JP3116664B2 - Electrode material made of Ti or Ti-based alloy with excellent corrosion resistance and current efficiency - Google Patents
Electrode material made of Ti or Ti-based alloy with excellent corrosion resistance and current efficiencyInfo
- Publication number
- JP3116664B2 JP3116664B2 JP05173038A JP17303893A JP3116664B2 JP 3116664 B2 JP3116664 B2 JP 3116664B2 JP 05173038 A JP05173038 A JP 05173038A JP 17303893 A JP17303893 A JP 17303893A JP 3116664 B2 JP3116664 B2 JP 3116664B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode material
- layer
- based alloy
- corrosion resistance
- current efficiency
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、海水電解による塩素や
塩素酸塩の製造、更にはソーダ電解等を始めとする各種
電気分解工業において利用される電極材に関し、殊に耐
食性および電流効率に優れ、しかも長寿命なＴｉまたは
Ｔｉ基合金製電極材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 material used in the production of chlorine and chlorate by seawater electrolysis, and also in various electrolysis industries such as soda electrolysis and the like. The present invention relates to an electrode material made of Ti or a Ti-based alloy having excellent and long life.
【０００２】[0002]
【従来の技術】上記の様な電気分解工業の分野において
用いられる電極材の素材としては、従来では導電性や耐
食性等を考慮して黒鉛が一般的に使用されてきた。しか
しながら近年では、耐食性の他加工性や経済性等の観点
からＴｉが電極材として使用される様になり、特にソー
ダ電解や二酸化マンガン製造用の電極として汎用されて
いる。2. Description of the Related Art As a material of an electrode material used in the field of the electrolysis industry as described above, graphite has conventionally been generally used in consideration of conductivity, corrosion resistance and the like. However, in recent years, Ti has come to be used as an electrode material from the viewpoints of workability, economy, and the like in addition to corrosion resistance, and is particularly widely used as an electrode for soda electrolysis and manganese dioxide production.
【０００３】しかしながら、Ｔｉ電極材をカソードに用
いた場合には、還元反応によって水素が発生してＴｉが
水素吸収を起こし、これによる水素脆化によって電極材
の機械的特性の劣化を招くので、Ｔｉ電極材はアノード
電極にしか使用されていないのが実情である。一方、Ｔ
ｉ電極材をアノード電極として使用した場合でも、Ｔｉ
の不働態化によって電極材表面に絶縁性のＴｉ酸化膜が
形されるために、電流効率が時間とともに減少していく
ので、ショットブラスト等で定期的に酸化皮膜を除去す
る必要がある。このような電流効率の問題は、電解工業
の生産性に直接的に結びつくことから、この問題の解決
は非常に重要である。[0003] However, when a Ti electrode material is used for the cathode, hydrogen is generated by a reduction reaction and Ti absorbs hydrogen, and the resulting hydrogen embrittlement causes deterioration of the mechanical properties of the electrode material. The fact is that the Ti electrode material is used only for the anode electrode. On the other hand, T
Even when the i-electrode material is used as the anode electrode, Ti
Since the passivation forms an insulating Ti oxide film on the surface of the electrode material, the current efficiency decreases with time. Therefore, it is necessary to periodically remove the oxide film by shot blasting or the like. Since the problem of such current efficiency is directly linked to the productivity of the electrolytic industry, the solution of this problem is very important.
【０００４】上記の様な問題を解決する手段として、こ
れまで（１）合金の開発、（２）白金族元素めっき、
（３）電気伝導性を有する白金族元素酸化物のコーテイ
ング等の技術が提案されているが、夫々下記に示す様な
欠点を有し、いずれの技術も十分な効果が得られている
とは言えない。As means for solving the above problems, there have been proposed (1) development of alloys, (2) plating of platinum group elements,
(3) Techniques such as coating of platinum group element oxides having electrical conductivity have been proposed, but each has the following disadvantages, and it is said that all techniques have sufficient effects. I can not say.
