JP2639993B2 - Manufacturing method of metal carrier - Google Patents
Manufacturing method of metal carrierInfo
- Publication number
- JP2639993B2 JP2639993B2 JP1006289A JP628989A JP2639993B2 JP 2639993 B2 JP2639993 B2 JP 2639993B2 JP 1006289 A JP1006289 A JP 1006289A JP 628989 A JP628989 A JP 628989A JP 2639993 B2 JP2639993 B2 JP 2639993B2
- Authority
- JP
- Japan
- Prior art keywords
- metal carrier
- honeycomb
- outer cylinder
- honeycomb portion
- flat plate
- 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.)
- Expired - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 38
- 239000002184 metal Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000005219 brazing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 10
- 238000005304 joining Methods 0.000 claims description 5
- 238000009792 diffusion process Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000969 carrier Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 238000012733 comparative method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は自動車の排気ガス浄化用触媒などに使用する
メタル担体の製造方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing a metal carrier used for a catalyst for purifying exhaust gas of automobiles and the like.
メタル担体はセラミックス担体に比べて昇温特性や耐
衝撃性に優れている等の利点を有するので、近年、例え
ば自動車などの車両用の排気ガス浄化用触媒の担体とし
て使用されている。メタル担体は通常ハニカム部を外筒
に収納した構造を有し、前記ハニカム部は例えば金属の
薄板からなる平板と波板とを交互に重ねて製造する。Metal carriers have advantages such as superior temperature-rise characteristics and impact resistance as compared with ceramic carriers, and have recently been used as carriers for exhaust gas purifying catalysts for vehicles such as automobiles. The metal carrier usually has a structure in which a honeycomb portion is housed in an outer cylinder, and the honeycomb portion is manufactured by alternately stacking a flat plate made of a thin metal plate and a corrugated plate, for example.
それ故、ハニカム部と外筒との接合が問題となる。例
えばアメリカ合衆国特許第4300956号明細書には、アル
ミニウムを含む合金からなる平板と波板とを重ねて巻回
し、次いで約1000℃ないし約1200℃の範囲の温度で約0.
5ないし５ミクロ気圧の水素雰囲気下で加熱することに
より平板と波板との接触部を拡散接合するメタル担体の
ハニカム部の製造方法が開示されている。又、接合には
前記拡散接合の外に例えばニッケル系ろう材などを用い
るろう付けがある。Therefore, joining of the honeycomb portion and the outer cylinder becomes a problem. For example, in U.S. Pat.No. 4,309,096, a flat plate made of an alloy containing aluminum and a corrugated plate are wound around one another and then heated at a temperature in the range of about 1000.degree. C. to about 1200.degree.
A method of manufacturing a honeycomb portion of a metal carrier in which a contact portion between a flat plate and a corrugated plate is diffusion-bonded by heating in a hydrogen atmosphere at a pressure of 5 to 5 micro-atmosphere is disclosed. For the joining, there is a brazing using, for example, a nickel-based brazing material in addition to the diffusion joining.
メタル担体を拡散接合で一体化する場合、強固な拡散
接合を得るには材料成分に0.5重量％以上のアルミニウ
ムが必要である。しかし例えばクラッド板としてアルミ
ニウムを添加した鋼板はアルミニウムと鋼板との溶接部
の延性が乏しく、後加工が難しいためメタン担体の外筒
としては使用しにくい。然して、メタル担体の外筒とし
てアルミニウムを含まない通常のステンレス板を使用す
る場合には、外筒と内部のハニカム部とはその接触部に
おいて十分な拡散接合強度が得られない。When a metal carrier is integrated by diffusion bonding, aluminum must be 0.5% by weight or more as a material component to obtain strong diffusion bonding. However, for example, a steel sheet to which aluminum is added as a clad plate is poor in ductility of a welded portion between aluminum and the steel sheet, and is difficult to perform post-processing, so that it is difficult to use it as an outer cylinder of a methane carrier. However, when a normal stainless steel plate containing no aluminum is used as the outer cylinder of the metal carrier, a sufficient diffusion bonding strength cannot be obtained at the contact portion between the outer cylinder and the internal honeycomb portion.
