JP2009196104A - Honeycomb structure - Google Patents
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Abstract
Description
本発明は、ハニカム構造体に関し、詳しくは、微粒子物質の捕集性に優れたフィルタを提供することができるハニカム構造体に関する。 The present invention relates to a honeycomb structure, and more particularly, to a honeycomb structure capable of providing a filter having excellent particulate matter trapping properties.
内燃機関、ボイラー、化学反応機器、燃料電池用改質器等の触媒作用を利用する触媒用担体、排ガス中のスス等の微粒子（特にディーゼルエンジンからの排気ガス中の微粒子物質（ＰＭ））の捕集フィルタ（以下、ＤＰＦという）等には、セラミックス製のハニカム構造体が用いられている。 Catalytic carrier utilizing catalytic action of internal combustion engine, boiler, chemical reaction equipment, fuel cell reformer, etc., particulates such as soot in exhaust gas (particularly particulate matter (PM) in exhaust gas from diesel engine) A ceramic honeycomb structure is used for a collection filter (hereinafter referred to as DPF).
セラミックス製のハニカム構造体は、一般に、多孔質のセラミックスよりなり、流体の流路となる複数のセルを隔壁で区画する隔壁部と、端面が市松模様状を呈するように隣接するセルが互いに反対側となる端部を封止するセラミックスよりなる封止部と、を有している。 A honeycomb structure made of ceramic is generally made of porous ceramics, and partition walls that divide a plurality of cells serving as fluid flow paths by partition walls, and adjacent cells are opposite to each other so that the end faces are in a checkered pattern. And a sealing portion made of ceramics that seals the end portion on the side.
セラミックス製のハニカム構造体よりなるＤＰＦは、隔壁部のセルを区画する隔壁を排気ガスが通過するウォールフロー型の触媒として用いられている。ウォールフロー型の触媒は、セル壁に形成された連続した細孔を排気ガスが通過し、細孔を通過できない排気ガス中のＰＭを捕集する。 A DPF made of a ceramic honeycomb structure is used as a wall flow type catalyst in which exhaust gas passes through partition walls that partition partition wall cells. The wall flow type catalyst collects PM in the exhaust gas through which the exhaust gas passes through the continuous pores formed in the cell wall and cannot pass through the pores.
従来の一般的なＤＰＦは、ＰＭを捕集する捕集率が向上してきて９９％以上を示すようになってきている。しかし、９９％以上を示したとしても、コンマ数％のわずかな捕集漏れがある。この捕集漏れは、特に捕集初期（エンジン始動直後）において顕著に表れる。ＰＭが捕集されると、捕集したＰＭ自身がＤＰＦの細孔径を小さくして捕集漏れがほぼなくなるためである。 The conventional general DPF has been improved in the collection rate for collecting PM, and has come to show 99% or more. However, even if it shows 99% or more, there is a slight collection leak of several percent of commas. This collection leakage is particularly noticeable in the early stage of collection (immediately after the engine is started). This is because when the PM is collected, the collected PM itself reduces the pore diameter of the DPF and almost no leakage of collection occurs.
また、一般的なＤＰＦは、ＰＭを捕集することを目的としているが、ＰＭよりさらに微細な粒子であるＳＰＭ（浮遊粒子状物質）を捕集することができず、ＳＰＭがＤＰＦを通過するという問題があった。ＳＰＭは、その粒径が０．０１〜０．１μｍであり、ＤＰＦの細孔径が数〜数十μｍであったためである。このように、従来の一般的なＤＰＦでは、ＳＰＭの捕集が困難となっていた。 Moreover, although general DPF aims at collecting PM, it cannot collect SPM (floating particulate matter) that is finer than PM, and SPM passes through DPF. There was a problem. This is because SPM has a particle size of 0.01 to 0.1 μm and a DPF has a pore size of several to several tens of μm. Thus, it has been difficult to collect SPM with a conventional general DPF.
ここで、従来のＤＰＦの捕集率は重量比または体積比により求められており、９９％以上の捕集率のＤＰＦで捕集できなかった１％未満の捕集漏れのＰＭには、莫大な数のＳＰＭ粒子が含まれている。 Here, the collection rate of the conventional DPF is determined by the weight ratio or the volume ratio, and the PM having a collection leakage of less than 1% that could not be collected by the DPF having a collection rate of 99% or more is enormous. A large number of SPM particles are included.
そして、このＳＰＭは、生態系に多大な被害を与えることが明らかとなっている。非特許文献１に示されている。非特許文献１には、一般に呼吸によって人体の体内に蓄積されて悪影響を及ぼすのはＳＰＭ、つまりナノサイズの粒子によるものが最も大きいことが示されている。すなわち、ＰＭは黒煙となって視覚的に環境に悪い印象を与えるが、真に生態系に被害を与えるのは目に見えないナノ粒子であるＳＰＭとも言える。 And it is clear that this SPM causes great damage to the ecosystem. It is shown in Non-Patent Document 1. Non-Patent Document 1 shows that SPM, that is, nano-sized particles has the largest adverse effect caused by accumulation in the human body by breathing. In other words, PM can be said to be SPM, which is an invisible nano-particle that becomes black smoke and visually gives a bad impression on the environment, but that truly damages the ecosystem.
このことからも、ＤＰＦなどのフィルタには、ナノサイズのＳＰＭを捕集初期から漏らさず捕集できるフィルタが求められている。
本発明は上記実情に鑑みてなされたものであり、ナノサイズの微細粒子までも捕集できるハニカム構造体を提供することを課題とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a honeycomb structure capable of collecting even nano-sized fine particles.
上記課題を解決するために本発明者らはハニカム構造体について検討を重ねた結果本発明をなすに至った。 In order to solve the above-mentioned problems, the present inventors have studied the honeycomb structure and have come to make the present invention.
本発明のハニカム構造体は、セラミックス粉末と、セラミックス粉末を構成するセラミックス粒子同士を結合する結合材と、を有する多孔質セラミックスよりなるハニカム構造体であって、セラミックス粉末は、１０％粒径（Ｄ１０）と９０％粒径（Ｄ９０）との間隔が１０μｍ以上であることを特徴とする。 A honeycomb structure of the present invention is a honeycomb structure made of porous ceramics having ceramic powder and a binder for bonding ceramic particles constituting the ceramic powder, and the ceramic powder has a particle size of 10% ( The distance between D10) and the 90% particle diameter (D90) is 10 μm or more.
本発明のハニカム構造体は、１０％粒径（Ｄ１０）と９０％粒径（Ｄ９０）との間隔が１０μｍ以上のセラミックス粒子を結合材で結合して形成されている。本発明のハニカム構造体では、粒径の異なるセラミックス粒子をもつこととなっている。粒径の異なるセラミックス粒子を用いると、セラミックス粒子の間のすき間が制御される。このすき間でＰＭを捕集するとともに、温度変化を生じたときのセラミックス粒子の体積変化を緩衝する。この結果、本発明のハニカム構造体は、耐熱衝撃性が向上する。 The honeycomb structure of the present invention is formed by bonding ceramic particles having a 10% particle size (D10) and 90% particle size (D90) interval of 10 μm or more with a binder. The honeycomb structure of the present invention has ceramic particles having different particle diameters. When ceramic particles having different particle diameters are used, the gap between the ceramic particles is controlled. While collecting PM in this gap, the volume change of the ceramic particles when a temperature change occurs is buffered. As a result, the honeycomb structure of the present invention has improved thermal shock resistance.
本発明のハニカム構造体は、セラミックス粉末と、セラミックス粉末を構成するセラミックス粒子同士を結合する結合材と、を有する多孔質セラミックスよりなる。本発明のハニカム構造体は、多孔質のセラミックスより構成されており、多数の細孔を有する。この細孔でＰＭを捕集する。 The honeycomb structure of the present invention is made of a porous ceramic having ceramic powder and a binder that bonds ceramic particles constituting the ceramic powder. The honeycomb structure of the present invention is made of porous ceramics and has a large number of pores. PM is collected by these pores.
本発明のハニカム構造体は、隣接するセラミックス粒子が結合材で固定された構成となっている。このような構成となっていることにより、多孔質セラミックスにおける細孔設計の自由度が向上している。つまり、細孔となるセラミックス粒子間のすき間の大きさおよび分布を容易に制御できる。そして、ナノサイズの粒子を捕集できる微細な細孔を均一な状態でもつ多孔質セラミックスを得ることができる。 The honeycomb structure of the present invention has a configuration in which adjacent ceramic particles are fixed with a binder. With such a configuration, the degree of freedom in pore design in the porous ceramic is improved. That is, the size and distribution of the gaps between the ceramic particles that become the pores can be easily controlled. And the porous ceramics which have the fine pore which can collect nanosize particle | grains in a uniform state can be obtained.