【０００５】まず電極用として開発された合金は、Ｎｉ
添加Ｔｉ基合金（例えば特開平３−１９９３６０号）が
代表的なものとして挙げられる。この様な合金開発は、
Ｔｉの不働態が保持する電流密度を上昇させることによ
って、高電流効率化を図ろうとするものであるが、却っ
てＴｉの耐食性が悪化し、電位のかからない部分（スプ
ラッシュゾーン）が腐食を起こし、寿命が短かくなると
いう欠点がある。また添加元素が溶出することによっ
て、電解物質（製品）に不純物が混入する原因にもな
る。更に、上記の様な添加元素が電極材に有用な特性を
付与する為には、かなり高濃度の添加が必要になり、こ
れによって電極材の機械加工性が悪くなるという欠点も
ある。[0005] First, an alloy developed for electrodes is Ni
A typical example is an added Ti-based alloy (for example, JP-A-3-199360). Such alloy development is
By increasing the current density held by the passivation of Ti, it is intended to increase the current efficiency. On the contrary, the corrosion resistance of Ti deteriorates, and a portion where no potential is applied (splash zone) is corroded. Has the disadvantage of being shorter. In addition, elution of the additional element may cause impurities to be mixed into the electrolytic substance (product). Furthermore, in order for the above-mentioned additive elements to impart useful properties to the electrode material, it is necessary to add a considerably high concentration thereof, which has the disadvantage that the machinability of the electrode material deteriorates.
【０００６】一方、Ｔｉに白金族元素めっき施した場合
には、Ｔｉとめっき層の十分な密着性が得られにくいこ
と、およびめっき層のピンホール等の欠陥を通してＴｉ
素地表面が腐食する可能性が大きいこと等の欠点があ
る。また自然な状態のＴｉは、その表面に緻密な酸化被
膜が形成されており、この上にめっきを密着性良く形成
することは困難であり、酸化皮膜を取り除く為の煩雑な
前処理が必要になる。更に、電解浴中での経年変化によ
って、めっき層が剥離したり、めっき層との接触部分が
欠陥や剥離によって溶液に接触して腐食が促進される可
能性がある。On the other hand, when a platinum group element is plated on Ti, it is difficult to obtain sufficient adhesion between the Ti and the plating layer, and the Ti is formed through defects such as pinholes in the plating layer.
There are drawbacks such as the possibility that the surface of the substrate is likely to corrode. Also, in the natural state of Ti, a dense oxide film is formed on the surface, and it is difficult to form a plating on the surface with good adhesion, and a complicated pretreatment for removing the oxide film is required. Become. Further, there is a possibility that the plating layer peels due to aging in the electrolytic bath, or that the contacting portion with the plating layer comes into contact with the solution due to defects or peeling, thereby promoting corrosion.
【０００７】尚上記した様な（１）合金の開発や（２）
白金族元素めっき等の技術では、水素吸収による水素脆
化の防止はできず、依然としてＴｉ電極材をカソード電
極として使用できない。The above-mentioned (1) development of alloys and (2)
Techniques such as platinum group element plating cannot prevent hydrogen embrittlement due to hydrogen absorption, and still cannot use a Ti electrode material as a cathode electrode.
【０００８】電気伝導性を有する白金族元素酸化物のコ
ーティングによっても、前記した様な問題の解決が図ら
れているのは上述した通りであるが、この技術において
も上記白金族元素めっきの場合と同様の欠点があった。
またこうしたコーティングは溶射によって行われるのが
一般的であるが、どの様な溶射法を採用しても十分な密
着性が得られず、またコーティング膜中の欠陥も問題に
なる。As described above, the above-mentioned problems have been solved by coating with a platinum group element oxide having electrical conductivity. Had the same disadvantages.
Further, such coating is generally performed by thermal spraying. However, no matter how the thermal spraying method is employed, sufficient adhesion cannot be obtained, and defects in the coating film become a problem.
