JPH0288785A - Production of electrolytic electrode material - Google Patents
Production of electrolytic electrode materialInfo
- Publication number
- JPH0288785A JPH0288785A JP63240032A JP24003288A JPH0288785A JP H0288785 A JPH0288785 A JP H0288785A JP 63240032 A JP63240032 A JP 63240032A JP 24003288 A JP24003288 A JP 24003288A JP H0288785 A JPH0288785 A JP H0288785A
- Authority
- JP
- Japan
- Prior art keywords
- alloy layer
- amorphous alloy
- ion
- electrode material
- base material
- 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.)
- Granted
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 150000002500 ions Chemical class 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 9
- 238000009684 ion beam mixing Methods 0.000 claims abstract description 8
- 230000001678 irradiating effect Effects 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 22
- 238000007740 vapor deposition Methods 0.000 claims description 9
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical group [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000005468 ion implantation Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052763 palladium Inorganic materials 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- -1 etc.) Inorganic materials 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 229910052741 iridium Inorganic materials 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 9
- 230000001133 acceleration Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 238000001659 ion-beam spectroscopy Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001017 electron-beam sputter deposition Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、電解電極材の製造方法に関し、特に耐食性の
優れた電解電極材の製造方法に係わる。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing an electrolytic electrode material, and particularly to a method for manufacturing an electrolytic electrode material with excellent corrosion resistance.
［従来の技術及び課題］
例えば、海水を電解して次亜塩素酸
（Ｎａ Ｃ）Ｏ）を発生させ、該海水をプラントの冷却
水、下水道などの滅菌に使用して水路が海洋生物によっ
て閉塞されるのを防ぐ方法は、広く採用されている。こ
の電解においては、陽極で塩素を発生させて次亜塩素酸
ナトリウムが生成されるが、同時に酸素発生を起こし易
いため、電解に用いる電極材は激しい腐蝕性環境に曝さ
れ、しかも高い電極活性が求められる。かかる環境に耐
える結晶質金属としては、従来より白金族金属が使用さ
れている。しかしなから、白金族金属は高価であるため
、経済性の観点から他の代替材料の開発が要望されてい
る。[Prior art and problems] For example, seawater is electrolyzed to generate hypochlorous acid (NaC)O), and the seawater is used to sterilize plant cooling water, sewerage systems, etc. to prevent waterways from becoming clogged with marine organisms. Methods to prevent this from occurring are widely used. In this electrolysis, chlorine is generated at the anode to produce sodium hypochlorite, but at the same time oxygen is likely to be generated, so the electrode materials used for electrolysis are exposed to a highly corrosive environment and have high electrode activity. Desired. Conventionally, platinum group metals have been used as crystalline metals that can withstand such environments. However, since platinum group metals are expensive, there is a demand for the development of other alternative materials from an economic standpoint.
このようなことから、電解電極材をアモルファス合金に
より製造することが検討されている。アモルファス合金
の中には、極めて高い耐食性を有するものがあり、塩素
を含む環境下でも腐蝕劣化を抑制できることが知られて
いる。しかしなから、アモルファス合金は通常、液体急
冷法で作られているため、その手法から形状的に薄帯、
細線、粉末等に制約される。このため、目的とする電解
電極材を製造することが困難であった。For these reasons, it is being considered to manufacture electrolytic electrode materials from amorphous alloys. Some amorphous alloys have extremely high corrosion resistance, and it is known that corrosion deterioration can be suppressed even in environments containing chlorine. However, since amorphous alloys are usually made using a liquid quenching method, their shape is similar to that of a thin ribbon.
Limited to fine wires, powder, etc. For this reason, it has been difficult to manufacture the desired electrolytic electrode material.
一方、活性の高いＴＩ基材をＰｔ−１ｒからなる合金層
で被覆したＴｉ系電解電極材が知られているが、電流効
率が８０％程度に止まるという問題があった。また、高
活性である酸化ルテニウム、酸化イリジウム又は酸化ス
ズからなる酸化物層でＴ１基材を被覆したＴｉ系電解電
極材が知られており、この電極材では８５％以上の電流
効率を示すものの、前記酸化物膜の基材からの離脱によ
る経時変化が認められ、使用初期のみにしか高電流効率
を実現できないとう問題があった。On the other hand, a Ti-based electrolytic electrode material in which a highly active TI base material is coated with an alloy layer made of Pt-1r is known, but there is a problem in that the current efficiency remains at about 80%. Furthermore, Ti-based electrolytic electrode materials are known in which a T1 base material is coated with an oxide layer made of highly active ruthenium oxide, iridium oxide, or tin oxide, and although this electrode material exhibits a current efficiency of 85% or more, However, there was a problem in that a change over time due to separation of the oxide film from the base material was observed, and high current efficiency could only be achieved at the initial stage of use.
