks were generated in the honeycomb-shaped ceramics, and the mold was considerably deformed. Specifically, the diameter of the lower part was slightly increased due to its own weight during drying.
Further, the lower honeycomb lattice was also twisted.
（比較例２） 実施例１と同様なハニカム構造体を押出成形で得た後、
９０℃の熱水中に３分間浸漬し、結合剤をゲル化させ
た。(Comparative Example 2) After a honeycomb structure similar to that of Example 1 was obtained by extrusion molding,
The binder was gelated by immersing in hot water at 90 ° C. for 3 minutes.
この時、結合剤をゲル化させるのに必要な所用時間の目
安としてはハニカム構造体を熱水中に浸漬し、気泡が出
なくなるまでと考えた。At this time, it was considered that the honeycomb structure was immersed in hot water until bubbles did not come out, as a guide for the time required to gel the binder.
その後、ハニカム構造体を熱水から引上げ、エアーガン
（０．５ｋｇ／ｃｍ２）で、格子中に残留している余分
な水分を除去しようとしたところ、成形体が徐々に冷却
され、軟化し、ハニカム格子は変形してしまった。After that, when the honeycomb structure was pulled up from hot water and an excess amount of water remaining in the lattice was removed with an air gun (0.5 kg / cm 2 ), the formed body was gradually cooled and softened, The honeycomb lattice has deformed.
（比較例３） 実施例１と同様なハニカム構造体を押出成形で得た後、
９０℃の熱水中に３分間浸漬し、結合剤をゲル化させ
た。(Comparative Example 3) After a honeycomb structure similar to that of Example 1 was obtained by extrusion molding,
The binder was gelated by immersing in hot water at 90 ° C. for 3 minutes.
その後、ハニカム構造体を熱水から引上げ、約１５０℃
の温風を０．５ｋｇ／ｃｍ２で送り、格子中に残留して
いる余分な水分を除去後、出力１．５ｋｗ、２４５０Ｍ
Hzの誘電加熱装置で６分間乾燥し、徐々に１２００℃ま
で焼成し、１時間ホールドし、ハニカム状セラミックス
を得た。After that, the honeycomb structure is pulled up from the hot water to about 150 ° C.
Hot air is sent at 0.5 kg / cm 2 to remove excess water remaining in the grid, then output 1.5 kw, 2450 M
It was dried by a dielectric heating device of Hz for 6 minutes, gradually burned to 1200 ° C., and held for 1 hour to obtain a honeycomb ceramic.
その結果、ハニカム状セラミックスには型くずれなく、
優れた寸法精度を維持させることができた。As a result, the honeycomb-shaped ceramics will not lose its shape,
It was possible to maintain excellent dimensional accuracy.
したがって、比較例１、２、３と比較して実施例１は乾
燥工程で明らかな差のあることがわかる。Therefore, it can be seen that Example 1 has a clear difference in the drying process as compared with Comparative Examples 1, 2, and 3.
（実施例２） 実施例１と同様なハニカム構造体を押出成形で得た後、
タンニン酸が５ｗｔ％、アニオン系界面活性剤（ジ・オ
クチル・スルホ・コハク酸ナトリウム）が０．１ｗｔ％
含まれる９０℃の熱水中に３分間浸漬し、結合剤をゲル
化、不溶化させた。(Example 2) After a honeycomb structure similar to that of Example 1 was obtained by extrusion molding,
Tannic acid 5wt%, Anionic surfactant (sodium di-octyl sulfo-succinate) 0.1wt%
The binder was gelated and insolubilized by immersing in the contained hot water of 90 ° C. for 3 minutes.
この時、結合剤をゲル化、不溶化させるのに必要な所用
時間の目安としてはハニカム構造体を熱水中に浸漬し、
気泡が出なくなってから、さらに２分間程度と判断し
た。At this time, gel the binder, as a measure of the time required to insolubilize, the honeycomb structure is immersed in hot water,
It was judged that it was about 2 minutes after the bubbles disappeared.
その後、ハニカム構造体を熱水から引上げ、エアーガン
（０．５ｋｇ／ｃｍ２）で、格子中に残留している余分
な水分を除去した。その後、１１０℃、２時間の熱処理
をい、充分な乾燥が行われた後、ハニカム構造体を徐々
に１２００℃まで焼成し、１時間ホールドし、ハニカム
状セラミックスを得た。Then, the honeycomb structure was pulled up from the hot water, and the excess water remaining in the lattice was removed with an air gun (0.5 kg / cm 2 ). Then, after heat treatment at 110 ° C. for 2 hours and sufficient drying, the honeycomb structure was gradually fired to 1200 ° C. and held for 1 hour to obtain a honeycomb ceramic.