【０００９】[0009]
【発明が解決しようとする課題】本発明はこうした事情
に着目してなされたものであって、機械加工性を損なう
ことなく、しかもＴｉやＴｉ基合金素地との密着性の問
題や欠陥の問題を本質的に含まない表面処理層を簡素な
工程で形成することによって、従来法では得られなかっ
た優れた耐食性および電流効率を達成し、アノード電極
材としては勿論のことカソード電極材としても最適なＴ
ｉまたはＴｉ基合金製電極材を提供することを目的とす
るものである。DISCLOSURE OF THE INVENTION The present invention has been made in view of such circumstances, and has no problems in machinability and has problems of adhesion to Ti or a Ti-based alloy base material and defects. By forming a surface treatment layer that is essentially free of sapphire in a simple process, it achieves excellent corrosion resistance and current efficiency that could not be obtained by the conventional method, and is optimal not only as an anode electrode material but also as a cathode electrode material Na T
It is an object to provide an electrode material made of i or Ti base alloy.
【００１０】[0010]
【課題を解決するための手段】上記目的を達成した本発
明のＴｉまたはＴｉ基合金製電極材は、ＴｉまたはＴｉ
基合金からなる電極材の表層部に、白金族元素の濃度富
化層が形成されると共に、当該表層部に更に酸化処理層
が形成されてなる点に要旨を有するものである。The electrode material made of Ti or Ti-based alloy according to the present invention, which achieves the above object, comprises Ti or Ti-based alloy.
The gist lies in that a concentration-enriched layer of a platinum group element is formed on a surface layer of an electrode material made of a base alloy, and an oxidation treatment layer is further formed on the surface layer.
【００１１】[0011]
【作用】本発明者らは、電解工業で使用する電極材につ
いて、かねてより研究を重ねてきた。そして研究の一環
として、合金開発の観点から、アノード電極として有用
なＴｉ合金製電極材を提案している（特願平４−２６４
２６６号）。この技術は、Ｍｎを0.01〜８重量％を含
み、必要によってＡｌ，Ｆｅ，Ｖ，Ｚｒ，Ｐｂ，Ｃｏ，
Ｎｉ，Ｍｏ，Ｐｄ，Ｒｕ等を含有し、残部Ｔｉおよび不
可避不純物からなるＴｉ合金を電極材として用いるもの
であり、これによってアノード電極として有用Ｔｉ合金
製電極材が実現できたのである。The present inventors have long studied the electrode materials used in the electrolytic industry. As part of their research, they proposed a Ti alloy electrode material useful as an anode electrode from the viewpoint of alloy development (Japanese Patent Application No. 4-264).
266). This technique contains 0.01 to 8% by weight of Mn, and optionally contains Al, Fe, V, Zr, Pb, Co,
A Ti alloy containing Ni, Mo, Pd, Ru, etc., and the balance of Ti and unavoidable impurities is used as an electrode material, whereby a Ti alloy electrode material useful as an anode electrode was realized.
【００１２】本発明者らは上記技術を完成した後におい
ても、表面処理の観点からも、有用な電極材の実現を目
指して検討を進めてきた。その結果、ＴｉまたはＴｉ基
合金からなる電極材の表層部に、白金族元素の濃度富化
層を形成すると共に、当該表層部に更に酸化処理層を形
成したものでは、優れた耐食性および電流効率を有し、
最適なＴｉまたはＴｉ基合金製電極材となり得ることを
見いだし、本発明を完成した。[0012] The present inventors have been studying, after completing the above technology, from the viewpoint of surface treatment, with the aim of realizing a useful electrode material. As a result, when a layer enriched with a platinum group element is formed on the surface layer of an electrode material made of Ti or a Ti-based alloy and an oxidation treatment layer is further formed on the surface layer, excellent corrosion resistance and current efficiency are obtained. Has,
The present inventors have found that the electrode material can be an optimal electrode material made of Ti or a Ti-based alloy, and completed the present invention.
