JPH0978298A - Electrolytic electrode and its production - Google Patents
Electrolytic electrode and its productionInfo
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- JPH0978298A JPH0978298A JP26101595A JP26101595A JPH0978298A JP H0978298 A JPH0978298 A JP H0978298A JP 26101595 A JP26101595 A JP 26101595A JP 26101595 A JP26101595 A JP 26101595A JP H0978298 A JPH0978298 A JP H0978298A
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- base material
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Abstract
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【発明の属する技術分野】この発明は、水溶液の電気分
解の陽極として使用する電解用電極であって、フッ素イ
オンやフッ化物イオンを含む水溶液中、特にクロムの電
気メッキ浴において、陽極として使用するのに適した電
解用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 electrolysis electrode used as an anode for electrolysis of an aqueous solution, which is used as an anode in an aqueous solution containing fluorine ions or fluoride ions, particularly in an electroplating bath of chromium. The present invention relates to an electrode for electrolysis suitable for use in 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
メッキ浴中にて電解用電極を使用し、陰極たる被メッキ
金属材の表面にＺｎ，Ｓｎ，Ｎｉ，Ｃｒなどの金属を電
気メッキすることが行われている。また金属の電気精錬
に際し、精錬浴中にて電解用電極を使用し、Ｍｎ、Ｚｎ
等の金属を電気精錬することが行われている。2. Description of the Related Art Generally, in electroplating a metal material, an electrode for electrolysis is used in an electroplating bath to electroplate a metal such as Zn, Sn, Ni, Cr on the surface of a metal material to be plated which is a cathode. Is being done. When electrorefining a metal, an electrode for electrolysis is used in a refining bath to remove Mn and Zn.
Electric refining of metal such as is performed.
【０００３】このうち、クロムメッキ、あるいは硫酸塩
浴による金属の電気精錬等には二酸化鉛電極が広く用い
られている。これは、二酸化鉛には、メッキに必要な電
流を供給するとともに、メッキ浴中で生成した３価クロ
ムを６価クロムに酸化する特性を有するためである。Of these, a lead dioxide electrode is widely used for chromium plating or electrorefining of metals with a sulfate bath. This is because lead dioxide has a property of supplying a current necessary for plating and oxidizing trivalent chromium generated in the plating bath to hexavalent chromium.
【０００４】この二酸化鉛電極としては、現在、主に鉛
イオンを含有する硝酸溶液、過塩素酸溶液あるいはアル
カリ溶液中で、チタンなどのバルブ金属を陽極として電
解することにより、バルブ金属の基体上に二酸化鉛を電
着させた被覆二酸化鉛電極が使用されている。As the lead dioxide electrode, at present, a valve metal such as titanium is electrolyzed in a nitric acid solution, a perchloric acid solution or an alkaline solution containing mainly lead ions as an anode to form a substrate on the valve metal. A coated lead dioxide electrode is used which is electrodeposited with lead dioxide.
【０００５】この被覆二酸化鉛電極の具体的な製造方法
は、特公昭５８−３１３９６号公報に見られるように、
チタン等のバルブ金属の基体上に白金、イリジウム等の
白金属金属およびそれらの酸化物を含む電気化学的に活
性な被覆を熱分解法により施し、更に、その上に硝酸鉛
浴で二酸化鉛を陽極電着させ、チタン等のバルブ金属の
基体と二酸化鉛被覆層との間に金網を介在させることに
より、二酸化鉛の密着力を向上させていた。しかし、電
極の製造工程が繁雑で工数を要し、高価となる欠点を有
していた。A specific manufacturing method of this coated lead dioxide electrode is as shown in Japanese Patent Publication No. 58-31396.
An electrochemically active coating containing platinum metal, such as platinum and iridium, and their oxides is applied on the substrate of valve metal such as titanium by a pyrolysis method, and lead dioxide is further applied on it with a lead nitrate bath. The adhesion of lead dioxide has been improved by electrodepositing the anode and interposing a wire mesh between the substrate of valve metal such as titanium and the lead dioxide coating layer. However, it has a drawback that the manufacturing process of the electrode is complicated, requires a lot of man-hours, and becomes expensive.
【０００６】[0006]
【発明が解決しようとする課題】前記のような被覆二酸
化鉛電極は、フッ化物イオンを含有する水溶液中で使用
した場合、電流密度により異なるが、１０００〜１５０
０ｈｒの通電により、二酸化鉛被覆層に電極母材である
バルブ金属の基体に貫通する微細なクラックが発生し、
このクラックからメッキ液が浸入して、電極母材が腐食
し溶解することがある。The above-mentioned coated lead dioxide electrode, when used in an aqueous solution containing fluoride ions, varies depending on the current density, but is 1000 to 150.
When the electric current is applied for 0 hr, fine cracks are formed in the lead dioxide coating layer to penetrate the valve metal substrate, which is the electrode base material,
The plating solution may infiltrate through these cracks, and the electrode base material may be corroded and dissolved.