本発明は、上記従来の課題を解決するためになされたも
ので、比較的低い陽極電位において高い電流効率を示し
、かつ耐食性及び耐久性に優れた電解電極材を製造し得
る方法を提供しようとするものである。The present invention has been made to solve the above-mentioned conventional problems, and aims to provide a method for producing an electrolytic electrode material that exhibits high current efficiency at a relatively low anode potential and has excellent corrosion resistance and durability. It is something to do.
［課題を解決するための手段］
本発明は、金属基材の表面に少なくとも１種以上の鉄族
元素（ＦｅＳＮ１％Ｃｏ）とＴｉ １Ｚｒ ％Ｎｂ及び
Ｔａから選ばれる少なくとも１種以上の金属元素と少な
くとも１種以上の白金族元素との合金からなるアモルフ
ァス合金層を前記合金の蒸着と同時に前記鉄族元素、金
属元素、白金族元素又は不活性ガスのイオンを照射する
イオンビームミキシング法により形成する工程と、この
アモルファス合金層を酸で処理する工程とを具備したこ
とを特徴とする電解電極材の製造方法である。[Means for Solving the Problems] The present invention provides a method in which the surface of a metal base material is coated with at least one iron group element (FeSN1%Co) and at least one metal element selected from Ti1Zr%Nb and Ta. An amorphous alloy layer made of an alloy with at least one platinum group element is formed by an ion beam mixing method in which ions of the iron group element, metal element, platinum group element, or inert gas are irradiated simultaneously with the vapor deposition of the alloy. This is a method for producing an electrolytic electrode material, comprising a step of treating the amorphous alloy layer with an acid.
上記鉄族元素としては、Ｆ ｅ ＳＮ Ｉ ｓ Ｃｏを
挙げることかできる。As the above-mentioned iron group element, Fe SN I s Co can be mentioned.
上記白金族元素としては、Ｐｔ、Ｐｄ、Ｉｒ、Ｒｈ ｓ
Ｒｕ ｓ Ｏｓを挙げることができる。The above platinum group elements include Pt, Pd, Ir, Rhs
RusOs can be mentioned.
上記合金の蒸着手段としては、各種の蒸着法を採用し得
るが、特に高真空度での成膜が可能な電子ビームによる
真空蒸着又はターゲットを利用したイオンビームスパッ
タ法が好ましい。Various vapor deposition methods can be employed as the means for vapor deposition of the above alloy, but vacuum vapor deposition using an electron beam or ion beam sputtering using a target is particularly preferable because it allows film formation at a high degree of vacuum.
また、本発明はアモルファス層の金属基材表面への形成
に先立ち、該基材表面に少なくとも１種以上の鉄族元素
、又はＴ Ｉ 、Ｚ ｒ −、Ｎ ｂ及びＴａから選ば
れる少なくとも１種以上の金属元素のイオンを照射して
イオン注入層を形成することを特徴とするものである。Further, the present invention provides that, prior to forming the amorphous layer on the surface of the metal base material, at least one iron group element or at least one element selected from T I , Z r -, N b and Ta is added to the surface of the base material. This method is characterized in that an ion-implanted layer is formed by irradiating ions of the above metal elements.
更に、本発明は金属基材の表面に少なくとも１種以上の
鉄族元素とＴｉ％Ｚ ｒ ＳＮ ｂ及びＴａから選ばれ
る少なくとも１種以上の金属元素との合金の蒸着と同時
に少なくとも１種以上の白金族元素イオンを照射するイ
オンビームミキシング法によりアモルファス合金層を形
成する工程と、このアモルファス合金層を酸で処理する
工程とを具備したことを特徴とする電解電極材の製造方
法である。Furthermore, the present invention provides a method for depositing on the surface of a metal base material an alloy of at least one iron group element and at least one metal element selected from Ti%ZrSNb and Ta. This is a method for producing an electrolytic electrode material, comprising a step of forming an amorphous alloy layer by an ion beam mixing method of irradiating platinum group element ions, and a step of treating the amorphous alloy layer with an acid.
