JP2002121084A - Cordierite-based ceramic honeycomb structure - Google Patents
Cordierite-based ceramic honeycomb structureInfo
- Publication number
- JP2002121084A JP2002121084A JP2000307901A JP2000307901A JP2002121084A JP 2002121084 A JP2002121084 A JP 2002121084A JP 2000307901 A JP2000307901 A JP 2000307901A JP 2000307901 A JP2000307901 A JP 2000307901A JP 2002121084 A JP2002121084 A JP 2002121084A
- Authority
- JP
- Japan
- Prior art keywords
- cordierite
- pores
- honeycomb structure
- porosity
- ceramic honeycomb
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0006—Honeycomb structures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processes For Solid Components From Exhaust (AREA)
- Filtering Materials (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ディーゼル機関か
ら排出される微粒子を捕集するフィルタに用いるコージ
ェライト質セラミックハニカム構造体に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cordierite ceramic honeycomb structure used for a filter for collecting fine particles discharged from a diesel engine.
【０００２】[0002]
【従来の技術】ディーゼル機関から排出される微粒子を
除去するため、コージェライト質ハニカム構造体の隔壁
を多孔質構造とし、その隔壁に微粒子を含んだ排気ガス
を通過せしめる構造の微粒子捕集用フィルタ（ディーゼ
ルパティキュレートフィルタ）を採用する検討が進めら
れている。このフィルタの特性に関しては、微粒子の捕
集効率、圧力損失（圧損）、微粒子の捕集時間（捕集開
始から一定圧損に達するまでの時間）の３つが重要とさ
れている。中でも、捕集効率と圧損は相反する関係にあ
り、捕集効率を高くしようとすると、圧損が増大し、捕
集時間が短くなり、また圧損を低くすると、捕集時間は
長くできるが、捕集効率が悪くなる。これらの相反する
フィルタの特性を満足するように、コージェライト質ハ
ニカム構造体に対しては、下記のように、その気孔率、
細孔分布を制御し、最適化する技術が従来から検討され
てきた。2. Description of the Related Art In order to remove fine particles emitted from a diesel engine, a filter for collecting fine particles has a structure in which a partition wall of a cordierite-based honeycomb structure has a porous structure and an exhaust gas containing the fine particles passes through the partition wall. (Diesel particulate filter) is being studied. Regarding the characteristics of this filter, three are important: the collection efficiency of the fine particles, the pressure loss (pressure loss), and the collection time of the fine particles (the time from the start of collection to the time when a certain pressure loss is reached). Above all, the collection efficiency and the pressure loss are in a contradictory relationship. To increase the collection efficiency, the pressure loss increases, the collection time becomes shorter, and if the pressure loss is made lower, the collection time can be made longer. The collection efficiency becomes worse. In order to satisfy the characteristics of these contradictory filters, the cordierite-based honeycomb structure has the following porosity,
Techniques for controlling and optimizing the pore distribution have been studied in the past.
【０００３】特開昭６１−１２９０１５号公報では、フ
ィルタ隔壁表面に存在する細孔を、孔径５〜４０μmの
小孔と、孔径４０〜１００μｍの大孔とから構成し、該
小孔の数が該大孔の数の５〜４０倍となるように構成し
た排ガス浄化用フィルタが開示されている。その気孔率
について記載はされていないが、累積細孔容積が０．３
〜０．７ｃｍ３／ｇであることからコージェライトの真
比重を２．５として気孔率を計算すると気孔率は４２〜
６４％となる。また、特公昭６１−５４７５０号公報に
は、オープンポロシティ（気孔率）と平均細孔径を制御
することによって、高捕集率タイプから低捕集率タイプ
までのフィルタを設計しうることが開示されている。本
公報では気孔率の好ましい範囲は３３〜９０％とされて
いる。一方、特許第２５７８１７６号公報には、気孔率
４０〜５５％で直径２μm以下の細孔容積が０．０１５
ｃｃ／ｇ以下である多孔質セラミックハニカムフィルタ
ーが開示され、直径２μm以下の細孔を一定量以下に抑
えることによって、捕集時間の長いフィルターが開示さ
れている。さらに、特許第２５６２１８６号公報では、
造孔剤として易燃焼性のカーボン粉を使用することによ
って、短い焼成時間で造孔剤の燃え残りや造孔剤の急激
な燃焼に伴う溶け不良のないディーゼルパティキュレー
トフィルターとして好適な多孔質セラミックハニカム構
造体の製法が開示されている。そして、特開平９−７７
５７３号公報には、高捕集率、低圧損を得るため、気孔
率５５〜８０％、平均細孔径が２５〜４０μmであり、
かつ隔壁表面の細孔は５〜４０μmの小孔と４０〜１０
０μmの大孔とよりなり、該小孔の数が該大孔の数の５
〜４０倍であるハニカム構造体が開示されている。In Japanese Patent Application Laid-Open No. 61-129015, pores present on the surface of a filter partition are composed of small pores having a pore diameter of 5 to 40 μm and large pores having a pore diameter of 40 to 100 μm. An exhaust gas purifying filter configured to have 5 to 40 times the number of the large holes is disclosed. Although the porosity is not described, the cumulative pore volume is 0.3
Since the porosity is calculated assuming that the true specific gravity of cordierite is 2.5, the porosity is 42 to 0.7 cm 3 / g.
64%. Japanese Patent Publication No. 61-54750 discloses that a filter from a high collection rate type to a low collection rate type can be designed by controlling the open porosity (porosity) and the average pore diameter. ing. In this publication, the preferable range of the porosity is 33 to 90%. On the other hand, Japanese Patent No. 2578176 discloses that the volume of pores having a porosity of 40 to 55% and a diameter of 2 μm or less is 0.015.
A porous ceramic honeycomb filter having a cc / g or less is disclosed, and a filter having a long collection time is disclosed by suppressing pores having a diameter of 2 μm or less to a certain amount or less. Further, in Japanese Patent No. 2562186,
Porous ceramic suitable as a diesel particulate filter with no burning residue due to rapid burning of the pore-forming agent in a short firing time by using easily combustible carbon powder as the pore-forming agent A method for manufacturing a honeycomb structure is disclosed. And Japanese Patent Application Laid-Open No. 9-77
No. 573 discloses that in order to obtain a high collection rate and a low pressure loss, the porosity is 55 to 80% and the average pore diameter is 25 to 40 μm.
And the pores on the partition wall surface are small pores of 5-40 μm and 40-10
0 μm large holes, and the number of the small holes is 5 times the number of the large holes.
Honeycomb structures of up to 40 times are disclosed.