【０００７】本発明は、水溶液の電気分解の陽極として
使用する電解用電極であって、フッ素やフッ化物イオン
を含む水溶液中、特にクロムの電気メッキ浴において、
耐食性に優れ、剥離がなく、長時間の使用に耐える電解
用電極及びその製造方法を提供するものである。The present invention is an electrode for electrolysis used as an anode for electrolysis of an aqueous solution, which is used in an aqueous solution containing fluorine or fluoride ions, particularly in an electroplating bath of chromium,
It is intended to provide an electrode for electrolysis which has excellent corrosion resistance, does not peel off, and can be used for a long time, and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】本発明は、電極母材を導
電性金属で構成し、電極最表層をＰｂＯ2 の被覆層とし
た電解用電極において、前記電極母材と電極最表層との
間に、２層からなる中間層を設け、そのうち電極母材側
の層を、電極母材に対して平行な層状構造を持つ絶縁性
酸化物の多孔質被膜で形成して、その空孔に電極母材成
分を充填した層とし、電極最表層側の層を、電極母材に
対して平行な層状構造を持つ絶縁性酸化物の多孔質被膜
で形成して、その空孔にＰｂＯ2 を充填した層としたこ
とを特徴とする電解用電極及びその製造方法である。Means for Solving the Problems The present invention relates to an electrode for electrolysis in which the electrode base material is made of a conductive metal and the electrode outermost layer is a PbO 2 coating layer, and the electrode base material and the electrode outermost layer are An intermediate layer consisting of two layers is provided between them, and the layer on the electrode base material side is formed by a porous coating of an insulating oxide having a layered structure parallel to the electrode base material and A layer filled with the electrode base material component, and a layer on the outermost surface side of the electrode is formed by a porous film of an insulating oxide having a layered structure parallel to the electrode base material, and PbO 2 is contained in the pores. The electrode for electrolysis and the method for producing the same are characterized in that a filled layer is formed.
【０００９】特に、中間層のうち電極母材側の層の厚み
が、５μｍ以上であること、この層を構成する、絶縁性
酸化物と、電極母材成分との体積比が６０：４０ないし
９５：５の範囲にあることを特徴とする。In particular, the thickness of the layer on the electrode base material side of the intermediate layer is 5 μm or more, and the volume ratio of the insulating oxide and the electrode base material component constituting this layer is 60:40 or more. It is characterized by being in the range of 95: 5.
【００１０】また、中間層のうち電極最表層側の層の厚
みが、５〜１９５μｍの範囲であること、この層を構成
する、絶縁性酸化物と、ＰｂＯ2 のとの体積比が６０：
４０ないし９５：５の範囲にあることを特徴とする。The thickness of the intermediate layer on the electrode outermost layer side is in the range of 5 to 195 μm, and the volume ratio of the insulating oxide and PbO 2 constituting this layer is 60:
It is characterized by being in the range of 40 to 95: 5.
【００１１】更に、電極最表層のＰｂＯ2 被覆層を、α
−ＰｂＯ2 とβ−ＰｂＯ2 の２層ないしは３層以上の多
層構造とするとよい。Further, the PbO 2 coating layer on the outermost layer of the electrode is
It is preferable to have a multi-layer structure of two or three or more layers of -PbO 2 and β-PbO 2 .
【００１２】また、本発明の、電極母材、２層からなる
中間層、及び電極最表層の４層からなる電解用電極の製
造方法は以下の通りである。すなわち、本発明の電解用
電極は、まず、電極母材上に絶縁性酸化物を溶射して、
空孔率５〜４０％の絶縁性酸化物の多孔質被膜を形成
し、次に、ＨＩＰ処理を施して電極母材と絶縁性酸化物
との間で相互拡散させることにより、電極母材側の中間
層を形成した後、電極母材を陽極として通電し、電着に
より、絶縁性酸化物の多孔質被膜の残りの空孔にＰｂＯ
2 を充填して、電極最表層側の中間層を形成することで
２層からなる中間層を設けたのち、電着によりＰｂＯ2
の電極最表層を形成して得られる。The method for producing an electrode for electrolysis comprising four layers of the electrode base material, the intermediate layer consisting of two layers, and the outermost surface layer of the electrode of the present invention is as follows. That is, the electrode for electrolysis of the present invention, first, by spraying an insulating oxide on the electrode base material,
A porous coating film of an insulating oxide having a porosity of 5 to 40% is formed, and then subjected to HIP treatment to cause mutual diffusion between the electrode base material and the insulating oxide. After forming the intermediate layer of PbO, the electrode base material is used as an anode and electricity is applied, and PbO is formed in the remaining pores of the porous film of the insulating oxide by electrodeposition.
2 is filled and an intermediate layer on the electrode outermost layer side is formed to form an intermediate layer consisting of two layers, and then PbO 2 is formed by electrodeposition.
It is obtained by forming the outermost layer of the electrode.
【００１３】特に、中間層のうち電極母材側の層は、温
度７５０〜１１００℃、圧力１０００〜２０００気圧の
不活性ガス雰囲気下でＨＩＰ処理を施して形成するとよ
い。In particular, the electrode base material side layer of the intermediate layer is preferably formed by HIP treatment in an inert gas atmosphere at a temperature of 750 to 1100 ° C. and a pressure of 1000 to 2000 atm.
