JPH05209299A - Insoluble electrode and its production - Google Patents
Insoluble electrode and its productionInfo
- Publication number
- JPH05209299A JPH05209299A JP4035843A JP3584392A JPH05209299A JP H05209299 A JPH05209299 A JP H05209299A JP 4035843 A JP4035843 A JP 4035843A JP 3584392 A JP3584392 A JP 3584392A JP H05209299 A JPH05209299 A JP H05209299A
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- layer
- valve metal
- electrode
- iro
- coating
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は不溶性電極及びその製
造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insoluble electrode and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】一般に金属材の電気メッキに際し、電気
メッキ浴中にて不溶性電極を使用し、陰極たる被メッキ
金属材の表面にＺｎ、Ｓｎ、Ｎｉなどの金属を電気メッ
キすることが行われている。2. Description of the Related Art Generally, in electroplating a metal material, an insoluble electrode is used in an electroplating bath to electroplate a metal such as Zn, Sn, or Ni on the surface of a metal material to be plated which is a cathode. ing.
【０００３】また金属の電気精錬に際し、精錬浴中にて
不溶性電極を使用し、Ｍｎ、Ｚｎ等の金属を電気精錬す
ることが行われている。In electrorefining of metals, insoluble electrodes are used in a refining bath to electrorefine metals such as Mn and Zn.
【０００４】この時の不溶性電極として、最も一般的に
使用されているものとして、Ｐｂ系合金があげられる。The most commonly used insoluble electrode at this time is a Pb-based alloy.
【０００５】この電極は、電気メッキ浴、電気精錬浴、
特に硫酸溶液中では、通電処理時その表面にＰｂＯ2が
生成する。This electrode is used for electroplating bath, electrorefining bath,
Particularly, in a sulfuric acid solution, PbO 2 is formed on the surface of the solution during energization.
【０００６】そのＰｂＯ2は、不溶性電極の機能を発揮
しているが、生成したＰｂＯ2とＰｂとの付着力が弱く
電解溶液中に混入しメッキ不良、あるいは不純物混入精
錬金属を生じてしまう。Although PbO 2 exhibits the function of an insoluble electrode, the generated PbO 2 and Pb have a weak adhesive force and are mixed in the electrolytic solution to cause defective plating or refining metal containing impurities.
【０００７】そこで対策として、電気メッキ浴、電気製
錬浴、特に硫酸溶液中で最も電気化学的に安定である白
金族酸化物であるＩｒＯ2を、母材であるバルブ金属
（Ｔｉ、Ｔａ、Ｚｒ等の金属で、通電により表面に絶縁
性の酸化物層を形成し通電をストップしてしまう金属）
層上に被膜化した電極が特公昭４８―３９５４号公報に
示されている。Therefore, as a countermeasure, an electroplating bath, an electric smelting bath, especially IrO 2 , which is a platinum group oxide, which is the most electrochemically stable in a sulfuric acid solution, is used as a base material for a valve metal (Ti, Ta, (A metal such as Zr that forms an insulating oxide layer on the surface and stops energization when energized)
An electrode coated on a layer is disclosed in JP-B-48-3954.
【０００８】さらにバルブ金属層の酸化を抑制する、あ
るいは密着性を向上させるために中間層にＴａ2Ｏ5等を
添加した被膜を形成し、この上にＩｒ Ｏ2層を形成した
不溶性電極を使用する方法が特公昭４６―２１８８４号
公報、特開昭６３―２３５４９３号公報に示されてい
る。Further, it suppresses the oxidation of the valve metal layer.
In order to improve adhesion,2OFiveEtc.
The added film is formed and Ir is formed on the film. O2Formed layers
The method of using an insoluble electrode is Japanese Patent Publication No. 46-21884.
Japanese Patent Laid-Open No. 63-235493
It
【０００９】図１にその電極構造を示す。１はＳＵＳ製
電極母材、２はバルブ金属層、３はＩｒＯ2―Ｔａ2Ｏ5
層、４はＩｒＯ2層である。FIG. 1 shows the electrode structure. 1 is a SUS electrode base material, 2 is a valve metal layer, 3 is IrO 2 —Ta 2 O 5
Layers 4 are IrO 2 layers.
