JPS6340777A - Cordierite honeycomb structure and manufacture - Google Patents
Cordierite honeycomb structure and manufactureInfo
- Publication number
- JPS6340777A JPS6340777A JP18282486A JP18282486A JPS6340777A JP S6340777 A JPS6340777 A JP S6340777A JP 18282486 A JP18282486 A JP 18282486A JP 18282486 A JP18282486 A JP 18282486A JP S6340777 A JPS6340777 A JP S6340777A
- Authority
- JP
- Japan
- Prior art keywords
- less
- average particle
- honeycomb structure
- particle size
- cordierite
- 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.)
- Granted
Links
- 229910052878 cordierite Inorganic materials 0.000 title claims description 49
- 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 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000011148 porous material Substances 0.000 claims description 57
- 239000002245 particle Substances 0.000 claims description 52
- 239000000454 talc Substances 0.000 claims description 29
- 229910052623 talc Inorganic materials 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 235000012211 aluminium silicate Nutrition 0.000 claims description 22
- 239000005995 Aluminium silicate Substances 0.000 claims description 21
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 description 9
- 230000035939 shock Effects 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000004927 clay Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- BDEDPKFUFGCVCJ-UHFFFAOYSA-N 3,6-dihydroxy-8,8-dimethyl-1-oxo-3,4,7,9-tetrahydrocyclopenta[h]isochromene-5-carbaldehyde Chemical compound O=C1OC(O)CC(C(C=O)=C2O)=C1C1=C2CC(C)(C)C1 BDEDPKFUFGCVCJ-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000280 densification Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001753 sapphirine Inorganic materials 0.000 description 1
- -1 sapphirine) Chemical compound 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はコージェライトハニカム構造体に関するもので
、さらに詳しくは耐熱衝撃性、気密性及び耐熱性にも優
れた回転蓄熱式又は伝熱式熱交換体用高気密性コージェ
ライトハニカム構造体及びその製造方法に関するもので
ある。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a cordierite honeycomb structure, and more specifically to a cordierite honeycomb structure that has excellent thermal shock resistance, airtightness, and heat resistance. The present invention relates to a highly airtight cordierite honeycomb structure for an exchanger and a method for manufacturing the same.
（従来の技術および解決しようとする問題点）近年工業
技術の進歩に伴い、耐熱性、耐熱衝撃性に優れた材料の
要求が増加している。セラミックスの耐熱衝撃性は、材
料の熱膨張率、熱伝導率、強度、弾性率、ポアソン比等
の特性に影響されると共に、製品の大きさや形状、さら
に加熱、冷却状態即ち熱移動速度にも影響される。(Prior Art and Problems to be Solved) With the progress of industrial technology in recent years, the demand for materials with excellent heat resistance and thermal shock resistance has increased. The thermal shock resistance of ceramics is influenced by the material's properties such as coefficient of thermal expansion, thermal conductivity, strength, modulus of elasticity, and Poisson's ratio, as well as the size and shape of the product, as well as heating and cooling conditions, that is, heat transfer rate. affected.
耐熱衝撃性に影響するこれらの諸因子のうち特に熱膨脹
係数の寄与率が大であり、とりわけ、熱移動速度が大で
あるときには熱膨脹係数のみに大きく左右されることが
知られており、耐熱衝撃性に優れた低膨張材料の開発が
強く望まれている。Among these factors that affect thermal shock resistance, the contribution rate of the coefficient of thermal expansion is particularly large.In particular, it is known that when the heat transfer rate is high, it is greatly influenced only by the coefficient of thermal expansion. There is a strong desire to develop low-expansion materials with excellent properties.
従来比較的低膨脂なセラミックス材料として、コージェ
ライトが知られているが、一般にコージェライトは、緻
密焼結化が難しく、特に室温から８００℃までの熱膨脹
係数が２．ＯＸｌ０−６／ ”Ｃ以下となるような低膨
脹性を示すコージェライト素地では、カルシア、アルカ
リ、カリ、ソーダのような融剤となるべき不純物量を極
めて小量に限定する必要があるためガラス相が非常に少
なく多孔質になる。Cordierite is conventionally known as a relatively low-swelling ceramic material, but cordierite is generally difficult to sinter into dense sintering, and its coefficient of thermal expansion from room temperature to 800°C is particularly low at 2. For cordierite substrates that exhibit low expansion properties such as OXl0-6/"C or less, it is necessary to limit the amount of impurities that serve as fluxing agents such as calcia, alkali, potash, and soda to an extremely small amount, so glass Very few phases and porous.
従ってこのようなコージェライトセラミックスを例えば
、ハニカム構造にして回転蓄熱式熱交換体に応用した場
合、その開気孔率が大きいためハニカム構造体貫通孔を
形成する隔壁表面の気孔、特に連通気孔を通して加熱流
体と熱回収側流体との相互間に流体のリークが発生し、
熱交換効率及び熱交換体が使用されるシステム全体の効
率が低下する重大な欠点を有している。Therefore, when such cordierite ceramics is applied to a rotating regenerative heat exchanger with a honeycomb structure, for example, because of its large open porosity, heating can occur through the pores on the surface of the partition wall that form the through holes of the honeycomb structure, especially through the communicating holes. Fluid leakage occurs between the fluid and the heat recovery fluid,
It has the serious disadvantage of reducing the heat exchange efficiency and the efficiency of the overall system in which the heat exchanger is used.
このようなことから耐熱衝撃性に優れた、低膨脹の高気
密性コージェライトハニカム構造体が強く望まれていた
。For these reasons, there has been a strong desire for a low-expansion, highly airtight cordierite honeycomb structure that has excellent thermal shock resistance.
従来、コージェライトセラミックスが低膨脹性を示すこ
とは公知であり、例えば米国特許筒３，８８５．９７７
号明細書（対応日本出願：特開昭５０−７５６１１号公
報）に開示されているように、２５〜１０００℃の間で
の熱膨脹係数が少なくとも一方向でｌｌＸｌ０−’／℃
より小さい配向したコージェライトセラミックスが知ら
れており、そこではこの配向性を起させる原因として板
状粘土、積層粘土に起因する平面的配向を記述している
が、本発明と異なって１０−２０μｍの粗いタルクを用
い、粘土も０．１〜１０μｍの広い範囲にわたり、しか
も細孔に関する記載は一切ない。It has been known that cordierite ceramics exhibit low expansion properties, for example, as disclosed in U.S. Patent No. 3,885.977.
