JPH02190491A - Electrolytic electrode - Google Patents
Electrolytic electrodeInfo
- Publication number
- JPH02190491A JPH02190491A JP1008578A JP857889A JPH02190491A JP H02190491 A JPH02190491 A JP H02190491A JP 1008578 A JP1008578 A JP 1008578A JP 857889 A JP857889 A JP 857889A JP H02190491 A JPH02190491 A JP H02190491A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- electrode
- titanium
- mol
- platinum
- 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
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims abstract description 11
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 84
- 239000010936 titanium Substances 0.000 claims description 56
- 229910052719 titanium Inorganic materials 0.000 claims description 52
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 44
- 229910052697 platinum Inorganic materials 0.000 claims description 38
- 238000005868 electrolysis reaction Methods 0.000 claims description 16
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 15
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 15
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 10
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 10
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 7
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 22
- 238000000576 coating method Methods 0.000 abstract description 22
- 239000002184 metal Substances 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 23
- 239000010410 layer Substances 0.000 description 23
- -1 platinum group metal oxide Chemical class 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910000048 titanium hydride Inorganic materials 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 150000002504 iridium compounds Chemical class 0.000 description 7
- 150000003482 tantalum compounds Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910003087 TiOx Inorganic materials 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical group CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100522123 Caenorhabditis elegans ptc-1 gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FCUFAHVIZMPWGD-UHFFFAOYSA-N [O-][N+](=O)[Pt](N)(N)[N+]([O-])=O Chemical compound [O-][N+](=O)[Pt](N)(N)[N+]([O-])=O FCUFAHVIZMPWGD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- URZWVLRNPNSHDV-UHFFFAOYSA-J potassium;iridium(3+);tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[K+].[Ir+3] URZWVLRNPNSHDV-UHFFFAOYSA-J 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
Description
【発明の詳細な説明】
発明は電解用電極に関し、さらに詳しくは、酸素過電圧
が低く、耐久性に優れ、卑な電位環境下でも安定で中間
層の膜抵抗が小さい、特に陽極に酸素発生を伴う海水の
電解、金属の表面処理、金5属箔製造、回収等の電解に
おける陽極として有用な電解用電極に関する。[Detailed Description of the Invention] The invention relates to an electrode for electrolysis, and more specifically, an electrode for electrolysis that has a low oxygen overvoltage, is excellent in durability, is stable even in a base potential environment, has a low membrane resistance in the intermediate layer, and particularly has an electrode that does not allow oxygen generation in the anode. The present invention relates to an electrode for electrolysis useful as an anode in electrolysis of seawater, surface treatment of metals, metal 5 metal foil production, recovery, etc.
従来、チタンはチタン合金よりなる基体上に、白金族金
属や白金族金属酸化物を被覆した電極が多くの電解工業
の分野において使用されている。BACKGROUND OF THE INVENTION Conventionally, titanium electrodes have been used in many fields of the electrolytic industry, in which a platinum group metal or a platinum group metal oxide is coated on a titanium alloy substrate.
しかし、高電流密度下で運転される金属の高速メツキや
金属箔製造の分野では、触媒と基体材料の界面が劣化し
て電導性が悪くなり、電極寿命が短くなってしまう問題
がある。However, in the fields of high-speed metal plating and metal foil production that operate under high current densities, there is a problem that the interface between the catalyst and the base material deteriorates, resulting in poor conductivity and shortened electrode life.
また、金属の表面処理のように陰極自身が製品になる分
野では、処理した後その陰極を交換する必要が生じ、そ
の都度電解を停止しなければならなくなる。この時、陽
極がショートサーキットを形成したりして卑な電位環境
下にさらされる場合が少なくなく、特に酸化物を被覆し
た電極は不安定となり電極寿命が短くなってしまう問題
がある。Furthermore, in fields where the cathode itself is a product, such as surface treatment of metals, it becomes necessary to replace the cathode after the treatment, and electrolysis must be stopped each time. At this time, there are many cases where the anode is exposed to a base potential environment due to the formation of a short circuit, and there is a problem in that the electrode coated with an oxide becomes unstable, and the life of the electrode is shortened.