本発明のハニカム構造体は、隣接するセラミックス粒子が結合材で固定されたことで、微細な細孔をもつことが可能となっている。従来のハニカム構造体を構成する多孔質セラミックスは、原料となるセラミックス粒子を所定の形状に成形した後に焼成してセラミックス粒子同士を結合させることで製造されている。つまり、従来のハニカム構造体は、焼結することでセラミックス粒子同士を一体に結合させているが、焼結条件によってはセラミックス粒子が粒成長を生じてセラミックス粒子間の微細な細孔が消失していた。つまり、従来のハニカム構造体では、多孔質セラミックスの細孔の調節が困難となっていた。これに対し、本発明は、セラミックス粒子を結合材で結合した構造であり、セラミックス粒子間の微細な細孔を残存させることができ、自由に細孔設計を行うことができる。 The honeycomb structure of the present invention can have fine pores because adjacent ceramic particles are fixed with a binder. The conventional porous ceramics constituting the honeycomb structure is manufactured by forming ceramic particles as a raw material into a predetermined shape and then firing them to bond the ceramic particles together. In other words, in the conventional honeycomb structure, ceramic particles are bonded together by sintering, but depending on the sintering conditions, the ceramic particles may grow and the fine pores between the ceramic particles disappear. It was. That is, in the conventional honeycomb structure, it is difficult to adjust the pores of the porous ceramic. On the other hand, the present invention has a structure in which ceramic particles are bonded with a binding material, fine pores between the ceramic particles can remain, and pore design can be performed freely.
本発明のハニカム構造体は、多数の微細な細孔を有しており、この細孔がハニカム構造体の熱膨張（収縮）時の体積変化を緩衝する。これにより、本発明のハニカム構造体は、さらに、セラミックス粒子の体積変化を緩衝することができる。 The honeycomb structure of the present invention has a large number of fine pores, and these pores buffer the volume change during thermal expansion (shrinkage) of the honeycomb structure. Thereby, the honeycomb structure of the present invention can further buffer the volume change of the ceramic particles.
そして、本発明のハニカム構造体は、セラミックス粒子が、１０％粒径（Ｄ１０）と９０％粒径（Ｄ９０）との間隔が１０μｍ以上である。つまり、本発明のハニカム構造体を構成するセラミックス粉末は、広い粒径分布をもつこととなる。すなわち、セラミックス粉末が粒径の異なる複数のセラミックス粒子よりなる。セラミックス粉末が粒径の異なる複数のセラミックス粒子よりなることで、粒径の小さなセラミックス粒子が粒径の大きなセラミックス粒子同士の間に位置することとなり（充填密度が増加し）、セラミックス粒子間に形成される細孔が微細化する。この結果、微細な多数の細孔をもつことが可能となる。ここで、セラミックス粒子のＤ１０とＤ９０の間隔は、５μｍ以上であれば好ましく、１０μｍ以上であればさらに好ましい。なお、セラミックス粒子の粒径がそろうほど、粒径分布を測定したときに得られるピークがシャープになる。そして、Ｄ１０とＤ９０の間隔が短くなるほど、セラミックス粉末を構成するセラミックス粒子の粒径のバラツキが減少し、そのようなセラミックス粉末を用いた多孔質セラミックスでは細孔径を小さくすることが困難となる。 In the honeycomb structure of the present invention, the ceramic particles have an interval between the 10% particle size (D10) and the 90% particle size (D90) of 10 μm or more. That is, the ceramic powder constituting the honeycomb structure of the present invention has a wide particle size distribution. That is, the ceramic powder is composed of a plurality of ceramic particles having different particle diameters. When the ceramic powder is composed of multiple ceramic particles with different particle diameters, the ceramic particles with small particle diameters are located between the ceramic particles with large particle diameters (the packing density is increased) and formed between the ceramic particles. The pores to be refined become finer. As a result, it becomes possible to have many fine pores. Here, the distance between D10 and D90 of the ceramic particles is preferably 5 μm or more, and more preferably 10 μm or more. In addition, the peak obtained when the particle size distribution is measured becomes sharper as the particle size of the ceramic particles becomes equal. As the distance between D10 and D90 becomes shorter, the variation in the particle size of the ceramic particles constituting the ceramic powder decreases, and it becomes difficult to reduce the pore diameter in porous ceramics using such ceramic powder.
さらに、シャープなピークをもつセラミックス粉末において、ピークで示される平均粒径が大きな場合には、このセラミックス粉末から製造されるハニカム構造体の細孔径が大きく（例えば１０μｍ以上）なり、フィルタ触媒としてＰＭやＳＰＭを捕集できなくなる。平均粒径が小さな場合には、細孔径の制御が困難となるだけでなく、気孔率が大きくなりすぎるようになる。気孔率が過剰に大きくなると、見かけの体積に占めるセラミックスの割合が減少し、結果として熱容量が減少する。この結果、フィルタ触媒での異常燃焼に耐えられなくなる。 Further, in the ceramic powder having a sharp peak, when the average particle size indicated by the peak is large, the pore diameter of the honeycomb structure manufactured from the ceramic powder becomes large (for example, 10 μm or more), and PM is used as a filter catalyst. And SPM cannot be collected. When the average particle size is small, not only is it difficult to control the pore size, but the porosity becomes too large. When the porosity becomes excessively large, the proportion of ceramics in the apparent volume decreases, and as a result, the heat capacity decreases. As a result, the filter catalyst cannot withstand abnormal combustion.
そして、本発明のハニカム構造体は、２０％粒径（Ｄ２０）と８０％粒径（Ｄ８０）とが、ｌｏｇＤ２０／ｌｏｇＤ８０が０．８５未満であることが好ましい。Ｄ２０及びＤ８０の対数の比は、セラミックス粉末の粒度分布の広がりを示す。つまり、粒度分布曲線がなだらかな山形をなすほど、Ｄ２０及びＤ８０の対数の比が小さくる。 The honeycomb structure of the present invention preferably has a 20% particle size (D20) and an 80% particle size (D80) and a log D20 / log D80 of less than 0.85. The logarithmic ratio of D20 and D80 indicates the spread of the particle size distribution of the ceramic powder. That is, the logarithmic ratio of D20 and D80 decreases as the particle size distribution curve forms a gentle mountain shape.
そして、本発明においては、Ｄ２０とＤ８０の対数の比が０．８５未満となっており、セラミックス粉末が広い粒径分布をもつ。すなわち、セラミックス粉末が粒径の異なるセラミックス粒子よりなっている。セラミックス粉末が粒径の異なる複数のセラミックス粒子よりなることで、粒径の小さなセラミックス粒子が粒径の大きなセラミックス粒子同士の間に位置することとなり（充填密度が増加し）、セラミックス粒子間に形成される細孔が微細化する。この結果、微細な多数の細孔をもつことが可能となる。本発明では、Ｄ２０及びＤ８０の対数の比（ｌｏｇＤ２０／ｌｏｇＤ８０）は、０．８５未満が好ましく、０．６以下が更に好ましい。 In the present invention, the logarithmic ratio of D20 and D80 is less than 0.85, and the ceramic powder has a wide particle size distribution. That is, the ceramic powder is made of ceramic particles having different particle sizes. When the ceramic powder is composed of multiple ceramic particles with different particle diameters, the ceramic particles with small particle diameters are located between the ceramic particles with large particle diameters (the packing density is increased) and formed between the ceramic particles. The pores to be refined become finer. As a result, it becomes possible to have many fine pores. In the present invention, the log ratio of D20 and D80 (log D20 / log D80) is preferably less than 0.85, and more preferably 0.6 or less.
なお、Ｄ２０及びＤ８０の対数の比が０．８５以上となると、粒径分布曲線がシャープなピークをもつこととなり、上記したように、ハニカム構造体をフィルタ触媒に用いることが困難となる。 When the log ratio of D20 and D80 is 0.85 or more, the particle size distribution curve has a sharp peak, and as described above, it becomes difficult to use the honeycomb structure as a filter catalyst.
本発明のハニカム構造体は、粒径分布の広いセラミックス粉末から形成されることで、多孔質セラミックスにおける細孔以外のセラミックスの充填密度が大きくなっている。つまり、ハニカム構造体に占めるセラミックスの割合が増加し、これにより、本発明のハニカム構造体は、セラミックス量に起因する熱容量が増加する。この結果、ハニカム構造体が晒される温度がより高い温度になっても、ひび割れの発生やセラミックスの変質（過熱による変質）が抑えられる。 The honeycomb structure of the present invention is formed from ceramic powder having a wide particle size distribution, so that the packing density of ceramics other than pores in the porous ceramics is increased. That is, the proportion of ceramics in the honeycomb structure increases, and as a result, the heat capacity resulting from the amount of ceramics increases in the honeycomb structure of the present invention. As a result, even if the temperature at which the honeycomb structure is exposed to a higher temperature, the occurrence of cracks and the alteration of ceramics (degeneration due to overheating) can be suppressed.
