JPH036234B2 - - Google Patents
Info
- Publication number
- JPH036234B2 JPH036234B2 JP63240032A JP24003288A JPH036234B2 JP H036234 B2 JPH036234 B2 JP H036234B2 JP 63240032 A JP63240032 A JP 63240032A JP 24003288 A JP24003288 A JP 24003288A JP H036234 B2 JPH036234 B2 JP H036234B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy layer
- amorphous alloy
- amorphous
- group element
- metal
- 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
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 38
- 150000002500 ions Chemical class 0.000 claims description 28
- 239000007772 electrode material Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000007740 vapor deposition Methods 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical group [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000009684 ion beam mixing Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 238000005468 ion implantation Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 230000001133 acceleration Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000000203 mixture Substances 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
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000013535 sea water Substances 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
- 238000001659 ion-beam spectroscopy Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910002835 Pt–Ir Inorganic materials 0.000 description 2
- 229910001361 White metal Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010969 white metal Substances 0.000 description 2
- 241000739883 Pseudotetracha ion Species 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 238000011161 development Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052745 lead 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
- 238000002156 mixing Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 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
- 239000010865 sewage Substances 0.000 description 1
- 238000004544 sputter deposition Methods 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
Landscapes
- Physical Vapour Deposition (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Description
［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。
［従来の技術及び課題］
例えば、海水を電解して次亜塩素酸（NaClO）
を発生させ、該海水をプラントの冷却水、下水道
などの減菌に使用して水路が海洋生物によつて閉
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
しながら、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。
このようなことから、電解電極材をアモルフア
ス合金により製造することが検討されている。ア
モルフアス合金の中には、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。しかしなが
ら、アモルフアス合金は通常、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つた。
一方、活性の高いTi基板をPt−Ir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
つた。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Ti
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
実現できないという問題があつた。
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。
［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（Fe、Ni、Co）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
らなるアモルフア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、このアモルフアス
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。
上記鉄族元素としては、Fe、Ni、Coを挙げる
ことができる。
上記白金族元素としては、Pt、Pd、Ir、Rh、
Ru、Osを挙げることができる。
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ツトを利用し
たイオンビームスパツタ法が好ましい。
また、本発明はアモルフア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
するものである。
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、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
アモルフアス合金層を形成する工程と、このアモ
ルフア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。
［作用］
本発明によれば、少なくとも１種以上の鉄族元
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つて、前
記合金からなる高純度のアモルフアス合金層を金
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、白金族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
ことによつて、前記アモルフアス合金層の基材に
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ア
ス合金層の緻密化、平滑化等を達成し易くなる。
こうしたアモルフア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
なつているため、該アモルフアス合金層の形成後
に酸で処理することによつて、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。従つて、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ア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、かつ該アモルフア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。
