JP7052093B2 - ハニカム構造体 - Google Patents
ハニカム構造体 Download PDFInfo
- Publication number
- JP7052093B2 JP7052093B2 JP2020571740A JP2020571740A JP7052093B2 JP 7052093 B2 JP7052093 B2 JP 7052093B2 JP 2020571740 A JP2020571740 A JP 2020571740A JP 2020571740 A JP2020571740 A JP 2020571740A JP 7052093 B2 JP7052093 B2 JP 7052093B2
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- JP
- Japan
- Prior art keywords
- honeycomb structure
- cell
- partition wall
- thermal conductivity
- 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.)
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Description
そこで、ハニカム構造体の破損を抑制するための対策として、特許文献1には、複数の柱状ハニカムセグメントの側面同士を接合した接合層を有するハニカム構造体が提案されている。
しかしながら、柱状ハニカムセグメントの隔壁の厚みを小さくすると、再生処理時にクラックが発生し易くなる。特に、ハニカム構造体の内部に堆積した粒子状物質は急激に燃焼することがあるが、柱状ハニカムセグメントの隔壁の厚みが小さいほど、急激な温度変化によってハニカム構造体にクラックが発生し易くなる。例えば、この粒子状物質の異常燃焼を評価するDTI(Drop To Idle)試験において、ハニカム構造体の内部に堆積した粒子状物質は、アイドリング状態で急激に燃焼してハニカム構造体の温度を著しく上昇させるため、その温度変化によってハニカム構造体にクラックが発生し易くなる。
前記柱状ハニカムセグメントの側面同士を接合するように配置された接合層
を備えるハニカム構造体であって、
前記隔壁は、珪素及び炭化珪素を含有し且つ平均厚みが0.152~0.254mmであり、
前記隔壁の熱伝導率が0.8~34W/m・Kであり、
前記接合層の熱伝導率が0.1~1.0W/m・Kであり、
前記接合層の平均厚みが0.5~3.0mmであり、
前記隔壁の気孔率が30~70%であり、
前記ハニカム構造体は以下の式(1)~(3)を満たす、ハニカム構造体である。
(1)y≦1000
(2)y≦717.92x-0.095
(3)y≧462.4x-0.153
式中、yはハニカム構造体の使用が許容される最高温度(℃)であり、xは以下の式で表される熱伝導因子である。
熱伝導因子=(隔壁の熱伝導率×接合層の熱伝導率)/(接合層の平均厚み×隔壁の気孔率)
図1に示されるように、ハニカム構造体100は、複数の柱状ハニカムセグメント10と、柱状ハニカムセグメント10の側面同士を接合するように配置された接合層20とを備える。また、ハニカム構造体100は、必要に応じて、外周部を研削加工するなどして、円柱状などの所定形状に加工することができる。この場合、加工によって柱状ハニカムセグメント10の内部の隔壁13及びセル12が露出した状態となるため、露出面をコーティング材で被覆するなどして外周コート層30を設けることができる。
ハニカム構造体100の形状は、特に限定されないが、円柱状の他、端面が楕円形の柱状、端面が正方形、長方形、三角形、五角形、六角形などの多角形の柱状などとすることができる。
隔壁13は、上記の成分以外に、コージェライト、ムライト、アルミナ、チタニア、スピネル、炭化珪素-コージェライト系複合材料、リチウムアルミニウムシリケート、チタン酸アルミニウム、鉄-クロム-アルミニウム系合金などの公知の成分を含有することができる。
(1)y≦1000
(2)y≦717.92x-0.095
(3)y≧462.4x-0.153
式中、yはハニカム構造体100の使用が許容される最高温度(℃)であり、xは以下の式で表される熱伝導因子である。
熱伝導因子=(隔壁13の熱伝導率×接合層20の熱伝導率)/(接合層20の平均厚み×隔壁13の気孔率)
上記の式(1)~(3)は、ハニカム構造体100の各種サンプルを作製して再生処理時のクラックの発生(具体的には、リングクラック又は端面クラックの発生)の有無、及びアイドリング状態の直前における煤の燃焼率を調査し、その調査結果から実験的に導出された関係式である。なお、リングクラックとは、ハニカム構造体100の外周において、外周方向に延びるように形成されるリング状のクラックである。また、端面クラックとは、ハニカム構造体100の端面の隔壁13に形成されるクラックである。
