JP2004307969A - Insoluble electrode, and its production method - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、電気めっきなどに使用される不溶性電極に関するものである。
【０００２】
【従来の技術】
一般に、電気めっき用の陽極として耐久性の高い不溶性電極の使用が考えられているが、更なる電極寿命の延長を図るため、例えば、特許文献１に示すように、チタン基体上に粒径１０〜６０μｍのチタン粉末を溶射して、厚さ１００〜２００μｍ、表面粗さＲａが５〜６．３μｍの粗面化溶射被膜を形成し、該被膜の上に白金族金属又はその酸化物を含む電極触媒物質をコーティングした不溶性電極が提案されている。なお、溶射法としては減圧プラズマ溶射が推奨されている。
しかし、この方法では、ある程度の寿命延長効果は認められたが、本発明が成膜対象とするＴｉ、Ｔａ、Ｎｂ、Ｚｒを既存の溶射法で溶射する場合には、高温であるため酸化が激しく、電気伝導性を低下させるおそれがある。また、減圧プラズマ溶射では被膜の密着性が十分でないという問題があった。
【０００３】
【特許文献１】
特開平１０−６０６９０号公報（特許請求の範囲）
【０００４】
【発明が解決しようとする課題】
本発明は、このような既存の溶射方式では得られないような十分な電気伝導性を有し、かつ、より高寿命の表面被膜を有する不溶性電極とその製造方法を提供することを課題とする。
【０００５】
【課題を解決するための手段】
上記課題を解決するための本発明の要旨は次のとおりである。
（１） Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかからなる母材の表面に、Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかと、該金属又は該合金の酸化物からなり、該酸化物の量が体積％で０．０１〜２％である中間層を有し、該中間層の表面に白金族金属酸化物からなる最表層を有することを特徴とする不溶性電極。
（２） Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかからなる母材の表面に、Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかと、体積％で０．０１〜２％の該金属又は該合金の酸化物、更に体積％で１０〜９０％の白金族金属酸化物からなる表層を有することを特徴とする不溶性電極。
（３） 中間層または表層の空隙率が１〜５０％であり、厚さが１〜１００μｍであることを特徴とする（１）又は（２）記載の不溶性電極。
（４） 最表層の厚さが１〜１００μｍであることを特徴とする（１）又は（３）記載の不溶性電極。
（５） 白金族金属酸化物がＩｒＯ２であることを特徴とする（１）〜（４）の何れか１項に記載の不溶性電極。
（６） 中間層を、Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかを原料として、コールドスプレーにより成膜し、最表層を塗布焼き付け法により形成することを特徴とする（１）、（３）〜（５）の何れか１項に記載の不溶性電極の製造方法
（７） 表層を、Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかと、体積％で１０〜９０％の白金族金属酸化物の混合物を原料として、コールドスプレーにより形成することを特徴とする（２）、（３）、（５）の何れか１項に記載の不溶性電極の製造方法。
（８） コールドスプレーの原料が、初期粒径０．００１〜１０μｍの白金族金属酸化物粒子と初期粒径１〜１００μｍのＴｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかの粒子とを造粒した大きさ１〜１００μｍの造粒粉であることを特徴とする（７）記載の不溶性電極の製造方法。
【０００６】
【発明の実施の形態】
以下、本発明の実施の形態について説明する。
まず、本発明にかかる不溶性電極は、電極母材の表面に被膜を形成したものであり、その被膜の一例は、中間層の表面に最表層が形成されている２層形態である。母材は、Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかからなる。母材の表面の中間層は、Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかと、その金属又は合金の酸化物からなり、その酸化物量が０．０１〜２体積％である。中間層の表面の最表層は、白金族金属酸化物を含む導電層である。