【００１０】この層３、４の施工方法は酸化物となる溶
液をバルブ金属層上に塗布し、それを酸化物となる温度
で焼成することを繰り返すことにより作製する、いわゆ
る塗布焼き付け法である。The method of applying the layers 3 and 4 is a so-called coating baking method in which a solution which becomes an oxide is applied to the valve metal layer and the baking is repeated at a temperature where it becomes an oxide. .
【００１１】[0011]
【発明が解決しようとする課題】特公昭４６―２１８８
４号公報、特開昭６３―２３５４９３号公報に提示され
ている塗布焼き付け法によるＩｒＯ2を主体とした層を
有する不溶性電極は、低電流密度（〜１００Ａ／ｄ
ｍ2）では長時間使用可能であるが、高電流密度下、特
に硫酸溶液中１５０Ａ／ｄｍ2で通電腐食試験を行う
と、３０００〜４０００時間で急激な電圧上昇が起こり
電極が使用不可能となる。[Problems to be Solved by the Invention] Japanese Patent Publication No. 46-2188
No. 4, JP-A-63-235493, an insoluble electrode having a layer mainly composed of IrO 2 formed by a coating and baking method has a low current density (up to 100 A / d).
m 2 ), it can be used for a long time, but when conducting an electrical corrosion test under a high current density, especially in a sulfuric acid solution at 150 A / dm 2 , a sharp voltage rise occurs in 3000 to 4000 hours and the electrode becomes unusable. Become.
【００１２】この電極の腐食メカニズムを図２により説
明する。ＩｒＯ2を含有する層３、４は溶液の熱処理に
より作製されるため溶液成分の揮発による気孔が、また
バルブ金属層とＩｒＯ2層との熱膨張差によって亀甲状
クラック５が被膜中に発生している。The corrosion mechanism of this electrode will be described with reference to FIG. Since the IrO 2 -containing layers 3 and 4 are formed by heat treatment of the solution, pores due to volatilization of the solution components are generated, and a hexagonal crack 5 is generated in the coating film due to the difference in thermal expansion between the valve metal layer and the IrO 2 layer. ing.
【００１３】このため被膜の空隙率が５〜３０％と大き
く、また比表面積も大きく単位面積当たりの電流密度が
低いため溶損スピードは遅い反面、この気孔とクラック
から、バルブ金属層２との直接通電が起こり、バルブ金
属層表面に絶縁性酸化物被膜６が形成され、更にバルブ
金属層と被膜界面を伝わりバルブ金属層の酸化が進み、
電圧上昇を引き起こし電極としての機能を失ってしま
う。この対策としては、気孔、クラックのない均質被膜
を作製することが必要である。Therefore, the porosity of the coating is as large as 5 to 30%, the specific surface area is large, and the current density per unit area is low, so that the melting loss speed is slow, but the pores and cracks cause the formation of the valve metal layer 2. Direct energization occurs, the insulating oxide film 6 is formed on the surface of the valve metal layer, and further the oxidation of the valve metal layer progresses through the interface between the valve metal layer and the film,
The voltage rises and the electrode function is lost. As a countermeasure against this, it is necessary to produce a homogeneous coating film without pores and cracks.
【００１４】従来特公昭４６―２１８８４号公報、日本
写真学会誌［Ｖｏｌ５１，Ｎｏ．１，ｐ３（１９８
８）］にＩｒ金属をスパッタするとともに基板上近傍で
酸化させ均質でクラック、気孔がほとんどない被膜を得
る方法として反応性スパッタ法、反応性蒸着法が示され
ている。Conventional Japanese Patent Publication No. 46-21884, Journal of the Photographic Society of Japan [Vol51, No. 1, p3 (198
8)], a reactive sputtering method and a reactive vapor deposition method are shown as a method of sputtering Ir metal and oxidizing it near the substrate to obtain a uniform coating film having almost no cracks or pores.
【００１５】しかし、この反応性スパッタ法、反応性蒸
着法により作製したＩｒＯ2被膜（以下ＩｒＯ2反応性ス
パッタ被膜、ＩｒＯ2反応性蒸着被膜とする）は１００
Ａ／ｄｍ2の低電流密度での通電により短時間で通電が
ストップしてしまうという欠点がある。However, the IrO 2 film (hereinafter referred to as IrO 2 reactive sputter film or IrO 2 reactive vapor deposition film) produced by this reactive sputtering method or reactive vapor deposition method is 100.