【００１４】[0014]
【発明の実施の形態】本発明で用いる電極母材は、導電
性金属であれば良いが、陽分極時に安定なバルブ金属
（Ｔｉ，Ｔａ，Ｚｒ，Ｎｂ）、またはフッ素イオンやフ
ッ化物イオンへの耐用性に優れたＮｉ含有量の高い材
料、例えばハステロイＣとすることが好ましい。電極母
材の形状は、板状、穴あき体、エキスパンドメッシュ等
各種の形状とすることができる。BEST MODE FOR CARRYING OUT THE INVENTION The electrode base material used in the present invention may be any conductive metal, but it is not limited to a valve metal (Ti, Ta, Zr, Nb) that is stable during anodic polarization, or a fluorine ion or a fluoride ion. It is preferable to use a material having high Ni content and high Ni content, for example, Hastelloy C. The shape of the electrode base material can be various shapes such as a plate shape, a perforated body, and an expanded mesh.
【００１５】本発明の電解用電極において、中間層を形
成する、絶縁性酸化物の多孔質被膜の材質としては、フ
ッ素イオンあるいはフッ化物イオンを含む溶液中でも比
較的安定な酸化物、例えばＡｌ2Ｏ3、Ｃｒ2Ｏ3、Ａｌ2
Ｏ3−Ｃｒ2Ｏ3等が好ましい。In the electrode for electrolysis of the present invention, the material for the porous coating of the insulating oxide forming the intermediate layer is a relatively stable oxide in a solution containing fluorine ions or fluoride ions, such as Al 2 O 3 , Cr 2 O 3 , Al 2
O 3 -Cr 2 O 3 and the like are preferable.
【００１６】絶縁性酸化物の多孔質被膜は、粒径約２０
〜４０μｍの絶縁性酸化物粉末を、例えばプラズマ溶射
により溶射することで形成できる。すなわち、原料粉末
は溶射により変形して厚み２μｍ、直径数１０μｍの円
盤型薄膜となり、これが堆積して多孔質被膜となる。The porous film of the insulating oxide has a particle size of about 20.
It can be formed by spraying an insulating oxide powder of ˜40 μm, for example, by plasma spraying. That is, the raw material powder is deformed by thermal spraying to form a disk-shaped thin film having a thickness of 2 μm and a diameter of several 10 μm, which is deposited to form a porous film.
【００１７】絶縁性酸化物の溶射条件は、空孔率が５〜
４０％となるように選択することが望ましい。これは、
中間層のうち電極母材側の層を構成する、絶縁性酸化物
と、電極母材成分との体積比を６０：４０ないし９５：
５の範囲とし、更に、電極最表層側の層を構成する、絶
縁性酸化物と、ＰｂＯ2 との体積比を６０：４０ないし
９５：５の範囲とするためである。絶縁性酸化物の体積
比が９５％以下であれば、中間層のうち電極最表層側の
層に、電極母材と電極最表層間の通電に充分な量のＰｂ
Ｏ2 を充填できる。また、絶縁性酸化物の体積比が６０
％以上であれば、中間層のうち電極最表層側の層により
電極母材成分のメッキ液に対する露出は十分に抑制され
る。なお、絶縁性酸化物の多孔質被膜の空孔率は、例え
ば被膜の縦または横断面を観察し、空孔の面積率から算
出することができる。The insulating oxide is sprayed under the conditions of porosity of 5 to 5.
It is desirable to select 40%. this is,
The volume ratio of the insulating oxide and the electrode base material component forming the layer on the electrode base material side of the intermediate layer is 60:40 to 95:
This is because the volume ratio of the insulating oxide to the outermost surface of the electrode and PbO 2 is 60:40 to 95: 5. When the volume ratio of the insulating oxide is 95% or less, a sufficient amount of Pb for conducting electricity between the electrode base material and the electrode outermost layer is provided in the electrode outermost layer side of the intermediate layer.
Can be filled with O 2 . The volume ratio of the insulating oxide is 60.
%, The exposure of the electrode base material component to the plating solution is sufficiently suppressed by the electrode outermost layer side of the intermediate layer. The porosity of the insulating oxide porous coating can be calculated, for example, by observing the longitudinal or transverse cross section of the coating and calculating the area ratio of the pores.
【００１８】中間層のうち電極最表層側の層の厚みは、
１９５μｍ以下とすることが望ましい。これは、この層
をこれ以上厚くしても、電極母材成分のメッキ液に対す
る露出がそれ以上抑制されることはなく、逆に被膜剥離
が起きやすくなるためである。また、中間層のうち電極
母材側の層の厚みは、５μｍ以上であれば、電極母材と
の密着性は十分に確保される。しかし、厚みが２５０μ
ｍ前後になると、層が剥離しやすくなるため、好ましい
とは言えない。一方、電極最表層側の層の厚みも、５μ
ｍ以上であれば、電極母材のメッキ液に対する露出は十
分に抑制される。従って、溶射により形成する絶縁性酸
化物の多孔質被膜の厚みは、１０μｍ以上とすることが
好ましい。Among the intermediate layers, the thickness of the outermost layer of the electrode is
It is desirable that the thickness be 195 μm or less. This is because even if this layer is made thicker than this, the exposure of the electrode base material component to the plating solution is not further suppressed, and conversely, film peeling is likely to occur. In addition, if the thickness of the layer on the electrode base material side of the intermediate layer is 5 μm or more, sufficient adhesion with the electrode base material is secured. However, the thickness is 250μ
When it is around m, the layer is likely to be peeled off, which is not preferable. On the other hand, the thickness of the outermost layer of the electrode is also 5 μm.