［作用］
本発明によれば、少なくとも１種以上の鉄族元素とＴ１
、Ｚｒ５Ｎｂ及びＴａから選ばれる少なくとも１種以上
の金属元素と少なくとも１種以上の白金族元素との合金
を電子ビームによる真空蒸着法などの蒸着手段により成
膜することによって、前記合金からなる高純度のアモル
ファス合金層を金属基材表面に形成できる。また、蒸着
と同時に鉄族元素、金属元素、白金属元素又は不活性ガ
スをイオン照射してイオンビームミキシングを行なうこ
とによって、前記アモルファス合金層の基材に対する密
着性を向上でき、しかもイオンビームの照射条件は独立
して制御できるため該アモルファス合金層の緻密化、平
滑化等を達成し易くなる。[Function] According to the present invention, at least one or more iron group elements and T1
, Zr5Nb, and Ta and at least one platinum group element by forming a film using a vapor deposition method such as a vacuum vapor deposition method using an electron beam. An amorphous alloy layer can be formed on the surface of a metal substrate. In addition, by performing ion beam mixing by irradiating iron group elements, metal elements, platinum metal elements, or inert gas at the same time as vapor deposition, it is possible to improve the adhesion of the amorphous alloy layer to the base material, and also to improve the adhesion of the amorphous alloy layer to the base material. Since the irradiation conditions can be controlled independently, it becomes easier to achieve densification, smoothing, etc. of the amorphous alloy layer.
こうしたアモルファス合金層の表面では、原子配列が乱
雑無秩序にかつ高密度で入り乱れた状態となっているた
め、該アモルファス合金層の形成後に酸で処理すること
によって、該合金層表面において白金属元素は腐蝕され
ず、他の金属成分のみが選択的かつ均一に腐蝕、溶出し
て表面に白金属元素が均一に残留する。従って、基材上
に表面に白金属元素が均一に露出し、かつ無数の微細な
凹凸を有すると共に前記原子配列の乱れをもつ極めて表
面活性の高いアモルファス合金層を形成できるため、比
較的低い陽極電位において高い電流効率を示し、かつ該
アモルファス合金層による耐食性及び耐久性が付与され
、更に形状的な制約を受けず任意形状の電解電極材を製
造できる。On the surface of such an amorphous alloy layer, the atomic arrangement is disordered and disordered at high density. Therefore, by treating with acid after the formation of the amorphous alloy layer, the platinum metal element can be removed on the surface of the alloy layer. It is not corroded, and only other metal components are selectively and uniformly corroded and eluted, leaving a uniform platinum metal element on the surface. Therefore, it is possible to form an amorphous alloy layer with extremely high surface activity, in which the platinum metal element is uniformly exposed on the surface of the base material, and has countless minute irregularities and the disordered atomic arrangement. It exhibits high current efficiency at potential, and is provided with corrosion resistance and durability due to the amorphous alloy layer, and furthermore, it is possible to manufacture electrolytic electrode materials of arbitrary shapes without being subject to shape constraints.
また、アモルファス合金層の金属基材表面への形成に先
立ち、該基材表面に少なくとも１種以上の鉄族元素、又
はＴｉ、Ｚｒ、Ｎｂ及びＴａから選ばれる少なくとも１
種以上の金属元素のイオンを照射することによって、イ
オン注入の打ち込み効果と基材の深さ方向に成分組成が
段階的に変化した構造を有する密着性の優れたイオン注
入層（界面Ｊｉｉｉ）を形成できるため、この後にアモ
ルファス層を形成し、酸で処理することにより、基材に
対して表面に白金属元素が均一に露出したアモルファス
合金層を一層密着性よく、かつ全体的に耐剥離性の富ん
だ電解電極材を製造できる。Furthermore, prior to forming the amorphous alloy layer on the surface of the metal base material, at least one iron group element or at least one element selected from Ti, Zr, Nb, and Ta is added to the surface of the base material.
By irradiating ions of more than one metal element, an ion-implanted layer (interface Jiii) with excellent adhesion, which has the implantation effect of ion implantation and a structure in which the component composition changes stepwise in the depth direction of the base material, is created. By forming an amorphous layer and treating it with acid, an amorphous alloy layer with uniformly exposed platinum metal elements on the surface of the substrate can be formed with even better adhesion and overall peeling resistance. It is possible to manufacture electrolytic electrode materials rich in .