まず、ハニカム構造体100の各種サンプルは、次のようにして作製した。
(柱状ハニカムセグメント10の作製)
原料として、炭化珪素粉末及び金属珪素粉末を20:35の質量割合で混合し、これに造孔材(炭化珪素粉末及び金属珪素粉末の合計質量に対して10質量%以下)、バインダ(炭化珪素粉末及び金属珪素粉末の合計質量に対して2~10質量%)、界面活性剤及び水を加えて混合及び混練して坏土とした。次に、得られた坏土を押出成形して切断し、マイクロ波及び熱風で乾燥することによって柱状ハニカム成形体を得た。次に、この柱状ハニカム成形体に対し、一方の端面(第1端面11a)と他方の端面(第2端面11b)とが相補的な市松模様を呈するように、1つのセル12の2つの端面のうちのいずれか一方の端面の開口端部を目封止した。目封止用スラリーには、柱状ハニカム成形体の原料と同様の材料を用いた。目封止用スラリーを開口端部に充填して乾燥させた後、目封止した柱状ハニカム成形体を大気雰囲気中にて200~600℃で脱脂した後、Ar不活性雰囲気中にて1420~1480℃で焼成することによって柱状ハニカムセグメント10を得た。柱状ハニカムセグメント10の隔壁13の平均厚みは、押出成形時に口金のスリット幅を調整することによって制御した。また、隔壁13の気孔率は、造孔材の量を調整することによって制御した。隔壁13の気孔率は、水銀ポロシメータ(Micromeritics社製、商品名:Autopore 9500)を用いて測定した。隔壁13の熱伝導率は、気孔率の調整や、焼成後の柱状ハニカムセグメント10に酸化処理を行うことによって制御した。酸化処理は、従来公知の方法により行うことができる。具体的には、焼成された柱状ハニカムセグメント10を、酸素雰囲気下(例えば、酸素濃度15~20質量%)で900~1400℃に加熱することにより、酸化処理を行うことができる。
接合材は、接合層20を形成するための材料であり、硬化させることで接合層20となる。柱状ハニカムセグメント10と同じ原料を配合して混合することによってペースト状の接合材を調製した。接合層20の熱伝導率は、気孔率の調整によって制御した。気孔率は、上記柱状ハニカムセグメント10と同様に、造孔材の量を調整することによって制御した。
柱状ハニカムセグメント10の側面に所定の平均厚みとなるように接合材を塗布し、別の柱状ハニカムセグメント10の側面と接合した。この工程を繰り返して、縦3個×横3個の柱状ハニカムセグメント10を接合した合計9個の柱状ハニカムセグメント10の積層体を作製した。その後、外部から圧力を加えることで柱状ハニカムセグメント10同士を圧着させ、120℃で2時間乾燥させることにより、柱状ハニカムセグメント10の接合体を得た。次に、得られた接合体の中心軸に垂直な方向の断面が円形となるように、接合体の外周を切削加工した。次に、その加工面に接合材と同じ組成の外周コーティング材を塗布した後、600℃で0.5時間以上加熱することで乾燥及び硬化させて外周コート層30を形成し、サンプルNo.A-1~A-9、B-1~B-9及びC-1~C-9のハニカム構造体100を得た。
上記で作製したハニカム構造体100の外周部にセラミックス製の無膨張マットを巻き、ステンレス鋼(SUS409)製の缶体にキャニングしてキャニング構造体とした。その後、ディーゼル燃料(軽油)の燃焼によって発生させた煤(粒子状物質)を含む燃焼ガスを、ハニカム構造体100の一方の端面より流入させ、他方の端面より流出させた。これにより、ハニカム構造体100内に煤を堆積させた。次に、キャニング構造体を排気系に接続し、DTI(Drop To Idle)試験を行った。具体的には、フルスロットル状態(2300rpm)でハニカム構造体100を排ガスの熱で昇温させた後、温度が650℃に達したところで速やかにアイドリング状態(600rpm)に移行させて煤を燃焼させることにより、ハニカム構造体100を再生処理した。フルスロットル状態における排ガスの酸素濃度は6%、アイドリング状態における酸素濃度は15%とした。
また、DTI試験の後、ハニカム構造体100のクラックの有無をX線CTによって調査した。
さらに、アイドリング状態の直前(フルスロットル状態)における煤の燃焼評価を行った。具体的には、アイドリング状態の直前における煤の燃焼率を、実測温度データに基づく煤燃焼モデルから算出した。
上記の結果を表1に示す。また、隔壁13の熱伝導率及び気孔率、並びに接合層20の熱伝導率及び平均厚みから算出される熱伝導因子xと、ハニカム構造体100の最高温度との関係を表すグラフを図3に示す。なお、表1では、クラックが発見されなかったものを〇、クラックが発見されたものを×と表す。