If it is m or more, the exposure of the electrode base material to the plating solution is sufficiently suppressed. Therefore, the thickness of the insulating oxide porous coating formed by thermal spraying is preferably 10 μm or more.
【００１９】次に、電極母材上に絶縁性酸化物の多孔質
被膜を溶射により施工した後に、ＨＩＰ処理を実施する
ことで、中間層のうち電極母材側の層を形成することが
できる。電極母材と絶縁性酸化物の多孔質被膜との間で
相互に拡散させることにより、目的とする中間層のうち
電極母材側の層を形成するためには、温度７５０℃以
上、かつ圧力１０００気圧以上の不活性ガス雰囲気下で
処理することが好ましい。また、電極母材の酸化、強度
劣化を防止するためには温度を１１００℃以下とするこ
とが好ましい。更に好ましくは、温度を８００〜１００
０℃の範囲内とするとよい。Next, a layer of the intermediate layer on the electrode base material side can be formed by performing a HIP process after applying a porous coating of an insulating oxide on the electrode base material by thermal spraying. . In order to form a layer on the electrode base material side of the intended intermediate layer by mutually diffusing between the electrode base material and the porous coating of the insulating oxide, a temperature of 750 ° C. or higher and a pressure are applied. It is preferable to perform the treatment in an atmosphere of an inert gas of 1000 atm or higher. Further, in order to prevent the oxidation and strength deterioration of the electrode base material, the temperature is preferably set to 1100 ° C. or lower. More preferably, the temperature is 800-100.
It is preferable that the temperature is within the range of 0 ° C.
【００２０】一方、圧力を２０００気圧より大きくした
場合には、絶縁性酸化物の多孔質被膜が緻密化してしま
い、空孔率が低下するため好ましくない。尚、処理時間
は、工業的に見合うようにするために１〜５時間位が適
当である。なお、電極最表層のＰｂＯ2 成膜後にＨＩＰ
処理を施すと、ＰｂＯ2 の被覆層が緻密化して剥離しや
すくなるため、ＨＩＰ処理はＰｂＯ2 を成膜する前に実
施する必要がある。On the other hand, when the pressure is higher than 2000 atm, the porous film of the insulating oxide is densified and the porosity is lowered, which is not preferable. The treatment time is preferably about 1 to 5 hours in order to be industrially commensurate. In addition, after forming PbO 2 on the outermost layer of the electrode, HIP
When the treatment is performed, the PbO 2 coating layer is densified and easily peeled off. Therefore, it is necessary to perform the HIP treatment before forming the PbO 2 film.
【００２１】その後、絶縁性酸化物の多孔質被膜の空孔
をＰｂＯ2 で充填し、更に電極最表層を形成する。この
時、β−ＰｂＯ2 を直接形成させると、この層は絶縁性
酸化物の多孔質被膜との密着性に劣るため好ましくな
い。従って、β−ＰｂＯ2 層の間にα−ＰｂＯ2 層をは
さむように形成して、多層化を図る。After that, the pores of the insulating oxide porous film are filled with PbO 2 to form the outermost layer of the electrode. At this time, if β-PbO 2 is directly formed, this layer is inferior in adhesion to the porous film of the insulating oxide, which is not preferable. Therefore, the α-PbO 2 layer is sandwiched between the β-PbO 2 layers to form a multilayer structure.
【００２２】α−ＰｂＯ2 層は、２０％程度の苛性ソー
ダ水溶液にＰｂＯ粉末を飽和するまで溶解し（３０〜４
０ｇ／リットル）これを電解浴として２０〜５０℃の温
度で０．１〜１０Ａ／ｄｍ2 の電流密度で電極母材を陽
極として電解することにより形成することができ、これ
によって絶縁性酸化物の多孔質被膜の空孔をα−ＰｂＯ
2 で充填することができる。その後、このα−ＰｂＯ2
の表面に、更にβ−ＰｂＯ2 を形成し、両者の多層化を
行なう。The α-PbO 2 layer is dissolved in a caustic soda aqueous solution of about 20% until the PbO powder is saturated (30 to 4).
It can be formed by electrolyzing this as an electrolytic bath at a temperature of 20 to 50 ° C. with a current density of 0.1 to 10 A / dm 2 and using an electrode base material as an anode, thereby producing an insulating oxide. The pores of the porous coating of α-PbO
Can be filled with 2 . Then, this α-PbO 2
On the surface of the further form beta-PbO 2, it performs both multi-layered.