更に、金属基材の表面に少なくとも１種以上の鉄族元素
とＴｉ 、Ｚｒ ｓ Ｎｂ及びＴａから選ばれる少なく
とも１種以上の金属元素との合金の蒸着と同時に少なく
とも１種以上の白金族元素イオンを照射するイオンビー
ムミキシング法によりアモルファス合金層を形成した後
、該アモルファス合金層を酸で処理することによって、
既述した方法と同様、基材上に表面に白金属元素が均一
に露出し、かつ無数の微細な凹凸を有すると共に前記原
子配列の乱れをもつ極めて表面活性の高いアモルファス
合金層を形成できるため、比較的低い陽極電位において
高い電流効率を示し、かつ該アモルファス合金層による
耐食性及び耐久性が付与され、更に形状的な制約を受け
ず任意形状の電解電極材を製造できる。Furthermore, at the same time as vapor depositing an alloy of at least one iron group element and at least one metal element selected from Ti, ZrsNb, and Ta, at least one platinum group element ion is deposited on the surface of the metal base material. After forming an amorphous alloy layer by the ion beam mixing method of irradiating with , by treating the amorphous alloy layer with acid,
Similar to the method described above, it is possible to form an amorphous alloy layer with extremely high surface activity, in which the platinum metal element is uniformly exposed on the surface of the base material, and has countless fine irregularities and the disordered atomic arrangement. , exhibits high current efficiency at a relatively low anode potential, is provided with corrosion resistance and durability by the amorphous alloy layer, and can manufacture electrolytic electrode materials of arbitrary shapes without being subject to shape constraints.
［実施例］ 以下、本発明の実施例を詳細に説明する。[Example] Examples of the present invention will be described in detail below.
実施例１
まず、基材としての２０ｘ ２０Ｘ ２１１ｍの寸法の
Ｔｉ板を用意し、この片面を鏡面研磨し、超音波洗浄を
施した後、イオン照射と蒸着機能を備えた真空チャンバ
内に設置した。つづいて、このチャンバ内を５ Ｘ １
Ｏ−６ｔｏｒｒに真空引きした後、イオン源からＡ「イ
オンを加速電圧５ ｋｅＶの条件でＴｉ板の鏡面に５分
間照射して表面清浄化のための前処理を施した。次いで
、Ｎｉ −４０ａｔ％Ｎｂ −１，５ａｔ％Ｐｄの組成
のターゲットを用い、加速電圧３ｋｅＶ、イオン電流１
．５ＡのＡ「イオンでイオンビームスパッタ蒸着を行な
うと同時に別のイオン源からＡｒイオンを引きだし、加
速電圧１５０ｋｅＶ、イオン電流密度２．０ｍＡ／ｄの
条件でイオン照射して厚さ８μｍで前記ターゲットとほ
ぼ同組成のアモルファス合金層が被覆された複合材料を
製造した。Example 1 First, a Ti plate with dimensions of 20 x 20 x 211 m was prepared as a base material, one side of which was mirror polished and subjected to ultrasonic cleaning, and then placed in a vacuum chamber equipped with ion irradiation and vapor deposition functions. . Next, inside this chamber, 5 x 1
After evacuation to O-6 torr, the mirror surface of the Ti plate was irradiated with A ions from the ion source at an acceleration voltage of 5 keV for 5 minutes to perform a pretreatment for surface cleaning. Using a target with a composition of %Nb -1.5at%Pd, an acceleration voltage of 3 keV and an ion current of 1
．． A of 5A: At the same time as ion beam sputter deposition is performed using ions, Ar ions are extracted from another ion source, and ions are irradiated under conditions of an acceleration voltage of 150 keV and an ion current density of 2.0 mA/d to form a film with a thickness of 8 μm on the target. A composite material coated with an amorphous alloy layer of approximately the same composition was produced.
実施例２
前記実施例１でのアモルファス合金層の形成に先立ち、
質量分離型イオン源からＮｂイオンを引きだし、加速電
圧１８０ ｋ ｅ Ｖ、ビーム電流１．５ｍＡでＴｌ板
表面に照射してＮｂイオン注入層を形成した以外、実施
例１と同様な方法によりＮｉ −４０ａｔ％Ｎｂ −１
，５ａｔ％Ｐｄの組成のアモルファス合金層が被覆され
た複合材料を製造した。Example 2 Prior to forming the amorphous alloy layer in Example 1,
Ni- 40at%Nb-1
A composite material coated with an amorphous alloy layer having a composition of , 5 at% Pd was manufactured.