【０００４】[0004]
【発明が解決しようとする課題】上記従来の技術では、
ハニカム構造体の隔壁にディーゼルパティキュレート用
のフィルタ機能を持たせるために、ハニカム構造体を構
成するコージェライト質セラミックスの気孔率は、ガソ
リンエンジン用の触媒担体の気孔率３０〜３５％に比べ
て大きな値となっている。しかしながら、多孔質体の強
度は、その気孔率と相反する関係にあることから、ハニ
カム構造体を構成するコージェライト質セラミックスの
気孔率が大きくなれば、必然的にハニカム構造体の強度
は低下することになるのである。しかも上記従来技術に
よれば、気孔を形成するための造孔剤としては、カーボ
ンや黒鉛等の比較的扁平形状をした粉末が主として使用
されていることから、その気孔はアスペクト比の大きい
鋭角部を有する形態となる。このため気孔先端に応力集
中が発生しやすく、ハニカム構造体の強度が低下する原
因になるのである。このような理由から、ディーゼル機
関の微粒子捕集用フィルタとして使用した場合、発生す
る熱応力や熱衝撃応力、組立時の機械的締め付け力や振
動による応力等により破損することなく、長期にわたり
耐久性のあるコージェライト質ハニカム構造体が得られ
ないという問題があった。In the above prior art,
In order for the partition walls of the honeycomb structure to have a filter function for diesel particulates, the porosity of the cordierite ceramics constituting the honeycomb structure is lower than the porosity of the catalyst carrier for gasoline engines, which is 30 to 35%. It has a large value. However, since the strength of the porous body is in a relationship opposite to its porosity, if the porosity of the cordierite ceramics constituting the honeycomb structure increases, the strength of the honeycomb structure necessarily decreases. It will be. Moreover, according to the above prior art, a relatively flat powder such as carbon or graphite is mainly used as a pore-forming agent for forming pores. It becomes the form which has. For this reason, stress concentration tends to occur at the tip of the pores, which causes the strength of the honeycomb structure to decrease. For this reason, when used as a filter for collecting particulates in diesel engines, it does not break due to thermal stress, thermal shock stress, mechanical tightening force during assembly, or stress due to vibration. There is a problem that a cordierite-type honeycomb structure having a problem cannot be obtained.
【０００５】本発明は、このような問題を解決するため
に、コージェライト質セラミックスの気孔率が５５％以
上の値であっても、ディーゼル機関から排出される微粒
子捕集用フィルタとして長期にわたり安定して使用する
ことのできる、高強度コージェライト質ハニカム構造体
を提供することを目的とする。According to the present invention, even if the porosity of the cordierite ceramics is 55% or more, the present invention provides a filter for collecting fine particles discharged from a diesel engine for a long period of time. It is an object of the present invention to provide a high-strength cordierite-based honeycomb structure that can be used as a honeycomb structure.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するた
め、本発明者は鋭意検討を行った結果、ハニカム構造体
に形成される細孔の形状を従来の鋭角形状から略円形に
することにより、ハニカム構造体の強度が向上すること
見出し、本発明に想到した。すなわち、本第１発明のコ
ージェライト質セラミックハニカム構造体は、主成分の
化学組成がＳｉＯ２：４２〜５６質量％、Ａｌ２Ｏ３：
３０〜４５質量％、ＭｇＯ：１２〜１６％であるコージ
ェライト質セラミックハニカム構造体であって、気孔率
が５５〜８０％、隔壁の任意断面において断面積が１０
００μm２以上である細孔のうち細孔の断面形状が略円
形状であるものが含まれていることを特徴とする。第２
発明のコージェライト質セラミックハニカム構造体は、
第１の発明において、隔壁の任意断面において断面積が
１０００μm２以上である細孔のうち細孔の真円度が１
〜１０である細孔の個数が５０％以上であることを特徴
とする。第３発明のコージェライト質セラミックハニカ
ム構造体は、主成分の化学組成がＳｉＯ２：４２〜５６
質量％、Ａｌ２Ｏ３：３０〜４５質量％、ＭｇＯ：１２
〜１６％であるコージェライト質セラミックハニカム構
造体であって、気孔率が５５〜８０％、ハニカム壁の任
意断面における断面積が１０００μm２以上である細孔
のうち、アスペクト比が２以下の細孔の個数が６０％以
上であることを特徴とする。第４発明のコージェライト
質セラミックハニカム構造体は、第１乃至第３のいずれ
かの発明において気孔率が６０〜７０％であることを特
徴とする。第５発明のコージェライト質ハニカム構造体
は、第１乃至第４のいずれかの発明において、細孔の平
均細孔径が１０〜４０μmであることを特徴とする。第
６発明のコージェライト質ハニカム構造体は、第１乃至
第５のいずれかの発明において、隔壁の厚さが０．１〜
０．４５ｍｍ、隔壁の間隔が１〜３．５ｍｍであること
を特徴とする。第７発明のコージェライト質ハニカム構
造体は、第１乃至第６のいずれかの発明において、Ａ軸
圧縮強度が３ＭＰａ以上であることを特徴とする。Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies, and as a result, have changed the shape of the pores formed in the honeycomb structure from a conventional acute angle shape to a substantially circular shape. Have found that the strength of the honeycomb structure is improved, and have reached the present invention. That is, in the cordierite ceramic honeycomb structure of the first invention, the chemical composition of the main component is SiO 2 : 42 to 56% by mass, and Al 2 O 3 :
A cordierite-based ceramic honeycomb structure having 30 to 45% by mass and MgO: 12 to 16%, having a porosity of 55 to 80% and a cross-sectional area of 10 to 10 at an arbitrary cross section of a partition wall.
It is characterized in that, among the pores having a size of not less than 00 μm 2 , those having a substantially circular cross section are included. Second
The cordierite-based ceramic honeycomb structure of the present invention comprises:
In the first aspect, among the pores having a cross-sectional area of 1000 μm 2 or more in any cross section of the partition wall, the roundness of the pores is 1 or more.
It is characterized in that the number of pores of 10 to 10 is 50% or more. In the cordierite-based ceramic honeycomb structure of the third invention, the chemical composition of the main component is SiO 2 : 42 to 56.
Mass%, Al 2 O 3: 30~45 wt%, MgO: 12
A cordierite-based ceramic honeycomb structure having a porosity of 55 to 80% and a cross-sectional area of an arbitrary cross section of a honeycomb wall of 1000 μm 2 or more out of fine pores having an aspect ratio of 2 or less. The number of holes is at least 60%. A cordierite-based ceramic honeycomb structure according to a fourth aspect of the present invention is characterized in that in any one of the first to third aspects, the porosity is 60 to 70%. A cordierite-based honeycomb structure according to a fifth aspect is characterized in that, in any one of the first to fourth aspects, the average pore diameter of the pores is 10 to 40 μm. The cordierite-based honeycomb structure according to a sixth aspect of the present invention is the cordierite-based honeycomb structure according to any one of the first to fifth aspects, wherein the partition walls have a thickness of 0.1 to 0.1.
It is characterized in that 0.45 mm and the interval between partition walls is 1 to 3.5 mm. A cordierite-based honeycomb structure according to a seventh aspect is characterized in that, in any one of the first to sixth aspects, the A-axis compressive strength is 3 MPa or more.