【００１３】本発明の電極材において、ＴｉまたはＴｉ
基合金からなる電極材の表層部に白金族元素の濃度富化
層を形成する手段としては、例えばイオン注入法が挙げ
られる。このイオン注入の手法は、加速された高エネル
ギーのイオンを目的とする部材表面に打ち込んでＴｉ電
極材の表面を改質するものであり、半導体分野における
不純物ドーピング手段として利用されている他、鋼を中
心とする金属材料の表面改質にもその適用が検討されて
いるが、半導体分野を除いてはこれまでのところ実用化
はあまり進んでいない。In the electrode material of the present invention, Ti or Ti
Means for forming a concentration-enriched layer of a platinum group element in the surface layer of an electrode material made of a base alloy include, for example, an ion implantation method. This ion implantation technique is to improve the surface of a Ti electrode material by implanting accelerated high-energy ions into a target member surface, and is used as an impurity doping means in the semiconductor field. Its application is also being considered for the surface modification of metallic materials, mainly, but its practical use has not so far advanced except in the field of semiconductors.
【００１４】本発明に係る電極材は、上記の様なイオン
注入の手法によって電極材の表層部に白金族元素の濃度
富化層を形成したものである。この様なイオン注入法を
適用すれば、ＴｉまたはＴｉ基合金の表層部に非熱平衡
物質層が形成されと共に、当該表層部に更に酸化処理に
よって密着性やクラック等の欠陥の問題を本質的に含ま
ない緻密でピンホールフリーな表面処理を行なえば、こ
れまで行なわれてきた熱プロセスによる合金化法や表面
処理の問題を克服し、従来法では予測できない特性を得
ることができる。換言すれば、イオン注入された元素と
同じ元素を添加して合金化し、その後酸化処理しても、
本発明の電極材の様な優れた耐食性、高電流効率化およ
び長寿命化は達成されないのである。The electrode material according to the present invention is obtained by forming a concentration-enriched layer of a platinum group element on the surface layer of the electrode material by the above-described ion implantation technique. When such an ion implantation method is applied, a non-thermal equilibrium material layer is formed on the surface layer of Ti or a Ti-based alloy, and the surface layer is further oxidized to substantially eliminate problems such as adhesion and cracks. If a fine and pinhole-free surface treatment that does not contain is performed, the problems of the alloying method and the surface treatment by the thermal process that have been performed so far can be overcome, and characteristics that cannot be predicted by the conventional method can be obtained. In other words, even if the same element as the ion-implanted element is added and alloyed, and then oxidized,
Excellent corrosion resistance, high current efficiency and long life like the electrode material of the present invention cannot be achieved.
【００１５】ところで、イオン注入によって、Ｔｉまた
はＴｉ基合金製電極材の表層部に濃度富化層を形成して
電極材の特性を改善するにあたっては、ＴｉまたはＴｉ
基合金電極材の表面にイオン注入を行ないさえすれば良
い問う言うものではなく、改善しようとする特性に合わ
せて特定のイオン種を選定し、且つその注入量、注入エ
ネルギー等を決定して最適な濃度富化層を形成する必要
がある。In order to improve the characteristics of the electrode material by forming a concentration-enriched layer on the surface of the electrode material made of Ti or Ti-based alloy by ion implantation, Ti or Ti
It is not a question that it is only necessary to perform ion implantation on the surface of the base alloy electrode material, but a specific ion species is selected according to the characteristics to be improved, and the implantation amount, implantation energy, etc. are determined and optimized. It is necessary to form a high concentration enriched layer.
【００１６】本発明者らは、種々の元素イオンについて
イオン注入実験を重ね結果、Ｔｉの耐食性を著しく改善
する濃度富化層を形成するには、白金族元素をイオン注
入することによって達成できることが分かった。また上
記濃度富化層が形成された表層部に、更に酸化処理層を
重畳して形成することによって、電極材としての特性は
飛躍的に改善されること、即ち白金族元素による濃度富
化層の形成と酸化処理層の形成という複合処理によっ
て、いずれか単独の処理の場合よりもその改善効果は飛
躍的に達成され、その信頼性も高揚することができたの
である。The present inventors have repeatedly conducted ion implantation experiments on various element ions. As a result, the formation of a concentration-enriched layer which significantly improves the corrosion resistance of Ti can be achieved by ion implantation of a platinum group element. Do you get it. Further, by superposing an oxidation treatment layer on the surface layer portion on which the concentration-enriched layer is formed, the characteristics as an electrode material are remarkably improved. By the combined treatment of the formation of the oxidized layer and the formation of the oxidized layer, the improvement effect was remarkably achieved as compared with the case of any one of the treatments alone, and the reliability thereof could be enhanced.
