JP3062062B2 - Electrode for electrolysis and method for producing the same - Google Patents
Electrode for electrolysis and method for producing the sameInfo
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- JP3062062B2 JP3062062B2 JP7261015A JP26101595A JP3062062B2 JP 3062062 B2 JP3062062 B2 JP 3062062B2 JP 7261015 A JP7261015 A JP 7261015A JP 26101595 A JP26101595 A JP 26101595A JP 3062062 B2 JP3062062 B2 JP 3062062B2
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Description
【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 electrode for electrolysis 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 a chromium electroplating bath. And a method for producing 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, and a metal such as Zn, Sn, Ni, Cr is electroplated on the surface of a metal material to be plated as a cathode. Has been done. Also, when electrorefining a metal, using an electrode for electrolysis in a refining bath, Mn, Zn
Electrorefining of metals such as has been 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。[0003] Among them, a lead dioxide electrode is widely used for electrorefining of a metal by chromium plating or a sulfate bath. This is because lead dioxide has a property of supplying a current required for plating and oxidizing trivalent chromium generated in a 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。At present, the lead dioxide electrode is formed by electrolyzing a valve metal such as titanium as an anode in a nitric acid solution, a perchloric acid solution or an alkaline solution containing mainly lead ions, so that the base material of the valve metal is formed. A coated lead dioxide electrode in which lead dioxide is electrodeposited is used.
【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。[0005] A specific manufacturing method of this coated lead dioxide electrode is disclosed in Japanese Patent Publication No. 58-31396.
An electrochemically active coating containing platinum metal, iridium and other white metal and their oxides is applied on a base of a valve metal such as titanium by a pyrolysis method, and further, lead dioxide is applied thereon by a lead nitrate bath. The adhesion of lead dioxide has been improved by anodic electrodeposition and by interposing a wire mesh between the base of a valve metal such as titanium and a lead dioxide coating layer. However, the manufacturing process of the electrode is complicated, requires man-hours, and has the disadvantage of being 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。When the coated lead dioxide electrode as described above is used in an aqueous solution containing fluoride ions, it depends on the current density.
By applying an electric current of 0 hr, a fine crack penetrating the base of the valve metal as the electrode base material occurs in the lead dioxide coating layer,
The plating solution may enter the cracks and corrode and dissolve the electrode base material.
【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 relates to 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 an object of the present invention to provide an electrode for electrolysis which has excellent corrosion resistance, does not peel off, and can withstand long-term use, 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。According to the present invention, there is provided an electrode for electrolysis in which an electrode base material is made of a conductive metal and an outermost layer of the electrode is a PbO 2 coating layer. In between, an intermediate layer consisting of two layers is provided, and the layer on the electrode base material side is formed of a porous coating of an insulating oxide having a layered structure parallel to the electrode base material, and the pores are formed in the holes. A layer filled with an electrode base material component, and a 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 PbO 2 is filled in its pores. An electrode for electrolysis characterized by being a filled layer and a method for producing the same.
【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 at least 5 μm, and the volume ratio of the insulating oxide to the electrode base material component constituting this layer is 60:40 or less. 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 to 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 as the outermost layer of the electrode is formed as α
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。A method for manufacturing an electrode for electrolysis according to the present invention, which comprises four layers, an electrode base material, an intermediate layer consisting of two layers, and an outermost layer of the electrode, is as follows. That is, the electrode for electrolysis of the present invention first sprays an insulating oxide on the electrode base material,
A porous film of an insulating oxide having a porosity of 5 to 40% is formed, and then a HIP process is performed to cause the electrode base material and the insulating oxide to interdiffuse, whereby an electrode base material side is formed. After the formation of the intermediate layer of PbO, the electrode base material is used as an anode and a current is passed. PbO is deposited in the remaining pores of the insulating oxide porous film by electrodeposition.
