JPH05339748A - Production of composite film - Google Patents
Production of composite filmInfo
- Publication number
- JPH05339748A JPH05339748A JP4149770A JP14977092A JPH05339748A JP H05339748 A JPH05339748 A JP H05339748A JP 4149770 A JP4149770 A JP 4149770A JP 14977092 A JP14977092 A JP 14977092A JP H05339748 A JPH05339748 A JP H05339748A
- Authority
- JP
- Japan
- Prior art keywords
- sprayed layer
- plating
- porosity
- composite film
- layer
- 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- Withdrawn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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属材料の表面に複合皮
膜を形成する方法に関し、例えば抄紙機用セラミックス
溶射型プレスロールの溶射層の形成に有利に適用しうる
同方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a composite coating on the surface of a metal material, and more particularly to the same method which can be advantageously applied to the formation of a sprayed layer of a ceramics spray type press roll for a paper machine.
【０００２】[0002]
【従来の技術】図１は抄紙機のプレスロールにセラミッ
クス溶射を施した例で、図４の（ａ）は全体の断面図で
ある。１，１′は金属製のシエルでその上にセラミック
ス溶射層２及び封孔処理のためのめっき層３が存在す
る。４は軸及びヘッドでシエル１，１′とは溶接などで
取り付けられている。図４の（ｂ），（ｃ）は図４の
（ａ）Ａ部の拡大図である。2. Description of the Related Art FIG. 1 is an example in which a press roll of a paper machine is sprayed with ceramics, and FIG. 4A is a sectional view of the whole. Reference numerals 1, 1 ′ are metal shells on which a ceramic sprayed layer 2 and a plating layer 3 for sealing treatment are present. A shaft and a head 4 are attached to the shells 1 and 1'by welding or the like. 4 (b) and 4 (c) are enlarged views of the portion A of FIG. 4 (a).
【０００３】図４の（ｂ）の場合、表面積はセラミック
ス溶射２のみであるため、シエル１′は高価なステンレ
ス鋼になっている。またセラミックス溶射層２とシエル
１′の接着は極く僅かな冶金的接合と機械的作用のみに
よっているため接合強度が低く高い線圧や温度サイクル
が作用した場合剥離が生じていた。In the case of FIG. 4B, since the surface area is only the ceramic sprayed 2, the shell 1'is expensive stainless steel. Further, since the ceramic sprayed layer 2 and the shell 1'are bonded only by a very slight metallurgical bond and mechanical action, the bond strength is low and peeling occurs when a high linear pressure or temperature cycle is applied.
【０００４】一方、図４の（ｃ）の場合は特開平３〜２
７７７７９号公報に示された方法と同様なプロセス、す
なわちセラミックス溶射２の後、電解めっきにより封孔
処理が行なわれているため優れた耐食性を有していた。
このため、シエル１は炭素鋼の使用が可能であった。し
かし寸法精度を出すため、あるいは表面粗さを改善する
ため表面を研摩した後、または使用中セラミックス溶射
層が摩耗した後では、めっき時表面に開口していなかっ
た孔が開口し、ここからシエル１の表面に腐食液が浸
入、シエル１を腐食させ、剥離などのトラブルが発生し
ていた。これはもともと溶射層に存在する孔が全て表面
に開口していないためと推定される。なお、このためか
セラミックス溶射とめっきを併用した場合においても密
着性の向上はわずかであった。On the other hand, in the case of FIG.
Since the sealing treatment was performed by electrolytic plating after the process similar to the method disclosed in Japanese Patent Publication No. 77779, that is, after the ceramic spraying 2, it had excellent corrosion resistance.
Therefore, the shell 1 could be made of carbon steel. However, after polishing the surface to improve dimensional accuracy or to improve the surface roughness, or after the ceramic sprayed layer has been worn during use, holes that were not opened during plating are opened and the shell The corrosive liquid infiltrated the surface of No. 1 and corroded the shell 1, and troubles such as peeling occurred. It is presumed that this is because all the holes originally present in the sprayed layer do not open on the surface. For this reason, the improvement in adhesion was slight even when ceramics thermal spraying and plating were used together.