【００１７】上記イオン注入法は、高エネルギーのイオ
ンを目的物質表層部に強制的に添加するものであるが、
当該表層部に堆積状態で改質層が付与されるわけではな
く、基材のマトリックス中に注入層が存在するものであ
るので、めっきやコーティング等の表面処理の様に基材
と異なる材質の皮膜を密着させる場合と異なり、基材と
の一体性は極めて良好であり、剥離の問題は本質的に含
まない。In the above ion implantation method, high-energy ions are forcibly added to the surface layer of the target substance.
The modified layer is not provided in a deposited state on the surface layer portion, and the injection layer is present in the matrix of the base material, so that a material different from the base material such as surface treatment such as plating or coating is used. Unlike the case where the film is adhered, the integrity with the substrate is extremely good, and the problem of peeling is essentially not included.
【００１８】本発明に係る電極材は上記の効果を発揮す
るものであるが、この効果を発揮するためには、イオン
注入によって注入される白金族元素の量は１×１０15イ
オン／ｃｍ2 以上であることが好ましい。しかしなが
ら、過剰に注入した場合には、注入エネルギーに応じて
スパッタ現象による表面切削現象が顕著になるので、注
入エネルギーと注入量は慎重に決定する必要がある。一
般的には、イオン注入に用いるエネルギー範囲では、イ
オン注入量は１×１０18イオン／ｃｍ2 以下であること
が好ましい。また上記の様な複合処理による効果は、濃
度化層の深さや広がりと酸化層が完全に外れている場合
には、どちらか一方の処理を施したときと同様の効果し
か得られないので、白金族元素の濃度富化層は深さ方向
に適切に形成されることが必要であり、そのためには注
入角度、注入エネルギーおよび注入量等を選定する必要
がある。尚本発明の効果を十分に発揮するためには完全
に濃度富化層と酸化層が重畳していることが望ましい
が、一部の重畳であってもその改善効果は期待できる。
また濃度富化層と酸化処理層が重畳している部分におけ
る酸化処理層は、少なくともＴｉの酸化物が形成されて
いるが、酸化処理条件によってまたはその種類によって
は、白金族元素も酸化物となっている。The electrode material according to the present invention exhibits the above-mentioned effects. In order to exhibit this effect, the amount of the platinum group element implanted by ion implantation is 1 × 10 15 ions / cm 2. It is preferable that it is above. However, in the case of excessive implantation, the surface cutting phenomenon due to the sputtering phenomenon becomes remarkable according to the implantation energy, so that the implantation energy and the implantation amount must be carefully determined. Generally, in the energy range used for ion implantation, the ion implantation amount is preferably 1 × 10 18 ions / cm 2 or less. In addition, the effect of the composite treatment as described above can be obtained only when the depth or spread of the concentration layer and the oxide layer are completely out of order, and only the same effect as when one of the treatments is performed. The concentration-enriched layer of the platinum group element needs to be appropriately formed in the depth direction, and for that purpose, it is necessary to select an implantation angle, an implantation energy, an implantation amount, and the like. In order to sufficiently exhibit the effects of the present invention, it is desirable that the concentration-enriched layer and the oxide layer are completely overlapped. However, even if a part of the layer is overlapped, the improvement effect can be expected.
Further, in the oxidized layer where the concentration-enriched layer and the oxidized layer overlap, at least an oxide of Ti is formed. Has become.