【０００７】次に、本発明における作用効果につき説明
する。本発明のハニカム構造体は、気孔率５５〜８０％
の多孔質コージェライト質セラミックス中に存在する比
較的細孔径の大きい細孔、すなわち隔壁の任意断面にお
いて断面積が１０００μｍ２以上である細孔の中に、細
孔の断面形態が略円形状をした細孔が含まれることによ
り、鋭角的な角部を有する細孔部が少なくなり細孔部角
部への応力集中が発生しにくくなり、ハニカム構造体の
強度の改善が認められるからである。ここで気孔率を５
５〜８０％に限定するのは、気孔率が５５％未満の場合
にはディーゼルパティキュレートフィルターとして使用
した時に、圧損が大きくなってしまい、ディーゼルエン
ジンの排気効率が悪くなり、ディーゼルエンジンの効率
が悪くなるからであり、気孔率が８０％を超える場合、
比較的大きな細孔の形態を略円形状にしても、気孔の割
合そのものが多くなるため強度の改善は認められないか
らであり、さらに、微粒子の捕集効率も悪くなるからで
ある。ここで略円形状とは例えば真円度が１〜１０の円
形を指す。この真円度は（円周長）×（円周長）／（４
×π×（面積））で表した。半径一定の円の場合、真円
度は１となり、細孔の形態が円形からずれるに従い大き
くなる。尚、本発明のハニカム構造体の略円形状をした
細孔は、隔壁の任意断面において断面積が１０００μm
２以上である細孔のうち細孔の真円度が１〜１０である
細孔の個数が５０％以上であることが望ましい。ここで
真円度は上記した通りである。従って、細孔の形態が略
円形である真円度１〜１０である細孔の個数が増えるこ
とにより、略円形からはずれた破壊の起点となり易い鋭
角部を有する細孔が少なくなるため、ハニカム構造体の
強度の改善がより認められる。Next, the function and effect of the present invention will be described. The honeycomb structure of the present invention has a porosity of 55 to 80%.
Among the pores having a relatively large pore diameter existing in the porous cordierite ceramics of the above, that is, pores having a cross-sectional area of 1000 μm 2 or more at an arbitrary cross section of the partition wall, the cross-sectional shape of the pores is substantially circular. This is because the inclusion of the formed pores reduces the number of pores having sharp corners, makes it difficult for stress concentration to occur at the corners of the pores, and improves the strength of the honeycomb structure. . Here, the porosity is 5
If the porosity is less than 55%, the pressure loss increases when the porosity is less than 55% when used as a diesel particulate filter, the exhaust efficiency of the diesel engine deteriorates, and the efficiency of the diesel engine decreases. This is because when the porosity exceeds 80%,
This is because, even if the shape of the relatively large pores is substantially circular, the strength of the fine particles is not improved because the proportion of the pores themselves increases, and the efficiency of collecting fine particles also deteriorates. Here, the substantially circular shape refers to, for example, a circular shape having a roundness of 1 to 10. This roundness is (circumferential length) × (circumferential length) / (4
× π × (area)). In the case of a circle having a constant radius, the roundness is 1, and the roundness increases as the shape of the pore deviates from the circle. Incidentally, the substantially circular pores of the honeycomb structure of the present invention have a cross-sectional area of 1000 μm in an arbitrary cross section of the partition wall.
It is desirable that the number of pores having a roundness of 1 to 10 among the pores of 2 or more is 50% or more. Here, the roundness is as described above. Accordingly, since the number of pores having a roundness of 1 to 10 in which the shape of the pores is substantially circular increases, the number of pores having acute angles which are likely to be the starting points of destruction deviating from the substantially circular shape is reduced, and thus the honeycomb is formed. An improvement in the strength of the structure is more noticeable.
【０００８】また、本発明のハニカム構造体は、気孔率
５５〜８０％の多孔質コージェライト質セラミックス中
に存在する比較的細孔径の大きい細孔、すなわち隔壁の
任意断面における断面積が１０００μｍ２以上である細
孔のうち、アスペクト比が２以下の細孔の個数を６０％
以上とすることにより、鋭角な角部を有する細孔が少な
くなることから、細孔部への応力集中が発生しにくくな
るため、ハニカム構造体の強度の改善が認められる。こ
こで、気孔率を５５〜８０％に限定するのは、気孔率が
５５％未満の場合にはディーゼルパティキュレートフィ
ルターとして使用した時に、圧損が大きくなってしま
い、ディーゼルエンジンの排気効率が悪くなり、ディー
ゼルエンジンの効率が悪くなるからであり、気孔率が８
０％を超える場合、比較的大きな細孔の形態を略円形状
にしても、気孔の割合そのものが多くなるため強度の改
善は認められないからであり、さらに、微粒子の捕集効
率も悪くなるからである。Further, the honeycomb structure of the present invention has pores having a relatively large pore diameter in porous cordierite ceramics having a porosity of 55 to 80%, that is, a cross-sectional area of an arbitrary cross section of the partition wall is 1000 μm 2. Among the above pores, the number of pores having an aspect ratio of 2 or less was reduced by 60%.
By doing so, the number of pores having sharp corners is reduced, so that stress concentration on the pores is less likely to occur, so that the strength of the honeycomb structure is improved. Here, the porosity is limited to 55 to 80% because when the porosity is less than 55%, the pressure loss increases when used as a diesel particulate filter, and the exhaust efficiency of the diesel engine deteriorates. This is because the efficiency of the diesel engine deteriorates and the porosity is 8
If it exceeds 0%, even if the shape of the relatively large pores is substantially circular, the strength of the fine particles is not improved because the proportion of the pores themselves increases, and the efficiency of collecting fine particles is also deteriorated. Because.
【０００９】尚、気孔率の範囲は、上記の理由から、更
に６０〜７０％の間が好ましい。また、本発明のハニカ
ム構造体中に存在する細孔の平均細孔径は１０〜４０μ
ｍが好適としたのは、平均細孔径が１０μｍ未満ではデ
ィーゼルパティキュレートフィルターとして使用した場
合、圧損が大きくなってしまい、ディーゼルエンジンの
効率が悪くなる場合が有るからであり、平均細孔径が４
０μｍを超える場合、比較的大きな細孔の形態を概略円
形状にしても、気孔の大きさ自体が大きくなるため強度
の改善は認められない場合が有るからであり、さらに、
小さな微粒子は捕捉されずにフィルターを通過してしま
い捕集効率も悪くなる場合も有る。また、本発明のハニ
カム構造体の好適な隔壁の厚さを０．１〜０．４５ｍ
ｍ、隔壁の間隔が１〜３．５ｍｍとしたのは、隔壁の厚
さが０．４５ｍｍを越える場合、或いは隔壁の間隔が１
ｍｍ未満の場合ではディーゼルパティキュレートフィル
ターとして使用した場合、圧損が大きくなってしまい、
十分なフィルター特性が得られない場合が有るからであ
り、隔壁ハニカム壁厚が０．１ｍｍ未満の場合、或い
は、隔壁の間隔が３．５ｍｍを越える場合、隔壁を構成
するコージェライト質セラミックス中の細孔の形態を制
御しても、ハニカム構造体の強度の改善は認められない
場合があるからである。Incidentally, the range of the porosity is more preferably between 60 and 70% for the above-mentioned reason. The average pore diameter of the pores present in the honeycomb structure of the present invention is 10 to 40 μm.
The reason why m is preferable is that when the average pore diameter is less than 10 μm, when used as a diesel particulate filter, the pressure loss increases, and the efficiency of the diesel engine may deteriorate.
If it exceeds 0 μm, even if the shape of the relatively large pores is substantially circular, there is a case where the strength is not improved because the size of the pores themselves becomes large.
In some cases, small fine particles pass through the filter without being captured, resulting in poor collection efficiency. Further, the preferable thickness of the partition wall of the honeycomb structure of the present invention is 0.1 to 0.45 m.
m, the interval between the partition walls is 1 to 3.5 mm when the thickness of the partition wall exceeds 0.45 mm or when the interval between the partition walls is 1
If it is less than mm, the pressure loss will increase when used as a diesel particulate filter,
This is because sufficient filter characteristics may not be obtained, and when the partition wall thickness is less than 0.1 mm, or when the interval between the partition walls exceeds 3.5 mm, the cordierite ceramics constituting the partition walls This is because, even if the morphology of the pores is controlled, the strength of the honeycomb structure may not be improved in some cases.
