JPH0947666A - Electric heating type metallic catalytic carrier with excellent structural durability - Google Patents
Electric heating type metallic catalytic carrier with excellent structural durabilityInfo
- Publication number
- JPH0947666A JPH0947666A JP7202340A JP20234095A JPH0947666A JP H0947666 A JPH0947666 A JP H0947666A JP 7202340 A JP7202340 A JP 7202340A JP 20234095 A JP20234095 A JP 20234095A JP H0947666 A JPH0947666 A JP H0947666A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- foil
- corrugated foil
- center electrode
- honeycomb body
- 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.)
- Withdrawn
Links
- 238000005485 electric heating Methods 0.000 title description 2
- 230000003197 catalytic effect Effects 0.000 title 1
- 239000011888 foil Substances 0.000 claims abstract description 132
- 229910052751 metal Inorganic materials 0.000 claims description 153
- 239000002184 metal Substances 0.000 claims description 153
- 239000003054 catalyst Substances 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 20
- 238000005219 brazing Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000001902 propagating effect Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属ハニカム体を
触媒担体としこれを通電発熱させて、短時間に触媒活性
温度に上昇できる構造を有する構造耐久性に優れた電気
加熱式金属触媒担体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrically heated metal catalyst carrier having a structure in which a metal honeycomb body is used as a catalyst carrier and can be heated by energization to raise the catalyst activation temperature in a short time and which has excellent structural durability. It is a thing.
【０００２】[0002]
【従来の技術】例えば、近年、自動車等内燃機関の排気
通路に浄化触媒を配し、排気中のＨＣ，ＣＯ，ＮＯｘ等
の有害成分を浄化する技術が知られている。しかし、排
気浄化触媒は、活性温度より低い温度では、排気浄化能
力が著しく低下するため、内燃機関の始動時等、触媒の
温度が低い間は、排気中の上記有害成分、特にＨＣ、Ｃ
Ｏ成分が触媒により浄化されず、そのまま大気中に放出
されるという問題を生ずる。2. Description of the Related Art For example, in recent years, a technique has been known in which a purifying catalyst is arranged in an exhaust passage of an internal combustion engine such as an automobile to purify harmful components such as HC, CO and NOx in exhaust gas. However, the exhaust purification catalyst remarkably deteriorates in exhaust purification ability at a temperature lower than the activation temperature. Therefore, while the temperature of the catalyst is low such as at the time of starting the internal combustion engine, the harmful components in the exhaust gas, particularly HC and C
There is a problem that the O component is not purified by the catalyst and is directly released into the atmosphere.
【０００３】この問題を解決するために、触媒担体に金
属を使用し、内燃機関の始動時にこの金属触媒担体に、
電流を流すことにより、金属触媒担体自体を発熱させ
て、短時間で触媒活性化温度（３００〜４００℃）まで
上昇させるようにした電気加熱式触媒装置が提案されて
いる。この種の電気加熱式触媒装置の例としては、特開
平５−２２０４０４号公報などに開示されたものがあ
る。In order to solve this problem, a metal is used for the catalyst carrier, and this metal catalyst carrier is used for starting the internal combustion engine.
An electrically heated catalyst device has been proposed in which a metal catalyst carrier itself is heated by passing an electric current to raise the temperature to a catalyst activation temperature (300 to 400 ° C.) in a short time. An example of this type of electrically heated catalyst device is disclosed in Japanese Patent Application Laid-Open No. 5-220404.
【０００４】この電気加熱式触媒装置は、概念的には図
３に示すように、排気ガス流路に接続された筒状のケー
シング１内に電気加熱式触媒担体２と主触媒担体３を直
列配設してなるもので、排ガスを電気加熱式金属触媒担
体２を経由して主触媒担体３に導き、ここで排ガスを浄
化して排出するように構成されている。As shown in FIG. 3, this electrically heated catalyst device conceptually has an electrically heated catalyst carrier 2 and a main catalyst carrier 3 in series in a cylindrical casing 1 connected to an exhaust gas passage. It is arranged so that the exhaust gas is guided to the main catalyst carrier 3 via the electrically heated metal catalyst carrier 2, where the exhaust gas is purified and discharged.
【０００５】ここで用いられる電気加熱式金属触媒担体
２は、図４に示すように、少なくとも一方の表面に絶縁
層を形成した金属製の平箔４と金属波箔５を重ねて中心
電極６の回りに巻き回して得られる、図５に示すような
円筒状の金属箔積層体（ハニカム体）７と、このハニカ
ム体を内装した外筒８と、この外筒に電気的に絶縁され
つつ装着された外部電極９と、この外部電極と前記中心
電極６間に通電する電源１０等から構成されており、ハ
ニカム体７に通電してこのハニカム体内に形成した電流
路で発熱させ、触媒活性化温度まで昇温させ、触媒反応
を促進する機能を有している。As shown in FIG. 4, the electrically heated metal catalyst carrier 2 used here has a central electrode 6 formed by stacking a metal flat foil 4 and a metal corrugated foil 5 on which an insulating layer is formed on at least one surface. A cylindrical metal foil laminate (honeycomb body) 7 as shown in FIG. 5, which is obtained by winding the honeycomb body, an outer cylinder 8 in which the honeycomb body is housed, and an electric insulation of the outer cylinder. It is composed of an external electrode 9 mounted and a power source 10 for energizing between the external electrode and the center electrode 6, etc., and energizes the honeycomb body 7 to generate heat in a current path formed in the honeycomb body, thereby activating the catalyst. It has the function of raising the temperature to the oxidation temperature and promoting the catalytic reaction.