【００２３】β−ＰｂＯ2 層は、例えば２００ｇ／リッ
トル以上の硝酸鉛浴を電解浴とし、α−ＰｂＯ2 層を形
成した電極母材を陽極として、５０〜７０℃の温度で１
〜１０Ａ／ｄｍ2 の電流密度で電解することにより、β
−ＰｂＯ2 層を形成することができ、これによって目的
とする電解用電極を得ることができる。For the β-PbO 2 layer, for example, a lead nitrate bath of 200 g / liter or more is used as an electrolytic bath, and the electrode base material on which the α-PbO 2 layer is formed is used as an anode, at a temperature of 50 to 70 ° C.
By electrolyzing at a current density of -10 A / dm 2 ,
It can form -PbO 2 layer, whereby it is possible to obtain the electrode for electrolysis of interest.
【００２４】本発明の電解用電極の構造を図１に示す。
本発明の電解用電極では、電極最表層であるＰｂＯ2 の
被覆層４に気孔及びクラック５が多数存在する場合に
も、絶縁性酸化物の多孔質被膜と電極母材成分とで構成
された中間層２、更に、絶縁性酸化物の多孔質被膜とＰ
ｂＯ2 とで構成された中間層３が存在するため、電極最
表層４に存在する気孔及びクラック５が電極母材１へ貫
通することはなく、従って、電極母材１の露出面積は少
ない。The structure of the electrode for electrolysis of the present invention is shown in FIG.
In the electrode for electrolysis of the present invention, even when a large number of pores and cracks 5 are present in the PbO 2 coating layer 4 which is the outermost layer of the electrode, the electrode is composed of the porous coating of the insulating oxide and the electrode base material component. The intermediate layer 2, and the insulating oxide porous film and P
Since the intermediate layer 3 composed of bO 2 is present, the pores and cracks 5 present in the outermost layer 4 of the electrode do not penetrate into the electrode base material 1, and therefore the exposed area of the electrode base material 1 is small.
【００２５】更に中間層２は、ＨＩＰ処理による拡散接
合により形成するため電極母材１との密着性が非常に優
れている。このように本発明の電解用電極は、電極母材
の露出面積が少ないため耐食性に優れ、密着性も優れる
ため機械的衝撃による剥離も防止でき、１００Ａ／ｄｍ
2以上の高電流密度下、更に、鋼板接触のような機械的
衝撃付加条件下でも長時間の使用に耐えることができ
る。Further, since the intermediate layer 2 is formed by diffusion bonding by HIP processing, it has very good adhesion with the electrode base material 1. As described above, the electrode for electrolysis of the present invention has a small exposed area of the electrode base material and thus has excellent corrosion resistance, and also has excellent adhesiveness, which can prevent peeling due to mechanical shock.
It can withstand long-term use under high current density of 2 or more, and even under the condition of mechanical shock such as steel plate contact.
【００２６】[0026]
【実施例】本発明の電解用電極、すなわち、電極母材を
導電性金属で構成し、電極最表層をＰｂＯ2 の被覆層と
した電解用電極において、前記電極母材と電極最表層と
の間に、２層からなる中間層を設け、そのうち電極母材
側の層を、電極母材に対して平行な層状構造を持つ絶縁
性酸化物の多孔質被膜で形成して、その空孔に電極母材
成分を充填した層とし、電極最表層側の層を、電極母材
に対して平行な層状構造を持つ絶縁性酸化物の多孔質被
膜で形成して、その空孔にＰｂＯ2 を充填した層とした
ことを特徴とする電解用電極についてその作製方法の一
例を述べる。EXAMPLES In the electrolysis electrode of the present invention, that is, in the electrolysis electrode in which the electrode base material is composed of a conductive metal and the electrode outermost layer is a PbO 2 coating layer, the electrode base material and the electrode outermost layer are An intermediate layer consisting of two layers is provided between them, and the layer on the electrode base material side is formed by a porous coating of an insulating oxide having a layered structure parallel to the electrode base material and A layer filled with the electrode base material component, and a layer on the outermost surface side of the electrode is formed by a porous film of an insulating oxide having a layered structure parallel to the electrode base material, and PbO 2 is contained in the pores. An example of a method for producing the electrode for electrolysis, which is characterized in that the layer is a filled layer, will be described.