【０００５】[0005]
【発明が解決しようとする課題】セラミックス溶射層と
シエルの密着性を十分に向上するためにはシエル表面に
できるだけ多くの面積にわたってめっき層を形成する必
要がある。また、研摩や摩耗によって封孔処理されてい
ない孔が開口し耐食性が低下することを防止するために
はめっきで封孔処理された層が研摩あるいは摩耗によっ
て除去されないようにする必要がある。In order to sufficiently improve the adhesiveness between the ceramic sprayed layer and the shell, it is necessary to form a plating layer over the surface of the shell as much as possible. Further, in order to prevent the unsealed holes from being opened due to polishing or abrasion and lowering the corrosion resistance, it is necessary to prevent the layer sealed by plating from being removed by polishing or abrasion.
【０００６】本発明は上記要望に応じ、従来技術におけ
るような不具合のない複合皮膜が形成される複合皮膜の
製造方法を提供しようとするものである。In response to the above demands, the present invention is to provide a method for producing a composite film, which is capable of forming a composite film having no problem as in the prior art.
【０００７】[0007]
【課題を解決するための手段】本発明は （１）金属材料の表面にセラミックス溶射層を形成させ
た後、該ピンホールを介して金属材料表面に達する金属
めっきを施工し、その後更にセラミックス溶射層を形成
することを特徴とする複合皮膜の製造方法、Means for Solving the Problems (1) After forming a ceramic sprayed layer on the surface of a metal material, metal plating is applied to reach the surface of the metal material through the pinhole, and then ceramic spraying is further performed. A method for producing a composite coating, which comprises forming a layer,
【０００８】（２）上記（１）記載の方法に続いて金属
めっきとセラミックス溶射を任意数繰り返し施工するこ
とを特徴とする複合皮膜の製造方法、(2) A method for producing a composite coating, characterized in that, following the method described in (1) above, metal plating and ceramics thermal spraying are applied repeatedly an arbitrary number of times.
【０００９】（３）初層のセラミックス溶射層の気孔度
をその上に形成するセラミックス溶射層のそれより大き
くすることを特徴とする上記（１）又は（２）記載の複
合皮膜の製造方法、(3) The method for producing a composite coating as described in (1) or (2) above, wherein the porosity of the ceramic sprayed layer of the first layer is made larger than that of the ceramic sprayed layer formed thereon.
【００１０】（４）セラミックス溶射後、金属めっきす
る前に該溶射層の気孔度を調べ、気孔度が目標以上とな
るよう該溶射層厚さを調節しながら複合皮膜を形成する
ことを特徴とする上記（１）〜（３）いずれかに記載の
複合皮膜の製造方法である。(4) After the ceramics thermal spraying, the porosity of the thermal sprayed layer is examined before metal plating, and the composite coating is formed while adjusting the thickness of the thermal sprayed layer so that the porosity is higher than the target. The method for producing a composite film according to any one of (1) to (3) above.
【００１１】すなわち、本発明の第一は、セラミックス
溶射とシエル界面にできるだけめっきが入ってゆき、密
着性を向上させるためにセラミックス溶射層が薄い状態
でめっきを施こし、引続き溶射にて研摩代，摩耗代分の
セラミックス溶射層を形成するものであり、これにより
優れた耐食性と共に高い密着力を得ることができる。That is, the first aspect of the present invention is that the plating is applied to the ceramic spraying and the shell interface as much as possible, and the plating is applied with the ceramic sprayed layer being thin in order to improve the adhesion, and the polishing allowance is subsequently applied by the spraying. , Which forms a ceramic sprayed layer for wear, which makes it possible to obtain excellent corrosion resistance and high adhesion.
【００１２】また、本発明の第二は上記第一の方法より
耐食性のさらなる向上あるいは膜の強度向上を計るため
にセラミックス溶射とシエル界面だけではなく、第一の
方法を施工後、めっきとセラミックス溶射を繰り返すも
のであり、この場合、膜の熱伝導率の向上も期待でき
る。The second aspect of the present invention is, in order to further improve the corrosion resistance or the strength of the film as compared with the first method, not only the ceramic spraying and shell interface but also the plating and the ceramics after the first method is applied. The thermal spraying is repeated, and in this case, improvement of the thermal conductivity of the film can be expected.
【００１３】また、本発明の第三は上記第一又は第二の
方法を行なうに当って、シエル表面とセラミックス溶射
層の密着性をできるだけ大きくする方法であって、初層
のセラミックス溶射層の気孔度を大きくしてめっき層の
部分を多くするようにするものであり、めっき後、さら
に溶射されるセラミックス溶射層の気孔度は小さくして
耐摩耗性が高くなるように緻密なものとする方法であ
る。A third aspect of the present invention is a method of increasing the adhesion between the shell surface and the ceramic sprayed layer as much as possible in performing the above first or second method. The porosity is increased to increase the portion of the plating layer, and after the plating, the ceramic sprayed layer further sprayed should have a small porosity and be dense so as to have high wear resistance. Is the way.