【０００６】ここで用いられるハニカム体７を構成する
金属平箔４、金属波箔５には、一般には導電性のある金
属箔が用いられており、短時間に触媒を活性温度にする
ための電流路を形成するために、金属平箔４、金属波箔
５の少なくとも一方の表面に、アルミナなどの金属酸化
物からなる絶縁被膜を形成させ、図４に示すように、ハ
ニカム体７の形成過程で金属平箔と金属波箔間にろう材
箔と、熱力学的に絶縁被膜を還元し得る強還元金属箔か
らなる接合材１１を介在させ、加熱処理することによ
り、金属平箔と金属波箔を局所てきに絶縁被膜を破壊し
つつ接合し、図６に示すように中心電極６側から金属外
筒８側に例えば螺旋状の電流路１２を形成することが行
われている。[0006] As the metal flat foil 4 and the metal corrugated foil 5 which compose the honeycomb body 7 used here, generally conductive metal foils are used, and in order to bring the catalyst to the activation temperature in a short time. In order to form a current path, an insulating coating film made of a metal oxide such as alumina is formed on at least one surface of the flat metal foil 4 and the corrugated metal foil 5 to form a honeycomb body 7 as shown in FIG. In the process, a brazing filler metal foil and a bonding material 11 made of a strongly reducing metal foil capable of thermodynamically reducing the insulating coating are interposed between the flat metal foil and the corrugated metal foil, and the heat treatment is performed. The corrugated foils are locally bonded to each other while destroying the insulating coating, and as shown in FIG. 6, for example, a spiral current path 12 is formed from the center electrode 6 side to the metal outer cylinder 8 side.
【０００７】従来、このようなハニカム体７の形成に際
して、アルミナなどの金属酸化物（以下「第一の金属の
酸化物」と称する）からなる絶縁酸化被膜を形成した金
属平箔４と絶縁被膜を有しない金属波箔５間に電流路を
形成する接合部を形成する場合には、例えば、図７
（ａ）に示すように、第一の金属の酸化物を熱力学的に
還元し得る強還元金属（以下「第二の金属」と称する）
の箔材１１ａとろう材箔１１ｂを積層してなる接合材１
１を、第二の金属１１ａが絶縁被膜４ｃを有する金属波
箔４に接し、ろう材箔１１ｂが絶縁被膜を有しない金属
波箔５に接するように配置し、非酸化性雰囲気中で加熱
してろう材箔が溶融するとともに、第二の金属１１ａが
絶縁被膜を還元することにより、図７（ｂ）に示すよう
に、第二の金属の酸化物１４がろう材中に分散析出し
て、ろう材が金属平箔４の素地に達することにより、金
属平箔４と金属波箔５間に電流路の形成を可能にしつつ
強固に接合するろう付け方法が提案されている。Conventionally, when forming such a honeycomb body 7, a metal flat foil 4 and an insulating film on which an insulating oxide film made of a metal oxide such as alumina (hereinafter referred to as “first metal oxide”) is formed. In the case of forming a junction forming a current path between the metal corrugated foils 5 that do not have a groove, for example, as shown in FIG.
As shown in (a), a strongly reduced metal capable of thermodynamically reducing the oxide of the first metal (hereinafter referred to as "second metal").
Bonding material 1 formed by laminating the foil material 11a and the brazing material foil 11b
1 is placed so that the second metal 11a contacts the metal corrugated foil 4 having the insulating coating 4c and the brazing material foil 11b contacts the metal corrugated foil 5 having no insulating coating, and heated in a non-oxidizing atmosphere. As the brazing material foil melts and the second metal 11a reduces the insulating coating, the second metal oxide 14 is dispersed and precipitated in the brazing material as shown in FIG. 7 (b). A brazing method has been proposed in which when the brazing material reaches the base of the flat metal foil 4, a strong current is formed between the flat metal foil 4 and the corrugated metal foil 5 while firmly joining them.
【０００８】このろう付け方法で、例えば、第一の金属
の酸化物としてアルミナを用いた場合は、第二の金属と
して、Ｚｒ、Ｌｉ、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｓｃ、
Ｙ、および原子番号が５７−７１の希土類元素等のアル
ミナを熱力学的に還元し得る金属あるいはこれらの金属
が含有されている合金が選択される。In this brazing method, for example, when alumina is used as the oxide of the first metal, as the second metal, Zr, Li, Be, Mg, Ca, Sr, Sc,
A metal capable of thermodynamically reducing alumina such as Y and a rare earth element having an atomic number of 57-71, or an alloy containing these metals is selected.
【０００９】このようにして得られる接合部１３は、図
６に示すように中心電極６から金属外筒８側に電流路１
２を形成するように配置されており、この電流路を形成
する接合部１３以外では金属平箔と金属波箔は接合され
ておらず、浄化性能は有するものの高速運転のような厳
しい条件下で使用した場合には、非接合部において、排
ガス流の圧力により金属平箔と金属波箔間にずれを生じ
る、いわゆるテレスコープ現象が生じることがあるた
め、特に応力の集中しやすい外周部および内周部はろう
付けを全面にわたって行い強度を高め、その他の部分を
ガラス封着などで補強接合することが有効である。The joint portion 13 thus obtained has a current path 1 extending from the center electrode 6 to the metal outer tube 8 side as shown in FIG.
2 is formed so that the flat metal foil and the corrugated metal foil are not joined except for the joining portion 13 that forms this current path, and they have purification performance, but under severe conditions such as high-speed operation. When used, a so-called telescope phenomenon may occur in the non-bonded portion due to the pressure of the exhaust gas flow, causing a gap between the flat metal foil and the corrugated metal foil. It is effective to braze the entire surface to increase the strength and to reinforced the other portion by glass sealing or the like.
【００１０】このように中心電極と波箔はろう付けによ
り強固に固定されているのであるが、エンジンの始動、
停止に伴いこハニカム体を含む電気加熱式金属触媒担体
に激しい熱サイクルが加えられる結果、中心電極６に近
接する金属波箔５は、図８に示す正常状態から図９に示
すように、幅方向に破断し通電不能になることがわかっ
た。As described above, the center electrode and the corrugated foil are firmly fixed by brazing.