本発明者らは、上記の如き従来の電解用電極がもつ欠点
を克服すべく鋭意研究を行なった結果、本発明を完成す
るに至ったものである。The present inventors have completed the present invention as a result of intensive research to overcome the drawbacks of the conventional electrolytic electrodes as described above.
かくして、本発明によれば、チタン又はチタン合金より
なる電極基体上に
(a) 基体表面が部分的に露出する程度に分散被覆
された白金と、少なくとも基体表面の露出部分を被覆す
る酸化イリジウム、酸化マンガン、酸化コバルト、酸化
スズ及び酸化アンチモンより選ばれる少なくとも1種の
金属酸化物0〜20モル%と酸化ニオブ、酸化タンタル
及び酸化ジルコニウムより選ばれる少なくとも1種の金
属酸化物80〜100モル%からなる複合金属酸化物又
は混合金属酸化物又は単一金属酸化物とから構成される
中間層と、
ω)酸化イリジウム5〜95モル%と、酸化ニオブ、酸
化タンタル及び酸化ジルコニウムより選ばれる少なくと
も1種の金属酸化物5〜95モル%からなる混合金属酸
化物から構成される外層
を設けてなることを特徴とする電解用電極が提供される
。Thus, according to the present invention, on an electrode base made of titanium or a titanium alloy, (a) platinum dispersed and coated to such an extent that the base surface is partially exposed, and iridium oxide covering at least the exposed portion of the base surface; 0 to 20 mol% of at least one metal oxide selected from manganese oxide, cobalt oxide, tin oxide, and antimony oxide, and 80 to 100 mol% of at least one metal oxide selected from niobium oxide, tantalum oxide, and zirconium oxide. an intermediate layer composed of a composite metal oxide, mixed metal oxide, or single metal oxide; An electrode for electrolysis is provided, characterized in that it is provided with an outer layer composed of a mixed metal oxide comprising 5 to 95 mol % of a seed metal oxide.
以下、本発明の電解用電極についてさらに詳細に説明す
る。Hereinafter, the electrode for electrolysis of the present invention will be explained in more detail.
本発明において使用される電極基体の材質としては、チ
タン又はチタン基合金が挙げられる。チタン基合金とし
ては、チタンを主体とする耐食性のある導電性の合金が
使用され、例えばTi−Ta−Nb1Ti−Pd、Ti
−Zr、Ti −W。The material of the electrode substrate used in the present invention includes titanium or a titanium-based alloy. As the titanium-based alloy, a corrosion-resistant and conductive alloy mainly composed of titanium is used. For example, Ti-Ta-Nb1Ti-Pd, Ti
-Zr, Ti-W.
Ti−A(1等の組合わせからなる、通常電極材料とし
て使用されているTi基合金が挙げられる。Examples include Ti-based alloys that are composed of a combination of Ti-A (1, etc.) and are commonly used as electrode materials.
これらの電極材料は板状、有孔板状、棒状、網板状等の
所望形状に加工して電極基材として用いることができる
。These electrode materials can be processed into a desired shape such as a plate shape, a perforated plate shape, a rod shape, a net plate shape, etc., and used as an electrode base material.
上記の如き電極基体には、通常行なわれているように、
予め前処理を施した後、中間層を設けるのが望ましい。For the above-mentioned electrode base, as is usually done,
It is desirable to provide the intermediate layer after pretreatment.
そのような前処理の好適具体例としては以下に述べるも
のが挙げられる。Preferred specific examples of such pretreatment include those described below.
先ず、前述したチタン又はチタン合金よりなる電極基体
(以下、チタン基体ということがある)表面を常法に従
い、例えばトリクロルエチレン、トリクロルエタン等で
洗浄し又はアルカリ溶液中での電解により脱脂した後、
フッ化水素濃度が約1〜約20重量%のフッ化水素酸又
はフッ化水素酸と硝酸、硫酸等の他の酸との混酸で処理
することにより、チタン基体表面の酸化膜を除去すると
ともにチタン結晶粒界単位の粗面化を行なう。該酸処理
はチタン基体の表面状態に応じて常温ないし約40°C
の温度において数分間ないし士数分間行なうことができ
る。なお、粗面化を十分性なうためにプラスト処理を併
用してもよい。First, the surface of the electrode substrate (hereinafter sometimes referred to as titanium substrate) made of titanium or titanium alloy described above is washed with trichloroethylene, trichloroethane, etc. in accordance with a conventional method, or degreased by electrolysis in an alkaline solution, and then
The oxide film on the surface of the titanium substrate is removed by treatment with hydrofluoric acid or a mixed acid of hydrofluoric acid and other acids such as nitric acid and sulfuric acid with a hydrogen fluoride concentration of about 1 to about 20% by weight. Roughening the titanium grain boundary unit. The acid treatment is performed at room temperature to about 40°C depending on the surface condition of the titanium substrate.
