JPH0657875B2 - Method for forming platinum group coating on metal electrode substrate - Google Patents
Method for forming platinum group coating on metal electrode substrateInfo
- Publication number
- JPH0657875B2 JPH0657875B2 JP61060814A JP6081486A JPH0657875B2 JP H0657875 B2 JPH0657875 B2 JP H0657875B2 JP 61060814 A JP61060814 A JP 61060814A JP 6081486 A JP6081486 A JP 6081486A JP H0657875 B2 JPH0657875 B2 JP H0657875B2
- Authority
- JP
- Japan
- Prior art keywords
- coating
- platinum group
- metal
- electrode substrate
- metal electrode
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Chemically Coating (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は例えば食塩電解の陽極として使用される白金族
被膜を有する金属電極の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a method for producing a metal electrode having a platinum group coating, which is used, for example, as an anode for salt electrolysis.
＜従来の技術＞ 基体金属の表面に貴金属を被膜した金属陽極は耐食性、
電気化学的特性が優れており、電解用電極として広く使
用されている。<Prior Art> A metal anode having a base metal surface coated with a noble metal has corrosion resistance,
It has excellent electrochemical characteristics and is widely used as an electrode for electrolysis.
この貴金属被膜金属電極の貴金属被覆膜の生成方法は概
ね次に示す二方法に大別される。The method of forming the noble metal coating film of the noble metal coated metal electrode is roughly classified into the following two methods.
基体金属表面に電気めっきにより貴金属膜を析出生成
させる方法。A method of depositing and forming a noble metal film on the surface of a base metal by electroplating.
基体金属表面に貴金属の塩化物を塗布し、該塗布塩化
物を加熱して貴金属被膜を基体金属表面に生成させる方
法。A method of applying a chloride of a noble metal to the surface of a base metal and heating the applied chloride to form a noble metal coating on the surface of the base metal.
この場合、具体的には加熱バーナーにより加熱してい
る。In this case, specifically, it is heated by a heating burner.
＜発明が解決しようとする課題＞ (1)基体金属に電気めっきにより貴金属膜を析出生成す
る方法は、生成膜にピンホールが生じ易く、又実際に電
極として使用した場合過酷な条件では膜が剥離すること
があるという欠点を有する。<Problems to be solved by the invention> (1) The method of depositing and forming a noble metal film on a base metal by electroplating tends to cause pinholes in the formed film, and when the film is actually used as an electrode, the film does not form under severe conditions. It has a drawback that it may peel off.
(2)貴金属の塩化物を塗布し、ついでバーナーで加熱し
て被膜を生成させる場合は、実際に貴金属の塩化物を含
む膠質溶液を先ず作り、次いでこのものを基体に塗布
し、不活性ガス中でバーナーで加熱して塩化物を分解す
ることにより、基体表面に貴金属被膜を生成させてい
る。(2) When a noble metal chloride is applied and then heated with a burner to form a film, an oncotic solution containing the noble metal chloride is first prepared, then this is applied to the substrate, and an inert gas is applied. A noble metal coating is formed on the surface of the substrate by heating with a burner to decompose chloride.
この方法においてはプロパン、ブタン、タウンガス等を
用いてバーナーで加熱しているが、焔の燃焼状態の定常
化、即ち燃焼焔の構成の管理や焔の先端と基体金属との
距離の維持等、耐食性に優れしかも剥離し難い被膜を形
成させるためには複雑な装置を必要とする。In this method, propane, butane, town gas, etc. are used for heating with a burner, but the combustion state of the flame is stabilized, that is, the composition of the flame is controlled and the distance between the tip of the flame and the base metal is maintained. However, in order to form a coating that is excellent in corrosion resistance and is difficult to peel off, a complicated device is required.
＜課題を解決するための手段＞ 本発明者らは前記公知の手段の有する欠点のない方法で
実用的に優れた方法を開発すべく研究の結果、白金族塩
化物とメチルセルロース及びナトリウムボロハイドライ
ド又はボラザン類の混合物を基体に塗付し遠赤外加熱す
ることにより目的を達することを知り本発明を完成し
た。本発明は特に白金族金属被膜を金属基体表面に生成
させるものであり、金属基体電極表面に白金族塩化物と
メチルセルロース及びナトリウムボロハイドライド、ボ
ラザン又はメチルボラザンを含有するスラリー状物質を
塗布後、遠赤外加熱により、該塗布表面を加熱して、該
塗布面に白金族金属被膜を生成せしめることを特徴とす
る金属基体電極に対する白金族被膜の生成方法に関す
る。<Means for Solving the Problems> As a result of research to develop a method that is practically excellent by the method without the drawbacks of the known means, the present inventors have found that platinum group chloride and methyl cellulose and sodium borohydride or The present invention has been completed, knowing that the object can be achieved by applying a mixture of borazans to a substrate and heating it in the far infrared. The present invention is particularly for producing a platinum group metal coating on the surface of a metal substrate, and after coating the surface of the metal substrate electrode with a slurry substance containing a platinum group chloride and methyl cellulose and sodium borohydride, borazane or methyl borazane, the far infrared The present invention relates to a method for producing a platinum group coating on a metal base electrode, which comprises heating the coating surface by external heating to produce a platinum group metal coating on the coating surface.