実施例３
実施例１と同様な研磨、表面清浄化処理を施したＴｉ板
の表面にＮ１−４０ａｔ％Ｎｂの組成のターゲットを用
いて加速電圧３ｋｅＶ、イオン電流１．５ ＡのＡｒイ
オンでイオンビームスパッタ蒸着を行なうと同時に別の
イオン源からＰｄイオンを引きだし、加速電圧１５０ｋ
ｅＶ、イオン電流密度０．５ｍＡ／ｄの条件でイオン照
射して厚さ３μｍでＮ１−４０ａｔ％Ｎｂ −１，５ａ
ｔ％Ｐｄの組成のアモルファス合金層が被覆された複合
材料を製造した。Example 3 The surface of a Ti plate that had been subjected to the same polishing and surface cleaning treatment as in Example 1 was ionized with Ar ions at an acceleration voltage of 3 keV and an ion current of 1.5 A using a target with a composition of N1-40at%Nb. At the same time as beam sputter deposition, Pd ions are extracted from another ion source and an acceleration voltage of 150k is applied.
eV and ion current density of 0.5 mA/d to a thickness of 3 μm with N1-40 at%Nb -1,5a.
A composite material coated with an amorphous alloy layer having a composition of t%Pd was produced.
比較例１
実施例１と同様な研磨、表面清浄化処理を施したＴｉ板
を市販のマグネトロンスパッタ装置により厚さ３ μｍ
のＮｉ −４０ａｔ％Ｎｂ −１，５８ｔ％Ｐｄのアモ
ルファス合金層を形成して複合材料を製造した。Comparative Example 1 A Ti plate subjected to the same polishing and surface cleaning treatment as in Example 1 was spun to a thickness of 3 μm using a commercially available magnetron sputtering device.
A composite material was manufactured by forming an amorphous alloy layer of Ni-40at%Nb-1,58t%Pd.
しかして、本実施例１〜３及び比較例１のアモルファス
合金層被覆複合材料について断面組織をＳＥＸで観察し
た。その結果、本実施例１〜３はいずれもアモルファス
合金層の組織が緻密で均一な相を有し、Ｔ１板との界面
にも何等の欠陥も認められなかった。これに対し、比較
例１の複合材料ではアモルファス合金層の組織に不均一
な相が一部認められ、またＴｉとの界面にボアー発生が
認められ、良質なアモルファス合金層とは評価し得なか
った。Therefore, the cross-sectional structures of the amorphous alloy layer-coated composite materials of Examples 1 to 3 and Comparative Example 1 were observed by SEX. As a result, in all of Examples 1 to 3, the amorphous alloy layer had a dense and uniform phase, and no defects were observed at the interface with the T1 plate. On the other hand, in the composite material of Comparative Example 1, some non-uniform phases were observed in the structure of the amorphous alloy layer, and the occurrence of bores was observed at the interface with Ti, so it could not be evaluated as a good quality amorphous alloy layer. Ta.
また、本実施例１〜３及び比較例１のアモルファス合金
層被覆複合材料を８０℃、ｐＨ４の４Ｍ−ＮａＣノ溶液
中に浸漬して電解試験を行なったところ、比較例の複合
材料ではＴｉ板との境界面で腐蝕が進行し、剥離状態と
なっが、本実施例１〜３の複合材料ではＴｉ板の境界面
での特別な腐蝕が進行する現象は認められず、界面での
耐久性の良好さが観察された。In addition, when the amorphous alloy layer-coated composite materials of Examples 1 to 3 and Comparative Example 1 were immersed in a 4M-NaC solution at 80°C and pH 4, an electrolytic test was conducted. However, in the composite materials of Examples 1 to 3, no special corrosion progress was observed at the interface between the Ti plate and the durability at the interface. Good quality was observed.