It can be carried out for several minutes to several minutes at a temperature of . Incidentally, in order to sufficiently roughen the surface, a blast treatment may be used in combination.
このように酸処理されたチタン基体表面を濃硫酸と接触
させて、該チタン結晶粒界内部表面を突起状に細かく粗
面化するとともに該チタン基体表面に水素化チタンの薄
い層を形成する。この突起状の細かい粗面化が後で白金
の分散被覆を形成させるのに重要な処理とな、る。The surface of the titanium substrate thus acid-treated is brought into contact with concentrated sulfuric acid to roughen the inner surface of the titanium grain boundaries into protrusions and form a thin layer of titanium hydride on the surface of the titanium substrate. This fine roughening of the surface in the form of protrusions is an important process for later forming a dispersion coating of platinum.
使用する濃硫酸は一般に40〜80重量%、好ましくは
50〜60重量%粒度の濃度のものが適当であり、この
濃硫酸には必要により、処理の安定化を図る目的で少量
の硫酸ナトリウムその他の硫酸塩等を添加してもよい。The concentrated sulfuric acid used generally has a particle size of 40 to 80% by weight, preferably 50 to 60% by weight, and if necessary, a small amount of sodium sulfate or other substances may be added to this concentrated sulfuric acid for the purpose of stabilizing the process. sulfate etc. may be added.
該濃硫酸との接触は通常チタン基体を濃硫酸の浴中に浸
漬することにより行なうことができ、その際の浴温は一
般に約100〜約150°C1好ましくは約110〜約
130℃の範囲内の温度とすることができ、また浸漬時
間は通常0.5〜約lO分間、好ましくは約1〜約3分
間で充分である。この硫酸処理により、チタン結晶粒界
内部表面を突起状に細かく粗面化するとともに、チタン
基体の表面にごく薄い水素化チタンの皮膜を形成させる
ことができる。The contact with the concentrated sulfuric acid can usually be carried out by immersing the titanium substrate in a bath of concentrated sulfuric acid, and the bath temperature at that time is generally in the range of about 100 to about 150°C, preferably about 110 to about 130°C. The temperature can be within 100 mL, and a soaking time of 0.5 to about 10 minutes, preferably about 1 to about 3 minutes, is sufficient. This sulfuric acid treatment makes it possible to roughen the inner surface of the titanium crystal grain boundaries into fine protrusions and form a very thin titanium hydride film on the surface of the titanium substrate.
硫酸処理されたチタン基体は硫酸浴から取り出し、好ま
しくは窒素、アルゴン等の不活性ガス雰囲気中で急冷し
てチタン基体の表面温度を約60°C以下に低下させる
。この急冷には洗浄も兼ねて大量の冷水を用いるのが適
当である。The titanium substrate treated with sulfuric acid is removed from the sulfuric acid bath and rapidly cooled, preferably in an inert gas atmosphere such as nitrogen or argon, to reduce the surface temperature of the titanium substrate to about 60° C. or less. It is appropriate to use a large amount of cold water for this rapid cooling, which also serves as washing.
このようにしてごく薄い水素化チタンの皮膜を形成した
チタン基体は、希フッ化水素酸又は希フッ化物水溶液(
例えばフッ化ナトリウム、フッ化カリウム等)中で浸漬
処理して該水素化チタン皮膜を生長させ該皮膜の均−化
及び安定化を図る。The titanium substrate on which a very thin titanium hydride film has been formed in this way is coated with dilute hydrofluoric acid or dilute fluoride aqueous solution (
For example, the titanium hydride film is grown by immersion treatment in sodium fluoride, potassium fluoride, etc., and the film is made uniform and stable.