一方、ろう付けによって外筒とハニカム部及びハニカ
ム部の平板と波板とを、端面のみで又は長さ方向全体で
接合する場合には、ろう付け部においてろう材と母材の
化学成分が相互に拡散し高温耐酸化性を損うため、例え
ば排気ガス浄化用触媒として使用した場合、排気ガスが
主に通過し触媒成分と反応するメタル担体中心部（ハニ
カム部の中央部）が異常酸化を起す不具合があった。On the other hand, when the outer cylinder and the honeycomb portion and the flat plate of the honeycomb portion and the corrugated plate are joined by brazing only at the end faces or over the entire length direction, the chemical components of the brazing material and the base material are mutually changed at the brazing portion. For example, when used as an exhaust gas purifying catalyst, the central part of the metal carrier (the central part of the honeycomb part) through which the exhaust gas mainly passes and reacts with the catalyst components may cause abnormal oxidation. There was a problem that occurred.
本発明は前記従来技術における問題点を解決するため
のものであり、その目的とするところはステンレス鋼製
の外筒を使用した場合でも外筒とハニカム部とが強固に
接合し、且つハニカム部の中央部においても排気ガス浄
化用触媒として使用中異常酸化反応を起さない耐久性に
優れたメタル担体を容易に得ることができる製造方法を
提供することにある。The present invention has been made to solve the problems in the conventional art, and has an object to firmly join the outer cylinder and the honeycomb portion even when a stainless steel outer cylinder is used, and to form the honeycomb portion. It is an object of the present invention to provide a production method capable of easily obtaining a metal carrier having excellent durability which does not cause an abnormal oxidation reaction during use as an exhaust gas purifying catalyst even in a central portion of the catalyst.
すなわち本発明のメタル担体の製造方法は、耐熱金属
製の平板と波板とを重ねて巻回した構造を有するハニカ
ム部を、耐熱金属製の外筒に収納してなるメタル担体を
製造するにあたり、ハニカム部と外筒との接触部並びに
ハニカム部の最外周及びその近傍の層合わせて数層の平
板と波板との接触部をろう付けし、ハニカム部の残りの
層の平板と波板との接触部を拡散接合することを特徴と
する。That is, the method for producing a metal carrier according to the present invention relates to a method for producing a metal carrier in which a honeycomb portion having a structure in which a heat-resistant metal flat plate and a corrugated sheet are stacked and wound, is housed in a heat-resistant metal outer cylinder. Then, the contact portion between the flat portion and the corrugated plate of the honeycomb portion and the outer cylinder and the outermost periphery of the honeycomb portion and the layer in the vicinity thereof are brazed, and the flat portion of the remaining layer of the honeycomb portion and the corrugated plate are brazed. And diffusion bonding of a contact portion with the contact.
耐熱金属としては例えばステンレススチールなどの慣
用の材料を使用することができる。外筒はアルミニウム
を含まないステンレスを使用した方が加工性が良いので
好ましい。ハニカム部の平板と波板はクラッド、メッ
キ、蒸着又は合金化などによりアルミニウムを例えば0.
5重量％以上含むステンレススチールを使用した方が拡
散接合が強固となるのでよい。Conventional materials such as stainless steel can be used as the heat-resistant metal. It is preferable to use stainless steel that does not contain aluminum as the outer cylinder has better workability. The flat plate and corrugated plate of the honeycomb portion are made of aluminum, for example, by cladding, plating, vapor deposition or alloying.
The use of stainless steel containing 5% by weight or more is preferable because the diffusion bonding becomes stronger.
外筒やハニカム部の大きさや形状は目的に応じて適宜
選択する。The size and shape of the outer cylinder and the honeycomb portion are appropriately selected according to the purpose.
ろう付けに使用するろう材はニッケル系ろう材などの
慣用のものであってよく、これをろう付けすべき部位に
塗布する。The brazing material used for brazing may be a conventional brazing material such as a nickel-based brazing material, which is applied to a portion to be brazed.
ハニカム部における層とは、波板と平板とを対にした
ものを言い、例えば最外周の波板とその内側の平板とを
対にしたものが最外周層である。本発明において、数層
とは５〜６層程度までを言う。通常２〜３層まででよ
い。それ故、通常例えば外側から２番目（及び３番目）
の層では波板とその層の平板及び前の層の平板との接触
部をろう付けする。又、この場合、ろう付けに加えて拡
散接合を併用するとより一層強固に接合することができ
るのでよい。外側から（３番目又は）４番目以降の層で
は平板と波板との接着部は拡散接合のみによって接合す
る。The layer in the honeycomb portion refers to a pair of a corrugated plate and a flat plate. For example, a pair of a corrugated plate at the outermost periphery and a flat plate inside the pair is the outermost peripheral layer. In the present invention, several layers mean up to about 5 to 6 layers. Usually it may be up to two or three layers. Therefore, usually eg the second (and third) from the outside
In the layer (2), the contact portions between the corrugated sheet, the plate of the layer and the plate of the previous layer are brazed. Further, in this case, if diffusion bonding is used in addition to brazing, the bonding can be further strengthened. In the (third or) fourth and subsequent layers from the outside, the bonding portion between the flat plate and the corrugated plate is bonded only by diffusion bonding.