本発明において、Ｄ２０とＤ８０を示す粒径の差は１０μｍ以上であることが好ましい。Ｄ２０とＤ８０の差が１０μｍ以上となることで、セラミックス粉末が広い粒径分布を持つこととなり、上記した微細な細孔を形成できる効果を発揮する。 In the present invention, the difference between the particle diameters indicating D20 and D80 is preferably 10 μm or more. When the difference between D20 and D80 is 10 μm or more, the ceramic powder has a wide particle size distribution and exhibits the effect of forming the fine pores described above.
本発明のハニカム構造体は、Ｄ８０とＤ２０の粒径の比が１：０．１７〜０．２７であることが好ましい。Ｄ８０とＤ２０の粒径の比がこの範囲内となることで、セラミックス粒子の充填密度が高くなる。最も好ましくは、Ｄ８０とＤ２０の粒径の比が１：０．２２である。 In the honeycomb structure of the present invention, the ratio of the particle sizes of D80 and D20 is preferably 1: 0.17 to 0.27. When the ratio of the particle sizes of D80 and D20 is within this range, the packing density of the ceramic particles is increased. Most preferably, the ratio of the particle sizes of D80 and D20 is 1: 0.22.
本発明のハニカム構造体は、セラミックス粉末が、粒径分布を測定したときに、２つ以上のピークをもつことが好ましい。すなわち、セラミックス粉末が、少なくとも２種類の粒径をもつセラミックス粒子を混合してなることが好ましい。このようなセラミックス粉末は、粒径（平均粒径）の異なるセラミックス粒子をもつ複数種のセラミックス粉末を混合することで、簡単に得ることができる。また、セラミックス粉末の粒径分布のピークを簡単に調節することができ、セラミックス粒子間のすき間を制御することができる。すなわち、多孔質セラミックスの細孔径や細孔分布を簡単に制御することができる。ここで、セラミックス粉末の粒径分布を測定したときに得られるピークの数は、二つ以上であればよく、三つや四つなど多ければ多いほど好ましい。粒径分布を測定したときに２つ以上のピークをもつセラミックス粉末では、２つ以上のピークがＤ１０とＤ９０の間に存在するものとなっている。 In the honeycomb structure of the present invention, the ceramic powder preferably has two or more peaks when the particle size distribution is measured. That is, the ceramic powder is preferably formed by mixing ceramic particles having at least two types of particle diameters. Such ceramic powder can be easily obtained by mixing a plurality of types of ceramic powder having ceramic particles having different particle diameters (average particle diameter). Further, the peak of the particle size distribution of the ceramic powder can be easily adjusted, and the gap between the ceramic particles can be controlled. That is, the pore diameter and pore distribution of the porous ceramic can be easily controlled. Here, the number of peaks obtained when the particle size distribution of the ceramic powder is measured may be two or more, and it is preferably as many as three or four. In the ceramic powder having two or more peaks when the particle size distribution is measured, two or more peaks exist between D10 and D90.
さらに、本発明のハニカム構造体は、粒径の異なるセラミックス粒子から形成されることで、多孔質セラミックスで細孔以外のセラミックスの充填密度が大きくなっている。つまり、ハニカム構造体に占めるセラミックスの割合が増加し、これにより、本発明のハニカム構造体は、セラミックス量に起因する熱容量が増加するものとなった。この結果、ハニカム構造体が晒される温度がより高い温度になっても、ひび割れの発生やセラミックスの変質（過熱による変質）が抑えられる。 Furthermore, the honeycomb structure of the present invention is formed of ceramic particles having different particle diameters, so that the packing density of ceramics other than pores is increased with porous ceramics. That is, the proportion of ceramics in the honeycomb structure increased, and as a result, the heat capacity resulting from the amount of ceramics increased in the honeycomb structure of the present invention. As a result, even if the temperature at which the honeycomb structure is exposed to a higher temperature, the occurrence of cracks and the alteration of ceramics (degeneration due to overheating) can be suppressed.
本発明のハニカム構造体は、セラミックス粉末の粒径分布の測定結果が二つのピークを示すときに、二つのピークが示す粗大粒子と微細粒子の粒径の比が１：０．１７〜０．２７であることが好ましい。ピークの粒径比がこの範囲内となることで、セラミックス粒子の充填密度が高くなる。最も好ましくは、粗大粒子と微細粒子の粒径の比が１：０．２２である。 In the honeycomb structure of the present invention, when the measurement result of the particle size distribution of the ceramic powder shows two peaks, the ratio between the coarse particles and the fine particles shown by the two peaks is 1: 0.17-0. 27 is preferable. When the particle size ratio of the peak is within this range, the packing density of the ceramic particles is increased. Most preferably, the ratio of the particle size of coarse particles to fine particles is 1: 0.22.
本発明において、セラミックス粒子の粒径分布を測定したときに得られるピークのうち、最も粒径の大きな粒子に対応したピークと最も粒径の小さな粒子に対応したピークの二つの粒径の差は１０μｍ以上であることが好ましい。粒径の差が１０μｍ以上となることで、上記した微細な細孔を形成できる効果を発揮する。 In the present invention, among the peaks obtained when measuring the particle size distribution of the ceramic particles, the difference between the two particle sizes of the peak corresponding to the largest particle size and the peak corresponding to the smallest particle size is It is preferable that it is 10 micrometers or more. When the difference in particle size is 10 μm or more, the above-described effect of forming fine pores is exhibited.
本発明は、結合材がセラミックス粒子を結合した構成となっていれば、具体的な結合材については限定されるものではない。 The present invention is not limited to a specific binding material as long as the binding material has a configuration in which ceramic particles are bonded.
結合材は、セラミックス粒子と混合した状態でセラミックス粒子の焼結温度以下の温度で加熱してセラミックス粒子を結合したことが好ましい。セラミックス粒子の焼結温度以下の温度での加熱により結合材がセラミックス粒子を結合することで、セラミックス粒子同士の焼結を抑えた状態でセラミックス粒子同士を結合することができる。本発明において、セラミックス粒子の焼結温度とは、セラミックス粒子が焼結する温度であり、一般的には、熱力学温度で融点の９０％以上の温度である。本発明において、セラミックス粒子が材質の異なる複数種のセラミックスよりなるときには、最も焼結温度が低いセラミックスの焼結温度に基づく。 It is preferable that the binder is mixed with the ceramic particles and heated at a temperature lower than the sintering temperature of the ceramic particles to bond the ceramic particles. The ceramic particles can be bonded together in a state where the sintering of the ceramic particles is suppressed by bonding the ceramic particles by heating at a temperature equal to or lower than the sintering temperature of the ceramic particles. In the present invention, the sintering temperature of the ceramic particles is a temperature at which the ceramic particles are sintered, and is generally a temperature of 90% or more of the melting point at the thermodynamic temperature. In the present invention, when the ceramic particles are made of a plurality of types of ceramics having different materials, the ceramic particles have the lowest sintering temperature.
また、このような結合材としては、たとえば、コロイダルシリカ、コロイダルアルミナなどをあげることができる。ここで、コロイダルシリカ（結合材）が結合する温度としては、６００℃以上が望ましい。 Examples of such a binder include colloidal silica and colloidal alumina. Here, the temperature at which colloidal silica (binding material) is bonded is preferably 600 ° C. or higher.
本発明において、多孔質セラミックスを構成するセラミックス粒子の材質については、特に限定されるものではない。セラミックス粒子は、チタン酸アルミニウム、炭化珪素、窒化珪素、コーディエライトより選ばれる一種を主成分とすることが好ましい。これらのうち、結合材との相性から、セラミックス粒子は、炭化珪素、窒化珪素の一種以上よりなることがより好ましい。 In the present invention, the material of the ceramic particles constituting the porous ceramic is not particularly limited. The ceramic particles are preferably mainly composed of one kind selected from aluminum titanate, silicon carbide, silicon nitride, and cordierite. Of these, the ceramic particles are more preferably composed of one or more of silicon carbide and silicon nitride because of compatibility with the binder.
本発明のハニカム構造体は、従来公知のハニカム構造体のように、複数部の分体を接合材で接合した構成としてもよい。このような構成は、分体ごとにその特性を変化させることができ、ハニカム構造体全体に所望の性能を付与できる。ハニカム構造体が複数部の分体よりなるときに、それぞれの分体の材質は同じであっても異なっていてもいずれでもよい。すなわち、ハニカム構造体は、多孔質セラミックスよりなる複数のハニカム分体と、複数のハニカム分体同士を接合する接合材層と、からなることが好ましい。 The honeycomb structure of the present invention may have a configuration in which a plurality of parts are joined with a joining material, as in a conventionally known honeycomb structure. Such a structure can change the characteristic for every split body, and can give desired performance to the whole honeycomb structure. When the honeycomb structure is composed of a plurality of parts, the material of each part may be the same or different. That is, the honeycomb structure preferably includes a plurality of honeycomb bodies made of porous ceramics and a bonding material layer that bonds the plurality of honeycomb bodies to each other.