ここで使用しうる希フッ化水素酸又はフッ化物水溶液中
のフッ化水素の濃度は一般に0.05〜3重量%、好ま
しくは0.3〜1重量%の範囲内とすることができ、ま
た、これらの溶液による浸漬処理の際の温度は一般に1
0〜40℃、好ましくは20〜30℃の範囲である。該
処理はチタン基体表面に通常0.5〜lOミクロン、好
ましくは1〜3ミクロンの厚さの水素化チタンの均一皮
膜が形成されるまで行なうことができる。この水素化チ
タン(Tidy、ここでyは1.5〜2の数である)は
水素化の程度に応じて灰褐色から黒褐色を呈するので、
上記範囲の厚さの水素化チタンの皮膜の生成は、経験的
に該基体表面の色調の変化を標準色源との明度対比によ
ってコントロールすることができる。The concentration of hydrogen fluoride in the dilute hydrofluoric acid or fluoride aqueous solution that can be used here can generally be in the range of 0.05 to 3% by weight, preferably 0.3 to 1% by weight, and , the temperature during immersion treatment with these solutions is generally 1
It is in the range of 0 to 40°C, preferably 20 to 30°C. The treatment can be carried out until a uniform coating of titanium hydride is formed on the surface of the titanium substrate, usually with a thickness of 0.5 to 10 microns, preferably 1 to 3 microns. This titanium hydride (Tidy, where y is a number from 1.5 to 2) exhibits a grayish-brown to blackish-brown color depending on the degree of hydrogenation.
The production of a titanium hydride film having a thickness within the above range can be controlled empirically by comparing the change in color tone of the substrate surface with a standard color source.
このようにしてチタン基体表面を粗面化すると共に水素
化チタンの皮膜を形成したチタン基体は、適宜水洗等の
処理を行なった後、その表面に、白金をチタン基体表面
が部分的に露出する程度に分散被覆する。The titanium substrate whose surface has been roughened in this way and a titanium hydride film has been formed thereon is subjected to appropriate treatments such as washing with water, and then platinum is partially exposed on the surface of the titanium substrate. Disperse and cover to a certain degree.
この白金の分散被覆は通常電気メツキ法により行なうこ
とができる。この電気メツキ法に使用しうるメツキ浴の
組成としては、例えばH3PtCI 1 NH,PtC
l い K、PtC1,、Pt(NHs)z 1ot)
a等の白金化合物を硫酸溶液(pH1〜3)又はアンモ
ニア水溶液に白金換算で約2〜約201/Qの濃度にな
るように溶解し、さらに必要に応じて浴の安定化のため
に硫酸ナトリウム(酸性浴の場合)、亜流酸ナトリウム
、硫酸ナトリウム(アルカリ性浴の場合)等を少量添加
した酸性又はアルカリ性のメツキ浴が挙げられる。かか
る組成のメツキ浴を用いての白金電気メツキは、チタン
基体表面に形成された水素化チタン皮膜の分解をできる
だけ抑制するため約30〜約60°Cの範囲の比較的低
温で行なうのが望ましい。This dispersion coating of platinum can usually be carried out by electroplating. The composition of the plating bath that can be used in this electroplating method includes, for example, H3PtCI 1 NH, PtC
l K, PtC1,, Pt(NHs)z 1ot)
A platinum compound such as a is dissolved in a sulfuric acid solution (pH 1 to 3) or an ammonia aqueous solution to a concentration of about 2 to about 201/Q in terms of platinum, and if necessary, sodium sulfate is added to stabilize the bath. (for acidic baths), acidic or alkaline plating baths to which a small amount of sodium sulfite, sodium sulfate (for alkaline baths), etc. are added. Platinum electroplating using a plating bath with such a composition is preferably carried out at a relatively low temperature in the range of about 30 to about 60°C in order to suppress as much as possible the decomposition of the titanium hydride film formed on the surface of the titanium substrate. .