As disclosed in the specification (corresponding Japanese application: JP-A-50-75611), the coefficient of thermal expansion between 25 and 1000°C is llXl0-'/°C in at least one direction.
Smaller oriented cordierite ceramics are known, and planar orientation caused by plate clay and laminated clay is described as the cause of this orientation, but unlike the present invention, the diameter is 10-20 μm. Coarse talc is used, and the clay size ranges widely from 0.1 to 10 μm, and there is no mention of pores.
さらに、米国特許筒３，９５０．１７５号明細書く特開
昭５０−７５６１２号）には、原料中のタルク又は粘土
の一部又は全量を、パイロフェライト、カイアナイト、
石英、溶融シリカのようなシリカ又はシリカアルミナ源
原料によって置換することにより少なくとも２０％の１
０μｍより大きな径の開孔を有するコージェライト系多
孔質セラミックスが得られることが開示されているが、
本発明と異なり２μｍ以上の細孔容積を平均粒径が５μ
ｍ以下の微細タルクにより ０．０５ｃｃ／ｇ以下に抑
制して気密性を高めることに関する記載は一切ない。Furthermore, in U.S. Pat.
At least 20% of
It is disclosed that cordierite porous ceramics having pores with a diameter larger than 0 μm can be obtained,
Unlike the present invention, the pore volume of 2 μm or more is changed to an average particle size of 5 μm.
There is no mention of increasing airtightness by suppressing the amount to 0.05 cc/g or less using fine talc of 0.05 cc/g or less.
さらに特開昭５３−８２８２２号には、タルク平均粒径
とコージェライトセラミックスの平均細孔径の正相関性
について述べられてはいるものの、本発明にて得られる
ような１．ＯｘｌＯ−”／ ’ｃ以下の熱膨脹係数にす
るためには、タルクの平均粒径を１０〜５０μｍの粗粒
にする必要があり、本発明に示される低膨脹で高気密性
のコージェライトセラミックスを容易に類推することは
できない。Furthermore, although JP-A-53-82822 describes a positive correlation between the average talc particle size and the average pore size of cordierite ceramics, 1. In order to have a coefficient of thermal expansion of less than OxlO-''/'c, it is necessary to make the average grain size of talc coarse particles of 10 to 50 μm. It is not easy to make an analogy.
さらに特開昭５９−１２２８９９号には、気孔率が２０
〜４５％のコージェライトを主成分とするハニカム構造
体の貫通孔を形成する隔壁表面の開気孔を充填物質にて
封着することを特徴とする高気密性コージェライト質回
転蓄熱式熱交換体が開示されているが、本発明のように
コージェライト原料に平均粒径が５μｍ以下の微細タル
クと２μｍ以下の微細カオリンを用いることにより２μ
ｍ以上の細孔容積を０．０５ｃｃ／ｇ以下に抑制し、気
密性を高めることに関する記載はない。また、特開昭５
９−１２２８９９号の製造方法では、焼成されたコージ
ェライト質ハニカムに充填物質を泥漿として担持し、さ
らに再焼成する工程が必要なため、本発明に比較してセ
ルの目詰りを生じ易く、コスト高になる欠点がある。Furthermore, in JP-A-59-122899, the porosity is 20.
A highly airtight cordierite rotary regenerative heat exchanger, characterized in that the open pores on the surface of the partition wall forming the through-holes of a honeycomb structure mainly composed of ~45% cordierite are sealed with a filling material. However, as in the present invention, fine talc with an average particle size of 5 μm or less and fine kaolin with an average particle size of 2 μm or less are used as the cordierite raw material.
There is no description of suppressing the volume of pores of m or more to 0.05 cc/g or less to improve airtightness. Also, JP-A-5
The manufacturing method of No. 9-122899 requires a step of supporting the filler material as a slurry on the fired cordierite honeycomb and then re-firing it, so compared to the present invention, the manufacturing method is more likely to cause cell clogging and is costly. It has the disadvantage of being expensive.
さらに、本発明者らは先願（特願昭６Ｏ−２９３６９１
）で７μｍ以下の微粒タルクと２μｍ以下の微粒カオリ
ンにより薄壁コージェライトハニカム構造体で５μｍ以
上の細孔容積を低減し、極めてリーク量の少なる組成を
見い出したが、さらに本発明では５μｍ以下の微粒タル
クと２μｍ以下の微粒カオリンに加えて、アルミナ原料
、シリカ原料の粒度、組成を検討することにより従来５
μｍ以上の大気孔径しか制御不可能であったのが２μｍ
以上の中気孔径をも制御を可能とした。またシリカ原料
の検討では、極めて低膨脹の組成を見い出し、大巾な高
気密化、低熱腫脹化が達成できた。Furthermore, the present inventors have also applied for a prior application (Japanese Patent Application No. 6O-293691)
), the volume of pores of 5 μm or more was reduced in a thin-walled cordierite honeycomb structure using fine talc of 7 μm or less and kaolin of 2 μm or less, and a composition with extremely low leakage was found. In addition to fine talc of 2 μm or less and kaolin of 2 μm or less, we investigated the particle size and composition of alumina raw materials and silica raw materials.
It was only possible to control atmospheric pore diameters of 2 μm or more.
It has also become possible to control the medium pore diameter. In addition, in examining silica raw materials, we found a composition with extremely low expansion, and were able to achieve significantly higher airtightness and lower thermal swelling.
本発明は従来のコージェライトセラミ７クスの問題点で
ある気密性と低膨脹性を両立させた高気密性コージェラ
イトハニカム構造体を提供することを目的とする。An object of the present invention is to provide a highly airtight cordierite honeycomb structure that achieves both airtightness and low expansion, which are the problems of conventional cordierite ceramics.