2 to form an intermediate layer on the outermost layer side of the electrode to provide an intermediate layer composed of two layers, and then PbO 2 by electrodeposition.
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 layer on the electrode base material side of the intermediate layer is preferably formed by performing HIP processing 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。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrode base material used in the present invention may be a conductive metal, but it is preferable to use a valve metal (Ti, Ta, Zr, Nb) which is stable at the time of anodic polarization, or a fluorine ion or a fluoride ion. It is preferable to use a material having excellent Ni durability and a 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 of the porous film of the insulating oxide forming the intermediate layer may be an oxide which is relatively stable even in a solution containing fluorine ions or fluoride ions, for example, Al 2 O 3. O 3 , Cr 2 O 3 , Al 2
O 3 —Cr 2 O 3 is preferred.
【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 coating of insulating oxide has a particle size of about 20
It can be formed by spraying an insulating oxide powder of ４０40 μm by, for example, 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 thermal spraying condition of the insulating oxide is such that the porosity is 5 to 5.
It is desirable to select so as to be 40%. this is,
The volume ratio between the insulating oxide and the electrode base material constituting the layer on the electrode base material side of the intermediate layer is 60:40 to 95:
This is because the volume ratio between the insulating oxide and PbO 2 constituting the layer on the outermost surface side of the electrode is in the range of 60:40 to 95: 5. When the volume ratio of the insulating oxide is 95% or less, a sufficient amount of Pb is applied to the intermediate layer on the outermost layer side of the electrode to supply an electric current between the electrode base material and the outermost layer of the electrode.
O 2 can be filled. Further, when the volume ratio of the insulating oxide is 60
% Or more, exposure of the electrode base material component to the plating solution is sufficiently suppressed by the layer on the outermost electrode side of the intermediate layer. The porosity of the porous film of the insulating oxide can be calculated from the area ratio of the porosity, for example, by observing the longitudinal or transverse section of the film.
【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。The thickness of the layer on the electrode outermost layer side of the intermediate layer is
It is desirable that the thickness be 195 μm or less. This is because even if this layer is made thicker, the exposure of the electrode base material component to the plating solution is not further suppressed, and conversely, the coating is liable to peel off. Further, if the thickness of the intermediate layer on the electrode base material side is 5 μm or more, the adhesion to the electrode base material is sufficiently ensured. However, the thickness is 250μ
When the distance is about m, the layer is easily peeled off, which is not preferable. On the other hand, the thickness of the layer on the outermost layer of the electrode is also 5μ.
If m or more, exposure of the electrode base material to the plating solution is sufficiently suppressed. Therefore, the thickness of the insulating oxide porous film 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 on the electrode base material side of the intermediate layer can be formed by performing a HIP treatment 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 diffusing the electrode base material and the insulating oxide porous film mutually, a temperature of 750 ° C. or higher and a pressure of 750 ° C. The treatment is preferably performed under an inert gas atmosphere of 1000 atm or more. Further, in order to prevent 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.
The temperature is preferably 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 2,000 atm, the porous film of the insulating oxide is densified and the porosity decreases, which is not preferable. In addition, about 1 to 5 hours is appropriate for the processing time in order to be industrially appropriate. After the PbO 2 film formation of the electrode outermost layer, the HIP
When the treatment is performed, the PbO 2 coating layer is densified and easily peeled off. Therefore, the HIP treatment needs to be performed 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。Thereafter, the pores of the porous film of the insulating oxide are filled with PbO 2 , and the outermost layer of the electrode is formed. At this time, if β-PbO 2 is directly formed, this layer is not preferable because of poor adhesion to the porous film of the insulating oxide. Therefore, it formed so as to sandwich the alpha-PbO 2 layer between the beta-PbO 2 layer, achieving multi-layered.
【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%).