その結果、ハニカム状セラミックスには型くずれなく、
優れた寸法精度を維持させることができた。また、本実
施例では熱水に界面活性剤を添加することにより、実施
例１よりもゲル化、不溶化に要する時間を大幅に短縮で
きた。As a result, the honeycomb-shaped ceramics will not lose its shape,
It was possible to maintain excellent dimensional accuracy. Further, in this example, by adding the surfactant to the hot water, the time required for gelation and insolubilization could be significantly shortened as compared with Example 1.
また、界面活性剤としてアニオン系界面活性剤（ジ・オ
クチル・スルホ・コハク酸ナトリウム）を使用したが、
特にこれに限定されることなく、カチオン系、ノニオン
系のものでも同様な効果が確認された。しかし、添加量
を最も少なくして効果を発揮できるのはアニオン系界面
活性剤であった。また、添加量はそれぞれの場合によっ
て異なるが、大体０．１〜２．０ｗｔ％含まれる熱水で
あれば本実施例の効果が期待できた。An anionic surfactant (sodium di-octyl-sulfo-succinate) was used as the surfactant.
Without being limited to this, a similar effect was confirmed with a cation type or nonion type. However, it was an anionic surfactant that was most effective when the amount added was minimized. Further, although the addition amount varies depending on each case, the effect of the present embodiment can be expected if the content of hot water is approximately 0.1 to 2.0 wt%.
（実施例３） 実施例１と同様なハニカム構造体（長さ２００ｍｍ）を
押出成形で得た後、タンニン酸が５ｗｔ％含まれる９０
℃の熱水中に９分間浸漬し、結合剤をゲル化、不溶化さ
せた。(Example 3) A honeycomb structure similar to that in Example 1 (length 200 mm) was obtained by extrusion molding, and then 90 wt% of tannic acid was contained 90.
The binder was gelated and insolubilized by immersing in hot water at ℃ for 9 minutes.
この時、結合剤をゲル化、不溶化させるのに必要な所用
時間の目安としてはハニカム構造体を熱水中に浸漬し、
気泡が出なくなってから、さらに３分間程度と判断し
た。At this time, gel the binder, as a measure of the time required to insolubilize, the honeycomb structure is immersed in hot water,
It was judged that it was about 3 minutes after the bubbles disappeared.
その後、ハニカム構造体を熱水拾から引上げ、エアーガ
ン（０．５ｋｇ／ｃｍ２）で、格子中に残留している余
分な水分を除去した。その後、１２０℃、２時間の熱処
理を行い、充分な乾燥が行われた。Then, the honeycomb structure was pulled up from hot water and an excess air remaining in the lattice was removed with an air gun (0.5 kg / cm 2 ). Then, heat treatment was performed at 120 ° C. for 2 hours, and sufficient drying was performed.
その結果、ハニカム構造体には上部中心付近に格子の歪
みを生じた。その理由としては、本ハニカム構造体のよ
うなセル密度が高く、長さの長いものの場合、結合剤を
ゲル化させるのに時間がかかりすぎ、なかなか上部中心
付近まで熱水が浸入して行きにくいためと考えられる。As a result, lattice distortion occurred in the honeycomb structure near the center of the upper part. The reason is that in the case of a honeycomb structure having a high cell density and a long length, it takes too long to gel the binder, and it is difficult for hot water to penetrate to the vicinity of the upper center. It is thought to be because.
（実施例４） 実施例１と同様なハニカム構造体（長さ２００ｍｍ）を
押出成形で得た後、タンニン酸５ｗｔ％、アニオン系界
面活性剤（ジ・オクチル・スルホ・コハク酸ナトリウ
ム）が０．１ｗｔ％含まれる９０℃の熱水中に４分間浸
漬し、結合剤をゲル化、不溶化させた。(Example 4) After a honeycomb structure (200 mm in length) similar to that of Example 1 was obtained by extrusion molding, 5 wt% of tannic acid and 0 of an anionic surfactant (sodium di-octyl-sulfo-succinate) were used. The binder was gelled and insolubilized by immersing in 90% hot water containing 1 wt% for 4 minutes.
この時、結合剤をゲル化、不溶化させるのに必要な所用
時間の目安としてはハニカム構造体を熱水中に浸漬し、
気泡が出なくなってから、さらに２分間程度と判断し
た。At this time, gel the binder, as a measure of the time required to insolubilize, the honeycomb structure is immersed in hot water,
It was judged that it was about 2 minutes after the bubbles disappeared.