（問題点を解決するための手段）
本発明者等は、平均粒子径５μｍ以下のタルクと平均粒
子径が２μｍ以下でかつタルク平均粒子径の１７３以下
の平均粒子径のカオリンと平均粒子径２μｍ以下のアル
ミナおよび／または水酸化アルミニウム、又はこれらと
平均粒子径８μｍ以下の高純度非晶質シリカを用いるこ
とにより、直径が２μｍ以上の総細孔容積を０．０５ｃ
ｃ／ｇ以下又は気孔率２５％未満における直径２μｍ以
上の総細孔容積を０．０８ｃｃ／ｇ以下にして実質的に
気密質にし、４０〜８００℃の間の熱膨脹係数を１．Ｏ
Ｘｌ０−’／ ”Ｃ以下としたものである。タルクの平
均粒径を５μｍ以下にすることは、細孔径を小さくする
ことに効果がある。また、２μｍ以下のカオリンを用い
ることは、気孔率を抑制することに効果がある。さらに
、平均粒子径５μｍ以下のタルクとタルク平均粒子径の
１７３以下の平均粒子径のカオリンを組合せて用いるこ
とは、コージェライトハニカム構造体のセル壁部でのコ
ージェライト結晶の配向を促進させ、低膨張化に寄与す
るものである。(Means for Solving the Problems) The present inventors have developed talc with an average particle size of 5 μm or less, kaolin with an average particle size of 2 μm or less and 173 or less of the talc average particle size, and kaolin with an average particle size of 2 μm or less. By using the following alumina and/or aluminum hydroxide, or these and high purity amorphous silica with an average particle size of 8 μm or less, the total pore volume with a diameter of 2 μm or more can be reduced to 0.05 c.
The total pore volume of 2 μm or more in diameter is 0.08 cc/g or less or the porosity is less than 25% to make it substantially airtight, and the thermal expansion coefficient between 40 and 800°C is 1. O
Xl0-'/'C or less. Setting the average particle size of talc to 5 μm or less is effective in reducing the pore size. Also, using kaolin with a diameter of 2 μm or less reduces the porosity. Furthermore, using a combination of talc with an average particle diameter of 5 μm or less and kaolin with an average particle diameter of 173 or less of the talc average particle diameter is effective in suppressing It promotes the orientation of cordierite crystals and contributes to lower expansion.
アルミナおよび／または水酸化アルミニウムの平均粒子
径を２μｍ以下にすることにより従来のタルク、カオリ
ンの微粒化だけでは得られなかった気孔径の微細化、低
気孔率化が達成される。By setting the average particle size of alumina and/or aluminum hydroxide to 2 μm or less, it is possible to achieve finer pore diameters and lower porosity, which could not be achieved by conventional atomization of talc or kaolin alone.
さらにアルミナではローソーダアルミナを使用すること
により安定した微細気孔径が得られる。Furthermore, by using alumina, a stable fine pore size can be obtained by using low soda alumina.
また高純度非晶質シリカの平均粒子径を８μｍ以下にす
ることは、いずれも気孔径および気孔率を抑制すること
に効果がある。ここで重要であるのはシリカは非晶質で
あることである。例えば石英等の結晶質シリカでは大幅
な気孔率増加をもたらし好ましくない。微粒アルミナ／
水酸化アルミニラムに加えて非晶質シリカの使用により
大幅な低熱膨脂が得られる。Further, setting the average particle size of high-purity amorphous silica to 8 μm or less is effective in suppressing the pore size and porosity. What is important here is that silica is amorphous. For example, crystalline silica such as quartz is undesirable because it causes a significant increase in porosity. Fine alumina/
The use of amorphous silica in addition to aluminum hydroxide provides significantly lower thermal expansion.
また、本発明者等は、該ハニカム構造体の化学組成が、
ＳｉＯ□にて４２〜５６重量％好ましくは４７〜５３重
景％、Ａ１□０．にて３０〜４５重量％好ましくは３２
〜３８重量％、ＭｇＯにて１２〜１６重量％好ましくは
１２．５〜１５重量％とすることが好適であることを見
出した。該ハニカム構造体は他に不可避的に混入する成
分例えば、Ｔｉ０ｚ ＋ ＣａＯ＋ ＫＮａＯ＋ Ｆｅ
ｚＯ：ｌを全体として２．５重量％以下含んでも良いが
、Ｐ２Ｏ，は０．１％未満であることが好ましい。これ
らの数値を限定する理由は、結晶相の主成分をコージェ
ライト相とし、不純物から生成する高膨張のガラス相を
除去するためである。In addition, the present inventors have discovered that the chemical composition of the honeycomb structure is
42-56% by weight in SiO□, preferably 47-53% by weight, A1□0. 30-45% by weight, preferably 32
It has been found that it is suitable to use 12-16% by weight, preferably 12.5-15% by weight of MgO. The honeycomb structure contains other components that are unavoidably mixed, for example, TiOz + CaO + KNaO + Fe
The total amount of zO:1 may be 2.5% by weight or less, but P2O is preferably less than 0.1%. The reason for limiting these values is to make the main component of the crystalline phase a cordierite phase and to remove a high expansion glass phase generated from impurities.
本発明の原料粒度コントロールにより１１００〜１３５
０℃の温度領域での平均昇温速度を特に限定する必要が
なくなったため低膨張化が可能な５０℃／Ｈｒ以上の早
い速度が適用できるようになり、耐熱衝撃性の改良に好
適であることがわかった。また、１３５０〜１４４０’
Ｃの温度にて焼成することにより、結晶相の主成分をコ
ージェライト相とすることができる。1100-135 due to the raw material particle size control of the present invention
Since it is no longer necessary to specifically limit the average heating rate in the 0°C temperature range, it is now possible to apply a faster rate of 50°C/Hr or higher, which allows for low expansion, and is suitable for improving thermal shock resistance. I understand. Also, 1350-1440'
By firing at a temperature of C, the main component of the crystalline phase can be made into a cordierite phase.
ハニカム構造体のセル密度を６２セル／ｃ＋ｎ２（４０
０セル／ｉｎ２）以上、リブ厚が２０３ 、Ｉｊｍ
（８ｍｉｌ）以下とするのは、該ハニカム構造体を熱交
換体として、高熱交換効率で低圧力損失のものにするた
めである。セルの形状には特に限定はないが、通常三角
形、正方形、長方形、六角形、その他フィン行のもの等
種々のものとすることができる。The cell density of the honeycomb structure is 62 cells/c+n2 (40
0 cell/in2) or more, rib thickness 203, Ijm
(8 mil) or less is to make the honeycomb structure a heat exchanger with high heat exchange efficiency and low pressure loss. There is no particular limitation on the shape of the cells, but they can be of various shapes, such as triangular, square, rectangular, hexagonal, and other fin row shapes.