【００１９】本発明で用いる白金族元素は、Ｒｕ，Ｒ
ｈ，Ｐｄ，Ｏｓ，Ｉｒ，Ｐｔのいずれも含み、これらの
元素をイオン注入等によって表層部に濃度富化層を形成
し、更に当該表層部に酸化層を重畳的に形成することに
よって本発明の効果が達成される。また本発明の電極材
の素材としては、Ｔｉは勿論のこと従来から汎用されて
いる各種Ｔｉ基合金を用いることができるが、本発明者
らが先に提案したＴｉ基合金電極部材（特願平４−２６
４２６６号）は、本発明の電極材の素材として最適であ
る。The platinum group element used in the present invention is Ru, R
h, Pd, Os, Ir, and Pt. The present invention is achieved by forming a concentration-enriched layer in the surface layer by ion implantation or the like of these elements, and further forming an oxide layer on the surface layer in a superimposed manner. The effect is achieved. As the material of the electrode material of the present invention, not only Ti but also various Ti-based alloys which have been widely used in the past can be used. Hei 4-26
No. 4266) is optimal as a material for the electrode material of the present invention.
【００２０】以下本発明を実施例によって更に詳細に説
明するが、下記実施例は本発明を限定するものではな
く、前・後記の趣旨に徴して設計変更することはいずれ
も本発明の技術的範囲に含まれるものである。Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples do not limit the present invention, and any design change in the spirit of the present invention will be described. It is included in the range.
【００２１】[0021]
【実施例】表１および表２に示す各種処理を行ったＴｉ
（ＪＩＳ２種に相当）電極材について、硫酸１モル水溶
液中で定電位電解（５ＶｖｓＡｇ／ＡｇＣｌ）した場合
の酸素発生量、電流密度の低下時間、電極表面層の損耗
量について調査した。尚このときの酸化処理は、大気中
で５００℃にて３０分間焼鈍して行なった。その結果
を、表３および表４に示す。また酸素発生量、電流密度
の低下時間、電極表面層の損耗量測定方法および評価基
準は、下記の通りである。EXAMPLE Ti subjected to various treatments shown in Tables 1 and 2 was used.
With respect to the electrode material (corresponding to JIS type 2), the amount of generated oxygen, the time required for decreasing the current density, and the amount of wear of the electrode surface layer when constant potential electrolysis (5 V vs Ag / AgCl) was performed in a 1 mol aqueous solution of sulfuric acid were investigated. The oxidation treatment at this time was performed by annealing at 500 ° C. in the air for 30 minutes. The results are shown in Tables 3 and 4. The methods for measuring the amount of generated oxygen, the time required for decreasing the current density, the amount of wear of the electrode surface layer, and the evaluation criteria are as follows.
【００２２】（酸素発生量）単位時間内に発生した酸素
量を測定し、純Ｔｉ（ＪＩＳ２種に相当）における発生
量を１とした相対値で示した。 （電流低下時間）初期の電流密度とその値が０．３とな
る時間を測定し、純Ｔｉ（ＪＩＳ２種に相当）における
時間を１とした場合に、各比較材および本発明材に関し
て相対的な時間を示している。尚この値は、電極の寿命
と相関をもっており、この値が大きい程寿命が長いこと
を示している。 （電極損耗量）一定時間電極として使用したときの減量
を算出し、純Ｔｉ（ＪＩＳ２種に相当）の減量を１とし
た相対的な損耗量を示し、この値が小さい程耐食性が良
好であることを示している。(Amount of Oxygen Generated) The amount of oxygen generated within a unit time was measured and expressed as a relative value with the amount generated in pure Ti (corresponding to JIS 2 types) being 1. (Current drop time) The initial current density and the time at which the value becomes 0.3 are measured, and when the time in pure Ti (corresponding to JIS 2) is set to 1, the relative time of each comparative material and the material of the present invention is determined. Time is shown. Note that this value has a correlation with the life of the electrode, and a larger value indicates a longer life. (Electrode wear amount) The weight loss when used as an electrode for a certain period of time is calculated, and the relative wear amount is shown with the weight loss of pure Ti (corresponding to JIS 2) set to 1. The smaller the value, the better the corrosion resistance. It is shown that.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【表３】 [Table 3]
【００２６】[0026]
【表４】 [Table 4]
【００２７】表１〜４から明らかな様に、本発明材は優
れた耐食性および電流効率を示しており、また長寿命で
あることがわかる。尚上記実施例では、硫酸水溶液中に
おける水の電気分解に関して本発明の効果を調査した
が、本発明は上記実施例で示した効果だけを有するもの
ではなく、広く電気分解工業の電極材としてその効果を
発揮するのは言うまでもない。また実施例における酸化
処理の条件は、上記の通りであり、この条件はイオン注
入層を形成する際のイオン種やイオン注入条件等に応じ
て最適化してイオン注入層と重畳する酸化処理層を形成
する必要があるが、その様な要求さえ満足すれれば、酸