There is a drawback that energization is stopped in a short time due to energization at a low current density of A / dm 2 .
【００１６】この理由は、ＩｒＯ2反応性スパッタ被
膜、ＩｒＯ2反応性蒸着被膜が厚膜化により剥離し易
く、作製最適膜厚が数１００〜数１０００Åで非常に薄
く、更に被膜が均質故に塗布焼き付けＩｒＯ2被膜と比
べ比表面積が少なく単位面積当たりの電流密度が大きく
溶損スピードが早いためである。The reason for this is that the IrO 2 reactive sputter coating and the IrO 2 reactive vapor deposition coating are easily peeled off by increasing the film thickness, and the optimum film thickness for production is several hundred to several thousand Å, which is very thin. This is because the specific surface area is smaller than that of the baked IrO 2 coating, the current density per unit area is large, and the melting speed is fast.
【００１７】本発明は、１５０Ａ／ｄｍ2以上の高電流
密度で電解を行っても耐食性に優れ、長時間の使用に耐
える不溶性電極及びその製造方法を提供するものであ
る。The present invention provides an insoluble electrode having excellent corrosion resistance even when electrolysis is carried out at a high current density of 150 A / dm 2 or more and capable of withstanding long-term use, and a method for producing the same.
【００１８】[0018]
【課題を解決するための手段】本発明の第１の発明は、
電極母材表面に第１層としてバルブ金属層、第２層とし
てバルブ金属とＩｒの酸化物層、第３層としてＩｒＯ2
層を持つことを特徴とする不溶性電極であり、第２の発
明は、電極母材表面に第１層としてバルブ金属層、第２
層としてバルブ金属とＩｒの酸化物層、第３層として緻
密質ＩｒＯ2層、第４層として空隙率５から３０％のポ
ーラスなＩｒＯ2層を持つことを特徴とする不溶性電極
である。The first invention of the present invention is as follows:
A valve metal layer as a first layer, a valve metal and Ir oxide layer as a second layer, and IrO 2 as a third layer on the surface of the electrode base material.
A second aspect of the present invention is an insoluble electrode having a layer, wherein the first invention is a valve metal layer and a second layer is a first layer on the surface of the electrode base material.
The insoluble electrode is characterized by having a valve metal and an Ir oxide layer as a layer, a dense IrO 2 layer as a third layer, and a porous IrO 2 layer having a porosity of 5 to 30% as a fourth layer.
【００１９】また第３の発明は、第１の発明と第２の発
明の不溶性電極の製造方法であり、該不溶性電極におけ
る第２層の酸化物層を５００〜８００℃、０．５ｈｒ以
上１０ｈｒ以内加熱して後、第３層を形成することを特
徴とする不溶性電極の製造方法である。A third invention is a method for producing an insoluble electrode according to the first invention and the second invention, wherein the oxide layer of the second layer in the insoluble electrode is 500 to 800 ° C., 0.5 hr to 10 hr. The method for producing an insoluble electrode is characterized in that the third layer is formed after heating within.
【００２０】[0020]
【作用】本発明の第１の発明及び第２の発明の電極構造
例を図３、４に示す。The electrode structure examples of the first and second inventions of the present invention are shown in FIGS.
【００２１】第１の発明の電極は図３に示すようにＩｒ
Ｏ2被膜（例えば塗布焼き付け法により作製した）とバ
ルブ金属層間に熱処理により形成したバルブ金属とＩｒ
Ｏ2の拡散層７を持つ。The electrode of the first invention is Ir as shown in FIG.
The valve metal and Ir formed by heat treatment between the O 2 film (for example, prepared by coating and baking) and the valve metal layer
It has an O 2 diffusion layer 7.
【００２２】このためバルブ金属層とＩｒＯ2被膜層間
の密着強度が高く、界面からのバルブ金属層の酸化進行
が抑制され、１５０Ａ／ｄｍ2 以上の高電流密度で電解
を行っても耐食性に優れ長時間の使用に耐えるという特
徴を持つ。Therefore, the valve metal layer and IrO2Between layers
Has high adhesion strength, and oxidation of valve metal layer progresses from the interface
Is suppressed, 150 A / dm2 Electrolysis at higher current density
It has excellent corrosion resistance and can be used for a long time.