また、本発明にかかる不溶性電極の他の例は、電極母材の表面に、被膜として表層が形成されている１層形態である。母材は、Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかからなり、表層は、Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかとその金属又は合金の酸化物を体積％で０．０１〜２％含有し、更に白金族金属酸化物を１０〜９０体積％含むものである。
【０００７】
上記の２層形態の被膜の中間層又は１層形態の被膜の表層において、層を構成する金属又は合金の酸化物量を０．０１〜２体積％の範囲に規定したのは、酸化物をこの範囲内に抑えれば導電性を低下させないからである。
また、これら中間層、表層は、その空隙率を１〜５０％とし、厚さを１〜１００μｍとすることが望ましい。特に、空隙率を５０％として緻密な被膜とせずに多孔質とすれば、電極比表面積を大きくできるため使用時の電圧が低くてすみ、寿命を延ばすこともできる。中間層、表層の厚みについては効果を発揮するには最低でも１μｍは必要であり、また、１００μｍを超えて成膜しても意味はない。特に、効果的な厚みとしては１０〜５０μｍの範囲を選択することが好ましい。更に、最表層の厚みに関しても、同様に１〜１００μｍの範囲とし、特に、１０〜６０μｍの範囲が好適である。
【０００８】
なお、本発明にかかる不溶性電極の最も好適な材料としては、電極母材がＴｉからなり、中間層又は表層の金属がＴａであり、白金族金属酸化物がＩｒＯ２である。母材をＴｉとしたのは、Ｔａ、Ｎｂ、Ｚｒに比較し安価な材料であることが理由であり、また、中間層又は表層の金属をＴａとしたのは、この層をＴａ或いはＴａと白金族金属酸化物の組成とすることで、顕著な寿命延長効果が期待できるという理由による。更に、白金族金属酸化物をＩｒＯ２としたのは、硫酸溶液中で電気化学的に安定であり、かつ良好な電気伝導性と酸素発生の触媒特性を持つものとしてＩｒＯ２が広く用いられていたという理由による。なお、通常の溶射ではＩｒＯ２は溶射中に還元されて金属Ｉｒとなり特性を失うが、後述するコールドスプレーで成膜すれば還元せず特性劣化もないという点も理由の一つである。
中間層、表層の酸化物量は、コールドスプレーで形成した中間層、表層の断面を研磨してエッチングし、組織写真を走査型電子顕微鏡（ＳＥＭという）にて、１０００倍で観察し、１０視野の写真を撮影し、そのＳＥＭ組織写真を用いて、画像処理によって求めることができる。画像処理には、図１に示したように、ＳＥＭ写真を模式化したスケッチ図を用いても良い。図１において、図面の黒く塗りつぶした部分が空隙部、ハッチング部が酸化物である。酸化物量は、上述のＳＥＭ組織写真又はスケッチ図の空隙部を画像処理によって除外してから、酸化物の単位面積当りの面積率を測定し、１０視野の単純平均値を体積％とすれば良い。
また、表層の白金族金属酸化物の体積％も、酸化物量と同様にして求めることができる。中間層及び表層の空隙率は、上述のＳＥＭ組織写真又はスケッチ図を用いて、画像処理し、空隙部の単位面積当りの面積率を測定し、１０視野の平均値として求めれば良い。
【０００９】
また、本発明は、上記した被膜を有する不溶性電極の製造方法として、その被膜をコールドスプレーによって成膜することを特徴するものである。
「コールドスプレー」とは、技術文献である「溶射技術」ＶＯＬ．２０−ＮＯ．２ 別刷（２０００年８月発行）の「新しい溶射プロセス」及び「溶射技術」ＶＯＬ．２１−ＮＯ．３ 別刷（２００２年２月５日発行）の「コールドスプレーテクノロジー」（いずれも信州大学 榊 和彦氏発表）に説明されているように、溶射材料の融点又は軟化温度よりも低い温度のガスを超音速流にして、前記超音速流のガス中に前記溶射材料の粒子を投入し、固相状態のまま基材に衝突させて被膜を形成する技術である。これを実現する設備として上記文献には、先細末広形の超音速ガスノズルの後方から所望の溶射粉末材料を加熱・加圧した作動ガスにて送給して基体表面に衝突させる形式のものが開示されている。
このコールドスプレーは、従来のプラズマ溶射法、フレーム溶射法、高速フレーム溶射法などに比べ、溶射材料粒子を加熱・加速する作動ガスの温度が著しく低く、溶射粒子をあまり加熱せずに固相状態のまま基材へ高速で衝突させ、そのエネルギーにより基材と粒子に塑性変形を生じさせて成膜させるものである。これによって得た被膜は、緻密で密度、熱・電気伝導性が高く、酸化や熱変質も少なく、密着性も良好であるという、優れた性質を有する。
【００１０】
本発明では、このコールドスプレーを不溶性電極の表面被膜形成に利用すれば、狙いとする優れた性質を有する被膜が得られることを知見したものである。すなわち、中間層と最表層を有する２層形態の被膜を形成する場合には、中間層として、Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかからなり、酸化物量が０．０１〜２体積％からなる材料を選択し、これを粒子の形で超音速ガス流にのせてコールドスプレーにより成膜する。また、最表層は、白金族金属酸化物（例えば、ＩｒＯ２）を塗布焼付け法により形成することが望ましい。塗布焼付け法は、Ｉｒ等の白金族金属化合物を主成分とする溶液を中間層に塗布し、酸化性雰囲気でＩｒ等の金属が酸化物になる温度で焼成し、所望の厚さになるまでこれを繰り返して行う方法である。