本発明のハニカム構造体において、ハニカム構造体が複数の分体を接合してなるときに、複数の分体の少なくともひとつが、セラミックス粉末と、セラミックス粉末を構成するセラミックス粒子同士を結合する結合材と、を有する多孔質セラミックスよりなることが好ましい。より好ましくは、全ての分体がセラミックス粉末と、セラミックス粉末を構成するセラミックス粒子同士を結合する結合材と、を有する多孔質セラミックスよりなることである。 In the honeycomb structure of the present invention, when the honeycomb structure is formed by joining a plurality of segments, at least one of the plurality of segments is a binder that binds ceramic powder and ceramic particles constituting the ceramic powder. And preferably made of porous ceramics. More preferably, all the split bodies are made of porous ceramics having ceramic powder and a binder that bonds ceramic particles constituting the ceramic powder.
複数のハニカム分体を接合する接合材層は、粒径分布を測定したときに、２つ以上のピークをもつセラミックス粒子をもつ接合材から形成されたことが好ましい。接合材が粒径の異なるセラミックス粒子をもつことで、粒径の小さなセラミックス粒子が粒径の大きなセラミックス粒子同士の間に位置することとなり（充填密度が増加し）、セラミックス粒子間に形成される細孔が微細化する。この結果、微細な多数の細孔をもつことが可能となる。ここで、接合材を構成するセラミックス粒子の粒径分布を測定したときに得られるピークの数は、二つ以上であればよく、三つや四つなど多ければ多いほど好ましい。 The bonding material layer for bonding a plurality of honeycomb bodies is preferably formed from a bonding material having ceramic particles having two or more peaks when the particle size distribution is measured. When the bonding material has ceramic particles having different particle sizes, the ceramic particles having a small particle size are located between the ceramic particles having a large particle size (the packing density increases), and are formed between the ceramic particles. The pores become finer. As a result, it becomes possible to have many fine pores. Here, the number of peaks obtained when the particle size distribution of the ceramic particles constituting the bonding material is measured may be two or more, and it is preferable that the number is three or four.
セラミックス分体を接合する接合材についても、従来公知の接合材を用いることができる。この接合材としては、例えば、ＳｉＣ系接合材を用いることができる。セラミックス分体を接合材で接合したときにセラミックス分体の間に形成される接合材層は、０．５〜５．０ｍｍの厚さで形成することが好ましい。 A conventionally known bonding material can also be used as the bonding material for bonding the ceramic body. As this bonding material, for example, a SiC-based bonding material can be used. The bonding material layer formed between the ceramic bodies when the ceramic bodies are joined with the joining material is preferably formed with a thickness of 0.5 to 5.0 mm.
本発明のハニカム構造体は、周方向の外周面上に、従来公知のハニカム構造体のように、外周材層を有することが好ましい。外周材層をもつことで、ハニカム構造体をＤＰＦなどに使用したときに生じる形状変化が抑えられる。具体的には、ハニカム構造体をＤＰＦなどの用途に使用したときに、ハニカム構造体は高熱にさらされる。そして、ハニカム構造体は、熱膨張を生じる。外周材層をもつことでこの熱膨張を抑えることができる。外周材層を構成する材質は、従来公知の材質を用いることができる。たとえば、ＳｉＣ、シリカ系化合物、チタン酸アルミニウムなどのアルミナ系化合物などを用いることができる。 The honeycomb structure of the present invention preferably has an outer peripheral material layer on the outer peripheral surface in the circumferential direction like a conventionally known honeycomb structure. By having the outer peripheral material layer, the shape change that occurs when the honeycomb structure is used for a DPF or the like can be suppressed. Specifically, when the honeycomb structure is used for applications such as DPF, the honeycomb structure is exposed to high heat. The honeycomb structure undergoes thermal expansion. This thermal expansion can be suppressed by having the outer peripheral material layer. A conventionally known material can be used as the material constituting the outer peripheral material layer. For example, SiC, silica compounds, alumina compounds such as aluminum titanate, and the like can be used.
外周材層は、粒径分布を測定したときに、２つ以上のピークをもつセラミックス粒子をもつ外周材スラリーを塗布してなることが好ましい。外周材が粒径の異なるセラミックス粒子をもつことで、粒径の小さなセラミックス粒子が粒径の大きなセラミックス粒子同士の間に位置することとなり（充填密度が増加し）、セラミックス粒子間に形成される細孔が微細化する。この結果、接合材層が微細な多数の細孔をもつことが可能となる。ここで、外周材を構成するセラミックス粒子の粒径分布を測定したときに得られるピークの数は、二つ以上であればよく、三つや四つなど多ければ多いほど好ましい。 The outer peripheral material layer is preferably formed by applying an outer peripheral material slurry having ceramic particles having two or more peaks when the particle size distribution is measured. When the outer peripheral material has ceramic particles having different particle sizes, the ceramic particles having a small particle size are positioned between the ceramic particles having a large particle size (the packing density increases), and are formed between the ceramic particles. The pores become finer. As a result, the bonding material layer can have a large number of fine pores. Here, the number of peaks obtained when the particle size distribution of the ceramic particles constituting the outer peripheral material is measured may be two or more, and it is more preferable that the number is three or four.
また、外周材層は、ハニカム構造体の形状により異なるため、その厚さが一概に決定できるものではないが、たとえば、０．５ｍｍ以上の厚さで形成することが好ましい。さらに好ましくは、０．５〜５．０ｍｍである。 In addition, since the thickness of the outer peripheral material layer varies depending on the shape of the honeycomb structure, the thickness thereof cannot be determined unconditionally. More preferably, it is 0.5-5.0 mm.
本発明のハニカム構造体は、ハニカム構造体を構成する多孔質セラミックスがセラミックス粒子と結合材とから構成される以外は、従来公知のハニカム構造体と同様の構成とすることができる。 The honeycomb structure of the present invention can have the same configuration as a conventionally known honeycomb structure except that the porous ceramics constituting the honeycomb structure is composed of ceramic particles and a binder.
つまり、本発明のハニカム構造体は、軸方向にのびる多数のセルをもつ形状に形成されたことが好ましい。本発明のハニカム構造体において、セルの形状（断面形状）は、特に限定されるものではなく、従来公知の断面形状とすることができる。従来公知のセル形状のうち、正方形状であることがより好ましい。 That is, the honeycomb structure of the present invention is preferably formed in a shape having a large number of cells extending in the axial direction. In the honeycomb structure of the present invention, the cell shape (cross-sectional shape) is not particularly limited, and may be a conventionally known cross-sectional shape. Of the conventionally known cell shapes, a square shape is more preferable.
本発明のハニカム構造体は、その外周形状が特に限定されるものではなく、従来公知の形状とすることができる。たとえば、断面が真円や楕円の略円柱状、断面が方形や多角形の角柱状とすることができ、より好ましくは円柱形状である。 The outer peripheral shape of the honeycomb structure of the present invention is not particularly limited, and can be a conventionally known shape. For example, the cross section may be a substantially circular or elliptical cylinder, and the cross section may be a square or polygonal prism, and more preferably a cylinder.
本発明のハニカム構造体は、多数のセルの一方の端部または他方の端部がセラミックスよりなる封止材に封止されていることが好ましい。セルの一方の端部または他方の端部が封止材で封止されることで、ウォールフロー型のハニカム構造体を形成できる。封止材を構成するセラミックスは、その材質が特に限定されるものではなく、ハニカム構造体を構成する多孔質のセラミックスと同じ材質であっても、異なる材質であっても、いずれでもよい。より好ましくは、多孔質のセラミックスを主成分としてなるセラミックスである。 In the honeycomb structure of the present invention, it is preferable that one end or the other end of a large number of cells is sealed with a sealing material made of ceramics. A wall flow type honeycomb structure can be formed by sealing one end or the other end of the cell with a sealing material. The material of the ceramic constituting the sealing material is not particularly limited, and may be the same as or different from the porous ceramic constituting the honeycomb structure. More preferably, the ceramic is mainly composed of porous ceramics.
本発明のハニカム構造体は、ＤＰＦに用いることが好ましい。本発明のハニカム構造体は、セルを区画する隔壁を排気ガス（気体）が通過するウォールフロー型のフィルタ触媒として用いることができ、このようなフィルタ触媒のうち特に、ＤＰＦとして用いることが好ましい。 The honeycomb structure of the present invention is preferably used for a DPF. The honeycomb structure of the present invention can be used as a wall flow type filter catalyst in which exhaust gas (gas) passes through partition walls that partition cells, and among these filter catalysts, it is particularly preferable to use as a DPF.
本発明のハニカム構造体をＤＰＦとして用いるときに、少なくとも隔壁部の細孔表面に、アルミナ等よりなる多孔質酸化物、Ｐｔ，Ｐｄ，Ｒｈ等の触媒金属の少なくともひとつを担持したことが好ましい。これらの物質を担持したことで、ＤＰＦとしてパティキュレートなどの浄化性能が向上する。 When the honeycomb structure of the present invention is used as a DPF, it is preferable to support at least one of a porous oxide made of alumina or the like and a catalyst metal such as Pt, Pd, or Rh on at least the pore surfaces of the partition walls. By carrying these substances, purification performance such as particulates as DPF is improved.