サンプルNo.A-7は、アイドリング状態の温度(最高温度)が高い(1000℃超)。ここで、サンプルNo.A-7と同様にアイドリング状態のハニカム構造体100の温度が高いサンプルNo.B-5におけるハニカム構造体100の温度分布図を参考として図4に示す。サンプルNo.B-5は、サンプルNo.A-7と同様に、隔壁13の熱伝導率が低いため、ハニカム構造体100内に熱がこもりながら徐々に熱が全体に広がっていく。そして、図4に示されるように、アイドリング状態ではハニカム構造体100の長さ方向の中央部付近が最高温度に到達する。その結果、ハニカム構造体100の長さ方向の中央部付近において、排ガスの流れ方向と直交するように熱膨張による引張応力が発生し易くなるため、リングクラックが発生すると考えられる。したがって、式(1)y≦1000を満たすことにより、リングクラックの発生を抑制することができる。
なお、サンプルNo.B-1、B-4、B-6及びB-8は、サンプルNo.B-2と比べて、ハニカム構造体100の軸方向(長さ方向)における温度分布が緩やかとなっていた。そのため、排ガス入口の端面付近において、ハニカム構造体100の軸方向の熱膨張による引張応力が低減されているため、端面クラックの発生がなかったと考えられる。したがって、式(3)y≧462.4x-0.153を満たすことにより、端面クラックの発生を低減することができる。
以上の結果から、上記の式(1)~(3)を満たすことにより、ハニカム構造体100の再生処理時にクラックの発生を抑制することができる。
(4)x≦2.3
式(4)も式(1)~(3)と同様に、実験的に導出された関係式である。式(4)を満たすことにより、ハニカム構造体100の再生処理時にクラックの発生を安定的に抑制することができる。熱伝導因子xは、より好ましくは1.5以下であり、更に好ましくは1.0以下であり、特に好ましくは0.3以下である。
ここで、本明細書において「熱伝導率」とは、レーザーフラッシュ法を用いて室温(25℃)で測定される熱伝導率のことを意味する。
ここで、本明細書において「気孔率」とは、水銀ポロシメータを用いて測定される気孔率を意味する。水銀ポロシメータとしては、Micromeritics社製、商品名:Autopore 9500を挙げることができる。
また、セル12は、所定の開口面積を有する第1セルと、第1セルと開口面積が異なる第2セルとが交互に配設されていてもよい。
造孔材としては、焼成後に気孔となるものであれば特に限定されないが、澱粉、発泡樹脂、吸水性樹脂、シリカゲル、炭素などが挙げられる。これらは、単独又は2種以上を組み合わせて用いることができる。
なお、接合層20は、上記の成分を含有するペースト状の接合材を用いて形成される。
11a 第1端面
11b 第2端面
12 セル
13 隔壁
14 目封止部
20 接合層
30 外周コート層
100 ハニカム構造体
Claims (5)
- 第1端面から第2端面まで延びる流体の流路となる複数のセルを区画形成する隔壁と、所定の前記セルの前記第1端面側の開口端部及び残余の前記セルの前記第2端面側の開口端部を目封止する目封止部とを有する複数の柱状ハニカムセグメント、並びに
前記柱状ハニカムセグメントの側面同士を接合するように配置された接合層
を備えるハニカム構造体であって、
前記隔壁は、珪素及び炭化珪素を含有し且つ平均厚みが0.152~0.254mmであり、
前記隔壁の熱伝導率が0.8~34W/m・Kであり、
前記接合層の熱伝導率が0.1~1.0W/m・Kであり、
前記接合層の平均厚みが0.5~3.0mmであり、
前記隔壁の気孔率が30~70%であり、
前記ハニカム構造体は以下の式(1)~(3)を満たす、ハニカム構造体。
(1)y≦1000
(2)y≦717.92x-0.095
(3)y≧462.4x-0.153
式中、yはハニカム構造体の使用が許容される最高温度(℃)であり、xは以下の式で表される熱伝導因子である。
熱伝導因子=(隔壁の熱伝導率×接合層の熱伝導率)/(接合層の平均厚み×隔壁の気孔率) - 前記ハニカム構造体は以下の式(4)を満たす、請求項1に記載のハニカム構造体。
(4)x≦2.3 - 前記セルが延びる方向に垂直な前記セルの断面形状が四角形である、請求項1又は2に記載のハニカム構造体。
- 前記セルは、所定の開口面積を有する第1セルと、前記第1セルと開口面積が異なる第2セルとが交互に配設されている、請求項1又は2に記載のハニカム構造体。
- 前記ハニカム構造体のセル密度が31~52個/cm2である、請求項1~4のいずれか一項に記載のハニカム構造体。
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