0 g / liter) can be formed as an electrolytic bath by electrolysis at a temperature of 20 to 50 ° C. and a current density of 0.1 to 10 A / dm 2 , using the electrode base material as an anode. Α-PbO
2 can be filled. Then, the 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。The β-PbO 2 layer is formed, for example, at a temperature of 50 to 70 ° C. using a lead nitrate bath of 200 g / liter or more as an electrolytic bath and an electrode base material on which an α-PbO 2 layer is formed as an anode.
By electrolysis at a current density of 10 A / dm 2 , β
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。FIG. 1 shows the structure of the electrode for electrolysis of the present invention.
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 was composed of the porous coating of the insulating oxide and the electrode base material component. Intermediate layer 2, furthermore, a porous coating of insulating oxide and P
Since the intermediate layer 3 composed of bO 2 exists, the pores and cracks 5 existing in the outermost layer 4 of the electrode do not penetrate into the electrode base material 1, so that 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, the adhesion to the electrode base material 1 is very excellent. Thus, the electrode for electrolysis of the present invention is excellent in corrosion resistance due to the small exposed area of the electrode base material, and excellent in adhesion, so that peeling due to mechanical impact can be prevented, and 100 A / dm.
It can withstand long-term use under high current densities of 2 or more, and even under mechanical shock applied conditions 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。DESCRIPTION OF THE PREFERRED EMBODIMENTS In an electrode for electrolysis according to the present invention, that is, an electrode for an electrode in which an electrode base material is made of a conductive metal and an outermost layer of the electrode is a PbO 2 coating layer, the electrode base material and the outermost layer In between, an intermediate layer consisting of two layers is provided, and the layer on the electrode base material side is formed of a porous coating of an insulating oxide having a layered structure parallel to the electrode base material, and the pores are formed in the holes. A layer filled with an electrode base material component, and a 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 PbO 2 is filled in its pores. An example of a method for manufacturing an electrode for electrolysis characterized by being 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ＣFIG. 2 is a flow chart showing the manufacturing process, and the description will be made in accordance with the flowchart. (1) Pretreatment of Electrode Base Material As an electrode base material, an expanded mesh of the following material 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 electrode base material is sprayed by the usual plasma spraying method using the following insulating oxide. Then, a porous coating 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 μm Porosity: 1 to 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 on which the porous coating of the insulating oxide was applied was replaced 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 atmospheres
【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 the outermost layer on the electrode side and formation of the outermost layer of the electrode in the intermediate layer The electrode base material subjected to the above treatment was saturated with PbO in a 25% aqueous sodium hydroxide solution. 1A / in an electrolytic bath at 40 ° C
Electrolysis was performed at a current density of dm 2 for 2 hours, and α-PbO 2 was filled in the pores of the porous film of the insulating oxide. In addition, 80g
Per liter of an aqueous solution of lead nitrate as an electrolyte, α-PbO 2
Was electrolyzed at the current density of 2 A / dm 2 for 8 hours to form an electrode outermost layer composed 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。Table 1 shows the results of the durability test of the electrode for electrolysis of the present invention thus obtained, along with the conventional product and the comparative product in the column of evaluation.
【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, using an electrode for electrolysis of the present invention, a comparative product or the present invention as an anode, a platinum plate as a cathode, and an aqueous solution containing 50 g and 100 g / l chromic anhydride and 4 g / l ammonium fluoride. Then, an energization test was performed at a current density of 200 A / dm 2 to measure the time until the voltage increased by 10 V.
Here, in Table 1, ○ indicates durability for a life of 2000 hr or more, and X indicates an electrode for electrolysis having a life of less than 2000 hr. As a result, it can be seen that all the electrodes for electrolysis of the present invention have a life of 2,000 hr or more and are 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] Shows the Cr 2 O 3 - Material symbols Hasute, A, C, respectively AC is Hastelloy C, Al 2 O 3, Cr 2 O 3, Al 2 O 3.
【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] Shows the Cr 2 O 3 - Material symbols Hasute, A, C, respectively AC is Hastelloy C, Al 2 O 3, Cr 2 O 3, Al 2 O 3.