この電気メツキによりチタン基体の水素化チタン被膜上
に分散被覆した白金を形成せしめることができる。その
際の白金の分散状態のコントロールは、例えば白金メツ
キ浴の浴組成及び/又はメツキ条件(電流密度や電流波
形等)を経験的に調整することによって行なうことがで
きる。This electroplating makes it possible to form a dispersed coating of platinum on the titanium hydride coating of the titanium substrate. The dispersion state of platinum at this time can be controlled, for example, by empirically adjusting the bath composition of the platinum plating bath and/or the plating conditions (current density, current waveform, etc.).
かくして、チタン基体上にその基体表面が部分的に露出
する程度に分散被覆された白金を析出せしめる。その分
散被覆の状態は、5000倍の電子顕微鏡で観察すると
、白金がチタン基体表面上に、点状、線状、網目状に分
散していることがわかる。白金の析出量としては、一般
に0.1〜201/m”、好ましくは0.2〜52 /
c m”トすることができる。白金の析出量があまり
にも少ないと得られる電極の耐久性に劣り、また反対に
あまりも多過ぎると得られる電極は卑な電位環境下で不
安定となる。In this way, a dispersed coating of platinum is deposited on the titanium substrate to such an extent that the surface of the substrate is partially exposed. When observing the state of the dispersion coating using an electron microscope with a magnification of 5,000 times, it can be seen that platinum is dispersed on the surface of the titanium substrate in the form of dots, lines, and networks. The amount of platinum deposited is generally 0.1 to 201/m", preferably 0.2 to 52/m".
If the amount of platinum precipitated is too small, the resulting electrode will have poor durability, while if it is too large, the resulting electrode will become unstable in a base potential environment.
かくして、白金の分散被覆の程度は、被覆率で表わして
、一般に10〜80%、好ましくは30〜50%の範囲
内とするのが適当である。本明細書において白金の「被
覆率」は、白金を分散被覆したチタン基体表面を40,
000倍の電子顕微鏡写真にとり、その写真よりチタン
基体表面1μm2当りの白金の被覆面積を測定し下記式
により算出される値をいう。Thus, it is appropriate that the degree of dispersion coating of platinum is generally in the range of 10 to 80%, preferably 30 to 50%, expressed as coverage. In this specification, the "coverage rate" of platinum refers to the surface of a titanium substrate coated with platinum dispersedly coated with 40%,
It is a value calculated by taking an electron micrograph at a magnification of 1,000 times, measuring the area covered by platinum per 1 μm2 of the titanium substrate surface from the photograph, and using the following formula.
このようにして白金を分散被覆したチタン基体は次いで
大気中で焼成することにより、水素化チタンの皮膜の層
を熱分解して該層中の水素化チタンの実質的に殆んどを
チタン金属に戻し、さらにチタンを低酸化状態の酸化チ
タンに変える。この焼成は一般に約300〜約600℃
、好ましくは約300〜約400°Cの温度で10分〜
4時間程度加熱することにより行なうことができる。The titanium substrate coated with platinum in a dispersed manner is then fired in the atmosphere to thermally decompose the titanium hydride film layer and remove substantially most of the titanium hydride in the layer from the titanium metal. and further converts the titanium into titanium oxide, which has a lower oxidation state. This firing is generally done at a temperature of about 300 to about 600℃.
, preferably at a temperature of about 300 to about 400°C for 10 minutes to
This can be done by heating for about 4 hours.
これによりチタン基体表面にごく薄い導電性の酸化チタ
ン層が形成される。この酸化チタン層の厚さは一般に1
00〜1.o、00人、好ましくは200〜600人の
範囲内にあるのが好適であり、また酸化チタンの組成は
TiOxとしてXが一般にl≦x < 2、特に1 、
9 < x < 2の範囲にあるのが望ましい。As a result, a very thin conductive titanium oxide layer is formed on the surface of the titanium substrate. The thickness of this titanium oxide layer is generally 1
00-1. o, 00 people, preferably in the range of 200 to 600 people, and the composition of titanium oxide is TiOx, where X is generally l≦x<2, especially 1,
It is desirable that the range is 9 < x < 2.