また、アモルフア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
射することによつて、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
層）を形成できるため、この後にアモルフアス層
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ア
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。
更に金属元素の表面に少なくとも１種以上の鉄
族元素と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ア
ス合金層を形成した後、該アモルフアス合金層を
酸で処理することによつて、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期原子配
列の乱れをもつ極めて表面活性の高いアモルフア
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、かつ該アモルフア
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。
［実施例］
以下、本発明の実施例を詳細に説明する。
実施例 １
まず、基材として20×20×２mm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
ヤンバ内に設置した。つづいて、このチヤンバ内
を５×10-6torrに真空引きした後、イオン源から
Arイオンを加速電圧5keVの条件でTi板の鏡面に
５分間照射して表面洗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
ターゲツトを用い、加速電圧3keV、イオン電流
1.5AのArイオンでイオビームスパツタ蒸着を行
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2.0ｍ
Ａ／cm2の条件でイオン照射して厚さ3μｍ前記タ
ーゲツトとほぼ同組成のアモルフアス合金層が被
覆された複合材料を製造した。
実施例 ２
前記実施例１でのアモルフアス合金層の形成に
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180keV、ビーム電流1.5ｍＡで
Ti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の組成のアモルフアス合金層が被
覆された複合材料を製造した。
実施例 ３
実施例１と同様な研磨、表面洗浄化処理を施し
たTi板の表面にNi−40at％Nbの組成のターゲツ
トを用いて加速電圧3keV、イオン電流1.5のArイ
オンでイオンビームスパツ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150keV、イオン電流密度0.5ｍＡ／cm2の条件
でイオン照射して厚さ3μｍでNi−40at％Nb−
1.5at％Pdの組成のアモルフアス合金層が被覆さ
れた複合材料を製造した。
比較例 １
実施例１と同様な研磨、表面洗浄化処理を施し
た、Ti板を市販のマグネトロンパツタ装置によ
り、厚さ3μｍのNi−40at％Nb−1.5at％Pbのア
モルフアス合金層を形成して複合材料を製造す
る。
しかして、本実施例１〜３及び比較例１のアモ
ルフアス合金層被覆複合材料について断面組織を
SEMで観察した。その結果、本実施例１〜３は
いずれもアモルフアス合金層の組織が緻密で均一
な相を有し、Ti板との界面にも何等の欠陥も認
められなかつた。これに対し、比較例１の複合材
料ではアモルフアス合金層の組織に不均一な相が
一部認められ、またTiとの界面にポアー発生が
認められ、良質なアモルフアス合金層とは評価い
得なかつた。
また、本実施例１〜３及び比較例１のアモルフ
アス合金層被覆複合材料を80℃、pH4の4M−
NaCl溶液中に浸漬して電解試験を行なつたとこ
ろ、比較例１の複合材料ではTi板との境界面で
腐蝕が進行し、剥離状態となつたが、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。
更に、本実施例１〜３のアモルフアス合金層被
覆複合材料を３重量％濃度のフツ酸溶液に数分間
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アス
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以上であつた。
電流効率の測定
海水電解の条件を擬似した3wt％NaCl水溶
液200ml（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４cm）を用いて直流電流密度を
1500A／m2、電気量100クローンの条件で電解
した後、電解液中の次亜塩素酸濃度を滴定法に
よつて測定し、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）を基準電極と
し、電解開始５分間後に電位計を用いて測定し
た。
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3wt％NaCl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5000A／m2で電解して飽和かんこう電
極基準で2.2V以上のに電圧が必要になつた時
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。
実施例 ４〜30
実施例１と同様の研磨、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のアモルフアス合金層を形成した。
但し、第１表〜第３表中でのスパツタ蒸着時での
Arイオンの照射は加速電圧3keV、イオン電流
1.5Aの条件で、ミキシングのためのイオン照射
は加速電圧120〜150keV、イオン電流密度0.5〜
2.0ｍＡ／cm2の条件で夫々行なつた。つづいて、
Ti板上のアモルフアス合金層を３重層％濃度の
フツ酸溶液に数分間浸漬して処理することによつ
て28種の電解電極材を製造した。
しかして、本実施例４〜30の電解電極材につい
て前述した、の方法に従つて電流効率及び電
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−Ir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3μｍのRuO2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。
[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. [Conventional technologies and issues] For example, seawater is electrolyzed to produce hypochlorous acid (NaClO).
A widely used method is to generate seawater and use the seawater to sterilize plant cooling water, sewage water, etc. to prevent waterways from being blocked by marine organisms.
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. For this reason, 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 produced by a liquid quenching method, the shape of the amorphous alloy is limited to ribbons, thin wires, powders, etc. due to this method. For this reason, it has been difficult to manufacture the desired electrolytic electrode material. On the other hand, a Ti-based electrolytic electrode material in which a highly active Ti substrate is coated with an alloy layer made of Pt-Ir is known, but there was a problem in that the current efficiency remained at around 80%. In addition, an oxide layer consisting of highly active ruthenium oxide, iridium oxide or tin oxide can
Ti-based electrolytic electrode materials coated on a base material are known.