【００２７】なお、図２にその製造フローチャートを示
し、これに従って説明する。 （１）電極母材前処理 電極母材として、下記材質の厚みｌｍｍのエキスパンド
メッシュを使用し、この電極母材表面を蓚酸を用いて洗
浄後、ブラストにより粗面化した。 材質；Ｔｉ、Ｎｂ、Ｔａ、ハステロイＣIncidentally, FIG. 2 shows a manufacturing flow chart thereof, and description will be given according to the flow chart. (1) Pretreatment of Electrode Base Material As an electrode base material, an expanded mesh of the following materials having a thickness of 1 mm was used, and the surface of the electrode base material was washed with oxalic acid and then roughened by blasting. Material: Ti, Nb, Ta, Hastelloy C
【００２８】（２）中間層作製 （２−１）絶縁性酸化物の多孔質被膜の形成 まず、下記材質の絶縁性酸化物を用いて通常のプラズマ
溶射法により電極母材に対して溶射を行い、電極母材上
に絶縁性酸化物の多孔質被膜を形成した。 材質；Ａｌ2Ｏ3，Ｃｒ2Ｏ3，Ａｌ2Ｏ3−Ｃｒ2Ｏ3 被膜厚み；５〜３００μｍ 空孔率：１〜４０％(2) Preparation of Intermediate Layer (2-1) Formation of Porous Coating of Insulating Oxide First, the insulating oxide of the following materials is used to spray the electrode base material by a usual plasma spraying method. Then, a porous coating film of an insulating oxide was formed on the electrode base material. Material; Al 2 O 3, Cr 2 O 3, Al 2 O 3 -Cr 2 O 3 coating thickness; 5 to 300 .mu.m porosity of 1-40%
【００２９】（２−２）中間層のうち電極母材側の層の
形成 絶縁性酸化物の多孔質被膜を施工した電極母材を、Ａｒ
雰囲気下でＨＩＰ処理した。この処理により、中間層の
うち電極母材側の層を形成した。 温度：６００〜１２００℃ 時間：３時間 圧力：１０００〜２０００気圧(2-2) Formation of a layer on the electrode base material side of the intermediate layer The electrode base material coated with a porous coating of an insulating oxide is treated with Ar.
HIP treatment was performed under an atmosphere. By this treatment, a layer on the electrode base material side of the intermediate layer was formed. Temperature: 600 to 1200 ° C Time: 3 hours Pressure: 1000 to 2000 atm
【００３０】（２−３）中間層のうち電極最表層側の層
の形成、及び電極最表層の成膜 上記処理を施した電極母材を、２５％水酸化ナトリウム
水溶液にＰｂＯを飽和させた４０℃の電解浴中で１Ａ／
ｄｍ2 の電流密度で２時間電解し、絶縁性酸化物の多孔
質被膜の空孔にα−ＰｂＯ2 を充填した。更に、８０ｇ
／リットルの硝酸鉛水溶液を電解液とし、α−ＰｂＯ2
を形成した電極母材を陽極に、２Ａ／ｄｍ2 の電流密度
で８時間電解し、β−ＰｂＯ2 からなる電極最表層を成
膜した。(2-3) Formation of a layer on the electrode outermost layer side of the intermediate layer and film formation of the electrode outermost layer The electrode base material subjected to the above treatment was saturated with PbO in a 25% sodium hydroxide aqueous solution. 1A / in a 40 ℃ electrolytic bath
Electrolysis was performed at a current density of dm 2 for 2 hours to fill the pores of the insulating oxide porous coating with α-PbO 2 . Furthermore, 80g
/ L lead nitrate aqueous solution is used as an electrolyte, and α-PbO 2
The electrode base material on which was formed was used as an anode for electrolysis at a current density of 2 A / dm 2 for 8 hours to form an electrode outermost layer of β-PbO 2 .
【００３１】表１に、こうして得られた本発明の電解用
電極の耐用性試験結果を評価の欄に従来品、比較品と共
に示した。In Table 1, the results of the durability test of the electrolytic electrode of the present invention thus obtained are shown in the column of evaluation together with the conventional product and the comparative product.
【００３２】なお、作製した電解用電極の耐用性評価は
以下の方法により行った。すなわち、陽極に従来品、比
較品あるいは本発明の電解用電極を、陰極に白金板を使
用し、５０℃、１００ｇ／リットルの無水クロム酸、及
び４ｇ／リットルのフッ化アンモニウムを添加した水溶
液中で、電流密度２００Ａ／ｄｍ2 の通電試験を行ない
電圧が１０Ｖ上昇するまでの時間を測定して行なった。
ここで、表１において、○は寿命２０００ｈｒ以上の耐
用性を示し、×は寿命２０００ｈｒ未満であった電解用
電極である。その結果、本発明の電解用電極はいずれも
２０００ｈｒ以上の寿命があり、耐用性に優れているこ
とがわかる。The durability of the produced electrode for electrolysis was evaluated by the following method. That is, in an aqueous solution in which a conventional product, a comparative product or an electrode for electrolysis of the present invention is used as an anode, a platinum plate is used as a cathode, and 50 g of 100 g / liter of chromic anhydride and 4 g / liter of ammonium fluoride are added. Then, an energization test with a current density of 200 A / dm 2 was performed and the time until the voltage increased by 10 V was measured.
Here, in Table 1, ∘ indicates durability for a life of 2000 hours or more, and x indicates an electrode for electrolysis having a life of less than 2000 hours. As a result, it can be seen that each of the electrolysis electrodes of the present invention has a life of 2000 hours or more and is excellent in durability.
【００３３】[0033]
【表１Ａ】 材質の記号ハステ，A，C，ACはそれぞれハステロイＣ，Al2O3，Cr2O3，Al2O3- Cr2O3を示す。[Table 1A] Material symbols Haste, A, C, AC represent Hastelloy C, Al 2 O 3 , Cr 2 O 3 , and Al 2 O 3 -Cr 2 O 3 , respectively.