更に、本実施例１〜３のアモルファス合金層被覆複合材
料を８重量％濃度のフッ酸溶液に数分間浸漬して処理し
、表面にＰｄが均一に露出し、かつ表面に無数の微細な
凹凸を有するアモルファス合金層が被覆された電解電極
材を製造し、これら電極材について以下に説明する試験
により電流効率及び寿命を測定した。その結果、実施例
１〜３の電極材の電流効率はいずれも飽和かんこう電極
を基準電位とした時の陽極電位が１．３０Ｖ／ＳＣＥで
９０％、寿命は１０ｄａｙ以上であった。Furthermore, the amorphous alloy layer-coated composite materials of Examples 1 to 3 were treated by immersing them in a hydrofluoric acid solution with a concentration of 8% by weight for several minutes, so that Pd was uniformly exposed on the surface and countless fine irregularities were formed on the surface. Electrolytic electrode materials coated with an amorphous alloy layer having the following were manufactured, and the current efficiency and life of these electrode materials were measured by the tests described below. As a result, the current efficiency of the electrode materials of Examples 1 to 3 was 90% at an anode potential of 1.30 V/SCE when the saturated electrode was set as a reference potential, and the life span was 10 days or more.
■、電流効率の測定
海水電解の条件を擬似した３ ｖｔ％ＮａＣノ水溶液２
００ Ｍ （温度＝２５℃）を電解液とし、陽極に本実
施例の電極材を、陰極にステンレス板（縦３ＣＭ×横４
ｃ１１）を用いて直流電流密度１５００Ａ ／ ｍ ２
、電気量１００クーロンの条件で電解した後、電解液中
の次亜塩素酸濃度を滴定法によって測定し、その結果か
ら塩素発生効率（％）を計算することにより電流効率を
求めた。なお、前記直流電流密度を得るに必要な陽極電
位は、飽和かんこう電極（ＳＣＥ）を基準電位とし、電
解開始５分間後に電位計を用いて測定した。■ Measurement of current efficiency 3 vt% NaC aqueous solution 2 simulating the conditions of seawater electrolysis
00 M (temperature = 25°C) as an electrolyte, the electrode material of this example was used as an anode, and a stainless steel plate (3 CM in length x 4 in width) was used as a cathode.
c11) using DC current density 1500A/m2
After electrolysis under the conditions of 100 coulombs of electricity, the concentration of hypochlorous acid in the electrolytic solution was measured by a titration method, and the current efficiency was determined by calculating the chlorine generation efficiency (%) from the results. The anode potential required to obtain the above-mentioned DC current density was measured using an electrometer 5 minutes after the start of electrolysis, using a saturated electrolyte electrode (SCE) as a reference potential.
■、電極寿命の測定
前記電流効率の測定終了後の陽極電極（電極材）を、電
解槽内の３ ｗｔ％Ｎａ（、ｊ？水溶液に浸漬し、この
電解槽を超音波水槽内に設置した後、電流密度５０００
Ａ ／ ｍ ２で電解して飽和かんこう電極基準で２．
２Ｍ以上のに電圧が必要になった時を電極寿命とし、こ
の寿命に達するまでの日数を求めて寿命を評価した。(2) Measurement of electrode life After completing the measurement of current efficiency, the anode electrode (electrode material) was immersed in a 3 wt% Na(,j?) aqueous solution in an electrolytic bath, and the electrolytic bath was placed in an ultrasonic water bath. After that, the current density is 5000
Electrolyze at A/m2 and 2. based on saturated electrode.
The electrode life was defined as the time when a voltage of 2M or more was required, and the life was evaluated by calculating the number of days until this life was reached.
実施例４〜３０
実施例１と同様な研磨、表面清浄化処理を施したＴｉ板
の表面に下記第１表〜第３表に示す条件で厚さ３μｍの
アモルファス合金層を形成した。Examples 4 to 30 An amorphous alloy layer with a thickness of 3 μm was formed on the surface of a Ti plate that had been subjected to the same polishing and surface cleaning treatment as in Example 1 under the conditions shown in Tables 1 to 3 below.
但し、第１表〜第３表中でのスパッタ蒸着時でのＡｒイ
オンの照射は加速電圧３ｋｅＶ、イオン電流１．５ Ａ
の条件で、ミキシングためのイオン照射は加速電圧１２
０〜１５０ ｋ ｅ Ｖ、イオン電流密度０．５〜２．
０ｍＡ／ｄの条件で夫々行なった。つづいて、ＴＩ板上
の各アモルファス合金層を３重量％濃度のフッ酸溶液に
数分間浸漬して処理することによって２８種の電解電極
材を製造した。However, in Tables 1 to 3, Ar ion irradiation during sputter deposition was performed at an acceleration voltage of 3 keV and an ion current of 1.5 A.