直径が２μｍ以上の細孔の総細孔容積を０．０５ｃｃ／
ｇ以下好ましくは０．０３ｃｃ／ｇ以下又は気孔率２５
％未満における２μｍ以上の細孔の総細孔容積を０．０
８ｃｃ／ｇ以下好ましくは０．０５ｃｃ／ｇ以下に限定
するのは、第１図に示すようにこのようなハニカム構造
体の薄壁を通じての流体の漏れが主に直径が２μｍ以上
の細孔によるためである。この条件を満足するためには
気孔率を少なくとも３０％以下より好ましくは２５％以
下にすることが好ましい。The total pore volume of pores with a diameter of 2 μm or more is 0.05 cc/
g or less, preferably 0.03 cc/g or less, or porosity 25
The total pore volume of pores of 2 μm or more in less than 0.0%
The reason why it is limited to 8 cc/g or less, preferably 0.05 cc/g or less, is because fluid leakage through the thin walls of such a honeycomb structure is mainly due to pores with a diameter of 2 μm or more, as shown in Figure 1. It's for a reason. In order to satisfy this condition, the porosity is preferably at least 30% or less, preferably 25% or less.
本発明はタルク、カオリンの微粒子化に際し、乾燥、焼
成時での収縮等によるハニカム構造体亀裂発生の抑制に
効果的な仮焼タルク、仮焼カオリンの使用をも包含する
。タルク、カオリンの仮焼温度の高温化は気孔率増加と
熱膨張率増加を招くため仮焼物の使用する場合は、仮焼
温度はできる限り低い温度の方が好ましい。粒度は生原
料と同様の微粒物を使用しなければ本発明の効果を得る
ことはできない。The present invention also includes the use of calcined talc and kaolin, which are effective in suppressing the occurrence of cracks in the honeycomb structure due to shrinkage during drying and firing, when talc and kaolin are made into fine particles. If the calcining temperature of talc or kaolin is increased, it will increase the porosity and the coefficient of thermal expansion, so when using a calcined product, it is preferable to keep the calcining temperature as low as possible. The effects of the present invention cannot be obtained unless fine particles having a particle size similar to that of the raw raw material are used.
なおコージェライト化原料中におけるアルカリ等不純物
量の適正化及び製造するハニカム構造体のリブ厚に応じ
て粗粒物のカット等粒度の適正化を図る必要がある。Note that it is necessary to optimize the amount of impurities such as alkali in the cordierite forming raw material and to optimize the particle size such as cutting of coarse grains depending on the rib thickness of the honeycomb structure to be manufactured.
また、カオリンのうち仮焼カオリンは湿式ボールミルに
より粉砕して調製すると緻密化に好適である。Further, among kaolins, calcined kaolin is suitable for densification when prepared by pulverizing it with a wet ball mill.
従って本発明は化学組成でＳｉＯ２が４２〜５６重量％
好ましくは４７〜５３重量％、Ａｈａ、が３０〜４５重
量％好ましくは３２〜３８重量％、ＭｇＯが１２〜１６
重景％好ましくは１２．５〜１５重量％となるように平
均粒子径５μｍ以下のタルクと平均粒子径２μｍ以下で
かつタルクの平均粒子径の１／３以下の平均粒子径のカ
オリンと平均粒子径２μｍ以下のアルミナおよび／また
は水酸化アルミニウムと、他のコージェライト化原料を
混合し、この混合物に可塑剤及び粘結剤を加えて可塑化
した変形可能なバッチとし、この可塑化したバッチを押
出し成形法により成形後乾燥し、次いで１３５０〜１４
４０℃にて焼成し、結晶相の主成分がコージェライト相
から成り、直径が２μｍ以上の細孔の総細孔容積が ０
．０５ｃｃ／ｇ以下又は気孔率２５％未満における直径
２μｍ以上の総細孔容積を０．０８ｃｃ／ｇ以下４０〜
８００℃の間の熱膨脹係数が１．０Ｘ１０−ｂ／ ’Ｃ
以下のコージェライトハニカム構造体を製造するもので
ある。Therefore, the chemical composition of the present invention is 42 to 56% by weight of SiO2.
Preferably 47-53% by weight, Aha 30-45% by weight, preferably 32-38% by weight, MgO 12-16% by weight.
Talc with an average particle size of 5 μm or less, kaolin with an average particle size of 2 μm or less and 1/3 or less of the average particle size of talc, and average particles so that the weight ratio is preferably 12.5 to 15% by weight. Alumina and/or aluminum hydroxide with a diameter of 2 μm or less and other cordierite forming raw materials are mixed, a plasticizer and a binder are added to this mixture to make a plasticized deformable batch, and this plasticized batch is made into a deformable batch. After molding by extrusion molding, drying, then 1350~14
Calcined at 40℃, the main component of the crystalline phase is cordierite phase, and the total pore volume of pores with a diameter of 2 μm or more is 0.
．． Total pore volume of 2 μm or more in diameter at 0.05 cc/g or less or less than 25% porosity is 40 to 0.08 cc/g or less
Thermal expansion coefficient between 800℃ is 1.0X10-b/'C
The following cordierite honeycomb structure is manufactured.
さらに本発明は化学組成でＳｉＯ□が４２〜５６重量％
好ましくは４７〜５３重量％、Ａｌ２Ｏ３が３０〜４５
重量％好ましくは３２〜３８重量％、ＭｇＯが１２〜１
６重量％好ましくは１２．５〜１５重量％となるように
平均粒子径５μｍ以下のタルクと平均粒子径２μｍ以下
でかつタルクの平均粒子径の１７３以下の平均粒子径の
カオリンと平均粒子径２μｍ以下のアルミナおよび／ま
たは水酸化アルミニウムと平均粒子径８μｍ以下の高純
度非晶質シリカと、他のコージェライト化原料を混合し
、この混合物に可塑剤及び粘結剤を加えて可塑化した変
形可能なバッチとし、この可塑化したバッチを押出し成
形法により成形後乾燥し、次いで１３５０〜１４４０℃
にて焼成し、結晶相の主成分がコージェライト相から成
り、直径が２μｍ以上の細孔の総細孔容積が０．０５ｃ
ｃ／ｇ以下又は気孔率２５％未満における直径２μｍ以
上の総細孔容積を０．０８ｃｃ／ｇ以下４０〜８００℃
の間の熱膨脹係数が１．０Ｘ１０−’／ ”Ｃ以下のコ
ージェライトハニカム構造体を製造するものである。Furthermore, the chemical composition of the present invention is 42 to 56% by weight of SiO□.