この加熱手段は極めて容易であって、遠赤外加熱ヒータ
ーを有する適宜の加熱炉が使用できる。そして遠赤外加
熱であるので、温度管理が容易であり、又加熱むらが生
じない。尚バーナー加熱では基体金属に生成せる金属被
膜中に微量の不純物、例えば金属酸化物が含まれるが、
本発明においては実施例に示されるように実質的に含ま
れることはない。又基体金属に塗布すべきスラリー状物
質中のナトリウムボロハイドライド、ボラザン又はメチ
ルボラザンは生成被膜の硬度を高めるものであり、又メ
チルセルロースは金属基体へのスラリー付着力の増加に
特に有効であり、又揮発性であるので、加熱により除去
され、白金族被膜に全く影響を与えることはない。尚、
本発明方法は通常使用されるすべての電極基体に全く同
様に適用できる。This heating means is extremely easy, and an appropriate heating furnace having a far infrared heater can be used. Further, since far-infrared heating is used, temperature control is easy and uneven heating does not occur. In the burner heating, a small amount of impurities, such as metal oxide, are contained in the metal coating formed on the base metal,
In the present invention, it is not substantially included as shown in Examples. Further, sodium borohydride, borazane or methylborazane in the slurry-like substance to be applied to the base metal enhances the hardness of the formed film, and methylcellulose is particularly effective in increasing the slurry adhesive force to the metal base and volatilizes. Since it has a property, it is removed by heating and does not affect the platinum group coating at all. still,
The method of the invention is equally applicable to all commonly used electrode substrates.
＜実施例＞ 実施例により本発明を説明する。<Example> The present invention will be described with reference to an example.
実施例１ １００mm×６mmφのチタニウム棒を塩化パラジウム２ｇ
（金属として０．９９８ｇ）、３６％塩酸５ml、ナトリ
ウムボロハイドライド０．２２ｇの混合物に、メチルセ
ルロース０．１ｇを添加した溶液に浸漬した後、遠赤外
加熱炉で２５０℃で９分間加熱処理して０．２９μｍの
パラジウム金属被膜を得た。次いで全く同様に浸漬加熱
を繰返し合計１０回行って２．９μｍのパラジウム金属
被膜を得た。Example 1 2 g of palladium chloride was used for a titanium rod of 100 mm × 6 mmφ.
(0.998 g as metal), 36% hydrochloric acid 5 ml, and sodium borohydride 0.22 g were immersed in a solution containing 0.1 g of methylcellulose, and then heat-treated at 250 ° C. for 9 minutes in a far infrared heating furnace. As a result, a 0.29 μm palladium metal film was obtained. Then, immersion heating was repeated exactly 10 times in total to obtain a 2.9 μm palladium metal coating.
この金属被膜にはＸ−線回析法により酸化物が含まれな
いことを確認した。又この被膜のビッカース硬度は６０
０であった。It was confirmed by the X-ray diffraction method that the metal coating did not contain any oxide. The Vickers hardness of this coating is 60
It was 0.
比較例１ 実施例１においてナトリウムボロハイドライドを使用し
ないで、全く同様の処理をした結果、得られた被膜のビ
ッカース硬度は４００であった。Comparative Example 1 As a result of completely the same treatment as in Example 1 except that sodium borohydride was not used, the Vickers hardness of the obtained coating was 400.
実施例２ 実施例２と全く同様のチタニウム棒を用い、浸漬液とし
て塩化イリジウム２ｇ（金属として１．２９ｇ）、３６
％塩酸１．５ml、ナトリウムボロハイドライド０．２
ｇ、メチルセルロース０．０５ｇを用い、実施例１と同
様に遠赤外加熱炉で３５０℃で１０分間加熱処理して
０．６２μｍのイリジウム金属被膜を得た。同様な処理
を合計１０回行って６．２μｍのイリジウム金属被膜を
得た。この金属被膜にはＸ−線回析法により酸化物が含
まれないことを確認した。又この金属被膜のビッカース
硬度は６２０であった。Example 2 Using the same titanium rod as in Example 2, 2 g of iridium chloride as an immersion liquid (1.29 g as metal), 36
% Hydrochloric acid 1.5 ml, sodium borohydride 0.2
g and 0.05 g of methyl cellulose were heat treated in a far infrared heating furnace at 350 ° C. for 10 minutes in the same manner as in Example 1 to obtain an iridium metal coating having a thickness of 0.62 μm. The same treatment was performed 10 times in total to obtain an iridium metal coating having a thickness of 6.2 μm. It was confirmed by the X-ray diffraction method that the metal coating did not contain any oxide. The Vickers hardness of this metal coating was 620.