As a result of the violent thermal cycle being applied to the electrically heated metal catalyst carrier including the honeycomb body due to the stop, the metal corrugated foil 5 close to the center electrode 6 changes from the normal state shown in FIG. 8 to the width shown in FIG. It was found that it was broken in the direction and it became impossible to energize.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、熱サイクル
によって中心電極に近い金属波箔先端部に生ずる破断を
防止して耐久性を向上できる電気加熱式金属触媒担体を
提供するものである。DISCLOSURE OF THE INVENTION The present invention provides an electrically heated metal catalyst carrier capable of improving the durability by preventing breakage at the tip of the metal corrugated foil near the center electrode due to thermal cycling.
【００１２】[0012]
【課題を解決するための手段】本発明の第一の発明は、
金属平箔と金属波箔の少なくとも一方に絶縁被膜を形成
し、この金属平箔と金属波箔を重ね、中心電極に円筒状
に巻きとって得られるハニカム体を金属外筒に収容して
なり、かつ金属平箔と金属波箔を局所接合して電流路を
形成した電気加熱式金属触媒担体において、中心電極に
巻きとられる金属波箔の巻きとり先端部が幅方向で分割
されていることを特徴とする構造耐久性に優れた電気加
熱式金属触媒担体。Means for Solving the Problems The first invention of the present invention is:
An insulating coating is formed on at least one of the metal flat foil and the metal corrugated foil, the metal flat foil and the metal corrugated foil are stacked, and the honeycomb body obtained by winding the center electrode in a cylindrical shape is housed in a metal outer cylinder. In an electrically heated metal catalyst carrier in which a flat metal foil and a metal corrugated foil are locally joined to form a current path, the winding tip of the metal corrugated foil wound around the center electrode is divided in the width direction. An electrically heated metal catalyst carrier with excellent structural durability.
【００１３】第二の発明は、金属平箔と金属波箔の少な
くとも一方に絶縁被膜を形成し、この金属平箔と金属波
箔を重ね、中心電極に円筒状に巻きとって得られるハニ
カム体を金属外筒に収容してなり、かつ金属平箔と金属
波箔を局所接合して電流路を形成した電気加熱式金属触
媒担体において、中心電極に巻きとられる金属波箔の巻
きとり先端部に複数個の貫通孔が設けられていることを
特徴とする構造耐久性に優れた電気加熱式金属触媒担
体。A second invention is a honeycomb body obtained by forming an insulating coating on at least one of a metal flat foil and a metal corrugated foil, stacking the metal flat foil and the metal corrugated foil, and winding the center electrode in a cylindrical shape. In an electrically heated metal catalyst carrier in which a metal flat tube and a metal corrugated foil are locally joined to form a current path, the winding tip of the metal corrugated foil is wound around the center electrode. An electrically heated metal catalyst carrier having excellent structural durability, which is characterized in that a plurality of through holes are provided in the.
【００１４】また、第三の発明は、第一の発明又は第二
の発明において、金属平箔と金属波箔の局所接合が、強
還元金属とろう材を積層してなる接合材を用いてろう付
けされていることを特徴とする構造耐久性に優れた電気
加熱式金属触媒担体である。A third invention is the same as the first invention or the second invention, wherein the local joining of the flat metal foil and the corrugated foil uses a joining material formed by laminating a strong reducing metal and a brazing material. It is an electrically heated metal catalyst carrier having excellent structural durability, which is characterized by being brazed.
【００１５】本発明においては、ハニカム体を形成する
金属波箔の中心電極に近い先端部を幅方向に分割し、熱
サイクルによって生ずる亀裂の伝播を防止することによ
って、あるいはハニカム体を形成する金属波箔の中心電
極に近い先端部に貫通孔を配設することによって熱膨張
を吸収して亀裂の発生伝播を防止することができ、金属
波箔の破断を防止し耐久性を向上することができる。In the present invention, the tip portion of the metal corrugated foil forming the honeycomb body, which is close to the center electrode, is divided in the width direction so as to prevent the propagation of cracks caused by the heat cycle, or the metal forming the honeycomb body. By disposing a through hole at the tip of the corrugated foil near the center electrode, it is possible to absorb thermal expansion and prevent the propagation of cracks, and prevent the metal corrugated foil from breaking and improving its durability. it can.
【００１６】本発明者等は、電気加熱式金属触媒担体を
形成するハニカム体において、中心電極に近い金属波箔
の先端部に生ずる破断現象のメカニズムについて検討
し、次の知見を得た。中心電極が熱応力が大きく昇温速
度が小さいのに対して金属箔は昇温速度が大きく昇温速
度が大きい。このため、中心電極に近接する金属波箔は
図１０（ａ）に示す昇温前の状態から図１０（ｂ）に示
すように、通電発熱によって金属波箔５が膨張し、中心
電極６との接合部に近い金属波箔５に引張り力が作用
し、ついで中心電極６が昇温して膨張した際には、図１
０（ｃ）に示すように金属波箔５に圧縮力が作用する結
果、金属波箔５が座屈し、この時、図１１（ａ）に示す
ように、排ガス流入側の金属波箔５端面部に幅方向の亀
裂１５が発生する。The present inventors have studied the mechanism of the rupture phenomenon occurring at the tip of the metal corrugated foil near the center electrode in the honeycomb body forming the electrically heated metal catalyst carrier, and obtained the following findings. The center electrode has a large thermal stress and a small heating rate, whereas the metal foil has a large heating rate and a large heating rate. Therefore, in the metal corrugated foil close to the center electrode, the metal corrugated foil 5 expands due to energization heat generation from the state before the temperature rise shown in FIG. When a tensile force acts on the metal corrugated foil 5 close to the joint of the center electrode 6 and the center electrode 6 is heated and expanded, as shown in FIG.