化処理層を形成する方法は何ら限定されるものではな
く、例えば溶液中における陽極酸化処理であっても良
い。As is clear from Tables 1 to 4, the material of the present invention shows excellent corrosion resistance and current efficiency and has a long life. In the above example, the effect of the present invention was investigated with respect to the electrolysis of water in an aqueous sulfuric acid solution.However, the present invention does not have only the effect shown in the above example, and is widely used as an electrode material in the electrolysis industry. Needless to say, it is effective. The conditions of the oxidation treatment in the embodiment are as described above, and the conditions are optimized according to the ion species and ion implantation conditions when forming the ion implantation layer, and the oxidation treatment layer overlapping the ion implantation layer is formed. It is necessary to form the oxidized layer as long as such a requirement is satisfied. The method of forming the oxidized layer is not limited at all, and may be, for example, anodic oxidation in a solution.
【００２８】[0028]
【発明の効果】本発明は以上の様に構成されており、従
来法では得られなかった優れた耐食性および電流効率を
達成し、アソード電極材は勿論のことカソード電極材と
しても最適なＴｉまたはＴｉ基合金製電極材が実現でき
た。As described above, the present invention achieves excellent corrosion resistance and current efficiency which could not be obtained by the conventional method, and is suitable for not only the anode electrode material but also the cathode electrode material, such as Ti or Ti. An electrode material made of a Ti-based alloy was realized.
フロントページの続き (72)発明者 佐藤 俊樹 兵庫県神戸市西区高塚台１丁目５番５号 株式会社神戸製鋼所 神戸総合技術研 究所内 (72)発明者 安永 龍哉 兵庫県神戸市西区高塚台１丁目５番５号 株式会社神戸製鋼所 神戸総合技術研 究所内 (72)発明者 河田 和久 兵庫県神戸市西区高塚台１丁目５番５号 株式会社神戸製鋼所 神戸総合技術研 究所内 (56)参考文献 特開 昭55−18503（ＪＰ，Ａ) 特開 昭51−63374（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C25B 1/00 - 15/08 C23C 28/00 Continuation of the front page (72) Inventor Toshiki Sato 1-5-5 Takatsukadai, Nishi-ku, Kobe-shi, Hyogo Kobe Steel, Ltd. Kobe Research Institute (72) Inventor Tatsuya Yasunaga 1 Takatsukadai, Nishi-ku, Kobe-shi, Hyogo Kobe Steel, Ltd.Kobe Institute of Technology, Kobe Steel, Ltd. (72) Inventor Kazuhisa Kawada 1-5-5, Takatsukadai, Nishi-ku, Kobe, Hyogo, Japan Kobe Steel, Ltd.Kobe Institute of Technology, (56) References JP-A-55-18503 (JP, A) JP-A-51-63374 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C25B 1/00-15/08 C23C 28 / 00
Claims (1)
表層部に、白金族元素の濃度富化層が形成されると共
に、当該表層部に更に酸化処理層が形成されてなること
を特徴とする耐食性および電流効率に優れたＴｉまたは
Ｔｉ基合金製電極材。1. An electrode material comprising Ti or a Ti-based alloy, wherein a concentration-enriched layer of a platinum group element is formed on a surface portion of the electrode material, and an oxidation treatment layer is further formed on the surface portion. Electrode material made of Ti or Ti-based alloy with excellent corrosion resistance and current efficiency.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05173038A JP3116664B2 (en) | 1993-07-13 | 1993-07-13 | Electrode material made of Ti or Ti-based alloy with excellent corrosion resistance and current efficiency |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05173038A JP3116664B2 (en) | 1993-07-13 | 1993-07-13 | Electrode material made of Ti or Ti-based alloy with excellent corrosion resistance and current efficiency |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0726390A JPH0726390A (en) | 1995-01-27 |
| JP3116664B2 true JP3116664B2 (en) | 2000-12-11 |
Family