【００１１】
一方、表層だけの１層形態の被膜を形成する場合には、Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかと、１０〜９０体積％の白金族金属酸化物を混合し、粒子の形で超音速ガス流にのせてコールドスプレーにより母材の表面に成膜すればよい。なお、原料を体積％で所定量として混合するには、予めＴｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金、白金族金属酸化物の密度を測定し、重量を体積に換算すればよい。
【００１２】
前記の中間層及び表層をコールドスプレーで成膜する際、コールドスプレーの原料は、初期粒径０．００１〜１０μｍの白金族金属酸化物粒子と、初期粒径１〜１００μｍの金属粒子（Ｔｉ、Ｔｉ合金、Ｔａ、Ｔａ合金、Ｎｂ、Ｎｂ合金、Ｚｒ、Ｚｒ合金の何れかの粒子）を燒結或いはバインダーを介して造粒した大きさ１〜１００μｍの造粒粉であることが望ましい。このような造粒粉を用いた場合、ナノレベルで材料が均一に分散することから、従来のような結晶粒界からの局部腐食が発生しない。この造粒粉をコールドスプレーする際には、空気、窒素或いはヘリウムを作動ガスとして、衝突速度を６００ｍ／ｓ以上として１０〜５０ｍｍの距離でロール本体表面に衝突させて成膜されることが確認された。
【００１３】
【実施例】
本発明を電気亜鉛めっきラインの電極（陽極）に適用した場合を実施例として示す。実施例のＮｏ．１〜４がＴｉ、Ｔａ、Ｎｂ、Ｚｒのいずれかからなる中間層とＩｒＯ２からなる最表層で被膜を形成した場合（２膜形態）、Ｎｏ．５〜１０がＴｉ、Ｔａ、Ｎｂ、ＺｒのいずれかとＩｒＯ２を配合した表層で被膜を形成した場合（１膜形態）を示す。なお、本発明の中間層及び表層はコールドスプレーで形成したものであり、本発明及び比較例の最表層は、塗布焼付け法にて形成したものである。
コールドスプレーの条件及びスプレー設備は、すべて前掲した技術文献（「溶射技術」）に記載された範囲内での条件や設備を用いた。めっき条件は次のとおりである。
・ライン速度：１８０ｍ／ｍ
・電流密度：１００Ａ／ｄｍ２
・めっき液：硫酸亜鉛２８０ｇ／ｌ、硫酸３０ｇ／ｌ、ｐＨ１．２、浴温６０℃
【００１４】
表１の酸化物量、空隙率及び本発明Ｎｏ．５〜１０の表層の組成におけるＩｒＯ２の体積％は、次のようにして算定した。すなわち、コールドスプレーで形成した中間層及び表層の断面を研磨し、エッチングして組織をＳＥＭにて１０００倍で観察し、１０視野の写真を撮影し、図１に例示したように模式化したスケッチ図とした。このスケッチ図を用いて画像処理により、空隙率、酸化物量及び表層のＩｒＯ２の体積％を求めた。
まず、図１の黒く塗りつぶした空隙部の、単位面積当りの面積率を測定し、１０視野の平均値を空隙率とした。次に、空隙部を除外して、図１のハッチング部である酸化物の単位面積当りの面積率を測定し、１０視野の単純平均値を体積％とした。表層のＩｒＯ２の体積％も酸化物量と同様にして求めた。表１のｖｏｌ％は体積％を意味する。
【００１５】
本発明により形成された被膜は、いずれも酸化物量はきわめて少なく、また、実施結果として示す電極の寿命延長効果についても比較例に比し高い寿命延長効果を有することが認められる。表１の寿命延長効果は、比較例を１００％として、本発明の寿命を百分率で示したものである。また、表には示していないが、密着性も良好であり、電気伝導性についても十分実用に耐える程度のものが得られた。
【００１６】
【表１】
【発明の効果】
以上説明したごとく本発明に係る不溶性電極によれば、良好な電気伝導性を有すると共に、従来のものより高寿命の表面被膜をもった電極とすることができるため、電気めっきラインの電極として最適なものといえる。また、本発明のコールドスプレーを利用した製造方法によって、上記した被膜を有する電極を容易に得ることができ、その産業上の利益は非常に大きい。
【図面の簡単な説明】
【図１】コールドスプレーで形成した被膜の断面組織写真に基づき模式化して作成したスケッチ図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an insoluble electrode used for electroplating and the like.
[0002]
[Prior art]