【００１０】また、本発明のハニカム構造体の好適なＡ
軸圧縮強度を３ＭＰａ以上としたのは、Ａ軸圧縮強度が
３ＭＰａ以上あれば、ディーゼル機関の微粒子捕集用フ
ィルタとして使用した場合、発生する熱応力や熱衝撃応
力、組立時の機械的締め付け力や振動による応力等によ
り破損しない、耐久性のあるコージェライト質ハニカム
構造体を提供できるからである。[0010] Further, the preferred A of the honeycomb structure of the present invention.
The reason why the axial compression strength is set to 3 MPa or more is that if the A-axis compression strength is 3 MPa or more, when used as a filter for collecting particulates of a diesel engine, the thermal stress or thermal shock stress generated, and the mechanical tightening force during assembly This is because it is possible to provide a durable cordierite-based honeycomb structure that is not damaged by stress due to vibration or vibration.
【００１１】[0011]
【発明の実施の形態】以下、本発明の実際の実施例を説
明する。 （実施例１）本発明のディーゼル微粒子捕集フィルター
用コージェライト質ハニカム構造体を製造するには、ま
ずコージェライト組成すなわちＳｉＯ２が４２〜５６質
量％、Ａｌ２Ｏ３が３０〜４５質量％、ＭｇＯが１２〜
１６質量％となるようにカオリン、仮焼カオリン、アル
ミナ、水酸化アルミニウム、シリカ、タルク、及び球状
造孔剤の所定量を混合する。次に、この混合物に可塑剤
及び粘結剤を加えて可塑化可能なバッチを作製し、この
バッチを公知の押出成形法により、直径１４３ｍｍ、長
さ１５２ｍｍの円筒形ハニカム構造体を成形した。次い
でこの成形体を乾燥した上で１３５０〜１４４０℃の温
度域で焼成して、第１図(ａ)、(ｂ)の正面図及び側面図
を示すように多孔質セラミック隔壁３と貫通孔２からな
る各種コージェライト質セラミックハニカム構造体１を
得た。ハニカム構造体の製造に当たっては、原料の配合
組成、成形条件或いは焼成条件等々を調整することによ
って、各種細孔特性及びハニカム壁構造を有する表１に
記載の試験Ｎｏ．１〜４のハニカム構造体を製造した。
ハニカム構造体の気孔率及び平均細孔径の測定にはMicr
omeritics社製のオートポアIII９４１０を使用し、水銀
圧入法で測定した。また断面積が１０００μｍ２以上の
細孔の形態は、ハニカム構造体を試料研磨用埋め込み樹
脂に埋め込んだ後、ハニカム壁の押出方向に垂直な面の
研磨を行った上で、ＳＥＭ観察を行い、ＳＥＭ像から目
視にて略円形の細孔の有無を確認した。また、断面積が
１０００μｍ２以上の細孔の真円度の測定は、上記ＳＥ
Ｍ観察をした画像データに対して市販の画像解析ソフト
ウェア（メディアサイバネティクス社製イメージプロプ
ラス ヴァージョン３．０）により解析を行った。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an actual embodiment of the present invention will be described. (Example 1) To produce a diesel particulate filter for cordierite honeycomb structure of the present invention, first cordierite composition i.e. SiO 2 is 42 to 56 wt%, Al 2 O 3 is 30 to 45 wt% , MgO is 12 ~
A predetermined amount of kaolin, calcined kaolin, alumina, aluminum hydroxide, silica, talc, and a spherical pore former is mixed so as to be 16% by mass. Next, a plasticizable batch was prepared by adding a plasticizer and a binder to the mixture, and the batch was formed into a cylindrical honeycomb structure having a diameter of 143 mm and a length of 152 mm by a known extrusion molding method. Next, after drying this formed body, it is fired in a temperature range of 1350 to 1440 ° C., and as shown in the front view and the side view of FIGS. Various cordierite-based ceramic honeycomb structures 1 were obtained. In the production of the honeycomb structure, by adjusting the composition of the raw materials, the molding conditions, the firing conditions, and the like, the test No. 1 having various pore characteristics and the honeycomb wall structure described in Table 1 having various pore characteristics. 1 to 4 honeycomb structures were manufactured.
Micr for measuring porosity and average pore size of honeycomb structures
The measurement was performed by a mercury intrusion method using Autopore III 9410 manufactured by Omeritics. In addition, the form of the pores having a cross-sectional area of 1000 μm 2 or more is obtained by embedding the honeycomb structure in the resin for polishing the sample, polishing the surface perpendicular to the extrusion direction of the honeycomb wall, and performing SEM observation. The presence or absence of a substantially circular pore was visually confirmed from the SEM image. The measurement of the roundness of pores having a cross-sectional area of 1000 μm 2 or more is based on the above SE.
The image data subjected to M observation was analyzed using commercially available image analysis software (Image Pro Plus Version 3.0, manufactured by Media Cybernetics).
【００１２】上記の様に作製したハニカム構造体から試
験片を切り出しＡ軸圧縮強度を測定した。Ａ軸圧縮強度
の測定は、社団法人自動車技術会が定める規格Ｍ５０５
−８７「自動車排気ガス浄化触媒用セラミックモノリス
担体の試験方法」に従って行った。A test piece was cut out from the honeycomb structure manufactured as described above, and the A-axis compressive strength was measured. The measurement of A-axis compressive strength is based on the standard M505 specified by the Society of Automotive Engineers of Japan.
-87 "Test Method for Ceramic Monolith Carrier for Automotive Exhaust Gas Purification Catalyst"
【００１３】その後このセラミックハニカム構造体の端
面を第２図（ａ）、（ｂ）にその正面図及び側面図を示
すように封じ材４により目封じし、多孔質セラミックハ
ニカムフィルターを得た。この得られた多孔質セラミッ
クハニカムフィルターのフィルター特性を、耐破損性、
圧損、捕集効率について評価を行った。その結果を表１
に示す。ここで、耐破損性は、Ａ軸圧縮強度の値で評価
し、これが３ＭＰａ以上の場合は合格とし（○）で、更
に７ＭＰａ以上の好ましい場合は(◎)で、３ＭＰａ未満
の場合には不合格とし（×）で示した。圧損は、圧力損
失テストスタンドにて空気流量７．５Ｎｍ３／ｍｉｎの
時のハニカムフィルター流入前と流出後の圧力損失で評
価を行ない、３００ｍｍＡｑ以下の圧力損失であれば合
格とし（○）で、更に好ましい２５０Ａｑ以下の場合は
（◎）で、３００ｍｍＡｑを超える圧力損失であれば不
合格とし（×）で示した。捕集効率は、上記ハニカムフ
ィルターを準備し、圧力損失テストスタンドにて空気流
量７．５Ｎｍ３／ｍｉｎに粒子径０．０４２μｍのカー
ボンを３ｇ／Ｈｒで２Ｈｒ投入後にハニカムフィルター
により捕捉したカーボン量が９０％を越えた場合を合格
とし（○）で、捕捉したカーボン量が９０％未満であれ
ば不合格とし（×）で示した。そして、総合判定とし
て、耐破損性、圧損、捕集効率のいずれも合格であるも
のを（○）、そのうち（◎）判定が一つ以上あった場合
は（◎）、いずれか１つでも不合格であるものを（×）
で評価した。Thereafter, the end face of the ceramic honeycomb structure was plugged with a sealing material 4 as shown in the front view and the side view in FIGS. 2 (a) and 2 (b) to obtain a porous ceramic honeycomb filter. The filter characteristics of the obtained porous ceramic honeycomb filter are
Pressure loss and collection efficiency were evaluated. Table 1 shows the results.