また別法として、白金の分散被覆を行なったチタン基体
は、上記の如き焼成処理を行わずに直接法の工程に付し
てもよい。この場合には、次工程での熱分解処理時にチ
タン基体表面の水素化チタンの皮膜の層は、チタン金属
及び低酸化状態の酸化チタンに変換される。Alternatively, the titanium substrate coated with platinum dispersion may be subjected to a direct process without the firing treatment as described above. In this case, during the thermal decomposition treatment in the next step, the titanium hydride film layer on the surface of the titanium substrate is converted into titanium metal and titanium oxide in a low oxidation state.
以上の如く白金が分散被覆されたチタン基体表面は、少
なくとも基体表面の白金未被覆部分を、(イ)酸化イリ
ジウム、酸化マンガン、酸化コバルト、酸化スズ及び酸
化アンチモンより選ばれる少なくとも1種の金属酸化物
0〜20モル%、好ましくは5〜15モル%と、(ロ)
酸化ニオブ、酸化タンタル及び酸化ジルコニウムより選
ばれる少なくとも1種の酸化物80〜100モル%、好
ましくは85〜95モル%
からなる金属酸化物又は混合金属酸化物(以下、中間酸
化物ということがある)で被覆する。As described above, the surface of the titanium substrate coated with platinum dispersedly has at least the portion of the substrate surface not coated with platinum covered with (a) oxidation of at least one metal selected from iridium oxide, manganese oxide, cobalt oxide, tin oxide, and antimony oxide. 0 to 20 mol%, preferably 5 to 15 mol%, and (b)
A metal oxide or mixed metal oxide (hereinafter sometimes referred to as an intermediate oxide) consisting of 80 to 100 mol%, preferably 85 to 95 mol%, of at least one oxide selected from niobium oxide, tantalum oxide, and zirconium oxide. ).
この中間酸化物は分散被覆された白金の隙間を埋めて得
られる電極の耐食性を向上させるのに役立つものである
。また、分散被服した白金は中間層の良好な電導性を維
持するのに役立つものである。該中間酸化物は部分的に
析出された白金の隙間(チタン基体の露出部分)を埋め
る(被覆する)のみならず、該白金上を覆っても支障は
ないが、白金上を覆う中間酸化物があまり厚くなると中
間層の膜電気抵抗が大きくなるので、中間酸化物の被覆
量は一般に0.5〜102/m”、好ましくは1〜59
7m”の範囲内とすることができる。This intermediate oxide is useful for filling the gaps in the dispersion-coated platinum and improving the corrosion resistance of the resulting electrode. The dispersed platinum also helps maintain good conductivity of the interlayer. The intermediate oxide not only fills (covers) the gaps of partially deposited platinum (exposed parts of the titanium substrate), but also covers the platinum without any problem. If it becomes too thick, the electrical resistance of the intermediate layer increases, so the coating amount of the intermediate oxide is generally 0.5 to 102/m", preferably 1 to 59
It can be within a range of 7m''.
中間酸化物において、上記(イ)の酸化物としては中で
も酸化イリジウムが好適である。Among the intermediate oxides, iridium oxide is particularly suitable as the oxide (a).
上記中間酸化物は、例えば、酸素含有ガス、通常空気中
での焼成により上記(イ)及び(ロ)の金属酸化物に転
換しうる金属化合物を金属酸化物換算で前記割合になる
ようにして適当な低沸点溶媒中に溶解し、得られる溶液
を前記の白金を分散被覆したチタン基体の該白金の分散
被覆表面に塗布し、溶媒を乾燥除去した後、酸素含有ガ
ス雰囲気中で焼成することにより形成することができる
。The intermediate oxide is made by, for example, containing a metal compound that can be converted into the metal oxides of (a) and (b) above by firing in an oxygen-containing gas, usually air, in the above ratio in terms of metal oxide. Dissolve in a suitable low boiling point solvent, apply the resulting solution to the platinum dispersion coated surface of the platinum dispersion coated titanium substrate, dry and remove the solvent, and then sinter in an oxygen-containing gas atmosphere. It can be formed by
以下、上記(イ)の金属酸化物が酸化イリジウムであり
且つ上記(ロ)の金属酸化物が酸化タンタルである場合
の中間酸化物を形成する場合についてより具体的に説明
する。Hereinafter, the case of forming an intermediate oxide in which the metal oxide in (a) above is iridium oxide and the metal oxide in (b) above is tantalum oxide will be described in more detail.