As a result of the compressive force acting on the metal corrugated foil 5 as shown in 0 (c), the metal corrugated foil 5 buckles, and at this time, as shown in FIG. A crack 15 in the width direction is generated in the portion.
【００１７】この座屈による亀裂１５は、排ガス流入側
で発生し、従来のように金属波箔５の先端が一枚に形成
されている場合においては、この亀裂１５を起点として
排ガス下流側に亀裂が容易に伝播して、図１１（ｂ）に
示すように金属波箔５は破断１５ｏを生ずる。The crack 15 due to this buckling occurs on the exhaust gas inflow side, and in the case where the tip of the metal corrugated foil 5 is formed as one sheet as in the conventional case, the crack 15 serves as a starting point on the exhaust gas downstream side. The cracks easily propagate and the metal corrugated foil 5 has a break 15o as shown in FIG. 11 (b).
【００１８】本発明者等は、これらの知見に基づき、金
属波箔の破断を防止（抑制）するためには、座屈により
排ガス流入側で発生した亀裂が排ガス下流側に伝播させ
ないことが有効であると認識し、その具体的手段として
本発明を完成するに至った。Based on these findings, the inventors of the present invention effectively prevent cracks generated on the exhaust gas inflow side due to buckling from propagating to the exhaust gas downstream side in order to prevent (suppress) the breakage of the metal corrugated foil. Therefore, the present invention has been completed as a specific means.
【００１９】すなわち、第一の発明では、破断を生じや
すい中心電極に近い金属波箔の先端部を幅方向に複数分
割して亀裂の伝播を防止（抑制）することを特徴とす
る。分割数、分割する先端部領域は、金属波箔の強度、
通電性をあまり損なわないようにする必要があり、分割
数は通常２〜５分割程度が適当である。この分割は必ず
しも均等である必要はない。例えば、亀裂が発生しやす
い排ガス流入側で分割数を多くすることも有効である。
分割する先端部領域は、中心電極を一周する程度の領域
で十分である。That is, the first invention is characterized by preventing (suppressing) the propagation of cracks by dividing the tip of the metal corrugated foil near the center electrode, which is likely to break, into a plurality of parts in the width direction. The number of divisions, the tip area to be divided, the strength of the metal wave foil
It is necessary not to impair the electrical conductivity so much that the number of divisions is usually about 2 to 5. This division does not necessarily have to be even. For example, increasing the number of divisions on the exhaust gas inflow side where cracks are likely to occur is also effective.
It is sufficient for the tip region to be divided to have a region around the center electrode.
【００２０】第二の発明では、破断を生じやすい中心電
極に近い金属波箔の先端部に、亀裂の伝播を防止（抑
制）する貫通孔を配設したことを特徴とする。貫通孔の
大きさ、数、配列、貫通孔を配置する先端部領域は、金
属波箔の強度、担体機能をあまり損なわないようにする
必要があり、通常の場合、貫通孔の大きさは２〜４mm程
度、数は５〜１０個程度を金属波箔の最内周に相当する
部分に、亀裂の伝播を遮断するように例えば規則配列、
千鳥状配列する。貫通孔を配置する先端部領域は、中心
電極を一周する程度の領域で十分である。The second invention is characterized in that a through hole for preventing (suppressing) the propagation of cracks is provided at the tip of the metal corrugated foil which is close to the center electrode where breakage is likely to occur. The size, number and arrangement of the through holes, and the tip end region where the through holes are arranged need to be set so as not to impair the strength of the metal corrugated foil and the carrier function. Normally, the size of the through holes is 2 Approximately 4 mm, the number of which is about 5 to 10 is arranged in a portion corresponding to the innermost circumference of the metal corrugated foil so as to prevent crack propagation, for example, a regular arrangement,
Staggered arrangement. It is sufficient that the tip end region in which the through hole is arranged is a region around the center electrode.
【００２１】[0021]
【発明の実施の形態】以下に本発明を図１〜図２に示す
実施態様例に基づいて説明する。図１は、本発明を採用
した電気加熱式金属触媒担体を示しており、基本的に
は、前記図６に示すような構成を有するものである。し
たがって、ここでは、本発明の要部、すなわち、中心電
極に接合する金属波箔の先端部の構造について、その概
要を説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below based on the embodiment examples shown in FIGS. FIG. 1 shows an electrically heated metal catalyst carrier adopting the present invention, and basically has a structure as shown in FIG. Therefore, the outline of the main part of the present invention, that is, the structure of the tip of the metal wave foil joined to the center electrode will be described here.
【００２２】図１（ａ）において、６は中心電極、４は
この中心電極に金属波箔５と重ねて巻き取りハニカム体
を形成する金属平箔である。ここで用いた金属波箔５の
先端部は、中心電極６をほぼ一周する範囲で、その排ガ
ス流入側で微小スリット１６ａを介して５ａ部と５ｂ部
に２分割され、それぞれその先端部は、中心電極６の外
周面に接合されている。In FIG. 1 (a), 6 is a center electrode, and 4 is a flat metal foil on which a metal corrugated foil 5 is laminated to form a rolled honeycomb body. The tip portion of the metal corrugated foil 5 used here is divided into two portions, 5a portion and 5b portion, through a minute slit 16a on the exhaust gas inflow side within a range that substantially circles the center electrode 6, and each tip portion is It is joined to the outer peripheral surface of the center electrode 6.
【００２３】本発明の電気加熱式金属触媒担体は、従来
と同様、金属波箔５と金属平箔４を重ねて中心電極６の
回りに巻き回し、中心部側から外周側に局所接合して電
流路を形成しながら円筒状のハニカム体を形成し、これ
を外部電極に接続した金属外筒に通電可能に収容・接合
することによって構成される。In the electrically heated metal catalyst carrier of the present invention, the metal corrugated foil 5 and the flat metal foil 4 are superposed and wound around the center electrode 6 as in the conventional case, and locally bonded from the center side to the outer periphery side. It is configured by forming a cylindrical honeycomb body while forming a current path, and accommodating and joining this in a metal outer cylinder connected to an external electrode so as to be able to conduct electricity.