ID=15953057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05173038A Expired - Lifetime JP3116664B2 (en) | 1993-07-13 | 1993-07-13 | Electrode material made of Ti or Ti-based alloy with excellent corrosion resistance and current efficiency |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3116664B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8486240B2 (en) | 2007-10-24 | 2013-07-16 | National University Corporation Nagoya Institute Of Technology | Ceramic electrode material and manufacturing method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100375934B1 (en) * | 2000-06-29 | 2003-03-10 | 주식회사 지인테크놀로지 | Electrode for disinfecting microbes from the water |
| JP5189781B2 (en) * | 2007-03-23 | 2013-04-24 | ペルメレック電極株式会社 | Electrode for hydrogen generation |
-
1993
- 1993-07-13 JP JP05173038A patent/JP3116664B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8486240B2 (en) | 2007-10-24 | 2013-07-16 | National University Corporation Nagoya Institute Of Technology | Ceramic electrode material and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0726390A (en) | 1995-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20060003174A1 (en) | Titanium material and method for manufacturing the same | |
| Potgieter | Alloys cathodically modified with noble metals | |
| JPS6013074B2 (en) | Electrolytic cathode and its manufacturing method | |
| FR2560610A1 (en) | LONG-TERM ELECTRODE FOR ELECTROLYSIS AND METHOD FOR MANUFACTURING THE SAME | |
| CA1159682A (en) | Electrode substrate titanium alloy for use in electrolysis | |
| JPH0477077B2 (en) | ||
| US3597172A (en) | Alloys having an aluminum-diffused surface layer | |
| JP3116664B2 (en) | Electrode material made of Ti or Ti-based alloy with excellent corrosion resistance and current efficiency | |
| JP2516252B2 (en) | Titanium-based alloy composition and anode structure | |
| JPS5912755B2 (en) | Stainless steel surface treatment method | |
| JP2003534635A (en) | Surface treatment of metal parts of electrochemical cells with improved adhesion and corrosion resistance | |
| JP6852454B2 (en) | Manufacturing method of Sn-based alloy-plated steel sheet and Sn-based alloy-plated steel sheet | |
| EP4116465A1 (en) | Ni-plated steel sheet, and method for manufacturing the same | |
| GB2146660A (en) | Surface-activated amorphous alloys for electrodes in the electrolysis of solutions | |
| Popov et al. | Surface treatment for inhibition of corrosion and hydrogen penetration of type 718 alloy | |
| JPH04365828A (en) | Titanium alloy for anode | |
| US1898765A (en) | Electrocleaning process | |
| JP2718310B2 (en) | Laminated plating Al plate and method for producing the same | |
| Chernova et al. | Increasing the passivation ability and corrosion resistance of chromium steel by surface alloying with palladium | |
| Singh et al. | The electrochemical behaviour of nitrogen-containing austenitic stainless steel in methanolic solution | |
| JPH09209108A (en) | Dip plating method for steel worked product | |
| JPS6024197B2 (en) | Pb alloy insoluble anode for electroplating | |
| JP2639950B2 (en) | Insoluble anode material | |
| JP3259870B2 (en) | Electrode substrate for electrolysis and method for producing the same | |
| JP2002097593A (en) | Machining material with high corrosion resistance for electronic device/component, electronic device/ component using the same, and method for manufacturing machining material with high corrosion resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20000905 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081006 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081006 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091006 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091006 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101006 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111006 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111006 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121006 Year of fee payment: 12 |