Preferably 47-53% by weight, Al2O3 is 30-45%
Weight% preferably 32-38% by weight, MgO 12-1
Talc with an average particle size of 5 μm or less, kaolin with an average particle size of 2 μm or less and 173 or less of the average particle size of talc, and an average particle size of 2 μm so that the amount is preferably 6% by weight and 12.5 to 15% by weight. A modified version in which the following alumina and/or aluminum hydroxide, high-purity amorphous silica with an average particle size of 8 μm or less, and other cordierite forming raw materials are mixed, and the mixture is plasticized by adding a plasticizer and a binder. This plasticized batch is formed by extrusion molding and then dried, and then heated to 1350-1440°C.
The main component of the crystal phase is cordierite phase, and the total pore volume of pores with a diameter of 2 μm or more is 0.05 c.
Total pore volume of 2 μm or more in diameter at 0.08 cc/g or less or less than 25% porosity at 40 to 800°C
The purpose is to manufacture a cordierite honeycomb structure having a coefficient of thermal expansion of 1.0 x 10-'/''C or less.
焼成は通常約０．５〜１２時間行なう。ハニカム構造体
は結晶相の主成分が９０重量％以上のコージェライトか
ら成っている。その他の結晶はムライト、スピネル（サ
フィリンを含む）が主であるが、これらは夫々２．５重
量％以下である。ハニカム構造体は２μｍ以上の細孔の
総細孔容積が０．０５ｃｃ／ｇ以下、特に０．０３ｃｃ
／ｇ以下のときに、圧力１．４ ｋｇ／ ｃｍ２のとき
のリーク量が３０ｇ／ｓｅｃ −ｍ”以下特に２０ｇ／
ｓｅｃ −ｍ”以下の実質的に気密性となり、熱交換体
用に好適のものとなる。Firing is usually carried out for about 0.5 to 12 hours. The main component of the honeycomb structure is 90% by weight or more of cordierite. Other crystals are mainly mullite and spinel (including sapphirine), each of which accounts for 2.5% by weight or less. The honeycomb structure has a total pore volume of pores of 2 μm or more of 0.05 cc/g or less, especially 0.03 cc.
/g or less, the leakage amount at a pressure of 1.4 kg/cm2 is 30g/sec -m” or less, especially 20g/cm2.
It has substantially airtightness of less than sec -m'' and is suitable for use as a heat exchanger.
（作 用）
本発明はハニカム構造体の２μｍ以上の細孔の総細孔容
積が０．０５ｃｃ／ｇ以下又は気孔率２５％未満の２μ
ｍ以上の細孔の総細孔容積が０．０８ｃｃ／ｇ以下と小
さい為、リーク量が小さく、熱交換効率が高い。(Function) The present invention provides a honeycomb structure in which the total pore volume of pores of 2 μm or more is 0.05 cc/g or less or the porosity is less than 25%.
Since the total pore volume of pores of m or more is as small as 0.08 cc/g or less, the amount of leakage is small and the heat exchange efficiency is high.
また、熱膨脹係数が４０〜８００℃で１．ＯＸｌ０−６
／ ”Ｃ以下と小さくさらに好ましいものでは０．６
ｘｌＯ−６／’ｃ以下と非常に小さいため、耐熱衝撃性
が高い。またリブ厚を２０３ μｍ （８ｍｉｌ）以
下と薄壁にすることができるため圧力損失が小さく、高
密度セル化が達成できるため熱交換効率の高いセラミッ
クス熱交換体を得ることができる。また、細孔径が小さ
く、気孔率も小さいためハニカム構造体の強度は従来の
ハニカム構造体より高く、薄壁化が可能である。Moreover, the coefficient of thermal expansion is 1. OXl0-6
/ “C or less, which is more preferable, is 0.6
Since it is very small, less than xlO-6/'c, it has high thermal shock resistance. In addition, since the rib thickness can be made as thin as 203 μm (8 mil) or less, pressure loss is small, and high-density cells can be achieved, so that a ceramic heat exchanger with high heat exchange efficiency can be obtained. Furthermore, since the pore diameter is small and the porosity is small, the strength of the honeycomb structure is higher than that of conventional honeycomb structures, and the walls can be made thinner.
（実施例）
以下本発明を実施例と比較例につきさらに詳細に説明す
る。(Examples) The present invention will be described in more detail below with reference to Examples and Comparative Examples.
去覇ｌ鉗り
次の第１表に示す化学分析値及び粒度の原料を第２表の
調合割合、タルク粒度、カオリン粒度に従って第２表阻
１〜隘４０のバッチを調合し、原料１００重量部に対し
てメチルセルローズ４．５重量部及び添加水を加え、混
練し、押出成形可能な坏土とした。ここでの使用原料は
総て篩目が６３μｍの篩を通過したものを使用した。次
いでそれぞれのバッチの坏土を公知の押出成形法により
リブ厚１２０μｍ、１平方センチ当りのセル数１６７ケ
、短辺／長辺＝１／１．７３の長方形セル構造を有する
直径９３龍高さ１００龍の円筒形ハニカム構造体を成形
した。Using the raw materials with the chemical analysis values and particle sizes shown in Table 1 below, prepare batches numbered 1 to 40 in Table 2 according to the blending ratio, talc particle size, and kaolin particle size in Table 2, and add 100 weight of the raw materials. 4.5 parts by weight of methylcellulose and added water were added to the mixture and kneaded to obtain an extrusion moldable clay. The raw materials used here all passed through a sieve with a mesh size of 63 μm. Next, each batch of clay was molded using a known extrusion method to form a rectangular cell structure with a rib thickness of 120 μm, number of cells per square centimeter of 167, and short side/long side = 1/1.73, with a diameter of 93 and a dragon height. A cylindrical honeycomb structure of 100 dragons was molded.