【００２４】この実施例においては、中心電極に接合し
た金属波箔の先端部は、幅方向に２分割されているの
で、熱サイクルによって排ガス流入側で中心電極に近接
する金属波箔の５ａ部に亀裂が発生しても、図２に示す
ように５ｂ部に伝播することを防止することができる。
したがって、５ａ部が破断することがあっても、５ｂ部
で強度、通電性を維持することができ、結果として耐久
性を向上することができる。In this embodiment, since the tip of the metal corrugated foil joined to the center electrode is divided into two in the width direction, the 5a portion of the metal corrugated foil which is close to the center electrode on the exhaust gas inflow side due to the heat cycle. Even if a crack is generated, it can be prevented from propagating to the portion 5b as shown in FIG.
Therefore, even if the portion 5a is broken, the strength and electric conductivity can be maintained at the portion 5b, and as a result, the durability can be improved.
【００２５】図１（ｂ）は、本発明の他の実施態様例を
示したもので、この例では、中心電極６に接合される金
属波箔５の先端部に、複数列の貫通孔１７からなる貫通
孔群１７ａ、１７ｂを千鳥状に配し、中心電極６に近接
する金属波箔５の熱膨張を吸収して、中心電極６の昇温
による生ずる圧縮力による座屈を軽微なものとするとと
もに、図２に示すように、排ガス流入側で、亀裂１５が
発生しても２列の貫通孔列１７ａ、１７ｂで遮断され、
排ガス下流側に伝播するのを防止することができ、金属
波箔の破断を防止し耐久性を向上することができる。FIG. 1 (b) shows another embodiment of the present invention. In this example, a plurality of rows of through holes 17 are formed at the tip of the metal corrugated foil 5 joined to the center electrode 6. The through hole groups 17a and 17b made of zigzag are arranged in a zigzag pattern to absorb the thermal expansion of the metal corrugated foil 5 adjacent to the center electrode 6 and to minimize the buckling due to the compressive force generated by the temperature rise of the center electrode 6. In addition, as shown in FIG. 2, even if the crack 15 occurs on the exhaust gas inflow side, it is blocked by the two through hole rows 17a and 17b,
It is possible to prevent the exhaust gas from propagating to the downstream side, prevent the metal corrugated foil from breaking, and improve the durability.
【００２６】また図１（ｃ）は、本発明の更に別の他の
実施態様例を示したもので、この例では、中心電極６に
接合される金属波箔５の排ガス流入側および排ガス下流
側の先端部を、微小スリット１６ｂ、１６ｃを配して３
分割して、排ガス流入側、排ガス下流側から亀裂が発生
しても排ガス下流側あるいは上流側の主要部に伝播する
のを防止することができ、金属波箔主要部の破断を防止
し耐久性を向上することができる。FIG. 1 (c) shows still another embodiment of the present invention. In this example, the exhaust gas inflow side and the exhaust gas downstream side of the metal corrugated foil 5 joined to the center electrode 6 are shown. 3 on the tip of the side by arranging the micro slits 16b and 16c.
Even if cracks occur from the exhaust gas inflow side and exhaust gas downstream side, they can be prevented from propagating to the main part of the exhaust gas downstream side or upstream side, and the metal corrugated foil main part can be prevented from breaking and durability. Can be improved.
【００２７】[0027]
【実施例】図１（ａ）に示す実施態様例に示した本発明
の電気加熱式金属触媒担体を用いて、実際の高温排ガス
流下において耐久性を試験した。なお、本発明の実施例
ａにおいては、図１（ａ）に示したような構成のもの
で、４は１１００℃の大気中で６０分の酸化処理を施
し、表面に厚さ１μｍ程度の酸化膜（アルミナ）を生成
させた幅１７μｍ、厚さ５０μｍのＦｅ−２０Ｃｒ−５
Ａｌ系のステンレス箔であって、先端部をａ部とｂ部に
分割してある。ａ部、ｂ部の幅はそれぞれ８．５mmで先
端から３０mmにわたって分割した。EXAMPLE Using the electrically heated metal catalyst carrier of the present invention shown in the embodiment example shown in FIG. 1 (a), durability was tested under actual high temperature exhaust gas flow. In the embodiment a of the present invention, the structure shown in FIG. 1A is used, and 4 is subjected to an oxidation treatment for 60 minutes in the atmosphere at 1100 ° C., and the surface is oxidized to a thickness of about 1 μm. Fe-20Cr-5 having a width of 17 μm and a thickness of 50 μm formed with a film (alumina)
This is an Al-based stainless steel foil, the tip of which is divided into a portion and a portion b. The widths of part a and part b were 8.5 mm, respectively, and were divided over 30 mm from the tip.
【００２８】また、実施例ｂにおいては、図１（ｂ）に
示すような構成のもので、金属波箔は、先端部に２列の
貫通孔を有する。貫通孔の数は各列６個、長さは２．５
mm、各列の貫通孔の中心間距離は５mm、列間距離は５mm
である。In Example b, the metal corrugated foil has a structure as shown in FIG. 1 (b) and has two rows of through holes at the tip. The number of through holes is 6 in each row and the length is 2.5
mm, distance between centers of through holes in each row is 5 mm, distance between rows is 5 mm
It is.
【００２９】５は、絶縁被膜を形成していないＦｅ−２
０Ｃｒ−５Ａｌ系のステンレス箔である。この波箔の波
ピッチは２．５mm、波高さは１．３mmである。中心電極
としては直径８mmのＳＵＳ３０４製の棒材を用い、金属
平箔４と金属波箔５とは溶接で固定した。No. 5 is Fe-2 having no insulating film formed.