Have signs.
【００２３】また第２の発明の電極は図４に示すように
バルブ金属層上に反応性スパッタ法、蒸着法等により作
製した薄膜緻密質ＩｒＯ2層８、更に熱処理により形成
したバルブ金属層とＩｒＯ2被膜の拡散層７を持つため
バルブ金属層とＩｒＯ2被膜層間の密着強度が非常に高
く界面からのバルブ金属層の酸化進行が抑制される。As shown in FIG. 4, the electrode of the second invention comprises a thin film dense IrO 2 layer 8 formed on the valve metal layer by a reactive sputtering method, a vapor deposition method or the like, and a valve metal layer formed by heat treatment. oxidation progression of valve metal layer from a very high interfacial adhesion strength of the valve metal layer and the IrO 2 film layers to have the diffusion layer 7 of the IrO 2 film is suppressed.
【００２４】また被膜上層として塗布焼き付けにより作
製した多孔質（ポーラス）被膜をもつため面積当たりの
電流密度が低く被膜の溶損も少ない。Further, since a porous (porous) coating produced by coating and baking is provided as an upper layer of the coating, the current density per area is low and the coating is less likely to be melted.
【００２５】このため１５０Ａ／ｄｍ2以上の高電流密
度で電解を行っても耐食性に優れ図３の電極に比べ更に
長時間の使用に耐えるという特徴を持つ。Therefore, even if electrolysis is performed at a high current density of 150 A / dm 2 or more, it has excellent corrosion resistance and can withstand a longer period of use than the electrode of FIG.
【００２６】[0026]
【実施例】以下今回試験試料の作製方法、評価方法及び
結果について詳細に述べる。[Examples] In the following, the method of preparing the test sample, the evaluation method and the result will be described in detail.
【００２７】まず、試験試料の作製方法を示す。 １）１００×１００×２０ｍｍのＴｉ母材の表面を蓚酸
を用いて洗浄First, a method for preparing a test sample will be described. 1) Cleaning the surface of 100 × 100 × 20 mm Ti base material with oxalic acid
【００２８】２）母材上に反応性スパッタ法、反応性蒸
着法またはＩｒＯ2塗布焼き付け法によりＩｒＯ2被膜を
成膜、以下各方法による被膜作製方法を示す。2) An IrO 2 film is formed on the base material by the reactive sputtering method, the reactive vapor deposition method or the IrO 2 coating and baking method, and the method for forming the film by each method will be described below.
【００２９】２―１）反応性スパッタ被膜 母材Ｔｉ板を真空中（８×１０-4ｔｏｒｒ）でＩｒ板と
対向させて設置した。真空槽中をＡｒ圧１×１０-1〜２
×１０-2ｔｏｒｒにし、ターゲットに１ｋＶの電位を印
加してＡｒイオンを放電させＩｒ板にあてＩｒ原子を叩
き出し、ガス圧４．５×１０-4ｔｏｒｒでＯ2ガスを基
材上に吹きつけ成膜速度２Å／ｓｅｃでＴｉ母材表面に
ＩｒＯ2反応性スパッタ被膜１０００Åを作製した。2-1) Reactive Sputtered Coating A base material Ti plate was placed in vacuum (8 × 10 −4 torr) so as to face the Ir plate. Ar pressure 1 × 10 -1 to 2 in the vacuum chamber
× to 10 -2 torr, by applying 1kV potential to target hammered the Ir atom devoted to Ir plate discharges the Ar ions, the O 2 gas onto the substrate at a gas pressure of 4.5 × 10 -4 torr An IrO 2 reactive sputter coating 1000 Å was formed on the surface of the Ti base material at a spraying film formation rate of 2 Å / sec.
【００３０】２―２）反応性蒸着被膜 母材Ｔｉ板を真空中（８×１０-4ｔｏｒｒ）でＩｒ板と
対向させて設置した。2-2) Reactive Vapor Deposition Coating A base material Ti plate was placed in vacuum (8 × 10 −4 torr) so as to face the Ir plate.