本発明のハニカム構造体は、その製造方法が限定されるものではなく、たとえば、以下のように製造することができる。 The manufacturing method of the honeycomb structure of the present invention is not limited. For example, the honeycomb structure can be manufactured as follows.
まず、平均粒径（Ｄ５０）の異なるセラミックス粒子を秤量する。併せて結合材や増粘材等の添加剤も秤量する。秤量された原料粉末を十分に混合（混練）する。そして、所定の形状（多数のセルをもつ分体の形状）に成形する。つづいて、所定のセルに目封じ用スラリーを注入して目封じを行う。その後、セラミックス粒子が焼結しない温度であって結合材がセラミックス粒子を結合できる温度で加熱する。これにより、粒径分布を測定したときに、２つ以上のピークをもつセラミックス粉末をもつハニカム分体が製造できる。 First, ceramic particles having different average particle diameters (D50) are weighed. In addition, additives such as binders and thickeners are also weighed. The weighed raw material powders are sufficiently mixed (kneaded). And it shape | molds to a predetermined shape (shape of the split body with many cells). Subsequently, sealing is performed by injecting a slurry for sealing into a predetermined cell. Thereafter, heating is performed at a temperature at which the ceramic particles do not sinter and at which the binder can bond the ceramic particles. Thereby, when the particle size distribution is measured, a honeycomb segment having a ceramic powder having two or more peaks can be manufactured.
平均粒径の異なるセラミックス粒子をもつ接合材（スラリー）を調製する。製造されたハニカム分体の外周面に接合材を塗布してハニカム分体同士を接合する。ハニカム分体の接合体の外周形状を成形した後に、外周材を塗布して外周材層を形成する。これにより、本発明のハニカム構造体は製造できる。 A bonding material (slurry) having ceramic particles having different average particle diameters is prepared. A bonding material is applied to the outer peripheral surface of the manufactured honeycomb bodies to bond the honeycomb bodies together. After forming the outer peripheral shape of the joined body of the honeycomb divided body, the outer peripheral material is applied to form the outer peripheral material layer. Thereby, the honeycomb structure of the present invention can be manufactured.
本発明のハニカム構造体は、多孔質セラミックスにおける細孔設計の自由度が向上している。そして、本発明のハニカム構造体においては、ナノサイズの粒子を捕集できる微細な細孔を均一な状態でもつことが好ましい。本発明のハニカム構造体において、細孔径や気孔率については、特に限定されるものではないが、ＳＰＭを捕捉できる程度の微細な細孔径の細孔を均一にもつことが好ましい。 In the honeycomb structure of the present invention, the degree of freedom in pore design in the porous ceramics is improved. In the honeycomb structure of the present invention, it is preferable to have fine pores in a uniform state capable of collecting nano-sized particles. In the honeycomb structure of the present invention, the pore diameter and the porosity are not particularly limited, but it is preferable that the pores have fine pore diameters that can capture SPM uniformly.
本発明のハニカム構造体は、平均細孔径が０．１〜５μｍで、気孔率が３０〜６０％であることが好ましい。平均細孔径がこの範囲内となることで、ＳＰＭを捕捉することができる。また、気孔率がこの範囲内となることで、圧損の上昇が抑えられる。より好ましくは、平均細孔径が１〜５μｍであり、気孔率が３５〜４５％である。 The honeycomb structure of the present invention preferably has an average pore diameter of 0.1 to 5 μm and a porosity of 30 to 60%. When the average pore diameter is within this range, SPM can be captured. Moreover, when the porosity falls within this range, an increase in pressure loss can be suppressed. More preferably, the average pore diameter is 1 to 5 μm and the porosity is 35 to 45%.
以下、実施例を用いて本発明を説明する。 Hereinafter, the present invention will be described using examples.
本発明の実施例として、ＤＰＦ用ハニカム構造体を製造した。 As an example of the present invention, a honeycomb structure for DPF was manufactured.
（実施例１）
本実施例のＤＰＦ用ハニカム構造体の製造方法を以下に示す。
Example 1
A method for manufacturing the DPF honeycomb structure of the present example will be described below.
まず、平均粒径（Ｄ５０）が１３μｍのＳｉＣ粉末（信濃電機製錬製、商品名：ＧＰ１０００Ｆ）を１６ｋｇ、Ｄ５０が７０μｍのＳｉＣ粉末（太平洋ランダム製、商品名：Ｆ２２０）を２４ｋｇ、Ｄ５０が２０μｍのＳｉ３Ｎ４粉末（電気化学工業製、商品名：ＳＮ−ＢＬ）を５ｋｇ、を秤量した。秤量された粉末を、結合材のコロイダルシリカ（アデライト工業製、商品名：ＡＴ−２０Ｇ）４ｋｇ、水１５ｋｇとともに十分に混合（混練）した後に、軸方向に多数のセルが形成された柱状の成形体を従来公知の製造方法である押出成形で製造した。この成形体は、断面が正方形状に区画されたセルをもつ。ここで、この成形体の外周形状（見かけの形状）は、本実施例のように角柱状だけでなく、ハニカム構造体を形成したときの外周形状と略一致する外周形状に形成することができる。 First, 16 kg of SiC powder with an average particle size (D50) of 13 μm (manufactured by Shinano Denki Smelting, trade name: GP1000F), 24 kg of SiC powder with 70 μm D50 (manufactured by Taiheiyo Random, trade name: F220), and D50 of 20 μm 5 kg of Si 3 N 4 powder (manufactured by Denki Kagaku Kogyo, trade name: SN-BL) was weighed. After the weighed powder is sufficiently mixed (kneaded) with 4 kg of binder colloidal silica (trade name: AT-20G, trade name: AT-20G) and 15 kg of water, columnar molding in which many cells are formed in the axial direction. The body was produced by extrusion, which is a conventionally known production method. This molded body has cells having a square section. Here, the outer peripheral shape (apparent shape) of the formed body can be formed not only in the shape of a prism as in the present embodiment, but also in the outer peripheral shape that substantially matches the outer peripheral shape when the honeycomb structure is formed. .
つづいて、主成分がハニカム構造体と同様のスラリーを調製した。なお、このスラリーは、粘度調整材等の添加剤を含む。そして、このスラリーを、乾燥させた成形体の両端の端部から所定のセルに注入し、８０℃で乾燥させた。ここで、所定のセルとは、スラリーが注入されたセルが市松模様状をなすようにもうけられている。また、セルの一方の端部または他方の端部のみにスラリーが注入された。そして、その後の工程で成形したときに、ハニカム構造体１の外周面を区画するセルには、その両端にスラリーを注入した。 Subsequently, a slurry having the same main component as that of the honeycomb structure was prepared. This slurry contains additives such as a viscosity modifier. And this slurry was inject | poured into the predetermined | prescribed cell from the edge part of the both ends of the dried molded object, and was dried at 80 degreeC. Here, the predetermined cell is provided so that the cell into which the slurry is injected has a checkered pattern. In addition, the slurry was injected only into one end or the other end of the cell. And when it shape | molded at the subsequent process, the slurry was inject | poured into the cell which divides the outer peripheral surface of the honeycomb structure 1 into the both ends.
その後、１３００℃でセルにスラリーが注入された成形体を熱処理して結合材でセラミックス粒子を結合するとともにスラリーを固化させて封止材３とし、封止材３で封止されたセル（封止部）をもつハニカム体２を形成した。セルの軸方向における封止材３の長さはそれぞれ３．０ｍｍであった。封止部が形成された状態を図１に模式的に示した。 Thereafter, the molded body in which the slurry is injected into the cell at 1300 ° C. is heat-treated to bond the ceramic particles with the binder, and the slurry is solidified to form the sealing material 3. A honeycomb body 2 having a stopper) was formed. The length of the sealing material 3 in the axial direction of the cell was 3.0 mm. The state in which the sealing part is formed is schematically shown in FIG.
そして、このハニカム体２を電動ノコギリを用いて切削して外周形状を成形した。電動ノコギリによる切削は、図１において破線で示された線に沿って、両端部に封止材が形成されたセルが外周面を形成する略円柱状をなすようになされた。成形後のハニカム体２（切削体）を図２に模式的に示した。 The honeycomb body 2 was cut using an electric saw to form an outer peripheral shape. The cutting with the electric saw was made into a substantially columnar shape in which the cells having the sealing material formed at both ends thereof formed the outer peripheral surface along the line indicated by the broken line in FIG. FIG. 2 schematically shows the honeycomb body 2 (cut body) after being formed.