比較例２ 実施例２においてナトリウムボロハイドライドを使用し
ないで全く同様の処理をした結果、得られた被膜のビッ
カース硬度は３９０であった。Comparative Example 2 As a result of performing the same treatment as in Example 2 without using sodium borohydride, the Vickers hardness of the obtained coating was 390.
実施例３〜６ 実施例２と同様のチタニウム棒を用い、次表に示す浸漬
液を用い、遠赤外加熱炉を用いて次表に示す条件で加熱
して夫々の金属被膜を得た。実施例２と同様１０回の処
理を繰返し次表に示す金属被膜を得た。Examples 3 to 6 Using the same titanium rods as in Example 2, the immersion liquid shown in the following table was used, and the far infrared heating furnace was used to heat under the conditions shown in the following table to obtain respective metal coatings. The same treatment as in Example 2 was repeated 10 times to obtain metal coatings shown in the following table.
実施例３〜６において生成せる金属被膜中には酸化物が
含まれないことをＸ−線回析法で確認した。 It was confirmed by an X-ray diffraction method that no oxide was contained in the metal coatings produced in Examples 3 to 6.
＜発明の効果＞ 本発明の方法は白金族塩化物とメチルセルロース及びナ
トリウムボロハイドライド、ボラザン又はメチルボラザ
ンとを実質的成分とするスラリーを電極基体に塗布し、
赤外線加熱するものであり、極めて容易に実施できる。
又生成貴金属膜はホウ化物を用いることにより硬度が増
加している。<Effects of the Invention> The method of the present invention comprises applying a slurry containing platinum group chloride, methyl cellulose and sodium borohydride, borazane or methyl borazane as a substantial component to an electrode substrate,
It is heated by infrared rays and can be implemented very easily.
The hardness of the produced noble metal film is increased by using boride.
更に、製造された金属基体に白金族被膜を有する電極
は、過酷な条件したでも被膜が剥離することはなく、電
極として実用的価値が高い。Furthermore, the electrode having a platinum group coating on the manufactured metal substrate does not peel off even under severe conditions, and has high practical value as an electrode.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭46−3411（ＪＰ，Ａ) 特開 昭50−60436（ＪＰ，Ａ) 特開 昭53−119292（ＪＰ，Ａ) 特公 昭46−29482（ＪＰ，Ｂ１) 特公 昭47−2007（ＪＰ，Ｂ１) 特公 昭56−15443（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-46-3411 (JP, A) JP-A-50-60436 (JP, A) JP-A-53-119292 (JP, A) JP-B-46- 29482 (JP, B1) JP47-2007 (JP, B1) JP56-15443 (JP, B2)
Claims (2)
セルロース及びナトリウムボロハイドライド、ボラザン
又はメチルボラザンを含有するスラリー状物質を塗布
後、遠赤外加熱により、該塗布表面を加熱して、該塗布
面に、白金族金属被膜を生成せしめることを特徴とする
金属電極基体に対する白金族被膜の生成方法。1. A metal electrode substrate surface is coated with a slurry-like substance containing a platinum group chloride, methylcellulose and sodium borohydride, borazane or methylborazane, and then the coating surface is heated by far infrared heating to carry out the coating. A method for forming a platinum group coating on a metal electrode substrate, which comprises forming a platinum group metal coating on the surface.
パラジウム、ルテニウム、インジウムのいずれかである
特許請求の範囲第１項の金属電極基体に対する白金族被
膜の生成方法。2. The platinum group of the platinum group chloride is platinum, rhodium,
The method for forming a platinum group coating on a metal electrode substrate according to claim 1, which is one of palladium, ruthenium and indium.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61060814A JPH0657875B2 (en) | 1986-03-20 | 1986-03-20 | Method for forming platinum group coating on metal electrode substrate |
| KR870001562A KR870009057A (en) | 1986-03-20 | 1987-02-24 | Method of Forming Platinum Group Coatings on Metal Electrode Gases |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61060814A JPH0657875B2 (en) | 1986-03-20 | 1986-03-20 | Method for forming platinum group coating on metal electrode substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62218591A JPS62218591A (en) | 1987-09-25 |
| JPH0657875B2 true JPH0657875B2 (en) | 1994-08-03 |
Family
ID=13153192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61060814A Expired - Lifetime JPH0657875B2 (en) | 1986-03-20 | 1986-03-20 | Method for forming platinum group coating on metal electrode substrate |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0657875B2 (en) |
| KR (1) | KR870009057A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3775284A (en) * | 1970-03-23 | 1973-11-27 | J Bennett | Non-passivating barrier layer electrodes |
-
1986
- 1986-03-20 JP JP61060814A patent/JPH0657875B2/en not_active Expired - Lifetime
-
1987
- 1987-02-24 KR KR870001562A patent/KR870009057A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| KR870009057A (en) | 1987-10-23 |
| JPS62218591A (en) | 1987-09-25 |
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