【００３４】[0034]
【表１Ｂ】 材質の記号ハステ，A，C，ACはそれぞれハステロイＣ，Al2O3，Cr2O3，Al2O3- Cr2O3を示す。[Table 1B] Material symbols Haste, A, C, AC represent Hastelloy C, Al 2 O 3 , Cr 2 O 3 , and Al 2 O 3 -Cr 2 O 3 , respectively.
【００３５】尚、表１において、１２は従来の電着法に
より作製した電極、また、１３〜１７は、比較のため
に、本発明と異なる条件で作製した電極である。比較品
１３は、絶縁性酸化物の多孔質被膜が厚すぎて通電前に
被膜が剥離した。比較品１４は、絶縁性酸化物の多孔質
被膜の気孔率が低すぎて、ＰｂＯ2 を充填することがで
きなかった。比較品１５は、ＨＩＰ処理温度が低く、電
極母材側の中間層が形成されず、電着後のＰｂＯ2 の被
覆層が剥離した。比較品１６は、ＨＩＰ処理温度が高
く、電極母材のチタンが劣化した。比較品１７は、中間
層による密着性向上、及び電極母材成分の露出抑制効果
が得られず短寿命であった。In Table 1, 12 is an electrode manufactured by the conventional electrodeposition method, and 13 to 17 are electrodes manufactured under the conditions different from those of the present invention for comparison. In Comparative Product 13, the porous film of the insulating oxide was too thick and the film was peeled off before energization. In Comparative Product 14, the porous film of the insulating oxide had too low a porosity to be filled with PbO 2 . In Comparative product 15, the HIP treatment temperature was low, the intermediate layer on the electrode base material side was not formed, and the PbO 2 coating layer after electrodeposition was peeled off. Comparative product 16 had a high HIP treatment temperature, and the titanium of the electrode base material was deteriorated. Comparative product 17 had a short life because neither the adhesiveness improvement due to the intermediate layer nor the effect of suppressing the exposure of the electrode base material component was obtained.
【００３６】[0036]
【発明の効果】本発明の電解用電極は、高電流密度で電
解を行なっても耐食性に優れ、剥離がなく、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、電
気精錬等の他の用途の電極としても極めて有用である。EFFECT OF THE INVENTION The electrode for electrolysis of the present invention is excellent in corrosion resistance even when electrolyzing at a high current density, does not peel off, and can be used for a long time. It is also extremely useful as an electrode for other uses such as.
【図１】本発明の電解用電極の構造を示す。FIG. 1 shows a structure of an electrode for electrolysis of the present invention.
【図２】本発明の電解用電極製造フローチャートを示
す。FIG. 2 shows a flowchart for manufacturing an electrode for electrolysis according to the present invention.
１ 電極母材（密斜線部） ２ 絶縁性酸化物の多孔質被膜（斑点部）と電極母材成
分（密斜線部）とで構成される層 ３ 絶縁性酸化物の多孔質被膜（斑点部）とＰｂＯ2
（斜線−点線部）とで構成される層 ４ ＰｂＯ2 （斜線−点線部）の被覆層 ５ 気孔とクラック1 Electrode Base Material (Densely Shaded Area) 2 Layer Composed of Insulating Oxide Porous Coating (Dotted Area) and Electrode Base Material Component (Densely Shaded Area) 3 Insulating Oxide Porous Coating (Dotted Area) ) And PbO 2
(Hatched-dotted line part) Layer 4 PbO 2 (hatched-dotted line part) Coating layer 5 Porosity and cracks
Claims (8)
表層をＰｂＯ2 の被覆層とした電解用電極において、前
記電極母材と電極最表層との間に、２層からなる中間層
を設け、そのうち電極母材側の層を、電極母材に対して
平行な層状構造を持つ絶縁性酸化物の多孔質被膜で形成
して、その空孔に電極母材成分を充填した層とし、電極
最表層側の層を、電極母材に対して平行な層状構造を持
つ絶縁性酸化物の多孔質被膜で形成して、その空孔にＰ
ｂＯ2 を充填した層としたことを特徴とする電解用電
極。1. An electrode for electrolysis, wherein the electrode base material is composed of a conductive metal and the electrode outermost layer is a PbO 2 coating layer, and an intermediate layer consisting of two layers is provided between the electrode base material and the electrode outermost layer. A layer in which a layer on the electrode base material side is formed by a porous coating of an insulating oxide having a layered structure parallel to the electrode base material, and the pores are filled with the electrode base material component. The layer on the outermost surface side of the electrode is formed of a porous coating of an insulating oxide having a layered structure parallel to the electrode base material, and P is formed in the pores.
An electrode for electrolysis, which is a layer filled with bO 2 .
る、絶縁性酸化物と、電極母材成分との体積比が６０：
４０ないし９５：５の範囲にあることを特徴とする請求
項第１項記載の電解用電極。2. The volume ratio of the insulating oxide and the electrode base material component constituting the layer on the electrode base material side of the intermediate layer is 60:
The electrode for electrolysis according to claim 1, which is in the range of 40 to 95: 5.