【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, reference numeral 12 denotes an electrode manufactured by a conventional electrodeposition method, and reference numerals 13 to 17 denote electrodes manufactured under conditions different from those of the present invention for comparison. In Comparative product 13, the porous coating of the insulating oxide was too thick, and the coating was peeled off before energization. Comparative product 14 could not be filled with PbO 2 because the porosity of the porous film of the insulating oxide was too low. 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 titanium of the electrode base material was deteriorated. The comparative product 17 had a short life because the effect of improving the adhesion by the intermediate layer and suppressing the exposure of the electrode base material component was not 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。The electrode for electrolysis of the present invention has excellent corrosion resistance even when electrolysis is performed at a high current density, does not peel off, and can be used for a long time. It is also very useful as an electrode for other uses.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明の電解用電極の構造を示す。FIG. 1 shows the structure of an electrode for electrolysis according to 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 flow chart 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Reference Signs List 1 electrode base material (dense hatched portion) 2 layer composed of porous film of insulating oxide (spotted portion) and electrode base material component (dense hatched portion) 3 porous coating of insulating oxide (spotted portion) ) And PbO 2
(Shaded-dashed line) 4 Coating layer of PbO 2 (shaded-dotted line) 5 Pores 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 in which an electrode base material is made of a conductive metal and an outermost layer of the electrode is a coating layer of PbO 2 , wherein an intermediate layer consisting of two layers is provided between the electrode base material and the outermost layer of the electrode. A layer in which a layer on the electrode base material side is formed of a porous coating of an insulating oxide having a layered structure parallel to the electrode base material, and the pores are filled with an electrode base material component. The layer on the outermost surface 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
An electrode for electrolysis, comprising 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. A volume ratio of an insulating oxide and an electrode base material component constituting a layer on the electrode base material side of the intermediate layer is 60:
2. The electrode for electrolysis according to claim 1, wherein said electrode 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 to PbO 2 constituting the layer on the electrode outermost layer side of the intermediate layer is 60:40.
The electrode for electrolysis according to claim 1 or 2, wherein the electrode is in the range of from 95 to 5: 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 a layer on the electrode base material side of the intermediate layer,
The electrode for electrolysis according to any one of claims 1 to 3, wherein the diameter is 5 µm or more.
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 claim 1, wherein a thickness of a layer on the electrode outermost layer side of the intermediate layer is in a 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 made of α-P
The electrode for electrolysis according to any one of claims the first to fifth paragraphs, characterized in that it 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 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 After forming a porous coating of an insulating oxide having a layered structure parallel to the electrode base material, filling the holes on the electrode base material side with the electrode base material component to form an electrode base material-side intermediate layer. , And furthermore, P
After filling bO 2 to form an intermediate layer on the outermost surface side of the electrode,
In the method of manufacturing an electrode for electrolysis in which the outermost layer of the electrode is formed of PbO 2 by an electrodeposition method, first, an insulating oxide is sprayed on an electrode base material to form an insulating oxide having a porosity of 5 to 40%. Is formed, and then an HIP process is performed to interdiffuse the electrode base material and the insulating oxide to form an intermediate layer on the electrode base material side. To provide a two-layer intermediate layer by filling the remaining pores of the insulating oxide porous film with PbO 2 by electrodeposition and forming an intermediate layer on the outermost layer side of the electrode by electrodeposition. A method for producing an electrode for electrolysis characterized by the following.
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 at 0 atm.
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|---|---|---|---|
| JP7261015A JP3062062B2 (en) | 1995-09-14 | 1995-09-14 | Electrode for electrolysis and method for producing the same |
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| 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 |
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| Publication Number | Publication Date |
|---|---|
| JPH0978298A JPH0978298A (en) | 1997-03-25 |
| JP3062062B2 true JP3062062B2 (en) | 2000-07-10 |
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