それぞれのバッチによるハニカム構造体は乾燥後第２表
に示す焼成条件で焼成し、焼結体の特性として４０’Ｃ
〜８００℃での熱膨脹係数、気孔率、２μｍ以上の細孔
の総細孔容積、リーク量、コージェライト結晶量、耐熱
衝撃性の評価を実施した。評価結果も第２表に示す。な
お、総てのバッチの焼結体の化学組成でＰ２Ｏ５は０．
１％未満であった。After drying, the honeycomb structure of each batch was fired under the firing conditions shown in Table 2, and the characteristics of the sintered body were 40'C.
The coefficient of thermal expansion at ~800°C, porosity, total pore volume of pores of 2 μm or more, amount of leakage, amount of cordierite crystals, and thermal shock resistance were evaluated. The evaluation results are also shown in Table 2. In addition, in the chemical composition of the sintered bodies of all batches, P2O5 is 0.
It was less than 1%.
第３表中、平均粒子径５μｍ以下のタルク、平均粒子径
２μｍ以下でかつタルクの粒子径の１／３以下のカオリ
ンに平均粒子径２μｍ以下のアルミナおよび／または水
酸化アルミニウムを添加した試験Ｎａ２〜５，８〜１５
．１７ 、１Ｂ 、 ２０、さらにこれらに平均粒子径
８μｍ以下の裔純度非晶質シリカを添加した試験階２２
、２３ 、２５ 、２７ 、２９〜４０は、本発明で
規定する２μｍ以上の細孔の総細孔容積を満たすことが
わかった。In Table 3, Na2 is a test in which alumina and/or aluminum hydroxide with an average particle size of 2 μm or less is added to talc with an average particle size of 5 μm or less, and kaolin with an average particle size of 2 μm or less and 1/3 or less of the talc particle size. ~5,8~15
．． 17, 1B, 20, and test floor 22 in which pure amorphous silica with an average particle size of 8 μm or less was added to these.
, 23, 25, 27, 29-40 were found to satisfy the total pore volume of pores of 2 μm or more defined in the present invention.
また、気孔率２５％未満とそれ以上に分けてテストピー
スリーク量と２μｍ以上の細孔容積との関係を加圧空気
圧１．４ ｋｇ／ｃｍ”の条件下で求めたところ第１図
に示す結果が得られた。第１図中、白丸は気孔率２５％
未満のデータを、また黒丸はそれ以上のデータを示して
いる。第１図から、本発明で必要とするリークＮ３０ｇ
／ｓｅｃ−ｍ”を満たすためには、気孔率２５％のもの
では２μｍ以上の細孔の細孔容積が０．０８ｃｃ／ｇ以
下、またそれ以上の気孔率のものでは０．０５ｃｃ／ｇ
以下の細孔容積が必要であることがわかった。In addition, the relationship between test piece leakage and pore volume of 2 μm or more was determined for porosity of less than 25% and porosity of 25% or more under the condition of pressurized air pressure of 1.4 kg/cm'' and is shown in Figure 1. The results were obtained. In Figure 1, the white circle indicates a porosity of 25%.
The black circles indicate the data below, and the black circles indicate the data above. From Figure 1, the leak N30g required by the present invention
/sec-m”, the pore volume of pores of 2 μm or more must be 0.08 cc/g or less for a product with a porosity of 25%, and 0.05 cc/g for a product with a porosity higher than that.
It was found that the following pore volumes were required:
なお、参考例とした試験ｍｌ、２４はタルクの粒径が５
μｍ以上であるため、試験阻６はアルミナの粒径が２μ
ｍ以上であるため、試験１１ｈ１６ 、１９ 。In addition, the test ml 24 used as a reference example has a talc particle size of 5.
Since the particle size of the alumina is 2μm or more, test barrier 6 has a particle size of 2μm or more.
Since it is more than m, test 11h16,19.
２６は水酸化アルミニウムの粒径が２μｍ以上であるた
め、試験患７はカオリンとタルクの平均粒子径比が１／
３以上であるため、試験寛２１はシリカの添加量が８．
０％以上であるため、試験寛２８は添加するシリカとし
て結晶質のシリカを使用したため、それぞれ細孔容積お
よび／または熱膨張特性を満足しない。In No. 26, the particle size of aluminum hydroxide is 2 μm or more, so in Test No. 7, the average particle size ratio of kaolin and talc is 1/1.
Since it is 3 or more, Test Kan 21 has an addition amount of silica of 8.
0% or more, Test Kan 28 used crystalline silica as the added silica, and therefore did not satisfy the pore volume and/or thermal expansion characteristics, respectively.
去硲炎１
第２表魔３６のバッチを実施例１と同様の方法によりセ
ル構造の異った口金により押出成形し、焼成して、第３
表に示すセル構造を有する直径９３龍、高さ１００ ｍ
ｍの円筒形ハニカム構造体隘４１〜阻５０を製造した。Castoritis 1 The second batch of 36 was extruded using a die with a different cell structure in the same manner as in Example 1, and fired, and the third batch was
Diameter 93, height 100 m with cell structure shown in table
Cylindrical honeycomb structures 41 to 50 were manufactured.
それぞれのハニカム構造体の圧力損失、リーク量、熱膨
脹係数（ＣＴＥ）を評価した。評価結果も第３表に示す
とともにその形状を第２図に示す。The pressure loss, leakage amount, and coefficient of thermal expansion (CTE) of each honeycomb structure were evaluated. The evaluation results are also shown in Table 3, and the shapes are shown in FIG.
第３表から本発明のセラミンクハニカム構造体は、所定
のリーク量を達成できることがわかった。Table 3 shows that the ceramic honeycomb structure of the present invention can achieve a predetermined amount of leakage.
（発明の効果）
以上の結果から、本発明によれば、２μｍ以上の細孔の
総細孔容積が０．０５ｃｃ／ｇ以下又は気孔率２５％未
満における２μｍ以上の細孔の総細孔容積が０．０８ｃ
ｃ／ｇ以下で、熱膨脹係数が１．ＯｘｌＯ−”／ ’ｃ
以下の、耐熱性に優れ、リーク量が極めて小さく、熱交
換効率に優れたハニカム構造体が得られる。(Effect of the invention) From the above results, according to the present invention, the total pore volume of pores of 2 μm or more is 0.05 cc/g or less, or the total pore volume of pores of 2 μm or more when the porosity is less than 25%. is 0.08c
c/g or less, and the coefficient of thermal expansion is 1. OxlO-"/'c
The following honeycomb structure with excellent heat resistance, extremely small amount of leakage, and excellent heat exchange efficiency can be obtained.