【００３１】このＩｒ板を２００Ｗで電子ビーム加熱
し、Ｉｒを蒸発させ、さらにガス圧６．５×１０-4ｔｏ
ｒｒでＯ2ガスを導入し成膜速度２Å／ｓｅｃでＴｉ母
材表面にＩｒＯ2反応性蒸着被膜１０００Åを作成し
た。This Ir plate was heated with an electron beam at 200 W to evaporate Ir, and the gas pressure was 6.5 × 10 −4 to.
An O 2 gas was introduced at rr to form an IrO 2 reactive vapor deposition film 1000 Å on the surface of the Ti base material at a film forming rate of 2 Å / sec.
【００３２】２―３）塗布焼き付け被膜 熱分解によりＩｒＯ2となるＨ2ＩｒＣｌ6をブタノール
に溶解してＩｒ金属濃度が６０ｇ／ｌになるように調整
した塗布焼き付け被膜溶液を筆で塗布し、乾燥後電気炉
に入れ４５０℃で焼き付ける操作を８回程度行いＩｒＯ
2塗布焼き付け法被膜を約５０μｍ形成した。2-3) Coating baking coating A coating baking coating solution prepared by dissolving H 2 IrCl 6 which becomes IrO 2 by thermal decomposition in butanol to adjust the Ir metal concentration to 60 g / l is coated with a brush, After drying, put in an electric furnace and bake at 450 ° C. about 8 times to make IrO
2 Coating and baking method A coating film of about 50 μm was formed.
【００３３】３）今回の試験ではＩｒＯ2被膜を成膜し
た後に、試験試料の熱処理を行った。加熱は大気中また
はＡｒ雰囲気中で行いこのときの温度は電極表面で測定
した。3) In this test, after the IrO 2 film was formed, the test sample was heat-treated. The heating was performed in the air or Ar atmosphere, and the temperature at this time was measured on the electrode surface.
【００３４】今回の試験試料作成において熱処理は塗布
焼き付け被膜作成後行ったが、反応性スパッタ法または
蒸着法により均質ＩｒＯ2被膜を形成した後、または塗
布焼き付け被膜作成中に行っても同様な効果を得た。In this test sample preparation, the heat treatment was carried out after the coating and baking coating was formed. However, the same effect can be obtained by forming the homogeneous IrO 2 coating by the reactive sputtering method or the vapor deposition method or during the preparation of the coating and baking coating. Got
【００３５】第１表に今回試験した試料の構成及び熱処
理条件を示した。Table 1 shows the constitution and heat treatment conditions of the samples tested this time.
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【表２】 [Table 2]
【００３８】作成した電極の耐用性評価は以下の方法に
より行いその結果を図５に示す。The durability evaluation of the prepared electrode was performed by the following method, and the result is shown in FIG.
【００３９】陽極に従来品、比較品及び本発明、陰極に
白金板を使用し、６０℃、５ｗｔ％硫酸溶液中、電流密
度１５０Ａ／ｄｍ2で通電腐食試験を行ない電圧の変化
を測定した。Using a conventional product, a comparative product and the present invention as the anode and a platinum plate as the cathode, an electrical corrosion test was performed at a current density of 150 A / dm 2 in a 5 wt% sulfuric acid solution at 60 ° C., and the change in voltage was measured.
【００４０】通電試験の結果、従来品は３０００〜４０
００時間で急激な電圧上昇が起こり電極が使用不可能と
なった。As a result of the energization test, the conventional product is 3000 to 40.
At 00 hours, the voltage suddenly increased and the electrode became unusable.
【００４１】これはＩｒＯ2被膜とバルブ金属層の界面
からのバルブ金属の腐食が進んだためと考えられる。It is considered that this is because the corrosion of the valve metal progressed from the interface between the IrO 2 film and the valve metal layer.
【００４２】また、比較品２、３、４、５も３０００〜
４０００時間で急激な電圧上昇が起こり電極が使用不可
能となった。Comparative products 2, 3, 4, and 5 are also 3000 to 300.
After 4000 hours, the voltage suddenly increased and the electrode became unusable.