It is a 0Cr-5Al type stainless steel foil. The wave pitch of this corrugated foil is 2.5 mm and the wave height is 1.3 mm. As the center electrode, a rod made of SUS304 having a diameter of 8 mm was used, and the flat metal foil 4 and the corrugated metal foil 5 were fixed by welding.
【００３０】ついで、中心電極６に金属平箔４と金属波
箔５を巻き付けてハニカム体７を形成した。その際、螺
旋状の電流路を形成するため、接合部１３を形成しよう
とする位置に予め、長さ１２mm、幅１mm、厚さ５μｍの
Ｚｒ箔１１ａと厚さ２５μｍのＢＮｉ−５規格のろう材
箔１１ｂからなる接合材１１を、Ｚｒ箔１１ａが金属波
箔５に接するように配置しながら巻き込んだ。また、補
強部を形成するために、幅１７mmの接合材１１を用い
て、内周部、外周部それぞれ５層分にわたって全面ろう
付けするために、接合材１１を金属平箔と金属波箔間に
全面的に配置した。Next, the flat metal foil 4 and the corrugated metal foil 5 were wound around the center electrode 6 to form the honeycomb body 7. At this time, in order to form a spiral current path, a Zr foil 11a having a length of 12 mm, a width of 1 mm and a thickness of 5 μm and a solder having a BNi-5 standard of a thickness of 25 μm are preliminarily provided at the position where the joint portion 13 is to be formed. The bonding material 11 made of the material foil 11b was wound while being arranged so that the Zr foil 11a was in contact with the metal corrugated foil 5. Further, in order to form the reinforcing portion, the bonding material 11 having a width of 17 mm is used, and in order to braze the entire inner peripheral portion and the outer peripheral portion for five layers, the bonding material 11 is used between the metal flat foil and the metal corrugated foil. Placed all over.
【００３１】ハニカム体７を形成した後、外筒８をハニ
カム体の外側に配置し、しかるのちに１２００℃で１５
分間、１０-4Torrの真空炉で加熱処理してろう付けし
た。加熱処理後、中心電極を外筒と絶縁しつつ外筒の外
側へ取り出した。その後各ハニカム体の電流路領域に、
Ａｌ2 Ｏ3 −ＭｎＯ−ＳｉＯ2 系のガラス粉末を散布
し、大気中１１００℃で６０分間焼き付け処理した。After the honeycomb body 7 is formed, the outer cylinder 8 is placed outside the honeycomb body, and then at 1200 ° C. for 15 minutes.
It was heat-treated and brazed in a vacuum furnace at 10 −4 Torr for 10 minutes. After the heat treatment, the center electrode was taken out of the outer cylinder while being insulated from the outer cylinder. After that, in the current path area of each honeycomb body,
Al 2 O 3 —MnO—SiO 2 type glass powder was sprinkled and baked at 1100 ° C. for 60 minutes in the air.
【００３２】耐久試験は、エンジンにおける耐久試験
（排気量２０００ｃｃのエンジンを毎分５０００回転で
運転し、排ガス温度を約８５０℃に１０分間保ち、その
後２０分間停止するサイクルを繰り返し破壊するかどう
かを調査）により評価した。比較例（従来例）として、
波箔を分割していない、あるいは貫通孔を有さない電気
加熱式金属触媒担体についても評価した。The endurance test was carried out by checking the endurance test on the engine (operating an engine with a displacement of 2000 cc at 5000 rpm, keeping the exhaust gas temperature at about 850 ° C. for 10 minutes, and then stopping for 20 minutes. Survey). As a comparative example (conventional example),
An electrically heated metal catalyst carrier without dividing the corrugated foil or having a through hole was also evaluated.
【００３３】本発明の実施例ａによる場合、５００回の
排ガス流入テストでも中心電極に近接する金属波箔の先
端部の５ａ部に、排ガス流入側からの破断が認められた
が５ｂ部には亀裂の発生は全く認められなかった。According to Example a of the present invention, even after 500 exhaust gas inflow tests, breakage from the exhaust gas inflow side was observed in the 5a part of the tip of the metal corrugated foil close to the center electrode, but in the 5b part. No cracks were found at all.
【００３４】また、実施例ｂによる場合、５００回の排
ガス流入テストでも中心電極に近接する金属波箔の先端
部に、排ガス流入側からの亀裂の発生が認められ、その
先端は排ガス流入側から貫通孔列に達しているものもあ
ったが、それより先への亀裂の伝播は認められなかっ
た。Also, in the case of Example b, cracks were observed from the exhaust gas inflow side at the tip of the metal corrugated foil close to the center electrode even after 500 exhaust gas inflow tests, and the tip was observed from the exhaust gas inflow side. Some of them reached the through-hole row, but no cracks were propagated beyond that.
【００３５】これに対して従来例による場合は、５００
回の排ガス流入テストで中心電極に近接する金属波箔の
先端部に、に排ガス流入側からの亀裂の発生して排ガス
下流側の端面近傍まで達しており破断寸前であった。On the other hand, in the case of the conventional example, 500
In the exhaust gas inflow test conducted twice, a crack was generated from the exhaust gas inflow side at the tip of the metal corrugated foil that was close to the center electrode and reached the vicinity of the end face on the exhaust gas downstream side, which was on the verge of fracture.
【００３６】このように、本発明によれば、金属波箔の
中心電極に近い先端部に生ずる熱膨張を吸収して、亀裂
の発生を抑制するとともに、亀裂の伝播を防止すること
ができ、金属波箔の破断を防止し耐久性を向上すること
ができることを確認できた。As described above, according to the present invention, it is possible to absorb the thermal expansion generated at the tip portion of the metal corrugated foil near the center electrode, suppress the occurrence of cracks, and prevent the propagation of cracks. It was confirmed that the metal corrugated foil could be prevented from breaking and the durability could be improved.