従って本発明は産業上極めて有用である。Therefore, the present invention is extremely useful industrially.
第１図は２μｍ以上の細孔量と加圧空気圧１．４ｋｇ／
ｃｍ”でのテストピースリーク量の関係を示す図、
第２図は本発明のハニカム構造体の一例を示す斜視図で
ある。
第１図
θθ２ θθ４ ００θ θＯθ２ｐｍ工
久上め細工事上ｃｃ／ｙノー
ａ
手 続 補 正 書
昭和６２年 ２月２６日
特許庁長官 黒 １） 明 雄 殴１、事件の
表示
昭和６１年特許願第１８２８２４号
２、発明の名称
３、補正をする者
事件との関係 特許 出願人
４、代 理 人
１、明細書第１０頁第８行と第９行の間に下記の文を加
入する。
「なお、タルク、カオリンの粒径は生、仮焼品の調合重
量比による平均粒子径より求めた。」２、同第２４頁第
２行と第３行の間に以下の文を加入する。
「実際の例として、第３図および第４図に複数個のコー
ジェライト質マトリックスセグメントより構成される回
転蓄熱式熱交換体の一例を示す。」
３、同第１９頁および第２０頁の第２表中備考欄の「参
考例」をすべて「比較例」と訂正する。
４、同第２１頁第１行の「第３表中」を「第２表中」と
訂正する。
５、同第２２頁第１行の「参考例とした」を削除する。
６、同第２４頁第１６行を下記の通り訂正する。
［斜視図、
第３図及び第４図は複数個のコージェライト質マトリッ
クスセグメントより構成される回転蓄熱式熱交換体を示
す図である。」
７、図面中、第３図および第４図を加入する。
第３図Figure 1 shows the pore volume of 2μm or more and the pressurized air pressure of 1.4kg/
Figure 2 is a perspective view showing an example of the honeycomb structure of the present invention. Noa Procedures Amendment Written February 26, 1980 Commissioner of the Patent Office Black 1) Yu Akira Hit 1, Indication of the case 1982 Patent Application No. 182824 2, Title of the invention 3, Person making the amendment Related Patent Applicant 4, Agent 1, add the following sentence between lines 8 and 9 on page 10 of the specification. 2. Add the following sentence between the second and third lines of page 24 of the same page. ``As an actual example, Figs. 3 and 4 show an example of a rotating regenerative heat exchanger composed of a plurality of cordierite matrix segments.'' 3, pages 19 and 20 of the same. All "Reference examples" in the notes column in Table 2 are corrected to "Comparative examples." 4. In the first line of page 21, "in Table 3" is corrected to "in Table 2." 5. Delete "used as a reference example" in the first line of page 22. 6. The same page 24, line 16 is corrected as follows. [Perspective view] Figures 3 and 4 are views showing a rotating regenerative heat exchanger composed of a plurality of cordierite matrix segments. 7. In the drawings, Figures 3 and 4 are added. Figure 3
Claims (1)
が２μｍ以上の細孔の総細孔容積が０．０５ｃｃ／ｇ以
下又は気孔率２５％未満における２μｍ以上の細孔の総
細孔容積が０．０８ｃｃ／ｇ以下、４０〜８００℃の間
の熱膨脹係数が１．０×１０＾−＾６／℃以下、化学組
成でＳｉＯ＿２が４２〜５６重量％、Ａｌ＿２Ｏ＿３が
３０〜４５重量％、ＭｇＯが１２〜１６重量％であるこ
とを特徴とするコージェライトハニカム構造体。 ２、直径が２μｍ以上の細孔の総細孔容積が０．０３ｃ
ｃ／ｇ以下又は気孔率２５％未満における２μｍ以上の
細孔の総細孔容積が０．０５ｃｃ／ｇ以下である特許請
求の範囲第１項記載のコージェライトハニカム構造体。 ３、セル密度が６２セル／ｃｍ＾２（４００セル／ｉｎ
＾２）以上、リブ厚が２０３μｍ（８ｍｉｌ）以下であ
る特許請求の範囲第１項記載のコージェライトハニカム
構造体。 ４、コージェライトハニカム構造体が熱交換体である特
許請求の範囲第１項記載のコージェライトハニカム構造
体。 ５、主成分の化学組成が重量基準でＳｉＯ＿２４２〜５
６％、Ａｉ＿２Ｏ＿３３０〜４５％、ＭｇＯ１２〜１６
％になるように平均粒子径５μｍ以下のタルク、平均粒
子径２μｍ以下でかつタルク平均粒子径の１／３以下の
平均粒子径のカオリンと平均粒子径２μｍ以下のアルミ
ナおよび／または水酸化アルミニウム及び他のコージェ
ライト化原料を混合し、この混合物に可塑剤及び粘結剤
を加えて可塑化した変形可能なバッチとし、この可塑化
したバッチを押出し成形法により成形後乾燥し、次いで
この乾燥物を１３５０〜１４４０℃にて焼成することを
特徴とするコージェライトハニカム構造体の製造方法。 ６、前記コージェライト化原料のうちアルミナのＮａ＿
２Ｏが０．１２％以下である特許請求の範囲第５項記載
のコージェライトハニカム構造体の製造方法。 ７、平均粒子径１μｍ以下のカオリンを用いる特許請求
の範囲第５項記載の製造方法。 ８、主成分の化学組成が重量基準でＳｉＯ＿２４２〜５
６％、Ａｉ＿２Ｏ＿３３０〜４５％、ＭｇＯ１２〜１６
％になるように平均粒子径５μｍ以下のタルク、平均粒
子径２μｍ以下でかつタルク平均粒子径の１／３以下の
平均粒子径のカオリンと平均粒子径２μｍ以下のアルミ
ナおよび／または水酸化アルミニウムと平均粒子径８μ
ｍ以下の高純度非晶質シリカ及び他のコージェライト化
原料を混合し、この混合物に可塑剤及び粘結剤を加えて
可塑化した変形可能なバッチとし、この可塑化したバッ
チを押出し成形法により成形後乾燥し、次いでこの乾燥
物を１３５０〜１４４０℃にて焼成することを特徴とす
るコージェライトハニカム構造体の製造方法。 ９、前記コージェライト化原料のうちアルミナのＮａ＿
２Ｏが０．１２％以下である特許請求の範囲第８項記載
のコージェライトハニカム構造体の製造方法。 １０、平均粒子径１μｍ以下のカオリンを用いる特許請
求の範囲第８項記載の製造方法。 １１、前記高純度非晶質シリカの添加量が８％以下であ
る特許請求の範囲第８項記載のコージェライトハニカム
構造体の製造方法。[Claims] 1. The main component of the crystal phase is cordierite phase, and the total pore volume of pores with a diameter of 2 μm or more is 0.05 cc/g or less, or the pores are 2 μm or more with a porosity of less than 25%. The total pore volume of the pores is 0.08 cc/g or less, the coefficient of thermal expansion between 40 and 800℃ is 1.0 x 10^-^6/℃ or less, and the chemical composition is 42 to 56% by weight of SiO_2 and Al_2O_3. A cordierite honeycomb structure characterized in that MgO is 30 to 45% by weight and MgO is 12 to 16% by weight. 2. The total pore volume of pores with a diameter of 2 μm or more is 0.03 c.