外筒とハニカム部との間には応力が生ずるので、外筒
をアルミニウムを含まないステンレススチール製とした
場合には拡散接合では十分な接合強度が得られない。そ
れ故、ハニカム部と外筒との接触部並びにハニカム部の
最外周及びその近傍の層合わせて数層の平板と波板との
接触部をろう付けすることにより十分な接合強度を得
る。又、排気ガス浄化用触媒として使用した場合、メタ
ル担体のハニカム部の外周部は排気ガスの流通量が中央
部ほどには多くないため、外周部をろう付けしても異常
酸化反応に起因するメタル担体の損傷が起らず、耐久性
が向上する。Since stress is generated between the outer cylinder and the honeycomb portion, when the outer cylinder is made of stainless steel containing no aluminum, sufficient bonding strength cannot be obtained by diffusion bonding. Therefore, sufficient bonding strength can be obtained by brazing the contact portion between the honeycomb portion and the outer cylinder, and the contact portion between the flat plate and the corrugated plate in several layers including the outermost periphery of the honeycomb portion and the layers in the vicinity thereof. Also, when used as an exhaust gas purifying catalyst, the outer peripheral portion of the honeycomb portion of the metal carrier has a smaller flow rate of exhaust gas than the central portion. The metal carrier is not damaged, and the durability is improved.
以下の実施例及び比較例において本発明を更に詳細に
説明する。なお、本発明は下記実施例に限定されるもの
ではない。The present invention will be described in more detail in the following Examples and Comparative Examples. Note that the present invention is not limited to the following examples.
アルミニウム５重量％を含むステンレス製の厚さ0.05
mmの平板２と同じ材料からなる波板３（凸の数:4個/c
m）とを重ねて巻回して、直径70mm、高さ130mmのハニカ
ム部１を製造し、これをステンレス製の外径73mm、内径
70mm、高さ130mmの外筒４内に挿入した。次いで真空炉
中で1200℃で60分加熱保持することにより拡散接合し
た。次いでニッケル系ろう材BNi−５（20Cr−10Si−Bal
Ni）をハニカム部１と外筒４との接触部５及び第１層〜
第３層の平板２と波板３との接触部6,7,8に塗布し（端
面から流下させる）、真空炉中で1150〜1200℃で５分間
加熱し、ろう付けしてメタル担体を得た。第１図は得ら
れたメタル担体を一端面側から見た図である。第２図は
本発明の方法によって得たメタル担体のろう付け部分を
示す説明図である。すなわち、第２図はメタル担体を長
さ方向に沿って切断した状態を示し、図中の斜線の部分
がろう付け層９である。第３図に第１図の部分拡大図を
示す。外筒４に対してハニカム部１の方が熱膨張係数が
大きい場合、拡散接合のみではハニカム部１が収縮し、
第４図のようにハニカム部１の最外周部に応力が集中し
て接合部が剥され隙間10が生ずるか又は波板３の凸部が
波状から三角形状に変形してしまう。然して、外筒４と
ハニカム部１との接合部のみを拡散接合に加えてろう付
けしても、ハニカム部１の収縮による応力緩和はできな
いため、最外周波板３と最外周平板２の間で剥れる。第
５図にメタル担体において、最外周及びその近傍層２〜
３層を拡散接合及びろう付けした場合（本発明方法）
と、拡散接合のみ又は外筒とハニカム部とを拡散接合及
びろう付けした場合（従来方法及び比較方法）との、ハ
ニカム部の層数と応力との関係を示す。図から明らかな
ように、本発明方法によって得られたメタル担体におい
ては、応力は最外周層でも大きくはならないことが判
る。Stainless steel thickness 0.05 containing 5% by weight of aluminum
mm corrugated plate 3 made of the same material as plate 2 (number of protrusions: 4 / c
m) to form a honeycomb part 1 having a diameter of 70 mm and a height of 130 mm, which is made of stainless steel having an outer diameter of 73 mm and an inner diameter of
It was inserted into an outer cylinder 4 having a height of 70 mm and a height of 130 mm. Next, diffusion bonding was performed by heating and holding at 1200 ° C. for 60 minutes in a vacuum furnace. Next, nickel-based brazing material BNi-5 (20Cr-10Si-Bal
Ni) is applied to the contact portion 5 between the honeycomb portion 1 and the outer cylinder 4 and the first layer to