Shown in Here, the fracture resistance was evaluated by the value of the A-axis compressive strength. If it was 3 MPa or more, it was judged as acceptable (合格), more preferably 7 MPa or more, (◎), and if it was less than 3 MPa, it was unacceptable. A pass was indicated by (x). The pressure loss was evaluated at the pressure loss test stand based on the pressure loss before and after the honeycomb filter inflow at an air flow rate of 7.5 Nm 3 / min. If the pressure loss was 300 mmAq or less, it was judged as acceptable (○). The case of 250 Aq or less is more preferable (◎), and the pressure loss exceeding 300 mmAq is rejected (×). The trapping efficiency was determined by preparing the above-mentioned honeycomb filter and measuring the amount of carbon trapped by the honeycomb filter after injecting carbon having a particle size of 0.042 μm into the air flow rate of 7.5 Nm 3 / min at a rate of 3 g / Hr for 2 hours at a pressure loss test stand. The case where it exceeded 90% was regarded as a pass (）), and the case where the amount of captured carbon was less than 90% was rejected (x). Then, as a comprehensive judgment, a sample that passed all of the breakage resistance, pressure loss, and collection efficiency (○), among which (◎) when there was one or more judgments (◎), failed any one Those that pass (×)
Was evaluated.
【００１４】表１に示す結果のうち、試験Ｎｏ．１〜４
に示すハニカム構造体では、断面積が１０００μｍ２以
上の細孔の形態が略円形状のものを含んでいることか
ら、真円度１〜１０の細孔の割合も高かったため、耐破
損性はいずれも合格した。また圧損、捕集効率について
も、合格し、総合判定は（○）、及び（◎）であった。
以上、表１の結果から明らかなように、微粒子捕集用フ
ィルターとして重要な特性である耐破損性、微粒子の捕
集効率、圧損の結果から総合判定すると、本発明の実施
例である試験Ｎｏ．１〜４のハニカム構造体フィルタは
いずれも耐破損性、捕集効率、圧損特性を満足するフィ
ルタであった。Of the results shown in Table 1, Test No. 1-4
In the honeycomb structure shown in the above, since the form of the pores having a cross-sectional area of 1000 μm 2 or more includes those having a substantially circular shape, the ratio of the pores having a roundness of 1 to 10 was also high, so that the breakage resistance was All passed. Also, the pressure loss and the collection efficiency were passed, and the comprehensive judgment was (○) and (◎).
As is clear from the results in Table 1, when comprehensive judgment is made from the results of breakage resistance, fine particle collection efficiency, and pressure loss, which are important characteristics as a fine particle collecting filter, Test No., which is an example of the present invention, . All of the honeycomb structure filters 1 to 4 satisfied the breakage resistance, the collection efficiency, and the pressure loss characteristics.
【００１５】（比較例１）ディーゼル微粒子捕集フィル
ター用コージェライト質ハニカム構造体を製造するた
め、まずコージェライト組成すなわちＳｉＯ２が４２〜
５６質量％、Ａｌ２Ｏ３が３０〜４５質量％、ＭｇＯが
１２〜１６質量％となるようにカオリン、仮焼カオリ
ン、アルミナ、水酸化アルミニウム、シリカ、タルク、
及び黒鉛粉末、カーボン粉末等のアスペクト比の大きい
扁平形状の造孔剤の所定量を混合する。次に、この混合
物に可塑剤及び粘結剤を加えて可塑化可能なバッチを作
製し、このバッチを公知の押出成形法により、直径１４
３ｍｍ、長さ１５２ｍｍの円筒形ハニカム構造体を成形
した。次いで、この成形体を乾燥した上で１３５０〜１
４４０℃の温度域で焼成して、第１図(ａ)、(ｂ)の正面
図及び側面図を示すように多孔質セラミック隔壁３と貫
通孔２からなる各種コージェライト質セラミックハニカ
ム構造体１を得た。ハニカム構造体の製造に当たって
は、原料の配合組成、成形条件或いは焼成条件等々を調
整することによって、表１に示す試験Ｎ０．５、６のハ
ニカム構造体を製造した。以下、実施例１と同様の方法
により、気孔率、平均細孔径、真円度、Ａ軸圧縮強度の
測定を行い、端面の目封じを行った上で、フィルター特
性の測定を行った。Comparative Example 1 In order to produce a cordierite-based honeycomb structure for a diesel particulate filter, first, the cordierite composition, ie, SiO 2 was 42 to
Kaolin, calcined kaolin, alumina, aluminum hydroxide, silica, talc, so that 56 mass%, Al 2 O 3 is 30 to 45 mass%, and MgO is 12 to 16 mass%.
A predetermined amount of a flat pore-forming agent having a large aspect ratio, such as graphite powder and carbon powder, is mixed. Next, a plasticizable batch is prepared by adding a plasticizer and a binder to the mixture, and the batch is formed into a batch having a diameter of 14 by a known extrusion method.
A cylindrical honeycomb structure having a length of 3 mm and a length of 152 mm was formed. Next, after drying this molded body, 1350-1
It is fired in a temperature range of 440 ° C., and as shown in the front view and the side view of FIGS. 1 (a) and 1 (b), various cordierite ceramic honeycomb structures 1 each comprising a porous ceramic partition wall 3 and a through hole 2. I got In manufacturing the honeycomb structure, the honeycomb structures of Tests N0.5 and N6 shown in Table 1 were manufactured by adjusting the composition of the raw materials, the molding conditions, the firing conditions, and the like. Hereinafter, the porosity, the average pore diameter, the roundness, and the A-axis compressive strength were measured in the same manner as in Example 1, and after the end face was plugged, the filter characteristics were measured.
【００１６】表１に記載の本発明の比較例である試験Ｎ
ｏ．５、６のハニカム構造体は、断面積が１０００μｍ
２以上の細孔の形態が角形状であったことから、必然的
に真円度を計測すること不可能であり、Ａ軸圧縮強度も
３ＭＰａを下回る値となったため、耐破損性はいずれも
不合格となり、総合判定は不合格（×）となった。Test N which is a comparative example of the present invention described in Table 1
o. The honeycomb structures 5 and 6 have a cross-sectional area of 1000 μm.
Since the shape of two or more pores was square, it was inevitably impossible to measure the roundness, and the A-axis compressive strength was less than 3 MPa. It was rejected and the comprehensive judgment was rejected (x).