In general, use of a highly durable insoluble electrode as an anode for electroplating is considered. However, in order to further extend the electrode life, for example, as shown in Patent Document 1, a particle size of 10チ タ ン 60 μm titanium powder is sprayed to form a roughened thermal spray coating having a thickness of 100 to 200 μm and a surface roughness Ra of 5 to 6.3 μm, and a platinum group metal or an oxide thereof is included on the coating. Insoluble electrodes coated with an electrocatalytic substance have been proposed. In addition, reduced pressure plasma spraying is recommended as a thermal spraying method.
However, in this method, although a certain effect of prolonging the life was recognized, when Ti, Ta, Nb, and Zr to be formed into a film in the present invention were sprayed by the existing thermal spraying method, oxidation was carried out because of the high temperature. Violently, the electric conductivity may be reduced. Further, there is a problem that the adhesion of the coating is not sufficient in the low pressure plasma spraying.
[0003]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 10-60690 (claims)
[0004]
[Problems to be solved by the invention]
It is an object of the present invention to provide an insoluble electrode having a sufficient electric conductivity that cannot be obtained by such an existing thermal spraying method, and having a surface coating having a longer life, and a method for producing the same. .
[0005]
[Means for Solving the Problems]
The gist of the present invention for solving the above problems is as follows.
(1) On the surface of a base material made of any of Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, Zr alloy, Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, An intermediate layer comprising any one of a Zr alloy and an oxide of the metal or the alloy, wherein the amount of the oxide is 0.01 to 2% by volume by volume; An insoluble electrode having an outermost layer made of a material.
(2) Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, An insoluble material having a surface layer composed of any one of a Zr alloy and 0.01 to 2% by volume of the metal or an oxide of the alloy, and further including 10 to 90% by volume of a platinum group metal oxide. electrode.