Under the conditions, ion irradiation for mixing was performed at an acceleration voltage of 12
0-150 k e V, ion current density 0.5-2.
Each test was conducted under the condition of 0 mA/d. Subsequently, each amorphous alloy layer on the TI plate was treated by immersing it in a 3% by weight hydrofluoric acid solution for several minutes to produce 28 types of electrolytic electrode materials.
しかして、本実施例４〜３０の電解電極材について前述
した■、■の方法に従って電流効率及び電極寿命を測定
した。その結果を同第１表〜第３表に併記した。なお、
第３表中には実施例１と同様な研磨、表面清浄化処理を
施したＴＩ板表面に厚さ３μｍのＰｔ−１ｒ合金層を形
成した電極材（比較例２）及び同Ｔｉ板表面に厚さ８μ
ｍのＲｕ ０２層を形成した電極材（比較例３）の電流
効率及び寿命の測定結果を併記した。The current efficiency and electrode life of the electrolytic electrode materials of Examples 4 to 30 were measured according to the methods (1) and (2) described above. The results are also listed in Tables 1 to 3. In addition,
Table 3 shows an electrode material (Comparative Example 2) in which a 3 μm thick Pt-1r alloy layer was formed on the surface of a TI plate that had been subjected to the same polishing and surface cleaning treatment as in Example 1, and Thickness 8μ
The measurement results of the current efficiency and life of the electrode material (Comparative Example 3) in which a Ru 02 layer of m is formed are also shown.
［発明の効果］
以上詳述した如く、本発明によれば表面に白金属元素が
均一に露出し、かつ表面に無数の微細な凹凸を有するア
モルファス合金層で被覆され、比較的低い陽極電位にお
いて高い電流効率を示し、かつ耐食性及び耐久性に優れ
た任意形状の電解電極材を製造し得る方法を提供できる
。[Effects of the Invention] As detailed above, according to the present invention, the platinum metal element is uniformly exposed on the surface, and the surface is coated with an amorphous alloy layer having countless fine irregularities, so that it can be used at a relatively low anode potential. It is possible to provide a method for producing an electrolytic electrode material of any shape that exhibits high current efficiency and has excellent corrosion resistance and durability.
Claims (3)
素とＴｉ、Ｚｒ、Ｎｂ及びＴａから選ばれる少なくとも
１種以上の金属元素と少なくとも１種以上の白金族元素
との合金からなるアモルファス合金層を前記合金の蒸着
と同時に前記鉄族元素、金属元素、白金族元素又は不活
性ガスのイオンを照射するイオンビームミキシング法に
より形成する工程と、このアモルファス合金層を酸で処
理する工程とを具備したことを特徴とする電解電極材の
製造方法。(1) The surface of the metal base material is made of an alloy of at least one iron group element, at least one metal element selected from Ti, Zr, Nb, and Ta, and at least one platinum group element. A step of forming an amorphous alloy layer by an ion beam mixing method in which ions of the iron group element, metal element, platinum group element, or inert gas are irradiated simultaneously with the vapor deposition of the alloy, and a step of treating the amorphous alloy layer with acid. A method for producing an electrolytic electrode material, comprising:
先立ち、該基材表面に少なくとも１種以上の鉄族元素、
又はＴｉ、Ｚｒ、Ｎｂ及びＴａから選ばれる少なくとも
１種以上の金属元素のイオンを照射してイオン注入層を
形成することを特徴とする請求項１記載の電解電極材の
製造方法。(2) Prior to forming the amorphous alloy layer on the surface of the metal base material, at least one or more iron group elements are added to the surface of the base material,
The method for manufacturing an electrolytic electrode material according to claim 1, characterized in that the ion implantation layer is formed by irradiating with ions of at least one metal element selected from Ti, Zr, Nb, and Ta.