【００１７】[0017]
【表１】 [Table 1]
【００１８】（実施例２）本発明のディーゼル微粒子捕
集フィルター用コージェライト質ハニカム構造体を製造
するには、まずコージェライト組成すなわちＳｉＯ２が
４２〜５６質量％、Ａｌ２Ｏ３が３０〜４５質量％、Ｍ
ｇＯが１２〜１６質量％となるようにカオリン、仮焼カ
オリン、アルミナ、水酸化アルミニウム、シリカ、タル
ク、及び球状造孔剤の所定量を混合する。次に、この混
合物に可塑剤及び粘結剤を加えて可塑化可能なバッチを
作製し、このバッチを公知の押出成形法により、直径１
４３ｍｍ、長さ１５２ｍｍの円筒形ハニカム構造体を成
形した。次いでこの成形体を乾燥した上で１３５０〜１
４４０℃の温度域で焼成して、第１図(ａ)、(ｂ)の正面
図及び側面図を示すように多孔質セラミック隔壁３と貫
通孔２からなる各種コージェライト質セラミックハニカ
ム構造体１を得た。ハニカム構造体の製造に当たって
は、原料の配合組成、成形口金の寸法、成形条件或いは
焼成条件等々を調整することによって、各種細孔特性及
びハニカム壁構造を有する表２記載の試験Ｎｏ．７〜２
０のハニカム構造体を製造した。ハニカム構造体の気孔
率及び平均細孔径の測定にはMicromeritics社製のオー
トポアIII９４１０を使用し、水銀圧入法で測定した。
また、断面積が１０００μｍ２以上の細孔の形態は、ハ
ニカム構造体を試料研磨用埋め込み樹脂に埋め込んだ
後、ハニカム壁の押出方向に垂直な面の研磨を行った上
で、ＳＥＭ観察を行い、ＳＥＭ像から目視にて略円形の
細孔の有無を確認した。また、断面積が１０００μｍ２
以上の細孔の真円度の測定は、上記ＳＥＭ観察をした画
像データに対して市販の画像解析ソフトウェア（メディ
アサイバネティクス社製イメージプロプラス ヴァージ
ョン３．０）により解析を行った。Example 2 In order to produce a cordierite-based honeycomb structure for a diesel particulate filter according to the present invention, first, the cordierite composition, that is, SiO 2 is 42 to 56% by mass and Al 2 O 3 is 30 to 30% by mass. 45% by mass, M
A predetermined amount of kaolin, calcined kaolin, alumina, aluminum hydroxide, silica, talc, and a spherical pore former is mixed so that gO becomes 12 to 16% by mass. Next, a plasticizable batch is prepared by adding a plasticizer and a binder to the mixture, and the batch is formed into a batch having a diameter of 1 by a known extrusion method.
A cylindrical honeycomb structure having a length of 43 mm and a length of 152 mm was formed. Next, after drying this molded product, 1350-1
It is fired in a temperature range of 440 ° C., and as shown in the front view and the side view of FIGS. 1 (a) and 1 (b), various cordierite ceramic honeycomb structures 1 each comprising a porous ceramic partition wall 3 and a through hole 2. I got In the production of the honeycomb structure, by adjusting the compounding composition of the raw materials, the dimensions of the molding die, the molding conditions or the firing conditions, etc., test No. 2 having various pore characteristics and a honeycomb wall structure described in Table 2 was performed. 7-2
No. 0 honeycomb structure was manufactured. The porosity and average pore diameter of the honeycomb structure were measured by a mercury intrusion method using Autopore III9410 manufactured by Micromeritics.
Further, in the form of pores having a cross-sectional area of 1000 μm 2 or more, after embedding the honeycomb structure in the embedding resin for polishing a sample, the surface perpendicular to the extrusion direction of the honeycomb wall was polished, and then subjected to SEM observation. The presence or absence of substantially circular pores was visually confirmed from the SEM images. The cross-sectional area is 1000 μm 2
The measurement of the roundness of the pores described above was performed by analyzing the image data obtained by the SEM observation using commercially available image analysis software (ImagePro Plus version 3.0 manufactured by Media Cybernetics).
【００１９】上記の様に作製したハニカム構造体から試
験片を切り出しＡ軸圧縮強度を測定した。Ａ軸圧縮強度
の測定は、社団法人自動車技術会が定める規格Ｍ５０５
−８７「自動車排気ガス浄化触媒用セラミックモノリス
担体の試験方法」に従って行った。A test piece was cut out from the honeycomb structure manufactured as described above, and the A-axis compressive strength was measured. The measurement of A-axis compressive strength is based on the standard M505 specified by the Society of Automotive Engineers of Japan.
-87 "Test Method for Ceramic Monolith Carrier for Automotive Exhaust Gas Purification Catalyst"
【００２０】その後このセラミックハニカム構造体の端
面を第２図（ａ）、（ｂ）にその正面図及び側面図を示
すように封じ材４により目封じし、多孔質セラミックハ
ニカムフィルターを得た。この得られた多孔質セラミッ
クハニカムフィルターのフィルター特性を、耐破損性、
圧損、捕集効率について評価を行った。その結果を表２
に示す。ここで、耐破損性は、Ａ軸圧縮強度の値で評価
し、これが３ＭＰａ以上の場合は合格とし（○）で、更
に７ＭＰａ以上の好ましい場合は(◎)で、３ＭＰａ未満
の場合には不合格とし（×）で示した。圧損は、圧力損
失テストスタンドにて空気流量７．５Ｎｍ３／ｍｉｎの
時のハニカムフィルター流入前と流出後の圧力損失で評
価を行ない、３００ｍｍＡｑ以下の圧力損失であれば合
格とし（○）で、更に好ましい２５０Ａｑ以下の場合は
（◎）で、３００ｍｍＡｑを超える圧力損失であれば不
合格とし（×）で示した。捕集効率は、上記ハニカムフ
ィルターを準備し、圧力損失テストスタンドにて空気流
量７．５Ｎｍ３／ｍｉｎに粒子径０．０４２μｍのカー
ボンを３ｇ／Ｈｒで２Ｈｒ投入後にハニカムフィルター
により捕捉したカーボン量が９０％を越えた場合を合格
とし（○）で、捕捉したカーボン量が９０％未満であれ
ば不合格とし（×）で示した。そして、総合判定とし
て、耐破損性、圧損、捕集効率のいずれも合格であるも
のを（○）、そのうち（◎）判定が一つ以上あった場合
は（◎）、いずれか１つでも不合格であるものを（×）
で評価した。Thereafter, the end face of the ceramic honeycomb structure was plugged with a sealing material 4 as shown in the front view and side view in FIGS. 2 (a) and 2 (b) to obtain a porous ceramic honeycomb filter. The filter characteristics of the obtained porous ceramic honeycomb filter are
Pressure loss and collection efficiency were evaluated. Table 2 shows the results.
Shown in Here, the fracture resistance was evaluated by the value of the A-axis compressive strength. If it was 3 MPa or more, it was judged as acceptable (合格), more preferably 7 MPa or more, (◎), and if it was less than 3 MPa, it was unacceptable. A pass was indicated by (x). The pressure loss was evaluated at the pressure loss test stand based on the pressure loss before and after the honeycomb filter inflow at an air flow rate of 7.5 Nm 3 / min. If the pressure loss was 300 mmAq or less, it was judged as acceptable (○). The case of 250 Aq or less is more preferable (◎), and the pressure loss exceeding 300 mmAq is rejected (×). The trapping efficiency was determined by preparing the above-mentioned honeycomb filter and measuring the amount of carbon trapped by the honeycomb filter after injecting carbon having a particle size of 0.042 μm into the air flow rate of 7.5 Nm 3 / min at a rate of 3 g / Hr for 2 hours at a pressure loss test stand. The case where it exceeded 90% was regarded as a pass (）), and the case where the amount of captured carbon was less than 90% was rejected (x). Then, as a comprehensive judgment, a sample that passed all of the breakage resistance, pressure loss, and collection efficiency (○), among which (◎) when there was one or more judgments (◎), failed any one Those that pass (×)
Was evaluated.