The third layer is applied to the contact portions 6, 7, 8 between the flat plate 2 and the corrugated plate 3 (fall down from the end face), heated in a vacuum furnace at 1150 to 1200 ° C. for 5 minutes, and brazed to remove the metal carrier. Obtained. FIG. 1 is a view of the obtained metal carrier viewed from one end face side. FIG. 2 is an explanatory view showing a brazed portion of a metal carrier obtained by the method of the present invention. That is, FIG. 2 shows a state in which the metal carrier is cut along the length direction, and the hatched portion in the figure is the brazing layer 9. FIG. 3 shows a partially enlarged view of FIG. When the honeycomb portion 1 has a larger thermal expansion coefficient than the outer cylinder 4, the honeycomb portion 1 contracts only by diffusion bonding,
As shown in FIG. 4, the stress concentrates on the outermost peripheral portion of the honeycomb portion 1, and the joining portion is peeled off to form a gap 10, or the convex portion of the corrugated plate 3 is deformed from a wavy shape to a triangular shape. However, even if only the joint between the outer cylinder 4 and the honeycomb portion 1 is subjected to diffusion bonding and brazing, the stress cannot be relaxed due to the contraction of the honeycomb portion 1. Peel off. FIG. 5 shows the outermost layer and its neighboring layers 2 to 5 in the metal carrier.
When diffusion bonding and brazing of three layers (the method of the present invention)
7 shows the relationship between the number of layers of the honeycomb portion and the stress when only diffusion bonding is performed or when the outer cylinder and the honeycomb portion are diffusion bonded and brazed (conventional method and comparative method). As is clear from the figure, in the metal carrier obtained by the method of the present invention, the stress does not increase even in the outermost layer.
比較例１ 実施例においてろう付けを行わなかったこと以外は同
様にしてメタル担体を得た。Comparative Example 1 A metal carrier was obtained in the same manner as in Example except that brazing was not performed.
比較例２ 実施例における拡散接合及びろう付けを行う代りに、
メタル担体の端面（一面）においてのみ外筒４とハニカ
ム部１及びハニカム部１の平板２と波板３とをろう付け
してメタル担体を得た。Comparative Example 2 Instead of performing diffusion bonding and brazing in the example,
Only on the end surface (one surface) of the metal carrier, the outer cylinder 4 and the honeycomb portion 1 and the flat plate 2 and the corrugated plate 3 of the honeycomb portion 1 were brazed to obtain a metal carrier.
＜性能比較試験＞ 実施例及び比較例１及び２のメタル担体について下記
条件で連続高速試験（条件１）及び冷熱耐久試験（条件
２）を行った。<Performance Comparison Test> A continuous high-speed test (condition 1) and a thermal durability test (condition 2) were performed on the metal carriers of the example and comparative examples 1 and 2 under the following conditions.
条件1:入ガス温度950℃で180時間保持 条件2:常温から高温（850℃）まで入ガス温度を変化さ
せ、１サイクル30分として計300時間実施 結果を下記第１表に示す。Condition 1: Inlet gas temperature is maintained at 950 ° C for 180 hours. Condition 2: Inlet gas temperature is changed from room temperature to high temperature (850 ° C), and a cycle is performed for 30 minutes for a total of 300 hours. The results are shown in Table 1 below.
第１表から明らかな如く、本発明の方法によって得ら
れたメタル担体は耐久性が非常に優れている。 As is clear from Table 1, the metal carrier obtained by the method of the present invention has excellent durability.