る、絶縁性酸化物と、ＰｂＯ2 との体積比が６０：４０
ないし９５：５の範囲にあることを特徴とする請求項第
１項、または第２項記載の電解用電極。3. The volume ratio of the insulating oxide and PbO 2 forming the layer on the electrode outermost layer side of the intermediate layer is 60:40.
3. The electrode for electrolysis according to claim 1 or 2, wherein the electrode is in the range of 95: 5 to 95: 5.
５μｍ以上であることを特徴とする請求項第１〜３項の
いずれかに記載の電解用電極。4. The thickness of the layer on the electrode base material side of the intermediate layer is
It is 5 micrometers or more, The electrode for electrolysis in any one of Claims 1-3 characterized by the above-mentioned.
が、５〜１９５μｍの範囲であることを特徴とする請求
項第１〜４項のいずれかに記載の電解用電極。5. The electrode for electrolysis according to any one of claims 1 to 4, wherein the thickness of the layer on the electrode outermost surface side of the intermediate layer is in the range of 5 to 195 μm.
ｂＯ2 とβ−ＰｂＯ2 の多層構造としたことを特徴とす
る請求項第１〜５項のいずれかに記載の電解用電極。6. The PbO 2 coating layer as the outermost layer of the electrode is formed of α-P.
The electrode for electrolysis according to any one of claims 1 to 5, which has a multilayer structure of bO 2 and β-PbO 2 .
極最表層の４層からなる電解用電極であって、電極母材
を導電性金属で構成し、その電極母材上に、電極母材に
対して平行な層状構造を持つ絶縁性酸化物の多孔質被膜
を形成した後、電極母材側の空孔に電極母材成分を充填
して電極母材側中間層を形成し、更にその上の空孔にＰ
ｂＯ2 を充填して電極最表層側中間層を形成したのち、
電着法により電極最表層をＰｂＯ2 で成膜する電解用電
極の製造方法において、まず、電極母材上に絶縁性酸化
物を溶射して、空孔率５〜４０％の絶縁性酸化物の多孔
質被膜を形成し、次に、ＨＩＰ処理を施して電極母材と
絶縁性酸化物との間で相互拡散させることにより電極母
材側の中間層を形成した後、電極母材を陽極として通電
し、電着により、絶縁性酸化物の多孔質被膜の残りの空
孔にＰｂＯ2 を充填して、電極最表層側の中間層を形成
することで２層からなる中間層を設けることを特徴とす
る電解用電極の製造方法。7. An electrode for electrolysis comprising four layers of an electrode base material, an intermediate layer consisting of two layers, and an electrode outermost layer, wherein the electrode base material is made of a conductive metal, and the electrode base material comprises: After forming a porous film of insulating oxide having a layered structure parallel to the electrode base material, the holes on the electrode base material side are filled with the electrode base material component to form the electrode base material side intermediate layer. , P in the hole above
After filling bO 2 to form an intermediate layer on the outermost surface of the electrode,
In the method for producing an electrode for electrolysis in which the outermost layer of the electrode is formed of PbO 2 by the electrodeposition method, first, an insulating oxide is sprayed on the electrode base material to form an insulating oxide having a porosity of 5 to 40%. After forming a porous coating film on the electrode base material and forming an intermediate layer on the electrode base material side by performing HIP treatment to cause mutual diffusion between the electrode base material and the insulating oxide, the electrode base material is anodized. As a result, the remaining pores of the insulating oxide porous film are filled with PbO 2 by electrodeposition to form an intermediate layer on the outermost surface side of the electrode, thereby providing an intermediate layer composed of two layers. A method for producing an electrode for electrolysis, comprising:
際に、温度７５０〜１１００℃、圧力１０００〜２００
０気圧の不活性ガス雰囲気下でＨＩＰ処理を施すことを
特徴とする請求項第７項記載の電解用電極の製造方法。8. A temperature of 750 to 1100 ° C. and a pressure of 1000 to 200 when forming a layer on the electrode base material side of the intermediate layer.
The method for producing an electrode for electrolysis according to claim 7, wherein the HIP treatment is performed in an inert gas atmosphere of 0 atm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7261015A JP3062062B2 (en) | 1995-09-14 | 1995-09-14 | Electrode for electrolysis and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7261015A JP3062062B2 (en) | 1995-09-14 | 1995-09-14 | Electrode for electrolysis and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0978298A true JPH0978298A (en) | 1997-03-25 |
| JP3062062B2 JP3062062B2 (en) | 2000-07-10 |
Family
ID=17355875
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7261015A Expired - Fee Related JP3062062B2 (en) | 1995-09-14 | 1995-09-14 | Electrode for electrolysis and method for producing the same |
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| Country | Link |
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Cited By (1)
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|---|---|---|---|---|
| JP2021050371A (en) * | 2019-09-24 | 2021-04-01 | 株式会社東芝 | Method for treating wire rod |
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1995
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Cited By (1)
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| JP2021050371A (en) * | 2019-09-24 | 2021-04-01 | 株式会社東芝 | Method for treating wire rod |
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