【００２１】表２に示す結果のうち、耐破損性について
は、試験Ｎｏ．７〜試験Ｎｏ．２０のハニカム構造体で
は、３ＭＰａ以上のＡ軸圧縮強度が得られたことから合
格した。中でも、試験Ｎｏ．９、１１、１５、１８、１
９のハニカム構造体では、７ＭＰａ以上のＡ軸圧縮強度
が得られた。試験Ｎｏ．９、１８では、隔壁の肉厚が厚
かったため、試験Ｎｏ．１１では気孔率が小さめであっ
たため、試験Ｎｏ．１５では平均細孔径が小さめであっ
たため、試験Ｎｏ．１９では隔壁のピッチが小さめであ
ったため、Ａ軸圧縮強度の極めて高いハニカム構造体が
得られた。Of the results shown in Table 2, regarding the breakage resistance, Test No. 7 to Test No. 7 The honeycomb structure of No. 20 passed because the A-axis compressive strength of 3 MPa or more was obtained. Among them, Test No. 9, 11, 15, 18, 1
In the honeycomb structure of No. 9, an A-axis compressive strength of 7 MPa or more was obtained. Test No. In Test Nos. 9 and 18, the thickness of the partition wall was large. In Test No. 11, the porosity was relatively small. In Test No. 15, the average pore diameter was relatively small. In No. 19, since the pitch of the partition walls was small, a honeycomb structure having extremely high A-axis compressive strength was obtained.
【００２２】次に、圧損については、試験Ｎｏ．７〜２
０のハニカム構造体はいずれも合格したが、中でも試験
Ｎｏ．１２、１６、１７、２０のハニカム構造体は優れ
た圧損を示した。試験Ｎｏ．１２では、気孔率が大きめ
であったため、試験Ｎｏ．１６では平均細孔径が大きめ
であったため、試験Ｎｏ．１７は隔壁の厚さが薄かった
ため、試験Ｎｏ．２０では隔壁のピッチが大きめであっ
たため、圧損が特に小さかった。また、捕集効率につい
ては、試験Ｎｏ．７〜２０のハニカム構造体は、すべて
合格であった。Next, with respect to the pressure loss, Test No. 7-2
All of the honeycomb structures of Test No. 0 passed the test. The honeycomb structures of 12, 16, 17, and 20 exhibited excellent pressure loss. Test No. In Test No. 12, the porosity was relatively large. In Test No. 16, the average pore diameter was relatively large. Test No. 17 was a test No. 17 because the thickness of the partition wall was thin. In No. 20, the pressure loss was particularly small because the pitch of the partition walls was large. Regarding the collection efficiency, Test No. All the honeycomb structures of 7 to 20 passed.
【００２３】以上、表２の結果から明らかなように、微
粒子捕集用フィルターとして重要な特性である耐破損
性、微粒子の捕集効率、圧損の結果から総合判定する
と、本発明の実施例である試験Ｎｏ．７〜２０のハニカ
ム構造体フィルタはいずれも耐破損性、捕集効率、圧損
特性を満足するフィルタであった。As is clear from the results in Table 2, when the comprehensive judgment is made from the results of the breakage resistance, the collection efficiency of the fine particles, and the pressure loss, which are important characteristics as the filter for collecting fine particles, the embodiment of the present invention shows that A certain test no. Each of the honeycomb structure filters 7 to 20 was a filter satisfying breakage resistance, collection efficiency, and pressure loss characteristics.
【００２４】（比較例２）ディーゼル微粒子捕集フィル
ター用コージェライト質ハニカム構造体を製造するた
め、まずコージェライト組成すなわちＳｉＯ２が４２〜
５６質量％、Ａｌ２Ｏ３が３０〜４５質量％、ＭｇＯが
１２〜１６質量％となるようにカオリン、仮焼カオリ
ン、アルミナ、水酸化アルミニウム、シリカ、タルク、
及び黒鉛粉末、カーボン粉末等アスペクト比の大きい扁
平形状の造孔剤の所定量を混合する。次に、この混合物
に可塑剤及び粘結剤を加えて可塑化可能なバッチを作製
し、このバッチを公知の押出成形法により、直径１４３
ｍｍ、長さ１５２ｍｍの円筒形ハニカム構造体を成形し
た。次いでこの成形体を乾燥した上で１３５０〜１４４
０℃の温度域で焼成して、第１図(ａ)、(ｂ)の正面図及
び側面図を示すように多孔質セラミック隔壁３と貫通孔
２からなる各種コージェライト質セラミックハニカム構
造体１を得た。ハニカム構造体の製造に当たっては、原
料の配合組成、成形条件或いは焼成条件等々を調整する
ことによって、表２に示す試験Ｎ０．２１〜２４のハニ
カム構造体を製造した。以下、実施例２と同様の方法に
より、気孔率、平均細孔径、真円度、Ａ軸圧縮強度の測
定を行い、端面の目封じを行った上で、フィルター特性
の測定を行った。Comparative Example 2 In order to manufacture a cordierite-based honeycomb structure for a diesel particulate filter, first, the cordierite composition, that is, SiO 2 was 42 to 40%.
Kaolin, calcined kaolin, alumina, aluminum hydroxide, silica, talc, so that 56 mass%, Al 2 O 3 is 30 to 45 mass%, and MgO is 12 to 16 mass%.
A predetermined amount of a flat pore-forming agent having a large aspect ratio, such as graphite powder and carbon powder, is mixed. Next, a plasticizer and a binder are added to the mixture to prepare a plasticizable batch, and the batch is formed into a batch having a diameter of 143 by a known extrusion molding method.
mm, and a 152 mm long cylindrical honeycomb structure was formed. Next, after drying this molded body, 1350-144
Firing in a temperature range of 0 ° C., various cordierite ceramic honeycomb structures 1 each having a porous ceramic partition wall 3 and a through hole 2 as shown in the front view and the side view of FIGS. 1 (a) and 1 (b). I got In manufacturing the honeycomb structure, the honeycomb structures of Test N0.21 to N24 shown in Table 2 were manufactured by adjusting the composition of the raw materials, the molding conditions, the firing conditions, and the like. Hereinafter, the porosity, the average pore diameter, the roundness, and the A-axis compressive strength were measured in the same manner as in Example 2, the end faces were plugged, and the filter characteristics were measured.
【００２５】表２に記載の本発明の比較例である試験Ｎ
ｏ．２１、２２のハニカム構造体は、断面積が１０００
μｍ２以上の細孔のうちアスペクト比が２以下の細孔の
個数が６０％を下回ったことから、Ａ軸圧縮強度が３Ｍ
Ｐａを下回る値となったため、耐破損性はいずれも不合
格となり、総合判定は不合格（×）となった。一方試験
Ｎｏ．２３のハニカム構造体は、気孔率が５５％を下回
ったため、圧損が不合格となり、総合判定は不合格
（×）となった。また、試験Ｎｏ．２４のハニカム構造
体では、気孔率が８０％を上まわったため、アスペクト
比２以上の個数割合が６０％以上であるにも拘わらず、
３ＭＰａ以上のＡ軸圧縮強度が得られず、耐破損性が不
合格となり、また捕集効率も不合格となったことから、
総合判定は不合格（×）となった。Test N which is a comparative example of the present invention described in Table 2
o. The honeycomb structures 21 and 22 have a cross-sectional area of 1000
Since the number of the pores having an aspect ratio of 2 or less among the pores of 2 μm or more was less than 60%, the A-axis compressive strength was 3M.