(3) The insoluble electrode according to (1) or (2), wherein the intermediate layer or the surface layer has a porosity of 1 to 50% and a thickness of 1 to 100 μm.
(4) The insoluble electrode according to (1) or (3), wherein the outermost layer has a thickness of 1 to 100 μm.
(5) a platinum group metal oxide is characterized in that it is a IrO 2 (1) insoluble electrode according to any one of - (4).
(6) The intermediate layer is formed by cold spraying using any of Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, and Zr alloy as a raw material, and the outermost layer is formed by coating and baking. (1) The method for producing an insoluble electrode according to any one of (1) and (3) to (5), wherein the surface layer is made of Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr , Zr alloy, and a mixture of 10 to 90% by volume of a platinum group metal oxide as a raw material, and formed by cold spraying. (2), (3), (5) 2. The method for producing an insoluble electrode according to claim 1.
(8) The raw materials of the cold spray are platinum group metal oxide particles having an initial particle diameter of 0.001 to 10 μm and Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, Zr having an initial particle diameter of 1 to 100 μm. (7) The method for producing an insoluble electrode according to (7), wherein the powder is a granulated powder having a size of 1 to 100 μm obtained by granulating any of the alloy particles.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described.
First, the insoluble electrode according to the present invention has a coating formed on the surface of the electrode base material, and one example of the coating is a two-layer form in which the outermost layer is formed on the surface of the intermediate layer. The base material is made of any of Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, and Zr alloy. The intermediate layer on the surface of the base material is made of any of Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, Zr alloy, and an oxide of the metal or alloy, and the amount of the oxide is 0.01 to 2% by volume. The outermost layer on the surface of the intermediate layer is a conductive layer containing a platinum group metal oxide.
Another example of the insoluble electrode according to the present invention is a one-layer form in which a surface layer is formed as a coating on the surface of the electrode base material. The base material is made of any of Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, Zr alloy, and the surface layer is Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, Zr. The alloy contains 0.01 to 2% by volume of any one of the alloys and the oxide of the metal or alloy, and further contains 10 to 90% by volume of a platinum group metal oxide.
[0007]
In the intermediate layer of the two-layered film or the surface layer of the one-layered film, the amount of the oxide of the metal or alloy constituting the layer is defined in the range of 0.01 to 2% by volume. This is because the conductivity is not reduced if the content is within the range.
The intermediate layer and the surface layer preferably have a porosity of 1 to 50% and a thickness of 1 to 100 μm. In particular, if the porosity is 50% and the coating is made porous instead of a dense coating, the electrode specific surface area can be increased, so that the voltage at the time of use can be reduced and the life can be extended. Regarding the thickness of the intermediate layer and the surface layer, a thickness of at least 1 μm is necessary for exhibiting the effect, and it is meaningless to form a film exceeding 100 μm. In particular, it is preferable to select an effective thickness in the range of 10 to 50 μm. Further, the thickness of the outermost layer is similarly set in the range of 1 to 100 μm, and particularly preferably in the range of 10 to 60 μm.
[0008]
In addition, as the most preferable material of the insoluble electrode according to the present invention, the electrode base material is made of Ti, the metal of the intermediate layer or the surface layer is Ta, and the platinum group metal oxide is IrO 2 . The reason why the base material was made of Ti was that it was an inexpensive material as compared with Ta, Nb, and Zr, and that the metal of the intermediate layer or the surface layer was made of Ta because this layer was made of Ta or Ta. The reason for this is that a significant life extension effect can be expected by using a platinum group metal oxide composition. Further, IrO 2 is used as the platinum group metal oxide because IrO 2 is widely used because it is electrochemically stable in a sulfuric acid solution and has good electric conductivity and catalytic properties for generating oxygen. For the reason. It should be noted that IrO 2 is reduced during thermal spraying to form Ir as a metal and loses its properties during normal thermal spraying. One of the reasons is that IrO 2 is not reduced and has no property deterioration when formed by a cold spray described later.