Although this electrode material exhibits a current efficiency of 85% or more, changes over time due to the separation of the oxide film from the base material were observed, and there was a problem in that high current efficiency could only be achieved in the early stages of use. 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. [Means for Solving the Problems] The present invention provides at least one iron group element (Fe, Ni, Co) and at least one element selected from Ti, Zr, Nb, and Ta on the surface of a metal base material. An ion beam mixing method in which an amorphous alloy layer made of an alloy of a metal element and at least one platinum group element is irradiated with ions of the iron group element, metal element, platinum group element, or inert gas simultaneously with the vapor deposition of the alloy. This is a method for producing an electrolytic electrode material, comprising the steps of: forming the amorphous alloy layer with an acid; and treating the amorphous alloy layer with an acid. Examples of the iron group elements include Fe, Ni, and Co. The above platinum group elements include Pt, Pd, Ir, Rh,
Ru, Os can be mentioned. Although various vapor deposition methods can be used as the means for vapor deposition of the above-mentioned alloy, vacuum vapor deposition using an electron beam or an ion beam sputtering method using a target is particularly preferable since it is possible to form a film at a high degree of vacuum. In addition, 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 metal element selected from Ti, Zr, Nb, and Ta is added to the surface of the base material. The method is characterized in that an ion-implanted layer is formed by irradiating with ions. Furthermore, the present invention provides at least one coating on the surface of the metal base material.
An amorphous amorphous alloy is produced by an ion beam mixing method in which ions of at least one platinum group element are irradiated at the same time as the vapor deposition of an alloy of at least one iron group element and at least one metal element selected from Ti, Zr, Nb, and Ta. This is a method for producing an electrolytic electrode material, comprising a step of forming a layer and a step of treating the amorphous alloy layer with an acid. [Operation] According to the present invention, 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 is formed by electron beam processing. A highly pure amorphous alloy layer made of the above alloy can be formed on the surface of a metal base material by forming a film by a vapor deposition method such as a vacuum vapor deposition method according to the present invention. Furthermore, by performing ion beam mixing by irradiating iron group elements, metal elements, platinum group 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. Since the beam irradiation conditions can be controlled independently, it becomes easier to achieve densification, smoothness, etc. of the amorphous alloy layer.
On the surface of such an amorphous amorphous alloy layer, the atomic arrangement is disordered and disordered at a high density. The elements are not corroded, and only other metal components are selectively and uniformly corroded and eluted, leaving the platinum metal element uniformly 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 fine irregularities and the disordered atomic arrangement, so that the surface activity is relatively low. It exhibits high current efficiency at an anode 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. Furthermore, prior to forming the amorphous alloy layer on the surface of the metal base material, ions of at least one iron group element or at least one metal element selected from Ti, Zr, Nb, and Ta are applied to the surface of the base material. By irradiating with By subsequently forming an amorphous amorphous layer and treating it with acid, the amorphous amorphous alloy layer, in which the white metal element is uniformly exposed on the surface of the base material, has even better adhesion and overall peeling resistance, creating an electrolytic electrode. material can be manufactured. Furthermore, at the same time as vapor deposition of an alloy of at least one iron group element and at least one metal element selected from Ti, Zr, Nb, and Ta, the surface of the metal element is irradiated with at least one platinum group element ion. After forming an amorphous amorphous alloy layer by the ion beam mixing method, the amorphous amorphous alloy layer is treated with an acid, so that the platinum metal element is uniformly exposed on the surface of the base material, as in the method described above.