そして、ＳｉＣが主成分のスラリー（テルニック工業株式会社製、商品名：ＢＥＴＡＣＫ１５６６），１．２６ｗｔ％でカルボキシルメチルセルロース（ＣＭＣ）を含むバインダ溶液（ダイセル化学工業製、商品名：ＣＭＣダイセル），コロイダルシリカ（日産化学工業製、商品名：スノーテックス３０），分散材（ユニケマ製、商品名：ＫＤ−２）を秤量し、十分に混合してスラリーを調製した。調製されたスラリーを切削体の外周面に塗布し、８０℃で乾燥した後に８５０℃で加熱してスラリーを固化させた。これにより、外周面上に外周材層４が形成できた。 Then, a slurry containing SiC as a main component (manufactured by Telnic Industries, trade name: BETACK 1566), a binder solution containing 1.26 wt% carboxymethyl cellulose (CMC) (trade name: CMC Daicel, manufactured by Daicel Chemical Industries), colloidal silica (Product name: Snowtex 30 manufactured by Nissan Chemical Industries, Ltd.) and dispersion material (product name: KD-2, manufactured by Unikema) were weighed and mixed well to prepare a slurry. The prepared slurry was applied to the outer peripheral surface of the cutting body, dried at 80 ° C., and then heated at 850 ° C. to solidify the slurry. Thereby, the outer peripheral material layer 4 was able to be formed on the outer peripheral surface.
以上により、本実施例のハニカム構造体１を製造することができた。本実施例のハニカム構造体を図３〜５に示した。なお、図３はハニカム構造体１の端面を、図４はハニカム構造体１の端面の周縁部近傍を、図５はハニカム構造体１の軸方向での断面を、それぞれ示した。 As described above, the honeycomb structure 1 of this example could be manufactured. The honeycomb structure of the present example is shown in FIGS. 3 shows the end face of the honeycomb structure 1, FIG. 4 shows the vicinity of the peripheral edge of the end face of the honeycomb structure 1, and FIG. 5 shows the cross section of the honeycomb structure 1 in the axial direction.
図に示したように、本実施例のハニカム構造体１は、軸方向にのびる多数のセルを備えた多孔質セラミックスよりなるハニカム体２と、多数のセルのうち所定のセルの一方の端部または他方の端部に充填された封止材３と、隔壁部の周方向の外周面上に形成された外周材層４と、を備えた構成を有している。なお、本実施例のハニカム構造体１のハニカム体２は、外径：９０．０ｍｍ、軸方向長さ：１５０．０ｍｍの略円柱状に形成されている。 As shown in the figure, the honeycomb structure 1 of the present example includes a honeycomb body 2 made of porous ceramics having a large number of cells extending in the axial direction, and one end portion of a predetermined cell among the large number of cells. Or it has the structure provided with the sealing material 3 with which the other edge part was filled, and the outer peripheral material layer 4 formed on the outer peripheral surface of the circumferential direction of a partition part. Note that the honeycomb body 2 of the honeycomb structure 1 of the present example is formed in a substantially cylindrical shape having an outer diameter: 90.0 mm and an axial length: 150.0 mm.
そして、本実施例のハニカム構造体１のハニカム体２は、粒径の異なるＳｉＣおよびＳｉ３Ｎ４がコロイダルシリカよりなる結合材で結合された構成を有している。ハニカム体２を構成するセラミックス粒子（ＳｉＣおよびＳｉ３Ｎ４）の粒径分布を測定したところ、１０％粒径（Ｄ１０）は１６μｍであり、２０％粒径（Ｄ２０）は２３．５μｍであり、８０％粒径（Ｄ８０）が４５μｍであり、９０％粒径（Ｄ９０）は４９μｍであった。なお、粒径分布は、液相沈降−Ｘ線透過法を用いて行われた。測定結果を図６に示した。 And the honeycomb body 2 of the honeycomb structure 1 of the present embodiment has a configuration in which SiC and Si 3 N 4 having different particle diameters are bonded with a binder made of colloidal silica. When the particle size distribution of the ceramic particles (SiC and Si 3 N 4 ) constituting the honeycomb body 2 was measured, the 10% particle size (D10) was 16 μm, and the 20% particle size (D20) was 23.5 μm. The 80% particle size (D80) was 45 μm and the 90% particle size (D90) was 49 μm. The particle size distribution was performed using a liquid phase sedimentation-X-ray transmission method. The measurement results are shown in FIG.
本実施例のハニカム構造体を構成するセラミックス粉末のＤ２０及びＤ８０の対数の比（ｌｏｇＤ２０／ｌｏｇＤ８０）は、０．８３であった。 The logarithmic ratio (log D20 / log D80) of D20 and D80 of the ceramic powder constituting the honeycomb structure of the present example was 0.83.
さらに、セラミックス粒子の粒径分布の測定結果では、ピークの頂点が１３μｍ，２０μｍ，７０μｍに位置する３本のピークが確認できた。これらのピークは、ＳｉＣ粉末を構成する２種類のＳｉＣ粒子およびＳｉ３Ｎ４粉末を構成するＳｉ３Ｎ４粒子のそれぞれに対応したピークである。 Furthermore, in the measurement result of the particle size distribution of the ceramic particles, three peaks whose peaks are located at 13 μm, 20 μm, and 70 μm were confirmed. These peaks are peaks corresponding to each the Si 3 N 4 particles constituting the two kinds of SiC particles and Si 3 N 4 powder constituting the SiC powder.
本実施例のＤＰＦ用ハニカム構造体１のハニカム体２の平均細孔径および気孔率を測定した。測定結果を図７に示した。平均細孔径は４．４μｍであり、気孔率は３８％であった。この平均細孔径および気孔率は、水銀ポロシメータ（島津製作所製、商品名：ポアサイザ９３１０）を用いてなされた。 The average pore diameter and porosity of the honeycomb body 2 of the DPF honeycomb structure 1 of this example were measured. The measurement results are shown in FIG. The average pore diameter was 4.4 μm and the porosity was 38%. The average pore diameter and porosity were made using a mercury porosimeter (manufactured by Shimadzu Corporation, trade name: Pore Sizer 9310).
また、本実施例のＤＰＦ用ハニカム構造体１のハニカム体２の細孔を、ＳＥＭ写真で確認した。撮影されたＳＥＭ写真を図８に示した。なお、図８（ａ）は１００倍の、（ｂ）は２００倍のＳＥＭ写真である。図８に示したように、本実施例のＤＰＦ用ハニカム構造体１では、微細な細孔がハニカム体２に均一に形成されていることが確認できた。 Further, the pores of the honeycomb body 2 of the DPF honeycomb structure 1 of the present example were confirmed by SEM photographs. The photographed SEM photograph is shown in FIG. FIG. 8A is a 100 × SEM photograph, and FIG. 8B is a 200 × SEM photograph. As shown in FIG. 8, it was confirmed that the fine pores were uniformly formed in the honeycomb body 2 in the DPF honeycomb structure 1 of the present example.
このように、本実施例のＤＰＦ用ハニカム構造体１のハニカム体２は、微細な細孔が均一に分散した多孔質セラミックスより形成されている。このような微細な細孔は、セラミックス粒子を焼結させることなく結合材で固定したことにより達成できた。 As described above, the honeycomb body 2 of the DPF honeycomb structure 1 of the present embodiment is formed of porous ceramics in which fine pores are uniformly dispersed. Such fine pores could be achieved by fixing the ceramic particles with a binder without sintering.
（実施例２）
実施例２のＤＰＦ用ハニカム構造体の製造方法を以下に示す。
(Example 2)
A method for manufacturing the DPF honeycomb structure of Example 2 will be described below.
まず、実施例１のハニカム体の製造と同様の方法でハニカム分体５を製造した。このハニカム分体５は、軸方向に垂直な断面での断面積が実施例１のハニカム体よりも小さい（区画されたセル数が少ない）こと以外は、実施例１のハニカム体２と同様な構成である。製造されたハニカム分体５は、セル中に封止材３よりなる封止部が形成されている。ハニカム分体５を図９に示した。なお、図９においては、封止材３は省略した。 First, the honeycomb segment 5 was manufactured by the same method as that for manufacturing the honeycomb body of Example 1. This honeycomb segment 5 is the same as the honeycomb body 2 of Example 1 except that the cross-sectional area in the cross section perpendicular to the axial direction is smaller than the honeycomb body of Example 1 (the number of partitioned cells is small). It is a configuration. In the manufactured honeycomb body 5, a sealing portion made of the sealing material 3 is formed in a cell. The honeycomb segment 5 is shown in FIG. In FIG. 9, the sealing material 3 is omitted.
そして、ハニカム分体５同士をＳｉＣ系接合材で接合した。接合材による接合は、厚さが１．０±０．５ｍｍとなるように接合材をハニカム分体５の外周面に塗布した後、別のハニカム分体５をこの面にすりあわせて接合した。この接合を繰り返して、断面が正方形をなすように１６個のハニカム分体５を接合し、８０℃で乾燥した。ハニカム分体５の接合体の端面を図１０に示した。 Then, the honeycomb bodies 5 were bonded to each other with a SiC bonding material. In the bonding with the bonding material, the bonding material was applied to the outer peripheral surface of the honeycomb body 5 so as to have a thickness of 1.0 ± 0.5 mm, and then another honeycomb body 5 was bonded to the surface. . This joining was repeated, and the 16 honeycomb bodies 5 were joined so that the cross section was a square, and dried at 80 ° C. The end face of the joined body of the honeycomb body 5 is shown in FIG.