【００１４】また、さらに本発明の第四は皮膜の密着性
を上げるため、あるいは溶射、めっき複合層の気孔度を
少なくして耐食性，耐摩耗性及び靱性を上げるため、め
っき面に表面からシエル表面あるいは先にめっきされた
面に達する気孔度が目標（例えば５０％）以上になるよ
うに溶射層厚さを調節しながら複合皮膜を製造する方法
である。Further, in the fourth aspect of the present invention, in order to improve the adhesion of the coating film, or to improve the corrosion resistance, wear resistance and toughness by reducing the porosity of the thermal spraying and plating composite layer, the shell surface of the plating surface is reduced. This is a method for producing a composite coating while adjusting the thickness of the thermal sprayed layer so that the porosity reaching the surface or the surface plated beforehand becomes a target (for example, 50%) or more.
【００１５】[0015]
【作用】シエルと溶射層の密着性を向上させるために
は、シエルと溶射粒子の隙間をできるだけ多くめっきで
うめることが望ましいが、溶射層が厚くなるとめっき液
が浸入できるように表面に開口した隙間あるいは孔の数
が少なくなる。この結果、界面でのめっき面積が小さく
なると共に密着力も低下する。このような状態を模式的
に示したのが図３である。本発明の効果を引き出すため
には必要なｂ，ｂ′（めっきによる密着力の増加分）が
得られる溶射膜厚以内でめっきをすることが必要であ
る。なおこのような最適膜厚は溶射条件によって異なる
ため各々の条件ごとに選定する必要がある。図３で実線
は気孔少の膜であり、破線は気孔多の溶射層の場合であ
り、密着力は同じ膜厚な気孔多の方が大である。但し溶
射のみの密着力は気孔多の方が小さくなる。すなわち、
適正な膜厚が設定できれば界面側に気孔の多い溶射層を
配し、めっき後気孔の少ない溶射層を配することにより
密着性も耐摩耗性も優れた皮膜を形成することができ
る。[Function] In order to improve the adhesion between the shell and the sprayed layer, it is desirable to fill the gap between the shell and the sprayed particle with plating as much as possible, but when the sprayed layer becomes thicker, the surface is opened so that the plating solution can penetrate. Fewer gaps or holes. As a result, the plating area at the interface is reduced and the adhesion is also reduced. FIG. 3 schematically shows such a state. In order to bring out the effect of the present invention, it is necessary to carry out plating within a sprayed film thickness at which necessary b and b '(increase in adhesion due to plating) can be obtained. Since such an optimum film thickness varies depending on the spraying conditions, it is necessary to select each optimum condition. In FIG. 3, the solid line shows a film with few pores, the broken line shows the case of a sprayed layer with many pores, and the adhesive force is larger for many pores with the same film thickness. However, the adhesion force only by thermal spraying becomes smaller with more pores. That is,
If a proper film thickness can be set, a sprayed layer having many pores is arranged on the interface side, and a sprayed layer having few pores is arranged after plating to form a film having excellent adhesion and wear resistance.
【００１６】以上のほか本発明の方法ではめっきする溶
射層の気孔が十分にシエル表面あるいは前のめっき部に
到達し有効に密着力向上に寄与できるかどうかをチェッ
クすることができる。すなわち、溶射層に電解液を注入
して電気抵抗を計るとか通気度を測定し溶射層の気孔度
（特に溶射層を貫通したもの）をチェックし、もし目標
の値に達しない場合には溶射層厚さを薄くして目標の気
孔度になったことを確認後めっきすることにより良好な
密着力を得ることができる。In addition to the above, in the method of the present invention, it can be checked whether or not the pores of the sprayed layer to be plated reach the shell surface or the previous plated portion and can effectively contribute to the improvement of the adhesion. That is, the porosity of the sprayed layer is checked by injecting the electrolytic solution into the sprayed layer to measure the electrical resistance or measuring the air permeability, and if the target value is not reached, spraying is performed. Good adhesion can be obtained by plating after confirming that the target porosity is achieved by reducing the layer thickness.