The oxide amount of the intermediate layer and the surface layer was determined by polishing and etching the cross section of the intermediate layer and the surface layer formed by cold spraying, and observing a micrograph of the structure with a scanning electron microscope (SEM) at 1000 times. A photograph can be taken and determined by image processing using the SEM micrograph. For the image processing, as shown in FIG. 1, a sketch diagram in which a SEM photograph is typically used may be used. In FIG. 1, black portions in the drawing are void portions, and hatched portions are oxides. The amount of oxide may be obtained by removing the voids in the above-mentioned SEM micrograph or sketch by image processing, measuring the area ratio per unit area of the oxide, and setting the simple average value of 10 visual fields as volume%. .
Further, the volume% of the platinum group metal oxide in the surface layer can be determined in the same manner as the amount of the oxide. The porosity of the intermediate layer and the surface layer may be obtained as an average value of 10 visual fields by performing image processing using the above-mentioned SEM micrograph or sketch drawing, measuring the area ratio of the void portion per unit area.
[0009]
According to the present invention, as a method for producing an insoluble electrode having the above-mentioned coating, the coating is formed by cold spraying.
"Cold spray" is a technical document of "spraying technology" VOL. 20-NO. 2 “New Spray Process” and “Spray Technology”, Vol. 21-NO. 3. As described in “Cold Spray Technology” in a separate print (issued on February 5, 2002) (both announced by Kazuhiko Sakaki, Shinshu University), a gas with a temperature lower than the melting point or softening temperature of the sprayed material is superimposed. This is a technique in which particles of the thermal spray material are charged into the supersonic flow gas in a sonic flow, and the particles are made to collide with a substrate in a solid state to form a coating. As a facility for realizing this, the above-mentioned document discloses a type in which a desired sprayed powder material is fed from behind a tapered and divergent supersonic gas nozzle with a heated and pressurized working gas to collide with a substrate surface. Have been.
Compared to conventional plasma spraying, flame spraying, and high-speed flame spraying, the cold spray uses a significantly lower temperature of the working gas that heats and accelerates the sprayed material particles. The substrate is made to collide with the substrate at high speed as it is, and the energy causes plastic deformation of the substrate and particles to form a film. The coating thus obtained has excellent properties of being dense, having high density, high thermal and electrical conductivity, less oxidation and thermal deterioration, and having good adhesion.
[0010]
In the present invention, it has been found that if this cold spray is used for forming a surface film of an insoluble electrode, a film having desired excellent properties can be obtained. That is, when forming a two-layered film having an intermediate layer and an outermost layer, the intermediate layer is made of any of Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, and Zr alloy, A material having an oxide amount of 0.01 to 2% by volume is selected, and the material is placed in a supersonic gas flow in the form of particles and formed into a film by cold spraying. The outermost layer is desirably formed by applying and baking a platinum group metal oxide (for example, IrO 2 ). In the coating baking method, a solution containing a platinum group metal compound such as Ir as a main component is applied to the intermediate layer, and baked in an oxidizing atmosphere at a temperature at which a metal such as Ir becomes an oxide, until a desired thickness is obtained. This is a method of repeating this.