素とＴｉ、Ｚｒ、Ｎｂ及びＴａから選ばれる少なくとも
１種以上の金属元素との合金の蒸着と同時に少なくとも
１種以上の白金族元素イオンを照射するイオンビームミ
キシング法によりアモルファス合金層を形成する工程と
、このアモルファス合金層を酸で処理する工程とを具備
したことを特徴とする電解電極材の製造方法。(3) At the same time as depositing an alloy of at least one iron group element and at least one metal element selected from Ti, Zr, Nb, and Ta on the surface of the metal base material, at least one platinum group metal element is deposited on the surface of the metal base material. A method for producing an electrolytic electrode material, comprising the steps of forming an amorphous alloy layer by an ion beam mixing method of irradiating elemental ions, and treating the amorphous alloy layer with an acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63240032A JPH0288785A (en) | 1988-09-26 | 1988-09-26 | Production of electrolytic electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63240032A JPH0288785A (en) | 1988-09-26 | 1988-09-26 | Production of electrolytic electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0288785A true JPH0288785A (en) | 1990-03-28 |
| JPH036234B2 JPH036234B2 (en) | 1991-01-29 |
Family
ID=17053453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63240032A Granted JPH0288785A (en) | 1988-09-26 | 1988-09-26 | Production of electrolytic electrode material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0288785A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5142229A (en) * | 1990-12-26 | 1992-08-25 | Biomagnetic Technologies, Inc. | Thin-film three-axis magnetometer and squid detectors for use therein |
| JPH05311402A (en) * | 1992-05-11 | 1993-11-22 | Limes:Kk | Composite corrosion resistant material and production thereof |
| WO2009097962A1 (en) * | 2008-02-04 | 2009-08-13 | Uhde Gmbh | Nickel alloy and nickel electrode having a concentration gradient in the edge zone |
| WO2018000795A1 (en) * | 2016-06-29 | 2018-01-04 | 中国科学院金属研究所 | Iron-based amorphous electrode material for wastewater treatment and use thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6296633A (en) * | 1985-08-02 | 1987-05-06 | Daiki Rubber Kogyo Kk | Surface-activated amorphous alloy for use in electrode for solution electrolysis and activating treatment thereof |
| JPS6296636A (en) * | 1985-08-02 | 1987-05-06 | Daiki Rubber Kogyo Kk | Surface activated amorphous alloy for electrode for solution electrolysis and activation treatment thereof |
| JPS6296635A (en) * | 1985-08-02 | 1987-05-06 | Daiki Rubber Kogyo Kk | Surface activate supersaturated solid solution alloy for electrode for solution electrolysis and activation treatment method thereof |
| JPS6296634A (en) * | 1985-08-02 | 1987-05-06 | Daiki Rubber Kogyo Kk | Surface activated amorphous alloy for electrode for solution electrolysis and activation treatment thereof |
| JPS62153290A (en) * | 1985-12-26 | 1987-07-08 | Sagami Chem Res Center | 2,6-epoxy-3,4,5,6,11,12-hexahydro-2h-naphtahceno (1,2-b)oxocin-9,16-dione derivative |
-
1988
- 1988-09-26 JP JP63240032A patent/JPH0288785A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6296633A (en) * | 1985-08-02 | 1987-05-06 | Daiki Rubber Kogyo Kk | Surface-activated amorphous alloy for use in electrode for solution electrolysis and activating treatment thereof |
| JPS6296636A (en) * | 1985-08-02 | 1987-05-06 | Daiki Rubber Kogyo Kk | Surface activated amorphous alloy for electrode for solution electrolysis and activation treatment thereof |
| JPS6296635A (en) * | 1985-08-02 | 1987-05-06 | Daiki Rubber Kogyo Kk | Surface activate supersaturated solid solution alloy for electrode for solution electrolysis and activation treatment method thereof |
| JPS6296634A (en) * | 1985-08-02 | 1987-05-06 | Daiki Rubber Kogyo Kk | Surface activated amorphous alloy for electrode for solution electrolysis and activation treatment thereof |
| JPS62153290A (en) * | 1985-12-26 | 1987-07-08 | Sagami Chem Res Center | 2,6-epoxy-3,4,5,6,11,12-hexahydro-2h-naphtahceno (1,2-b)oxocin-9,16-dione derivative |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5142229A (en) * | 1990-12-26 | 1992-08-25 | Biomagnetic Technologies, Inc. | Thin-film three-axis magnetometer and squid detectors for use therein |
| JPH05311402A (en) * | 1992-05-11 | 1993-11-22 | Limes:Kk | Composite corrosion resistant material and production thereof |
| WO2009097962A1 (en) * | 2008-02-04 | 2009-08-13 | Uhde Gmbh | Nickel alloy and nickel electrode having a concentration gradient in the edge zone |
| WO2018000795A1 (en) * | 2016-06-29 | 2018-01-04 | 中国科学院金属研究所 | Iron-based amorphous electrode material for wastewater treatment and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH036234B2 (en) | 1991-01-29 |
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