ここで、ハニカム分体５同士を接合するＳｉＣ系接合材は、上記の外周材層を形成するために製造されたスラリーである。 Here, the SiC-based bonding material for bonding the honeycomb divided bodies 5 to each other is a slurry manufactured to form the outer peripheral material layer.
そして、この接合体を電動ノコギリを用いて切削して外周形状を成形した。電動ノコギリによる切削は、両端部に封止材が形成されたセルが外周面を形成する略円柱状をなすようになされた。この切削時に、封止材のセルからの剥離がみられなかった。 Then, this joined body was cut using an electric saw to form an outer peripheral shape. The cutting with the electric saw was made so that the cell in which the sealing material was formed at both ends formed a substantially cylindrical shape forming the outer peripheral surface. During this cutting, no peeling of the sealing material from the cell was observed.
そして、主成分がＳｉＣよりなるスラリーを調製し、成形体の外周面に塗布し、８０℃で乾燥した後に８５０℃で加熱して接合材およびスラリーを固化させた。これにより、外周面上に外周材層４が形成できた。 And the slurry which a main component consists of SiC was prepared, and it apply | coated to the outer peripheral surface of a molded object, and after drying at 80 degreeC, it heated at 850 degreeC and solidified the joining material and the slurry. Thereby, the outer peripheral material layer 4 was able to be formed on the outer peripheral surface.
以上により、本実施例のハニカム構造体１を製造することができる。本実施例のハニカム構造体をその端面で図１１に示した。 As described above, the honeycomb structure 1 of this example can be manufactured. The honeycomb structure of the present example is shown in FIG. 11 at its end face.
図に示したように、本実施例のハニカム構造体１は、複数の多孔質のＳｉＣセラミックスよりなるハニカム分体５が接合材層６を介して接合されてなるハニカムと、多数のセルのうち所定のセルの一方の端部または他方の端部に充填された封止材３と、隔壁部の周方向の外周面上に形成された外周材層４と、を備えた構成を有している。 As shown in the figure, the honeycomb structure 1 of the present example includes a honeycomb structure in which a plurality of honeycomb bodies 5 made of porous SiC ceramics are bonded via a bonding material layer 6, and a large number of cells. It has a configuration including a sealing material 3 filled in one end or the other end of a predetermined cell, and an outer peripheral material layer 4 formed on the outer peripheral surface of the partition wall in the circumferential direction. Yes.
そして、本実施例のハニカム構造体１のハニカムは、実施例１の時と同様に、粒径の異なるＳｉＣおよびＳｉ３Ｎ４がコロイダルシリカよりなる結合材で結合されたハニカム分体５を備えた構成を有している。ハニカム分体５を構成するセラミックス粒子（ＳｉＣおよびＳｉ３Ｎ４）の粒径分布を測定したところ、実施例１のハニカム体と同様な結果が得られた。 And the honeycomb of the honeycomb structure 1 of the present embodiment is provided with a honeycomb body 5 in which SiC and Si 3 N 4 having different particle diameters are bonded with a binder made of colloidal silica, as in the first embodiment. It has a configuration. When the particle size distribution of the ceramic particles (SiC and Si 3 N 4 ) constituting the honeycomb body 5 was measured, the same result as that of the honeycomb body of Example 1 was obtained.
本実施例のＤＰＦ用ハニカム構造体１のハニカム体２の平均細孔径および気孔率を、実施例１の時と同様に測定した。平均細孔径は２．４μｍであり、気孔率は４２％であった。また、本実施例のＤＰＦ用ハニカム構造体１のハニカム体２においては、微細な細孔がハニカム体２に均一に形成されていることが確認できた。 The average pore diameter and the porosity of the honeycomb body 2 of the DPF honeycomb structure 1 of this example were measured in the same manner as in Example 1. The average pore diameter was 2.4 μm, and the porosity was 42%. Moreover, in the honeycomb body 2 of the DPF honeycomb structure 1 of the present example, it was confirmed that fine pores were uniformly formed in the honeycomb body 2.
このように、本実施例のＤＰＦ用ハニカム構造体１のハニカム体２は、微細な細孔が均一に分散した多孔質セラミックスより形成されている。このような微細な細孔は、セラミックス粒子を焼結させることなく結合材で固定したことにより達成できた。 As described above, the honeycomb body 2 of the DPF honeycomb structure 1 of the present embodiment is formed of porous ceramics in which fine pores are uniformly dispersed. Such fine pores could be achieved by fixing the ceramic particles with a binder without sintering.
（比較例）
まず、平均粒径（Ｄ５０）が１３μｍのＳｉＣ粉末（信濃電気製錬製、商品名：ＧＰ−１０００Ｆ）を４０ｋｇ，カーボン（ＳＥＣカーボン株式会社製、商品名：ファインパウダー）５ｋｇ，球状シリカ（電気化学工業製、商品名：ＳＮ）５ｋｇ，上記のＣＭＣを含む溶液５００ｇ，水１５ｋｇを秤量し、十分に混合（混練）した後に、軸方向に多数のセルが形成された柱状の成形体を従来公知の製造方法である押出成形で製造した。この成形体は、実施例１の成形体と同様の形状である。
(Comparative example)
First, 40 kg of SiC powder having an average particle diameter (D50) of 13 μm (manufactured by Shinano Denki Smelting, trade name: GP-1000F), 5 kg of carbon (trade name: fine powder, manufactured by SEC Carbon Co., Ltd.), spherical silica (electric A columnar molded body having a number of cells formed in the axial direction after weighing and weighing (mixing) knead (product name: SN) 5 kg, solution 500 g containing the above CMC, and water 15 kg, and mixing them well (kneading) It was manufactured by extrusion molding, which is a known manufacturing method. This molded body has the same shape as the molded body of Example 1.
つづいて、実施例１の時と同様にして、固形分がほぼＳｉＣ粒子よりなるスラリーを調製し、成形体の両端の端部から所定のセルに注入した。 Subsequently, in the same manner as in Example 1, a slurry having a solid content substantially consisting of SiC particles was prepared, and injected into predetermined cells from both ends of the molded body.
その後、２３００℃でセルにスラリーが注入された成形体を熱処理して成形体を焼成するとともにスラリーを固化させて封止材３とし、封止材３で封止されたセル（封止部）をもつハニカム体２を形成した。 Thereafter, the molded body in which the slurry is injected into the cell at 2300 ° C. is heat-treated, and the molded body is fired, and the slurry is solidified to form the sealing material 3. A honeycomb body 2 having the structure was formed.
そして、実施例１の時と同様に外周形状を成形した。 And the outer periphery shape was shape | molded similarly to the time of Example 1. FIG.
そして、主成分が平均粒径（Ｄ５０）が２０μｍのＳｉＣよりなるスラリーを調製し、切削体の外周面に塗布し、８０℃で乾燥した後に８５０℃で加熱してスラリーを固化させた。これにより、外周面上に外周材層４が形成できた。 And the slurry which a main component consists of SiC whose average particle diameter (D50) is 20 micrometers was prepared, and it apply | coated to the outer peripheral surface of a cutting body, and it dried at 80 degreeC, Then, it heated at 850 degreeC and solidified the slurry. Thereby, the outer peripheral material layer 4 was able to be formed on the outer peripheral surface.
以上により、本比較例のハニカム構造体１を製造することができた。 As described above, the honeycomb structure 1 of this comparative example could be manufactured.
本比較例のハニカム構造体１は、軸方向にのびる多数のセルを備えた多孔質のＳｉＣセラミックスよりなるハニカム体２と、多数のセルのうち所定のセルの一方の端部または他方の端部に充填された封止材３と、隔壁部の周方向の外周面上に形成された外周材層４と、を備えた構成を有している。なお、本実施例のハニカム構造体１のハニカム体２は、外径：９０．０ｍｍ、軸方向長さ：１５０．０ｍｍの略円柱状に形成されている。 The honeycomb structure 1 of this comparative example includes a honeycomb body 2 made of porous SiC ceramics having a large number of cells extending in the axial direction, and one end portion or the other end portion of a predetermined cell among the many cells. And the outer peripheral material layer 4 formed on the outer peripheral surface in the circumferential direction of the partition wall. Note that the honeycomb body 2 of the honeycomb structure 1 of the present example is formed in a substantially cylindrical shape having an outer diameter: 90.0 mm and an axial length: 150.0 mm.
