JP6423160B2 - ハニカム構造体 - Google Patents
ハニカム構造体 Download PDFInfo
- Publication number
- JP6423160B2 JP6423160B2 JP2014041376A JP2014041376A JP6423160B2 JP 6423160 B2 JP6423160 B2 JP 6423160B2 JP 2014041376 A JP2014041376 A JP 2014041376A JP 2014041376 A JP2014041376 A JP 2014041376A JP 6423160 B2 JP6423160 B2 JP 6423160B2
- Authority
- JP
- Japan
- Prior art keywords
- honeycomb
- particles
- bonding layer
- plate
- honeycomb structure
- 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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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2466—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure of the adhesive layers, i.e. joints between segments
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2451—Honeycomb filters characterized by the geometrical structure, shape, pattern or configuration or parameters related to the geometry of the structure
- B01D46/2478—Structures comprising honeycomb segments
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
- C04B37/005—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of glass or ceramic material
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
- C04B41/5089—Silica sols, alkyl, ammonium or alkali metal silicate cements
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- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
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- B01D46/2418—Honeycomb filters
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- B01D46/2498—The honeycomb filter being defined by mathematical relationships
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/101—Glass
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
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- B32B2264/107—Ceramic
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- 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
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- C04B2111/34—Non-shrinking or non-cracking materials
- C04B2111/343—Crack resistant materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24149—Honeycomb-like
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- Chemical & Material Sciences (AREA)
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- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Geometry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Filtering Materials (AREA)
- Ceramic Products (AREA)
- Processes For Solid Components From Exhaust (AREA)
- Filtering Of Dispersed Particles In Gases (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Civil Engineering (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
Description
本発明のハニカム構造体の一の実施形態は、図1〜図3に示すような柱状のハニカム構造体100である。つまり、ハニカム構造体100は、複数個の柱状のハニカムセグメント22と、複数個のハニカムセグメント22の側面同士を接合する接合層24と、を備えている。ハニカムセグメント22は、流体の流路となる一方の端面である流入端面11から他方の端面である流出端面12まで延びる複数のセル2を区画形成する多孔質の隔壁1を有している。ハニカム構造体100は、接合層24が、複数の板状粒子30を含有している。また、板状粒子30は、接合層24を接合層24の厚さ方向に切断した断面(図3参照)において、接合層24の厚さ方向Xに積層されて存在している。そして、接合層24を接合層24の厚さ方向に切断した断面において、接合層24の厚さ方向に平行で長さが1000μmの走査線である縦方向走査線S1(図3参照)を想定する。このとき、縦方向走査線S1と交差する板状粒子30のうち縦方向走査線S1とのなす角度が45°以上である板状粒子30の数を粒子数αとする。更に、上記断面(粒子数αを数えた断面)において、接合層24の厚さ方向に垂直で長さが1000μmの走査線である横方向走査線を想定する。このとき、横方向走査線S2(図3参照)と交差する板状粒子30のうち横方向走査線S2とのなす角度が45°以上である板状粒子30の数を粒子数βとする。この場合、ハニカム構造体100は、粒子数αが、式:粒子数α>10を満たし、粒子数αと粒子数βとが、式:(粒子数α/粒子数β)>3の関係を満たしている。なお、ハニカム構造体100は、その外周に外周コート層26を備えているがこの外周コート層26は必須ではない。