【００１７】[0017]
（実施例１）図１の炭素鋼製シエル１の上にプラズマ溶
射により（Ａｌ2 Ｏ3 ＋１３％ＴｉＯ2 ）溶射膜２を２
０μｍ（厚さａ）を形成後、電気めっき法によりＮｉめ
っき３を施こした。更に引続き、２００μｍ（厚さｂ）
の（Ａｌ2 Ｏ3 ＋１３％ＴｉＯ2 ）を溶射後、複合皮膜
４を得、抄紙白水中での浸漬試験及び密着性の試験をし
た。また、一方（Ａｌ2 Ｏ3 ＋１３％ＴｉＯ2 ）を２２
０μｍ溶射後、Ｎｉめっきしたものを得、これら両者を
比較した結果、白水中での浸漬試験では１００時間後に
おいても両方とも錆の発生はなかったが、これら両者の
ものを２０μｍ研摩して２００μｍの膜厚になったもの
は、前者では１００時間においても錆の発生はなかった
のに対し後者のものは３０時間で錆の発生をみた。また
密着力は前者の方が後者の３倍以上であった。(Embodiment 1) A sprayed film (Al 2 O 3 + 13% TiO 2 ) 2 is formed on the carbon steel shell 1 shown in FIG. 1 by plasma spraying.
After forming 0 μm (thickness a), Ni plating 3 was applied by electroplating. Further, 200μm (thickness b)
(Al 2 O 3 + 13% TiO 2 ) was sprayed, then a composite coating 4 was obtained, and a dipping test in papermaking white water and an adhesion test were conducted. On the other hand, one (Al 2 O 3 + 13% TiO 2 ) was added to 22
After 0 μm thermal spraying, a Ni-plated product was obtained. As a result of comparing the two, no rust was found even after 100 hours in the immersion test in white water, but both of them were polished to 20 μm to 200 μm. In the former case, rust did not occur even after 100 hours, whereas in the latter case, rust occurred after 30 hours. The adhesive strength of the former was more than three times that of the latter.
【００１８】以上のように、従来の方法で得られたもの
は溶射のまゝで使う以外は実用が難しいのに対し、本発
明の方法で得られたものは研摩の必要なものにも適用が
可能であった。すなわち、従来の方法で得られたものは
研摩後では殆んど摩耗代がないのに対し、本発明の方法
で得られたものはなお２００μｍ程度が残っており、寿
命比にすると数百倍以上が期待できる。As described above, the one obtained by the conventional method is difficult to use except for using it until the thermal spraying, while the one obtained by the method of the present invention is applicable to the one requiring polishing. Was possible. That is, while the one obtained by the conventional method has almost no wear margin after polishing, the one obtained by the method of the present invention still has about 200 μm, which is several hundred times as long as the life ratio. The above can be expected.
【００１９】（実施例２）実施例１において、Ｎｉの電
気めっきに代えて（Ｎｉ−Ｐ）の無電解めっきを採用し
たが、実施例１と同様の効果が得られた。(Example 2) In Example 1, electroless plating of (Ni-P) was adopted in place of the electroplating of Ni, but the same effect as in Example 1 was obtained.
【００２０】（実施例３）図２に示すように炭素鋼製シ
エル１の上にプラズマ溶射により（Ａｌ2 Ｏ3 ＋１３％
ＴｉＯ2 ）２を２０μｍ（厚さａ1 ）と電気めっき法に
よるＮｉめっき３を交互に実施し、（夫々の厚さａ2 ・
・・・ａn ）２２０μｍの複合皮膜５を形成した。これ
と（Ａｌ2 Ｏ3 ＋１３％ＴｉＯ2 ）溶射膜２２０μｍを
形成後、Ｎｉめっきを施した複合皮膜を比較したところ
複合皮膜の熱抵抗は前者の場合、後者の１／２以下とな
った。なお耐食性、密着力については実施例１とほゞ同
様であった。(Embodiment 3) As shown in FIG. 2, a carbon steel shell 1 was subjected to plasma spraying (Al 2 O 3 + 13%).
TiO 2 ) 20 μm (thickness a 1 ) and Ni plating 3 by electroplating are alternately carried out (each thickness a 2 ·
... a n ) 220 μm of composite film 5 was formed. When this was compared with a composite coating in which a (Al 2 O 3 + 13% TiO 2 ) sprayed coating of 220 μm was formed and then Ni-plated, the thermal resistance of the composite coating was 1/2 or less of the latter in the former case. The corrosion resistance and the adhesion were almost the same as in Example 1.