本比較例のハニカム構造体１のハニカム体２は、単一の平均粒径をもつＳｉＣが焼結して形成された。ハニカム体２を構成するセラミックス粒子（ＳｉＣ）の粒径分布を測定したところ、１本のピークが確認できた。 The honeycomb body 2 of the honeycomb structure 1 of this comparative example was formed by sintering SiC having a single average particle diameter. When the particle size distribution of the ceramic particles (SiC) constituting the honeycomb body 2 was measured, one peak was confirmed.
本比較例のＤＰＦ用ハニカム構造体のハニカム体２の平均細孔径および気孔率を、実施例１の時と同様に測定した。平均細孔径は１５μｍであり、気孔率は４３％であった。 The average pore diameter and the porosity of the honeycomb body 2 of the DPF honeycomb structure of this comparative example were measured in the same manner as in Example 1. The average pore diameter was 15 μm and the porosity was 43%.
また、本比較例のＤＰＦ用ハニカム構造体のハニカム体２の細孔を、ＳＥＭ写真で確認した。撮影されたＳＥＭ写真を図１２に示した。なお、図１２（ａ）は１０００倍の、（ｂ）は１００００倍の写真である。図１２に示したように、本比較例のＤＰＦ用ハニカム構造体では、セラミックス粒子が焼結してネックの成長により、微細な細孔がほとんど確認できなかった。 Further, the pores of the honeycomb body 2 of the DPF honeycomb structure of this comparative example were confirmed by SEM photographs. The photographed SEM photograph is shown in FIG. Note that FIG. 12A is a 1000 × photograph, and FIG. 12B is a 10000 × photo. As shown in FIG. 12, in the honeycomb structure for DPF of this comparative example, ceramic particles were sintered, and fine pores were hardly confirmed due to neck growth.
これに対し、上記の各実施例のＤＰＦ用ハニカム構造体１のハニカム体２は、微細な細孔が均一に分散した多孔質セラミックスより形成されていることが確認できる。この微細な細孔は、ブロードな粒径分布曲線を持つセラミックス粉末を用いて、焼結させることなく結合材で固定したことにより達成できた。つまり、各実施例のハニカム構造体は、微細な粒子も捕集できるフィルタに用いることができるハニカム構造体となっている。 In contrast, it can be confirmed that the honeycomb body 2 of the DPF honeycomb structure 1 of each of the above embodiments is formed of porous ceramics in which fine pores are uniformly dispersed. These fine pores could be achieved by using ceramic powder having a broad particle size distribution curve and fixing with a binder without sintering. That is, the honeycomb structure of each example is a honeycomb structure that can be used for a filter that can collect fine particles.
１：ハニカム構造体
２：ハニカム体
３：封止材
４：外周材層
５：ハニカム分体
６：接合材層
1: Honeycomb structure 2: Honeycomb body 3: Sealing material 4: Peripheral material layer 5: Honeycomb segment 6: Bonding material layer
Claims (10)
該セラミックス粉末は、１０％粒径（Ｄ１０）と９０％粒径（Ｄ９０）との間隔が１０μｍ以上であることを特徴とするハニカム構造体。 A honeycomb structure made of porous ceramics having ceramic powder and a binder that bonds ceramic particles constituting the ceramic powder,
A honeycomb structure characterized in that the ceramic powder has an interval between a 10% particle size (D10) and a 90% particle size (D90) of 10 μm or more.
前記多孔質セラミックスよりなる複数のハニカム分体と、
複数の該ハニカム分体同士を接合する接合材層と、
からなる請求項１〜５のいずれかに記載のハニカム構造体。 The honeycomb structure is
A plurality of honeycomb bodies made of the porous ceramic;
A bonding material layer for bonding a plurality of the honeycomb bodies;
The honeycomb structure according to any one of claims 1 to 5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009269807A (en) * | 2008-05-09 | 2009-11-19 | Tokyo Yogyo Co Ltd | SiC CERAMIC, METHOD OF MANUFACTURING THE SAME AND HONEYCOMB STRUCTURE |
| JP2011201722A (en) * | 2010-03-25 | 2011-10-13 | Ngk Insulators Ltd | Zeolite structure and production method thereof |
| WO2016052682A1 (en) * | 2014-09-30 | 2016-04-07 | 日立金属株式会社 | Ceramic honeycomb filter and method for manufacturing same |
| WO2022202910A1 (en) | 2021-03-26 | 2022-09-29 | 日立金属株式会社 | Silicon carbide-based ceramic honeycomb structure and production method therefor |
| CN116685386B (en) * | 2021-03-26 | 2024-04-26 | 株式会社博迈立铖 | Silicon carbide ceramic honeycomb structure and method for producing same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04187578A (en) * | 1990-11-22 | 1992-07-06 | Ibiden Co Ltd | Production of sintered compact of porous silicon carbide |
| JPH05269388A (en) * | 1992-01-30 | 1993-10-19 | Ngk Insulators Ltd | Ceramic honeycomb structure, its production and coat material therefor |
| JP2001064084A (en) * | 1999-07-21 | 2001-03-13 | Inst Fr Petrole | Honeycomb monolithic structure of fine pore ceramic material and its use as particle filter |
| WO2004106265A1 (en) * | 2003-05-29 | 2004-12-09 | Ngk Insulators, Ltd. | Method for producing honeycomb structure and silicon carbide particles used for producing honeycomb structure |
| WO2005026074A1 (en) * | 2003-09-12 | 2005-03-24 | Ibiden Co., Ltd. | Sintered ceramic compact and ceramic filter |
| WO2007012776A2 (en) * | 2005-07-28 | 2007-02-01 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | High specific surface silicon carbide catalytic filter and support |
| JP2007191329A (en) * | 2006-01-17 | 2007-08-02 | Tokyo Yogyo Co Ltd | Sic-based joining material |
-
2008
- 2008-02-19 JP JP2008037236A patent/JP5149032B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04187578A (en) * | 1990-11-22 | 1992-07-06 | Ibiden Co Ltd | Production of sintered compact of porous silicon carbide |
| JPH05269388A (en) * | 1992-01-30 | 1993-10-19 | Ngk Insulators Ltd | Ceramic honeycomb structure, its production and coat material therefor |
| JP2001064084A (en) * | 1999-07-21 | 2001-03-13 | Inst Fr Petrole | Honeycomb monolithic structure of fine pore ceramic material and its use as particle filter |
| WO2004106265A1 (en) * | 2003-05-29 | 2004-12-09 | Ngk Insulators, Ltd. | Method for producing honeycomb structure and silicon carbide particles used for producing honeycomb structure |
| WO2005026074A1 (en) * | 2003-09-12 | 2005-03-24 | Ibiden Co., Ltd. | Sintered ceramic compact and ceramic filter |
| WO2007012776A2 (en) * | 2005-07-28 | 2007-02-01 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | High specific surface silicon carbide catalytic filter and support |
| JP2007191329A (en) * | 2006-01-17 | 2007-08-02 | Tokyo Yogyo Co Ltd | Sic-based joining material |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009269807A (en) * | 2008-05-09 | 2009-11-19 | Tokyo Yogyo Co Ltd | SiC CERAMIC, METHOD OF MANUFACTURING THE SAME AND HONEYCOMB STRUCTURE |
| JP2011201722A (en) * | 2010-03-25 | 2011-10-13 | Ngk Insulators Ltd | Zeolite structure and production method thereof |
| WO2016052682A1 (en) * | 2014-09-30 | 2016-04-07 | 日立金属株式会社 | Ceramic honeycomb filter and method for manufacturing same |
| JPWO2016052682A1 (en) * | 2014-09-30 | 2017-08-17 | 日立金属株式会社 | Ceramic honeycomb filter and manufacturing method thereof |
| US9981881B2 (en) | 2014-09-30 | 2018-05-29 | Hitachi Metals, Ltd. | Ceramic honeycomb filter and its production method |
| US10556833B2 (en) | 2014-09-30 | 2020-02-11 | Hitachi Metals, Ltd. | Ceramic honeycomb filter and its production method |
| WO2022202910A1 (en) | 2021-03-26 | 2022-09-29 | 日立金属株式会社 | Silicon carbide-based ceramic honeycomb structure and production method therefor |
| JP7188652B1 (en) * | 2021-03-26 | 2022-12-13 | 日立金属株式会社 | Silicon carbide ceramic honeycomb structure and manufacturing method thereof |
| JP7215636B1 (en) | 2021-03-26 | 2023-01-31 | 日立金属株式会社 | Silicon carbide ceramic honeycomb structure and manufacturing method thereof |
| JP2023022129A (en) * | 2021-03-26 | 2023-02-14 | 株式会社プロテリアル | Silicon carbide ceramic honeycomb structure and production method of the same |
| CN116685386A (en) * | 2021-03-26 | 2023-09-01 | 株式会社博迈立铖 | Silicon carbide ceramic honeycomb structure and method for producing same |
| CN116685386B (en) * | 2021-03-26 | 2024-04-26 | 株式会社博迈立铖 | Silicon carbide ceramic honeycomb structure and method for producing same |
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