接合層は、上述の通り、複数の板状粒子を含有している。この板状粒子とは、以下の条件A、Bを満たす粒子のことである。即ち、条件A:接合層を接合層の厚さ方向に切断した断面(厚さ方向断面)において、厚さが1〜10μmで幅が40〜500μmである。条件B:上記厚さ方向断面に直行するように切断した断面において、接合層の厚さ方向に直行する方向の長さが40〜500μmである。なお、上記厚さ、幅、及び長さは、任意の領域を複数選択して測定したときの平均値である。
ハニカムセグメントは、炭化珪素、アルミナチタネート、窒化珪素、及びコージェライトからなる群より選択される少なくとも一種からなることが好ましい。耐熱性に優れ、耐化学性に優れている鉱物であり、接合層が耐熱性及び耐化学性に優れるものになるためである。
次に、本発明のハニカム構造体の製造方法は、以下の方法を採用できる。まず、流体の流路となる一方の端面である流入端面から他方の端面である流出端面まで延びる複数のセルを区画形成する多孔質の隔壁を有する複数個の柱状のハニカムセグメントを作製するハニカム成形体作製工程を行う。次に、得られた複数のハニカムセグメントの側面に、板状粒子を含有する接合材を塗工して接合膜を形成し、その後、この接合膜に、接合膜の厚さ方向の外圧0.1〜0.6MPaを加えてハニカムセグメントを接合するハニカムセグメント接合工程を行う。このようにして、本発明のハニカム構造体を製造することができる。
まず、以下の方法で、ハニカム成形体を作製する。ハニカム成形原料、バインダ、界面活性剤、造孔材、水等を混合してハニカム成形原料を作製する。このハニカム成形原料には、炭化珪素、アルミナチタネート、窒化珪素、及び、コージェライトよりなる群から選択される少なくとも一種を含むことが好ましい。なお、このハニカム成形原料は、焼成後にコージェライトとなるコージェライト化原料を含むことも好ましい。
次に、ハニカム接合体を作製する。まず、ハニカムセグメントを接合する接合層を形成するための接合材を作製する。
SiC粉末及び金属Si粉末を80:20の質量割合で混合し、これに造孔剤として澱粉、発泡樹脂を加え、更に、メチルセルロース及びヒドロキシプロポキシルメチルセルロース、界面活性剤及び水を添加して可塑性の坏土を作製した。
「最大スス堆積温度」の測定については、以下のように行った。2.2Lディーゼルエンジンを搭載するエンジンベンチにて運転し、所定量のPM(パティキュレートマター)を、作製したハニカムフィルタ(ハニカム構造体)に堆積させた。その後、再生処理(ポストインジェクションによりPMを燃焼させる処理)を行い、ハニカムフィルタに流入するガス(入口ガス)の温度を上昇させた。その後、ハニカムフィルタ前後の圧力損失(ガスの入口側と出口側における圧力損失)が低下し始めたところで、ポストインジェクションを止め、エンジンをアイドル状態に切り替えた。その後、再生処理前のPM堆積量を徐々に増加させ、ハニカムフィルタにクラックが生じるまで同じ試験を繰り返し行った。このとき、DPFの排ガスの出口側の端面付近における中央セグメントの温度を熱電対で測定した。中央セグメントは、ハニカムフィルタの外周面を構成するハニカムセグメントである外周セグメント以外のハニカムセグメントのことである。そして、ハニカムフィルタにクラックが生じない場合におけるハニカムフィルタ内の最高の温度を「最大スス堆積温度」とした。なお、各評価において、クラック発生の有無の確認は、目視にて行った。
「最大スス堆積温度改善率」の算出を行った。なお、「最大スス堆積温度改善率」とは、ハニカム基材が同じフィルタ同士で板状粒子を接合層内に含まない比較例のハニカム構造体を100%(基準)とした時の改善率を意味する。「最大スス堆積温度改善率」の算出については、比較例2〜4、実施例1〜12については、比較例1を基準に計算した。実施例13については、比較例5を基準に計算した。実施例14については、比較例6を基準に計算した。実施例15については、比較例7を基準に計算した。「最大スス堆積温度改善率」が0%以下である場合には、ハニカム接合体を構成するハニカムセグメントにクラックが発生する。「最大スス堆積温度改善率」が0%超で1%未満のある場合には、ハニカム接合体を構成するハニカムセグメントにクラックが発生することを抑制する効果が、顕著ではないがわずかに確認できる。「最大スス堆積温度改善率」が1%以上で5%未満の場合には、「ハニカム接合体を構成するハニカムセグメントにクラックが発生することを抑制することができる」と判断することができる。更に5%以上の場合には、「ハニカム接合体を構成するハニカムセグメントにクラックが発生することを更によく抑制することができる」と判断することができる。
「ハニカムセグメントが抜け落ち」については、上記試験後、ハニカムセグメントに1100Nの圧力を印加して、ハニカム構造体からハニカムセグメントが抜け落ちないことを確認した。
各条件を、表1に示すように変更した以外は、実施例1と同様にしてハニカム構造体を作製した。実施例1の場合と同様にして、作製したハニカム構造体について、「最大スス堆積温度(℃)」、及び「最大スス堆積温度改善率(%)」の各評価を行った。結果を表1に示す。また、ハニカム構造体からハニカムセグメントが抜け落ちるか否かを確認した。
Claims (4)
- 流体の流路となる一方の端面である流入端面から他方の端面である流出端面まで延びる複数のセルを区画形成する多孔質の隔壁を有する複数個のハニカムセグメントと、
前記複数個のハニカムセグメントの側面同士を接合する接合層と、を備え、
前記接合層が、複数の板状粒子を含有し、
前記板状粒子が、前記接合層を前記接合層の厚さ方向に切断した断面において、前記接合層の厚さ方向に積層されて存在しており、
前記接合層を前記接合層の厚さ方向に切断した断面において、前記接合層の厚さ方向に平行で長さが1000μmの走査線である縦方向走査線を想定したとき、前記縦方向走査線と交差する前記板状粒子のうち前記縦方向走査線とのなす角度が45°以上である前記板状粒子の数を粒子数αとし、且つ、当該断面において、前記接合層の厚さ方向に垂直で長さが1000μmの走査線である横方向走査線を想定したとき、前記横方向走査線と交差する前記板状粒子のうち前記横方向走査線とのなす角度が45°以上である前記板状粒子の数を粒子数βとした場合、
前記粒子数αが、式:粒子数α>10を満たし、前記粒子数αと前記粒子数βとが、式:(粒子数α/粒子数β)>3の関係を満たすハニカム構造体。 - 前記接合層中の前記板状粒子が、前記接合層を前記接合層の厚さ方向に切断した断面において、厚さが1〜10μmで幅が40〜500μmの粒子を含むものである請求項1に記載のハニカム構造体。
- 前記接合層中の前記板状粒子が、マイカ、タルク、窒化ホウ素、及び、ガラスフレークからなる群より選択される少なくとも一種からなるものである請求項1または2に記載のハニカム構造体。
- 前記ハニカムセグメントが、炭化珪素、アルミナチタネート、窒化珪素、及びコージェライトからなる群より選択される少なくとも一種からなる請求項1〜3のいずれか一項に記載のハニカム構造体。
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