【００４３】これは加熱時間が０．１ｈｒと短い場合及
び加熱温度が５００℃と低い場合にはバルブ金属層とＩ
ｒＯ2被膜間で拡散が起こらず熱処理の効果がないた
め、加熱温度が８００℃と高い場合及びＡｒ中で加熱し
た場合にはＩｒＯ2がＩｒ金属に還元され耐食性が低下
したためと考えられる。This is because when the heating time is as short as 0.1 hr and the heating temperature is as low as 500 ° C., the valve metal layer and I
It is considered that, since diffusion does not occur between the rO 2 coatings and there is no heat treatment effect, when the heating temperature is as high as 800 ° C. or when the heating is performed in Ar, IrO 2 is reduced to Ir metal and the corrosion resistance is reduced.
【００４４】また、比較品９、１０、１１、１２、１
６、１７、１８、１９では１２０００〜１４０００時間
で急激な電圧上昇が起こり電極が使用不可能となった。Comparative products 9, 10, 11, 12, 1
In Nos. 6, 17, 18 and 19, a sharp voltage increase occurred between 12,000 and 14,000 hours and the electrodes became unusable.
【００４５】この電極の寿命が従来品にくらべ優れるの
は熱処理による効果はないが、被膜下層にバルブ金属と
密着力の強い均質薄膜を持ちバルブ金属層の腐食を抑制
する効果があったためと考えられる。The life of this electrode is superior to that of the conventional product, although it is not affected by heat treatment, but it is considered that it has a homogeneous thin film having a strong adhesive force with the valve metal under the coating and has an effect of suppressing the corrosion of the valve metal layer. Be done.
【００４６】これに対し本発明品６、７、８では１８０
００〜２００００時間、１３、１４、１５、２０、２
１、２２では２２０００〜２４０００時間で電圧上昇が
起こり長時間の使用に耐えることがわかった。On the other hand, in the products 6, 7 and 8 of the present invention, 180
00 to 20000 hours, 13, 14, 15, 20, 2
It was found that in Nos. 1 and 22, a voltage rise occurred in 22,000 to 24,000 hours and the device could withstand long-term use.
【００４７】これは本発明品６、７、８では、バルブ金
属層とＩｒＯ2被膜の拡散層を持ちバルブ金属層とＩｒ
Ｏ2被膜界面からのバルブ金属層の酸化が進み難いた
め、本発明品１３、１４、１５、２０、２１、２２では
バルブ金属層への貫通孔がなくかつ、バルブ金属層とＩ
ｒＯ2被膜の拡散層を持ちバルブ金属層とＩｒＯ2被膜界
面からのバルブ金属層の酸化が更に進み難いためと考え
られる。In the products 6, 7 and 8 according to the present invention, the valve metal layer and the IrO 2 coating diffusion layer were provided, and the valve metal layer and Ir were provided.
Oxidation of the valve metal layer from the interface of the O 2 coating is difficult to proceed, so that in the products 13, 14, 15, 20, 21, and 22 of the present invention, there is no through hole to the valve metal layer,
It is considered that this is because the valve metal layer has a diffusion layer of the rO 2 coating and the oxidation of the valve metal layer from the interface between the valve metal layer and the IrO 2 coating does not proceed further.
【００４８】また本発明品８、１５、２２では長時間の
熱処理を施したが耐用性は特に向上しておらず、経済上
から長時間の熱処理は効果ないものと考えられる。The products 8, 15, and 22 of the present invention were subjected to a heat treatment for a long time, but the durability was not particularly improved, and it is considered that the heat treatment for a long time is not effective from the economical viewpoint.
【００４９】[0049]
【発明の効果】本発明の不溶性電極は、１５０Ａ／ｄｍ
2以上の高電流密度で電解をおこなっても耐食性に優
れ、長時間の使用に耐えるものであり、電気メッキ用電
極に限らず他の用途の電極として極めて有用である。The insoluble electrode of the present invention is 150 A / dm
It has excellent corrosion resistance even when electrolysis is performed at a high current density of 2 or more, and can withstand long-term use, and is extremely useful as an electrode for other applications as well as an electrode for electroplating.
【図１】従来の電極構造例を示す断面説明図である。FIG. 1 is a cross-sectional explanatory view showing an example of a conventional electrode structure.