【００３７】[0037]
【発明の効果】本発明においては、ハニカム体を形成す
る金属波箔の中心電極に近い先端部を幅方向に分割し、
熱サイクルによって生ずる亀裂の伝播を防止することに
よって、あるいはハニカム体を形成する金属波箔の中心
電極に近い先端部に貫通孔を配設することによって熱膨
張を吸収して亀裂の発生伝播を防止することができ、金
属波箔の破断を防止し耐久性を向上することができる。In the present invention, the tip portion of the metal corrugated foil forming the honeycomb body near the center electrode is divided in the width direction,
By preventing the propagation of cracks caused by thermal cycling or by arranging a through hole at the tip of the metal corrugated foil forming the honeycomb body near the center electrode, thermal expansion is absorbed and crack propagation is prevented. It is possible to prevent breakage of the metal corrugated foil and improve durability.
【図１】（ａ）図は本発明の実施例を示すもので、中心
電極に巻き取る金属波箔の先端部構造を示す立体概要説
明図、（ｂ）図は本発明の他の実施例を示すもので、中
心電極に巻き取る金属波箔の先端部構造を示す立体概要
説明図、（ｃ）図は本発明のその他の実施例を示すもの
で、中心電極に巻き取る金属波箔の先端部構造を示す立
体概要説明図。FIG. 1 (a) shows an embodiment of the present invention, and is a three-dimensional schematic explanatory view showing the tip structure of a metal corrugated foil wound around a center electrode, and FIG. 1 (b) shows another embodiment of the present invention. FIG. 3C is a three-dimensional schematic explanatory view showing the tip structure of the metal corrugated foil wound around the center electrode, and FIG. 7C shows another embodiment of the present invention. FIG. 3 is a three-dimensional schematic explanatory view showing the tip structure.
【図２】本発明の実施例の効果説明図。FIG. 2 is an explanatory diagram of effects of the embodiment of the present invention.
【図３】従来の電気加熱式触媒装置例を示す側断面概要
説明図。FIG. 3 is a side cross-sectional schematic explanatory view showing an example of a conventional electrically heated catalyst device.
【図４】従来の電気加熱式触媒担体用のハニカム体の形
成方法例を示す立体概要説明図。FIG. 4 is a three-dimensional schematic explanatory view showing an example of a conventional method for forming a honeycomb body for an electrically heated catalyst carrier.
【図５】従来の電気加熱式触媒担体用のハニカム体端面
の平面概要説明図。FIG. 5 is a schematic plan view of an end face of a honeycomb body for a conventional electrically heated catalyst carrier.
【図６】従来の電気加熱式触媒担体用のハニカム体にお
ける電流路形成例を示す端面の平面概要説明図。FIG. 6 is a schematic plan view of an end face showing an example of forming a current path in a conventional honeycomb body for an electrically heated catalyst carrier.
【図７】（ａ）図は、従来の電気加熱式触媒担体用のハ
ニカム体に電流路形成するための接合例における接合材
の配置例を示す正面概要説明図。（ｂ）図は、（ａ）図
の接合材配置例によって得られる接合状態例を示す正面
概要説明図。[Fig. 7] Fig. 7 (a) is a front schematic explanatory view showing an arrangement example of a bonding material in a bonding example for forming a current path in a conventional honeycomb body for an electrically heated catalyst carrier. FIG. 6B is a schematic front view showing a joining state example obtained by the joining material arrangement example of FIG.
【図８】従来の電気加熱式触媒担体用のハニカム体にお
ける中心電極近接部端面の部分平面概要説明図。FIG. 8 is a schematic partial plan view of an end face of a central electrode proximity portion in a conventional honeycomb body for an electrically heated catalyst carrier.
【図９】従来の電気加熱式触媒担体用のハニカム体にお
ける中心電極近接部端面の金属波箔破断の部分平面概要
説明図。FIG. 9 is a schematic partial plan view of a broken metal wave foil on the end face of the central electrode neighboring portion in the conventional honeycomb body for an electrically heated catalyst carrier.
【図１０】従来の電気加熱式触媒担体用のハニカム体の
中心電極近接部での金属波箔破断のメカニズムを示す平
面概要説明図で、（ａ）図はハニカム体昇温前の状態
を、（ｂ）図はハニカム体昇温時（ハニカム体に引張り
力作用時）の状態を、（ｃ）図は中心電極昇温時（ハニ
カム体に圧縮力作用時）の状態をそれぞれ示す。FIG. 10 is a schematic plan view showing the mechanism of metal wave foil breakage in the vicinity of the central electrode of the honeycomb body for a conventional electrically heated catalyst carrier, wherein (a) shows the state before the temperature rise of the honeycomb body, The figure (b) shows the state when the temperature of the honeycomb body is raised (when the tensile force acts on the honeycomb body), and the figure (c) shows the state when the temperature of the center electrode is raised (when the compressive force acts on the honeycomb body).
【図１１】従来の電気加熱式触媒担体用のハニカム体の
中心電極近接部での金属波箔亀裂−破断のメカニズムを
示す立体概要説明図で、（ａ）図は亀裂の発生状態を示
し、（ｂ）図は破断状態を示す。FIG. 11 is a three-dimensional schematic explanatory view showing the mechanism of metal wave foil crack-breakage in the vicinity of the central electrode of the honeycomb body for the conventional electrically heated catalyst carrier, FIG. (B) The figure shows a fractured state.