[0011]
On the other hand, in the case of forming a single-layer coating film having only the surface layer, any one of Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, and Zr alloy is mixed with 10 to 90% by volume of a platinum group metal oxide. The materials may be mixed, placed in a supersonic gas flow in the form of particles, and formed into a film on the surface of the base material by cold spraying. In order to mix the raw materials as a predetermined amount in volume%, the density of Ti, Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, Zr alloy, and platinum group metal oxide is measured in advance, and the weight is measured by volume. It can be converted to
[0012]
When the intermediate layer and the surface layer are formed by cold spraying, the raw materials for cold spraying include platinum group metal oxide particles having an initial particle size of 0.001 to 10 μm and metal particles having an initial particle size of 1 to 100 μm (Ti, It is desirable to use granulated powder having a size of 1 to 100 μm obtained by granulating Ti alloy, Ta, Ta alloy, Nb, Nb alloy, Zr, or Zr alloy) through sintering or a binder. When such a granulated powder is used, since the material is uniformly dispersed at the nano level, local corrosion from the crystal grain boundary does not occur as in the related art. When cold-spraying this granulated powder, it was confirmed that the film was formed by colliding with air, nitrogen or helium as a working gas at a collision speed of 600 m / s or more at a distance of 10 to 50 mm at a distance of 10 to 50 mm. Was done.
[0013]
【Example】
An example in which the present invention is applied to an electrode (anode) of an electrogalvanizing line will be described. No. of the embodiment. Nos. 1 to 4 were formed of a coating of an intermediate layer made of any of Ti, Ta, Nb, and Zr and an outermost layer made of IrO 2 (two-film form). Nos. 5 to 10 show the case where a coating was formed with a surface layer containing one of Ti, Ta, Nb and Zr and IrO 2 (one film form). The intermediate layer and the surface layer of the present invention were formed by cold spraying, and the outermost layers of the present invention and the comparative examples were formed by coating and baking.
The cold spray conditions and spray equipment used were all within the ranges described in the above-mentioned technical literature ("spraying technique"). The plating conditions are as follows.
・ Line speed: 180m / m
・ Current density: 100 A / dm 2
-Plating solution: zinc sulfate 280 g / l, sulfuric acid 30 g / l, pH 1.2, bath temperature 60 ° C
[0014]
Table 1 shows the amount of oxide, porosity, and No. Vol% of IrO 2 in the surface layer of the composition of 5 to 10 was calculated as follows. That is, the cross section of the intermediate layer and the surface layer formed by the cold spray is polished, etched, and the structure is observed with a SEM at a magnification of 1000 times. A photograph of 10 fields of view is taken, and a sketch schematically illustrated as illustrated in FIG. Figure. The porosity, the amount of oxide, and the volume percentage of IrO 2 in the surface layer were determined by image processing using the sketch diagram.
First, the area ratio per unit area of the black void portion in FIG. 1 was measured, and the average value of 10 visual fields was defined as the void ratio. Next, excluding the voids, the area ratio per unit area of the oxide, which is the hatched portion in FIG. 1, was measured, and the simple average value of 10 visual fields was defined as volume%. The volume percentage of IrO 2 in the surface layer was determined in the same manner as the oxide amount. In Table 1, vol% means% by volume.
[0015]
It is recognized that the coatings formed according to the present invention have very small amounts of oxides, and that the electrode has a longer life-extending effect than the comparative example. The life extension effect in Table 1 shows the life of the present invention as a percentage, with the comparative example taken as 100%. Although not shown in the table, the adhesiveness was good, and the electrical conductivity was sufficiently high to withstand practical use.
[0016]
[Table 1]
【The invention's effect】
As described above, the insoluble electrode according to the present invention has good electrical conductivity and can be an electrode having a surface coating having a longer life than conventional ones, and thus is most suitable as an electrode for an electroplating line. It can be said that. Further, by the manufacturing method using the cold spray of the present invention, an electrode having the above-mentioned coating can be easily obtained, and its industrial advantage is very large.
[Brief description of the drawings]
FIG. 1 is a sketch diagram schematically created based on a photograph of a cross-sectional structure of a film formed by cold spraying.
Claims (8)
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| JP2003105539A JP4163986B2 (en) | 2003-04-09 | 2003-04-09 | Insoluble electrode and method for producing the same |
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| JP2003105539A JP4163986B2 (en) | 2003-04-09 | 2003-04-09 | Insoluble electrode and method for producing the same |
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