その後、ハニカム構造体を熱水から引上げ、エアーガン
（０．５ｋｇ／ｃｍ２）で、格子中に残留している余分
な水分を除去した。その後、１２０℃、２時間の熱処理
を行い、充分な乾燥が行われた後、ハニカム構造体を徐
々に１２００℃っまで焼成し、１時間ホールドし、ハニ
カム状セラミックスを得た。Then, the honeycomb structure was pulled up from the hot water, and the excess water remaining in the lattice was removed with an air gun (0.5 kg / cm 2 ). Then, heat treatment was performed at 120 ° C. for 2 hours, and after sufficient drying, the honeycomb structure was gradually fired to 1200 ° C. and held for 1 hour to obtain a honeycomb ceramic.
その結果、ハニカム状セラミックスには型くずれなく、
優れた寸法精度を維持させることができた。本実施例で
は実施例３に比べ、界面活性剤の効果が発揮されてい
る。As a result, the honeycomb-shaped ceramics will not lose its shape,
It was possible to maintain excellent dimensional accuracy. In this example, the effect of the surfactant is exhibited as compared with Example 3.
発明の効果 本発明によれば、ある温度以上になるとゲル化する結合
剤を用い、熱水中にタンニン酸を、好ましくは界面活性
剤とともに含ませることにより、従来問題となっていた
型くずれを解決でき、寸法精度に優れたハニカム状セラ
ミックスを生産性よく製造することができる。EFFECTS OF THE INVENTION According to the present invention, a binder that gels at a certain temperature or higher is used, and tannic acid is contained in hot water, preferably together with a surfactant. It is possible to manufacture the honeycomb-shaped ceramics excellent in dimensional accuracy with high productivity.
図は本発明の一実施例におけるハニカム状セラミックス
の製造方法を示す工程図である。The drawings are process diagrams showing a method for manufacturing a honeycomb-shaped ceramic according to an embodiment of the present invention.
Claims (4)
になるとゲル化する性質を有する結合剤を添加し、ハニ
カム状に押出成形した後、タンニン酸を含み前記結合剤
がゲル化する温度以上の熱水中に浸漬し、ハニカム構造
体を保形させ、その後、乾燥、焼成することを特徴とす
るハニカム状セラミックスの製造方法。1. A temperature at which a binder having a property of gelling at a certain temperature or higher is added to an inorganic material powder as a raw material, the mixture is extruded into a honeycomb shape, and then the binder contains tannic acid and gels. A method for producing a honeycomb-shaped ceramic, which comprises immersing the honeycomb structure in the hot water as described above to retain its shape, and then drying and firing.
ものである請求項１記載のハニカム状セラミックスの製
造方法。2. The method for producing a honeycomb-shaped ceramic according to claim 1, wherein the hot water contains a surfactant in addition to tannic acid.
ロピルセルロース、ヒドロキシプロピルメチルセルロー
スよりなる群から選ばれたものであることを特徴とする
請求項１または２記載のハニカム状セラミックスの製造
方法。3. The method for producing a honeycomb-shaped ceramic according to claim 1, wherein the binder is selected from the group consisting of methyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose.
ｔ％、Ａｌ２Ｏ３ ５〜１８ｗｔ％、ＴｉＯ２ ２〜６
ｗｔ％、Ｋ２Ｏ ０．４〜１．５ｗｔ％の組成を有する
ことを特徴とする請求項１または２記載のハニカム状セ
ラミックスの製造方法。4. A honeycomb structure comprising SiO 2 80-92w.
t%, Al 2 O 3 5 to 18 wt%, TiO 2 2 to 6
The method for manufacturing a honeycomb-shaped ceramic according to claim 1 or 2, wherein the composition has a composition of wt% and K 2 O 0.4 to 1.5 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1172232A JPH0645500B2 (en) | 1989-07-03 | 1989-07-03 | Manufacturing method of honeycomb ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1172232A JPH0645500B2 (en) | 1989-07-03 | 1989-07-03 | Manufacturing method of honeycomb ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0337153A JPH0337153A (en) | 1991-02-18 |
| JPH0645500B2 true JPH0645500B2 (en) | 1994-06-15 |
Family
ID=15938056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1172232A Expired - Lifetime JPH0645500B2 (en) | 1989-07-03 | 1989-07-03 | Manufacturing method of honeycomb ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0645500B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007111281A1 (en) * | 2006-03-23 | 2007-10-04 | Ngk Insulators, Ltd. | Honeycomb structure, process for producing the same, and bonding material |
-
1989
- 1989-07-03 JP JP1172232A patent/JPH0645500B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0337153A (en) | 1991-02-18 |
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