2. The cordierite honeycomb structure according to claim 1, wherein the total pore volume of pores of 2 μm or more is 0.05 cc/g or less or at a porosity of less than 25%. 3. Cell density is 62 cells/cm^2 (400 cells/in
^2) The cordierite honeycomb structure according to claim 1, wherein the rib thickness is 203 μm (8 mil) or less. 4. The cordierite honeycomb structure according to claim 1, wherein the cordierite honeycomb structure is a heat exchanger. 5. The chemical composition of the main component is SiO_242~5 on a weight basis
6%, Ai_2O_330-45%, MgO12-16
% of talc with an average particle size of 5 μm or less, kaolin with an average particle size of 2 μm or less and 1/3 or less of the talc average particle size, alumina and/or aluminum hydroxide with an average particle size of 2 μm or less, and Other cordierite forming raw materials are mixed, a plasticizer and a binder are added to this mixture to make a plasticized deformable batch, this plasticized batch is molded by extrusion molding and then dried, and then this dried product is A method for producing a cordierite honeycomb structure, comprising firing at 1350 to 1440°C. 6. Among the raw materials for forming cordierite, Na_ of alumina
The method for manufacturing a cordierite honeycomb structure according to claim 5, wherein 2O is 0.12% or less. 7. The manufacturing method according to claim 5, using kaolin having an average particle diameter of 1 μm or less. 8. The chemical composition of the main component is SiO_242~5 on a weight basis
6%, Ai_2O_330-45%, MgO12-16
% of talc with an average particle size of 5 μm or less, kaolin with an average particle size of 2 μm or less and 1/3 or less of the talc average particle size, and alumina and/or aluminum hydroxide with an average particle size of 2 μm or less. Average particle size 8μ
m or less high purity amorphous silica and other cordierite forming raw materials are mixed, a plasticizer and a binder are added to this mixture to make a plasticized deformable batch, and this plasticized batch is processed by extrusion molding. 1. A method for manufacturing a cordierite honeycomb structure, which comprises molding and drying, and then firing the dried product at 1,350 to 1,440°C. 9. Among the raw materials for forming cordierite, Na_ of alumina
9. The method for manufacturing a cordierite honeycomb structure according to claim 8, wherein 2O is 0.12% or less. 10. The manufacturing method according to claim 8, which uses kaolin having an average particle diameter of 1 μm or less. 11. The method for producing a cordierite honeycomb structure according to claim 8, wherein the amount of the high-purity amorphous silica added is 8% or less.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18282486A JPS6340777A (en) | 1986-08-05 | 1986-08-05 | Cordierite honeycomb structure and manufacture |
| DE8686310130T DE3680496D1 (en) | 1985-12-27 | 1986-12-24 | CORDIERITE ITEM WITH HONEYCOMB STRUCTURE AND METHOD FOR THEIR PRODUCTION. |
| EP86310131A EP0232621B1 (en) | 1985-12-27 | 1986-12-24 | Catalyst carrier of cordierite honeycomb structure and method of producing the same |
| EP86310130A EP0227482B1 (en) | 1985-12-27 | 1986-12-24 | Cordierite honeycomb structural body and method of producing the same |
| DE8686310131T DE3671390D1 (en) | 1985-12-27 | 1986-12-24 | CATALYST SUPPORT WITH CORDIERITE HONEYCOMB STRUCTURE AND METHOD FOR THE PRODUCTION THEREOF. |
| US06/946,901 US4877670A (en) | 1985-12-27 | 1986-12-29 | Cordierite honeycomb structural body and method of producing the same |
| US07/320,629 US5030398A (en) | 1985-12-27 | 1989-03-08 | Method of producing a cordierite honeycomb structural body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18282486A JPS6340777A (en) | 1986-08-05 | 1986-08-05 | Cordierite honeycomb structure and manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6340777A true JPS6340777A (en) | 1988-02-22 |
| JPH0212898B2 JPH0212898B2 (en) | 1990-03-29 |
Family
ID=16125102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18282486A Granted JPS6340777A (en) | 1985-12-27 | 1986-08-05 | Cordierite honeycomb structure and manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6340777A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009013567A1 (en) | 2008-03-31 | 2009-10-01 | Ngk Insulators, Ltd., Nagoya | Process for producing a honeycomb structure |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19704144A1 (en) * | 1997-02-04 | 1998-08-06 | Emitec Emissionstechnologie | Extruded honeycomb body, in particular catalyst carrier body, with reinforced wall structure |
-
1986
- 1986-08-05 JP JP18282486A patent/JPS6340777A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009013567A1 (en) | 2008-03-31 | 2009-10-01 | Ngk Insulators, Ltd., Nagoya | Process for producing a honeycomb structure |
| US8529826B2 (en) | 2008-03-31 | 2013-09-10 | Ngk Insulators, Ltd. | Manufacturing method of honeycomb structure |
| DE102009013567B4 (en) | 2008-03-31 | 2019-07-11 | Ngk Insulators, Ltd. | Process for producing a honeycomb structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0212898B2 (en) | 1990-03-29 |
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