１ 筒状ケーシング ２ 電気加熱式金属触媒担体 ３ 主触媒担体 ４ 金属平箔 ５ 金属波箔 ５ａ、５ｂ、５ｃ 金属箔の先端分割部 ５ｔ 絶縁被膜 ６ 中心電極 ７ ハニカム体 ８ 外筒 ９ 外部電極 １０ 電源 １１ 接合材 １１ａ 第二の金属（箔） １１ｂ ろう材箔 １２ 電流路 １３ 接合部 １４ 第一の金属の酸化物 １５ 亀裂 １５ｏ 破断 １６ａ、１６ｂ、１６ｃ 微小スリット １７ 貫通孔 １７ａ、１７ｂ 貫通孔群 DESCRIPTION OF SYMBOLS 1 Cylindrical casing 2 Electric heating type metal catalyst carrier 3 Main catalyst carrier 4 Metal flat foil 5 Metal corrugated foil 5a, 5b, 5c Tip division part of metal foil 5t Insulating film 6 Center electrode 7 Honeycomb body 8 Outer cylinder 9 External electrode 10 Power supply 11 Joining material 11a Second metal (foil) 11b Brazing material foil 12 Current path 13 Joining portion 14 First metal oxide 15 Crack 15o Break 16a, 16b, 16c Small slit 17 Through hole 17a, 17b Through hole group
───────────────────────────────────────────────────── フロントページの続き (72)発明者 加古 卓三 東京都千代田区大手町２−６−３ 新日本 製鐵株式会社内 (72)発明者 中島 郁二 千葉県君津市君津１番地 新日本製鐵株式 会社君津製鐵所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takuzo Kako 2-6-3 Otemachi, Chiyoda-ku, Tokyo Within Nippon Steel Co., Ltd. (72) Ikuji Nakajima 1 Kimitsu, Kimitsu-shi, Chiba New Japan Kimitsu Steel Works, Ltd.
Claims (3)
絶縁被膜を形成し、この金属平箔と金属波箔を重ね、中
心電極に円筒状に巻きとって得られるハニカム体を金属
外筒に収容してなり、かつ金属平箔と金属波箔を局所接
合して電流路を形成した電気加熱式金属触媒担体におい
て、中心電極に巻きとられる金属波箔の巻きとり先端部
が幅方向で分割されていることを特徴とする構造耐久性
に優れた電気加熱式金属触媒担体。1. A metal outer cylinder comprising a honeycomb body obtained by forming an insulating coating on at least one of a metal flat foil and a metal corrugated foil, stacking the metal flat foil and the metal corrugated foil, and winding the honeycomb body around the center electrode in a cylindrical shape. In the electrically heated metal catalyst carrier in which the flat metal foil and the metal corrugated foil are locally joined to form a current path, the winding end of the metal corrugated foil wound around the center electrode is wide in the width direction. An electrically heated metal catalyst carrier having excellent structural durability, which is characterized by being divided.
絶縁被膜を形成し、この金属平箔と金属波箔を重ね、中
心電極に円筒状に巻きとって得られるハニカム体を金属
外筒に収容してなり、かつ金属平箔と金属波箔を局所接
合して電流路を形成した電気加熱式金属触媒担体におい
て、中心電極に巻きとられる金属波箔の巻きとり先端部
に複数個の貫通孔が設けられていることを特徴とする構
造耐久性に優れた電気加熱式金属触媒担体。2. A honeycomb body obtained by forming an insulating coating on at least one of a metal flat foil and a metal corrugated foil, stacking the metal flat foil and the metal corrugated foil, and winding the honeycomb body around the center electrode in a cylindrical shape. In the electrically heated metal catalyst carrier, which is housed in a metal flat foil and a metal corrugated foil and locally formed a current path, a plurality of metal corrugated foils are wound around the center electrode. An electrically heated metal catalyst carrier having excellent structural durability, which is provided with through holes.
元金属とろう材を積層してなる接合材を用いてろう付け
されていることを特徴とする請求項１又は２記載の構造
耐久性に優れた電気加熱式金属触媒担体。3. The local joining of the flat metal foil and the metal corrugated foil is brazed by using a joining material formed by laminating a strong reducing metal and a brazing material. An electrically heated metal catalyst carrier with excellent structural durability.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7202340A JPH0947666A (en) | 1995-08-08 | 1995-08-08 | Electric heating type metallic catalytic carrier with excellent structural durability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7202340A JPH0947666A (en) | 1995-08-08 | 1995-08-08 | Electric heating type metallic catalytic carrier with excellent structural durability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0947666A true JPH0947666A (en) | 1997-02-18 |
Family
ID=16455925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7202340A Withdrawn JPH0947666A (en) | 1995-08-08 | 1995-08-08 | Electric heating type metallic catalytic carrier with excellent structural durability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0947666A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6761980B2 (en) * | 2000-11-15 | 2004-07-13 | Nissan Motor Co., Ltd. | Metallic catalyst carrier |
| JP2011520062A (en) * | 2008-05-07 | 2011-07-14 | エミテック ゲゼルシヤフト フユア エミツシオンス テクノロギー ミツト ベシユレンクテル ハフツング | Honeycomb body formed of metal foil and method for manufacturing honeycomb body |
| JP2013198887A (en) * | 2012-02-24 | 2013-10-03 | Denso Corp | Honeycomb structure body |
-
1995
- 1995-08-08 JP JP7202340A patent/JPH0947666A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6761980B2 (en) * | 2000-11-15 | 2004-07-13 | Nissan Motor Co., Ltd. | Metallic catalyst carrier |
| JP2011520062A (en) * | 2008-05-07 | 2011-07-14 | エミテック ゲゼルシヤフト フユア エミツシオンス テクノロギー ミツト ベシユレンクテル ハフツング | Honeycomb body formed of metal foil and method for manufacturing honeycomb body |
| US8491846B2 (en) | 2008-05-07 | 2013-07-23 | Emitec Gesellschaft Fuer Emissionstechnologie Mbh | Honeycomb body formed of metallic foils, method for the production thereof and motor vehicle |
| JP2013198887A (en) * | 2012-02-24 | 2013-10-03 | Denso Corp | Honeycomb structure body |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20021105 |