Since the value was less than Pa, any of the breakage resistances was rejected, and the comprehensive judgment was rejected (x). On the other hand, Test No. The honeycomb structure of No. 23 had a porosity of less than 55%, so the pressure loss was unacceptable, and the overall judgment was unacceptable (x). Test No. In the honeycomb structure of No. 24, the porosity exceeded 80%, so that the number ratio of the aspect ratio of 2 or more was 60% or more.
Since the A-axis compression strength of 3 MPa or more was not obtained, the breakage resistance was rejected, and the collection efficiency was also rejected,
The overall judgment was failed (x).
【００２６】[0026]
【表２】 [Table 2]
【００２７】[0027]
【発明の効果】本発明によれば、ハニカム構造体フィル
ターを構成するコージェライト質セラミックス中の断面
積１０００μｍ２以上の細孔の形態を略円形状のものが
含まれるようにしているため、或いは断面積１０００μ
ｍ２以上の細孔のうちアスペクト比２以下の細孔の個数
割合を６０％以上としているため、気孔率が５５〜８０
％の高い値であっても、ディーゼルパティキュレートフ
ィルターとして使用した際に発生する熱応力や熱衝撃応
力、組立時の機械的締め付け力や振動による応力に対し
ても破損しない、耐久性に優れたコージェライト質セラ
ミックハニカム構造体が得られる。According to the present invention, the shape of pores having a cross-sectional area of 1000 μm 2 or more in the cordierite ceramics constituting the honeycomb structure filter is substantially circular. Cross section 1000μ
Since the m 2 or more and the number ratio of the aspect ratio of 2 or less of pores of the pore was less than 60%, a porosity of 55 to 80
% Even when used as a diesel particulate filter, it is not damaged by thermal stress and thermal shock stress generated when it is used as a diesel particulate filter, mechanical tightening force during assembly, and stress due to vibration. A cordierite-based ceramic honeycomb structure is obtained.
【図１】（ａ）及び（ｂ）はそれぞれハニカム構造体の
一例を示す正面図及び側面図である。FIGS. 1A and 1B are a front view and a side view, respectively, showing an example of a honeycomb structure.
【図２】（ａ）及び（ｂ）はそれぞれハニカム構造体を
使用したフィルターの一例を示す正面図及び側面図であ
る。FIGS. 2A and 2B are a front view and a side view showing an example of a filter using a honeycomb structure.
１ セラミックハニカム構造体、 ２ 隔壁、 ３ 貫
通孔、４ セラミックハニカムフィルタ、５ 封じ材Reference Signs List 1 ceramic honeycomb structure, 2 partition wall, 3 through hole, 4 ceramic honeycomb filter, 5 sealing material
Claims (7)
６質量％、Ａｌ２Ｏ ３：３０〜４５質量％、ＭｇＯ：１
２〜１６％であるコージェライト質セラミックハニカム
構造体であって、気孔率が５５〜８０％、隔壁の任意断
面において断面積が１０００μm２以上である細孔のう
ち細孔の断面形状が略円形状であるものが含まれている
ことを特徴とするコージェライト質セラミックハニカム
構造体。1. The chemical composition of a main component is SiO.2: 42-5
6% by mass, Al2O 3: 30 to 45% by mass, MgO: 1
2-16% cordierite ceramic honeycomb
A structure having a porosity of 55 to 80% and a partition wall
The cross-sectional area is 1000μm on the surface2Or more
Includes pores whose cross-sectional shape is substantially circular
Cordierite-type ceramic honeycomb characterized by the following:
Structure.
０μm２以上である細孔のうち細孔の真円度が１〜１０
である細孔の個数が５０％以上であることを特徴とする
請求項１記載のコージェライト質セラミックハニカム構
造体。2. A sectional area of an arbitrary cross section of the partition wall is 100.
Among the pores having a diameter of 0 μm 2 or more, the roundness of the pores is 1 to 10
The cordierite-based ceramic honeycomb structure according to claim 1, wherein the number of pores is 50% or more.
６質量％、Ａｌ２Ｏ ３：３０〜４５質量％、ＭｇＯ：１
２〜１６％であるコージェライト質セラミックハニカム
構造体であって、気孔率が５５〜８０％、隔壁の任意断
面において断面積が１０００μm２以上である細孔のう
ち、アスペクト比が２以下の細孔の個数が６０％以上で
あることを特徴とするコージェライト質セラミックハニ
カム構造体。3. The chemical composition of a main component is SiO.2: 42-5
6% by mass, Al2O 3: 30 to 45% by mass, MgO: 1
2-16% cordierite ceramic honeycomb
A structure having a porosity of 55 to 80% and a partition wall
The cross-sectional area is 1000μm on the surface2Or more
If the number of pores having an aspect ratio of 2 or less is 60% or more,
Cordierite-based ceramic honeycomb
Cam structure.
とする請求項１乃至請求項３のいずれかに記載のコージ
ェライト質セラミックハニカム構造体。4. The cordierite-based ceramic honeycomb structure according to claim 1, wherein the porosity is 60 to 70%.
ることを特徴とする請求項１乃至４のいずれかに記載の
コージェライト質セラミックハニカム構造体。5. The cordierite-based ceramic honeycomb structure according to claim 1, wherein the average pore diameter of the pores is 10 to 40 μm.
壁の間隔が１〜３．５ｍｍであることを特徴とする請求
項１乃至５のいずれかに記載のコージェライト質セラミ
ックハニカム構造体。6. The cordierite-based ceramic honeycomb according to claim 1, wherein the thickness of the partition walls is 0.1 to 0.45 mm, and the interval between the partition walls is 1 to 3.5 mm. Structure.
を特徴とする請求項１乃至６のいずれかに記載のコージ
ェライト質セラミックハニカム構造体。7. The cordierite ceramic honeycomb structure according to claim 1, wherein the A-axis compressive strength is 3 MPa or more.
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|---|---|---|---|
| JP2000307901A JP3329798B2 (en) | 2000-10-06 | 2000-10-06 | Cordierite ceramic honeycomb structure |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000307901A JP3329798B2 (en) | 2000-10-06 | 2000-10-06 | Cordierite ceramic honeycomb structure |
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| Publication Number | Publication Date |
|---|---|
| JP2002121084A true JP2002121084A (en) | 2002-04-23 |
| JP3329798B2 JP3329798B2 (en) | 2002-09-30 |
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ID=18788325
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|---|---|---|---|
| JP2000307901A Expired - Lifetime JP3329798B2 (en) | 2000-10-06 | 2000-10-06 | Cordierite ceramic honeycomb structure |
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| Country | Link |
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| JP2005511294A (en) * | 2001-12-13 | 2005-04-28 | コーニング インコーポレイテッド | Composite cordierite filter |
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