【図２】従来の電極例の腐食メカニズムの説明図であ
る。FIG. 2 is an explanatory diagram of a corrosion mechanism of a conventional electrode example.
【図３】本発明電極構造例を示す断面図である。FIG. 3 is a cross-sectional view showing an example of the electrode structure of the present invention.
【図４】本発明電極構造例を示す断面図である。FIG. 4 is a cross-sectional view showing an example of the electrode structure of the present invention.
【図５】従来の電極例の通電腐食試験結果を示す図であ
る。FIG. 5 is a diagram showing the results of a galvanic corrosion test of a conventional electrode example.
１ ＳＵＳ製電極母材 ２ バルブ金属層 ３ ＩｒＯ2―Ｔａ2Ｏ5塗布焼き付け被膜 ４ ＩｒＯ2塗布焼き付け被膜 ５ クラック ６ 絶縁性酸化物 ７ Ｔｉ―ＩｒＯ2拡散層 ８ ＩｒＯ2反応性スパッタ被膜DESCRIPTION OF SYMBOLS 1 SUS electrode base material 2 Valve metal layer 3 IrO 2 —Ta 2 O 5 coating baking coating 4 IrO 2 coating baking coating 5 crack 6 insulating oxide 7 Ti—IrO 2 diffusion layer 8 IrO 2 reactive sputter coating
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年３月１０日[Submission date] March 10, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項３[Name of item to be corrected] Claim 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Name of item to be corrected] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１９】また第３の発明は、第１の発明と第２の発
明の不溶性電極の製造方法であり、該不溶性電極におけ
る第３層となる酸化物層を５００〜８００℃、０．５ｈ
ｒ以上１０ｈｒ以内加熱して、第２層を形成することを
特徴とする不溶性電極の製造方法である。A third aspect of the present invention is the method for producing an insoluble electrode according to the first and second aspects of the invention, wherein the oxide layer serving as the third layer in the insoluble electrode is 500 to 800 ° C. for 0.5 h.
The method for producing an insoluble electrode is characterized in that the second layer is formed by heating for not less than r and not more than 10 hours.
Claims (3)
層、第２層としてバルブ金属とＩｒの酸化物層、第３層
としてＩｒＯ2層を持つことを特徴とする不溶性電極。1. An insoluble electrode having a valve metal layer as a first layer, a valve metal and Ir oxide layer as a second layer, and an IrO 2 layer as a third layer on the surface of an electrode base material.
層、第２層としてバルブ金属とＩｒの酸化物層、第３層
として緻密質ＩｒＯ2層、第４層として空隙率５から３
０％のポーラスなＩｒＯ2層を持つことを特徴とする不
溶性電極。2. A valve metal layer as the first layer, an oxide layer of valve metal and Ir as the second layer, a dense IrO 2 layer as the third layer, and a porosity of 5 to 3 as the fourth layer on the surface of the electrode base material.
An insoluble electrode having a 0% porous IrO 2 layer.
０．５ｈｒ以上１０ｈｒ以内加熱し、しかる後３層を形
成することを特徴とする不溶性電極の製造方法。3. The second oxide layer is 500 to 800 ° C.,
A method for producing an insoluble electrode, which comprises heating for 0.5 hr or more and within 10 hr, and then forming three layers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4035843A JPH05209299A (en) | 1992-01-28 | 1992-01-28 | Insoluble electrode and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4035843A JPH05209299A (en) | 1992-01-28 | 1992-01-28 | Insoluble electrode and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05209299A true JPH05209299A (en) | 1993-08-20 |
Family
ID=12453268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4035843A Withdrawn JPH05209299A (en) | 1992-01-28 | 1992-01-28 | Insoluble electrode and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05209299A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007507612A (en) * | 2003-10-08 | 2007-03-29 | アクゾ ノーベル エヌ．ブイ． | electrode |
| US7566389B2 (en) | 2003-10-08 | 2009-07-28 | Akzo Nobel N.V. | Electrode |
-
1992
- 1992-01-28 JP JP4035843A patent/JPH05209299A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007507612A (en) * | 2003-10-08 | 2007-03-29 | アクゾ ノーベル エヌ．ブイ． | electrode |
| US7566389B2 (en) | 2003-10-08 | 2009-07-28 | Akzo Nobel N.V. | Electrode |
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