In addition, it is possible to form an amorphous amorphous alloy layer with extremely high surface activity that has countless minute irregularities and disordered atomic arrangement, so it exhibits high current efficiency at a relatively low anode potential, and the amorphous amorphous alloy layer has excellent corrosion resistance and durability. Furthermore, electrolytic electrode materials of arbitrary shapes can be manufactured without being subject to shape constraints. [Examples] Examples of the present invention will be described in detail below. Example 1 First, a Ti plate with dimensions of 20 x 20 x 2 mm 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. did. Next, after evacuating the chamber to 5×10 -6 torr, the ion source was
The mirror surface of the Ti plate was irradiated with Ar ions for 5 minutes at an acceleration voltage of 5 keV to perform pretreatment for surface cleaning. Next, using a composition target of Ni-40at%Nb-1.5at%Pd, an acceleration voltage of 3keV and an ion current were applied.
Ion beam sputter deposition is performed using Ar ions at 1.5 A, and at the same time Ar ions are extracted from another ion source at an acceleration voltage of 150 keV and an ion current density of 2.0 m.
Ion irradiation was performed under conditions of A/cm 2 to produce a composite material coated with an amorphous alloy layer having a thickness of 3 μm and having approximately the same composition as the target. Example 2 Prior to forming the amorphous alloy layer in Example 1, Nb ions were extracted from a mass-separated ion source and heated at an accelerating voltage of 180 keV and a beam current of 1.5 mA.
Ni-40 at%
A composite material coated with an amorphous alloy layer having a composition of Nb-1.5at%Pd was manufactured. 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 subjected to ion beam sputtering with Ar ions at an acceleration voltage of 3 keV and an ion current of 1.5 using a target with a composition of Ni-40at%Nb. At the same time as the evaporation, Pd ions were extracted from another ion source and ion irradiation was performed under the conditions of an acceleration voltage of 150 keV and an ion current density of 0.5 mA/cm 2 to deposit Ni-40at%Nb- to a thickness of 3 μm.
A composite material coated with an amorphous alloy layer having a composition of 1.5 at% Pd was manufactured. Comparative Example 1 A 3 μm thick Ni-40at%Nb-1.5at%Pb amorphous alloy layer was formed on a Ti plate that had been subjected to the same polishing and surface cleaning treatment as in Example 1 using a commercially available magnetron sputtering device. to produce composite materials. Therefore, the cross-sectional structure of the amorphous amorphous alloy layer-coated composite materials of Examples 1 to 3 and Comparative Example 1 was determined.
Observed with SEM. 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 Ti 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 amorphous alloy layer, and pores were observed at the interface with Ti, and it could not be evaluated as a good quality amorphous alloy layer. Ta. In addition, the amorphous alloy layer-coated composite materials of Examples 1 to 3 and Comparative Example 1 were coated with 4M-4M at 80°C and pH 4.
When an electrolytic test was conducted by immersing it in a NaCl solution, the composite material of Comparative Example 1 showed corrosion at the interface with the Ti plate, resulting in a peeling state.
In the composite materials No. 3 to 3, no special corrosion progressing phenomenon was observed at the interface between the Ti plates, and good durability at the interface was observed. Furthermore, the amorphous amorphous alloy layer-coated composite materials of Examples 1 to 3 were treated by immersing them in a 3% by weight hydrofluoric acid solution 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 properties were manufactured, and the current efficiency and life of these electrode materials were measured by the tests described below. As a result, Examples 1 to 3
The current efficiency of the electrode materials is 1.30 V/SCE when the anode potential is set to the saturated electrode as the reference potential.
In 90% of cases, the lifespan was 10 days or more. Measurement of current efficiency Using 200 ml of a 3 wt% NaCl aqueous solution (temperature: 25°C), which simulates the conditions of seawater electrolysis, as the electrolyte, the electrode material of this example was used as the anode, and a stainless steel plate (3 cm long x 4 cm wide) was used as the cathode. DC current density
After electrolyzing under the conditions of 1500A/m 2 and 100 clones of electricity, the hypochlorous acid concentration in the electrolyte was measured by titration method, and the current efficiency was determined by calculating the chlorine generation efficiency (%) from the results. I asked for
The anode potential required to obtain the above-mentioned DC current density was measured using an electrometer using a saturated electrolytic electrode (SCE) as a reference electrode 5 minutes after the start of electrolysis. Measurement of electrode life After completing the current efficiency measurement, the anode electrode (electrode material) was immersed in a 3wt% NaCl aqueous solution in an electrolytic tank, and the electrolytic tank was placed in an ultrasonic water tank.