【００２１】（実施例４）炭素鋼製シエルの上に１０μ
ｍのＷＣ−Ｃｏの溶射膜を形成後、無電解めっき法によ
りＮｉ−Ｐのめっきを実施し、その後１００μｍのＷＣ
−Ｃｏの溶射膜を形成した。一方、比較材として１１０
μｍのＷＣ−Ｃｏ溶射膜を形成後同様に無電解めっき法
によりＮｉ−Ｐのめっきを施したものを製作した。(Embodiment 4) 10 μ on a carbon steel shell
m WC-Co sprayed film, Ni-P plating is performed by electroless plating, and then 100 μm WC
-Co sprayed film was formed. On the other hand, as a comparison material, 110
After forming a WC-Co sprayed film having a thickness of μm, a Ni-P plated film was similarly prepared by the electroless plating method.
【００２２】上記２種類の密着性及び耐食性（水浸漬テ
スト）を比較した結果、耐食性については差はみられな
かったが、密着性は本発明のものが後者の１．４倍以上
となった。As a result of comparing the above two types of adhesion and corrosion resistance (water immersion test), no difference was found in corrosion resistance, but the adhesion of the present invention was 1.4 times or more of that of the latter. ..
【００２３】（実施例５）実施例１の溶射層の表面に、
幅１５０μｍ、深さ１００μｍ、ピッチ２５０μｍの溝
をスパイラル状に加工後、紙離れ改善のため樹脂を溝部
に封入したプレスロールを試作したところ、本発明のも
のでは１０００時間後の使用においても錆の発生はなか
ったのに対して溶射完了後めっきをしたものに同じ処理
したものは５０時間後に錆の発生がみられた。Example 5 On the surface of the sprayed layer of Example 1,
A groove having a width of 150 μm, a depth of 100 μm, and a pitch of 250 μm was processed into a spiral shape, and then a trial production of a press roll in which a resin was sealed in the groove portion to improve paper separation was confirmed. While no rust was generated, rust was observed after 50 hours in the same plating after the completion of thermal spraying.
【００２４】（実施例６）実施例１においてシエル表面
に施工する溶射層の気孔度を約２倍にしてめっき後、以
下同様の方法によって膜を形成後、皮膜の密着力を比較
したところ、この実施例で得られた複合皮膜は本発明の
実施例１のものに比し１．４〜２．４倍の密着力が得ら
れた。(Example 6) In Example 1, after coating the sprayed layer applied on the shell surface with the porosity approximately doubled, the film was formed by the same method as described below, and the adhesion of the film was compared. The composite film obtained in this example provided 1.4 to 2.4 times the adhesive force as compared with that of Example 1 of the present invention.
【００２５】（実施例７）実施例６において、めっき前
の溶射層の厚さを２０μｍ一定とするのではなく、食塩
水を含浸させたろ紙を溶射層表面に押し付け交流２Ｖの
電圧をかけ流れる電流でもって定義した気孔度が２倍と
なるよう膜厚をコントロールしてめっきしたところ、密
着力は実施例１の１．９〜２．４倍となり実施例６に比
しバラツキが小で平均密着力の向上した複合皮膜が得ら
れた。(Example 7) In Example 6, the thickness of the sprayed layer before plating is not kept constant at 20 μm, but a filter paper impregnated with saline is pressed against the surface of the sprayed layer and a voltage of 2V AC is applied to flow. When the plating was performed by controlling the film thickness so that the porosity defined by the electric current would be doubled, the adhesion was 1.9 to 2.4 times that of Example 1 and the variation was small as compared with Example 6 and the average. A composite film with improved adhesion was obtained.
【００２６】すなわち、密着力をある一定値以上に確保
するためには金属表面に達する溶射層のピンホールの数
を目標値以上にする必要がある。金属表面に達するピン
ホールの数は溶射層の厚さを厚くなると少なくなるが、
溶射層厚と金属表面に達するピンホールの数は必ずしも
比例しないので各溶射条件ごとにピンホールの数を求め
る必要がある。この実施例の場合、上記の手段でピンホ
ールの数を測定し、金属表面に達するピンホールの数が
２倍となるように溶射層の厚さを初期の７０％にするこ
とによって得られた値である。That is, in order to secure the adhesion force above a certain value, the number of pinholes in the sprayed layer reaching the metal surface must be above the target value. The number of pinholes reaching the metal surface decreases as the thickness of the thermal spray layer increases,
Since the thickness of the sprayed layer and the number of pinholes reaching the metal surface are not necessarily proportional, it is necessary to find the number of pinholes for each spraying condition. In the case of this example, the number of pinholes was measured by the above means, and the thickness of the sprayed layer was set to 70% of the initial thickness so that the number of pinholes reaching the metal surface was doubled. It is a value.