上述の如く本発明のメタル担体の製造方法は、ハニカ
ム部と外筒との接触部並びにハニカム部の最外周及びそ
の近傍の層合わせて数層の平板と波板との接触部をろう
付けし、ハニカム部の残りの層の平板と波板との接触部
を拡散接合するため、外筒とハニカム部及びハニカム部
の平板と波板とが強固に接合され耐久性が非常に向上し
たメタル担体を容易に得ることができる。As described above, the method for producing a metal carrier of the present invention comprises the steps of brazing the contact portion between the honeycomb portion and the outer cylinder, and the contact portion between the flat plate and the corrugated plate of several layers in total at the outermost periphery of the honeycomb portion and the vicinity thereof. In order to diffusely bond the contact portion between the flat plate and the corrugated plate of the remaining layer of the honeycomb portion, the outer cylinder and the honeycomb portion, and the flat plate of the honeycomb portion and the corrugated plate are firmly bonded, and the metal carrier has extremely improved durability. Can be easily obtained.
又、本発明の方法は特別な操作を必要とせず、従来の
設備や手法をそのまま適用できるので実用上有利であ
る。Further, the method of the present invention does not require any special operation, and the conventional equipment and method can be applied as it is, which is practically advantageous.
第１図は本発明の方法によって得られたメタル担体の一
例の端面図、 第２図は本発明の方法におけるメタル担体のろう付け部
分を示す説明図、 第３図は第１図のメタル担体の部分拡大図、 第４図は比較例の担体の第３図に相当する図、 第５図は本発明方法並びに従来方法及び比較方法によっ
て得られたメタル担体のハニカム部の層数と応力との関
係を表わす図である。 図中、 １……ハニカム部、２……平板、３……波板、４……外
筒、５……接触部、6,7,8……接触部、９……ろう付け
層、10……隙間FIG. 1 is an end view of an example of a metal carrier obtained by the method of the present invention, FIG. 2 is an explanatory view showing a brazed portion of the metal carrier in the method of the present invention, and FIG. 3 is a metal carrier of FIG. FIG. 4 is a diagram corresponding to FIG. 3 of the carrier of the comparative example, and FIG. 5 is a diagram showing the number of layers and the stress of the honeycomb portion of the metal carrier obtained by the method of the present invention and the conventional method and the comparative method. FIG. In the drawing, 1 ... honeycomb portion, 2 ... flat plate, 3 ... corrugated plate, 4 ... outer cylinder, 5 ... contact portion, 6, 7, 8 ... contact portion, 9 ... brazing layer, 10 ... gap
フロントページの続き (72)発明者 杉本 利治 愛知県豊田市トヨタ町１番地 トヨタ自 動車株式会社内 (56)参考文献 特開 平１−270947（ＪＰ，Ａ)Continuation of the front page (72) Inventor Toshiharu Sugimoto 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (56) References JP-A-1-270947 (JP, A)
Claims (1)
た構造を有するハニカム部を、耐熱金属製の外筒に収納
してなるメタル担体を製造するにあたり、ハニカム部と
外筒との接触部並びにハニカム部の最外周及びその近傍
の層合わせて数層の平板と波板との接触部をろう付け
し、ハニカム部の残りの層の平板と波板との接触部を拡
散接合することを特徴とするメタル担体の製造方法。1. A method for manufacturing a metal carrier in which a honeycomb portion having a structure in which a flat plate made of a heat-resistant metal and a corrugated sheet are wound and stacked on each other in a heat-resistant metal outer tube is used. Brazing the contact portion between the flat plate and the corrugated plate in several layers including the contact portion of the honeycomb portion and the outermost layer of the honeycomb portion and the layer in the vicinity thereof, and diffusing the contact portion between the flat plate of the remaining layer of the honeycomb portion and the corrugated plate A method for producing a metal carrier, comprising joining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1006289A JP2639993B2 (en) | 1989-01-14 | 1989-01-14 | Manufacturing method of metal carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1006289A JP2639993B2 (en) | 1989-01-14 | 1989-01-14 | Manufacturing method of metal carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02187151A JPH02187151A (en) | 1990-07-23 |
| JP2639993B2 true JP2639993B2 (en) | 1997-08-13 |
Family
ID=11634230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1006289A Expired - Lifetime JP2639993B2 (en) | 1989-01-14 | 1989-01-14 | Manufacturing method of metal carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2639993B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395599A (en) * | 1991-08-01 | 1995-03-07 | Nippon Yakin Kogyo Co., Ltd. | Catalyst-carrying metallic carrier and production method thereof |
-
1989
- 1989-01-14 JP JP1006289A patent/JP2639993B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02187151A (en) | 1990-07-23 |
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