The life of the electrode was defined as the time when a voltage of 2.2 V or more was required based on a saturated electrode during electrolysis at a current density of 5000 A/m 2 , and the life was evaluated by calculating the number of days until this life was reached. Examples 4 to 30 An amorphous alloy layer having 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.
However, during sputter deposition in Tables 1 to 3,
Ar ion irradiation uses an acceleration voltage of 3keV and an ion current.
Ion irradiation for mixing is performed at an acceleration voltage of 120 to 150 keV and an ion current density of 0.5 to 150 keV under the conditions of 1.5 A.
Each test was conducted under the condition of 2.0 mA/cm 2 . Continuing,
Twenty-eight types of electrolytic electrode materials were manufactured by immersing an amorphous amorphous alloy layer on a Ti plate in a hydrofluoric acid solution with a concentration of 3% for several minutes. The current efficiency and electrode life of the electrolytic electrode materials of Examples 4 to 30 were measured according to the method described above. The results are also listed in Tables 1 to 3. In addition, Table 3 shows the electrode material (Comparative Example 2) in which a Pt-Ir alloy layer with a thickness of 3 μm is formed on the surface of a Ti plate that has been subjected to the same polishing and surface cleaning treatment as in Example 1, and the same Ti plate. The measurement results of current efficiency and life of an electrode material (Comparative Example 3) with two 3 μm thick RuO layers formed on the surface are also shown.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
［発明の効果］
以上詳述した如く、本発明によれは表面に白金
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ア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。[Table] [Effects of the Invention] As detailed above, according to the present invention, the white metal element is uniformly exposed on the surface, and the surface is coated with an amorphous alloy layer having countless fine irregularities, and the surface resistance is relatively low. Shows high current efficiency at anodic potential,
Moreover, it is possible to provide a method for producing an electrolytic electrode material having an arbitrary shape and excellent corrosion resistance and durability.
Claims (1)
元素と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アス合金層
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、このアモルフア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。 ２ アモルフア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。 ３ 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、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アス
合金層を形成する工程と、このアモルフアス合金
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。[Claims] 1. 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 on the surface of a metal base material. forming an amorphous alloy layer made of an alloy 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 vapor deposition of the alloy; and a step of forming the amorphous alloy layer with an acid. 1. A method for manufacturing an electrolytic electrode material, comprising a step of treating. 2. Prior to forming an amorphous alloy layer on the surface of a metal base material, ions of at least one iron group element or at least one metal element selected from Ti, Zr, Nb, and Ta are added to the surface of the base material. 2. The method of manufacturing an electrolytic electrode material according to claim 1, wherein the ion implantation layer is formed by irradiation. 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 a metal substrate, at least one platinum group element ion is applied. 1. A method for producing an electrolytic electrode material, comprising the steps of: forming an amorphous amorphous alloy layer by an ion beam mixing method; and treating the amorphous 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 JPH0288785A (en) | 1990-03-28 |
| JPH036234B2 true 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) |
Families Citing this family (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 |
| JP2625316B2 (en) * | 1992-05-11 | 1997-07-02 | 株式会社ライムズ | Composite corrosion resistant material and method for producing the same |
| DE102008007605A1 (en) * | 2008-02-04 | 2009-08-06 | Uhde Gmbh | Modified nickel |
| EP3480342A4 (en) * | 2016-06-29 | 2020-02-19 | Institute Of Metal Research Chinese Academy Of Sciences | Iron-based amorphous electrode material for wastewater treatment and use thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0288785A (en) | 1990-03-28 |
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