【００２７】[0027]
【発明の効果】本発明により、密着性が向上し、研摩あ
るいは摩耗しても耐食性の低下せず、靱性、衝撃抵抗の
優れた複合皮膜が得られる。また、溶射層にレーザ彫刻
などにより溝加工が可能（加工しても耐食性の低下がな
い）であるため、高離水性プレスロールへの適用可能な
複合皮膜が提供される。EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a composite film which has improved adhesion, does not deteriorate in corrosion resistance even when polished or worn, and has excellent toughness and impact resistance. Further, since grooves can be formed on the sprayed layer by laser engraving or the like (there is no reduction in corrosion resistance even if processed), a composite film applicable to a high water-repellent press roll is provided.
【図１】本発明の一実施例の説明図。FIG. 1 is an explanatory diagram of an embodiment of the present invention.
【図２】本発明の他の実施例の説明図。FIG. 2 is an explanatory view of another embodiment of the present invention.
【図３】溶射層膜厚と密着力の関係を示す模式図。FIG. 3 is a schematic diagram showing a relationship between a sprayed layer film thickness and an adhesive force.
【図４】従来の複合皮膜の説明図。FIG. 4 is an explanatory view of a conventional composite film.
Claims (4)
形成させた後、該ピンホールを介して金属材料表面に達
する金属めっきを施工し、その後更にセラミックス溶射
層を形成することを特徴とする複合皮膜の製造方法。1. A composite comprising forming a ceramic sprayed layer on the surface of a metal material, performing metal plating to reach the surface of the metal material through the pinhole, and then forming a further ceramic sprayed layer. Method of manufacturing film.
とセラミックス溶射を任意数繰り返し施工することを特
徴とする複合皮膜の製造方法。2. A method for producing a composite coating, which comprises performing metal plating and ceramic spraying any number of times subsequently to the method according to claim 1.
の上に形成するセラミックス溶射層のそれより大きくす
ることを特徴とする請求項１又は請求項２記載の複合皮
膜の製造方法。3. The method for producing a composite coating according to claim 1, wherein the porosity of the ceramic sprayed layer of the first layer is made larger than that of the ceramic sprayed layer formed thereon.
に該溶射層の気孔度を調べ、気孔度が目標以上となるよ
う該溶射層厚さを調節しながら複合皮膜を形成すること
を特徴とする請求項１〜請求項３いずれかに記載の複合
皮膜の製造方法。4. A composite coating is formed after ceramics thermal spraying and before metal plating, by examining the porosity of the sprayed layer and adjusting the thickness of the sprayed layer so that the porosity is above a target. The manufacturing method of the composite film in any one of Claims 1-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4149770A JPH05339748A (en) | 1992-06-10 | 1992-06-10 | Production of composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4149770A JPH05339748A (en) | 1992-06-10 | 1992-06-10 | Production of composite film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05339748A true JPH05339748A (en) | 1993-12-21 |
Family
ID=15482356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4149770A Withdrawn JPH05339748A (en) | 1992-06-10 | 1992-06-10 | Production of composite film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05339748A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1010269C2 (en) * | 1998-10-08 | 2000-04-11 | Stichting Energie | Method for coating a carrier plate and MCFC cell provided with such a carrier plate. |
-
1992
- 1992-06-10 JP JP4149770A patent/JPH05339748A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1010269C2 (en) * | 1998-10-08 | 2000-04-11 | Stichting Energie | Method for coating a carrier plate and MCFC cell provided with such a carrier plate. |
| WO2000021152A1 (en) * | 1998-10-08 | 2000-04-13 | Stichting Energieonderzoek Centrum Nederland | Method for coating a support plate and fuel cell provided with such a support plate |
| US6761927B1 (en) | 1998-10-08 | 2004-07-13 | Stichting Energieonderzoek Centrum Nederland | Method for coating a support plate and fuel cell provided with such a support plate |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19990831 |