前記の如く白金が分散被覆されたチタン基体表面上に、
イリジウム化合物とタンタル化合物を含む溶媒溶液、好
ましくは低級アルコール溶液を適用し塗布した後乾燥す
ることにより、イリジウム化合物のタンタル化合物を付
着せしめる。ここで使用しうるイリジウム化合物及びタ
ンタル化合物としては、後述する焼成条件下に熱分解し
てそれぞれ酸化イリジウム及び酸化タンタルに転化しう
る低級アルコール溶媒に可溶性の化合物が包含される。On the titanium substrate surface coated with platinum dispersed as described above,
The tantalum compound of the iridium compound is deposited by applying a solvent solution containing an iridium compound and a tantalum compound, preferably a lower alcohol solution, and drying the coating. The iridium compound and tantalum compound that can be used here include compounds soluble in lower alcohol solvents that can be thermally decomposed under the firing conditions described below and converted into iridium oxide and tantalum oxide, respectively.
そのようなイリジウム化合物としては塩化イリジウム酸
、塩化イリジウム、塩化イリジウムカリ等が例示され、
またタンタル化合物としては、例えば塩化タンタルが挙
げられる。一方、これらのイリジウム化合物及びタンタ
ル化合物を溶解しうる低級アルコールとしては、例えば
メタノール、エタノール、グロパノール、イソプロパツ
ール、ブタノール又はこれらの混合物が挙げられる。Examples of such iridium compounds include chloroiridic acid, iridium chloride, iridium potassium chloride, etc.
Further, examples of the tantalum compound include tantalum chloride. On the other hand, examples of lower alcohols that can dissolve these iridium compounds and tantalum compounds include methanol, ethanol, glopanol, isopropanol, butanol, or mixtures thereof.
該低級アルコール溶液の白金を分散被覆したチタン基体
への適用は、例えば刷毛塗り、スプレー浸漬等の手段で
行なうことができる。The lower alcohol solution can be applied to the titanium substrate dispersedly coated with platinum by, for example, brush coating, spray dipping, or the like.
このようにしてイリジウム化合物及びタンタル化合物の
低級アルコール溶液を適用した該基板は、約20〜約1
50°Cの範囲内の比較的低温で乾燥させた後、大気中
で焼成する。以上に述べた処理は中間酸化物の被覆量が
前記の所期の範囲内に達するまで繰り返して行なうこと
ができる。該焼成は例えば電気炉、ガス炉、赤外線炉な
どの適当な加熱炉中で一般に約400〜約700°C1
好ましくは約450〜約600℃の範囲内の温度に加熱
することによって行なうことができる。その際の加熱時
間は焼成すべき基体の大きさに応じて大体5分〜2時間
程度とすることができる。The substrate to which the lower alcohol solution of the iridium compound and the tantalum compound was applied in this way has a yield of about 20 to about 1
After drying at a relatively low temperature in the range of 50°C, it is fired in air. The above-described treatment can be repeated until the amount of intermediate oxide coated falls within the desired range. The firing is generally carried out at about 400 to about 700° C. in a suitable heating furnace such as an electric furnace, a gas furnace, an infrared furnace, etc.
Preferably, this can be carried out by heating to a temperature within the range of about 450 to about 600°C. The heating time at this time can be approximately 5 minutes to 2 hours depending on the size of the substrate to be fired.
この焼成によりイリジウム化合物及びタンタル化合物は
それぞれ酸化イリジウム及び酸化タンタルに変わり、中
間酸化物を形成する。By this firing, the iridium compound and the tantalum compound are changed into iridium oxide and tantalum oxide, respectively, to form an intermediate oxide.
前述した他の複合金属酸化物又は混合金属酸化物又は単
一金属酸化物も同様にして形成せしめることができる。Other composite metal oxides, mixed metal oxides, or single metal oxides described above can be formed in the same manner.
以上述べた如くして分散被覆された白金と中間酸化物と
から構成される中間層の上には、さらに、(i) 酸
化イリジウム5〜95モル%、好ましくは20〜80モ
ル%と、
61)酸化ニオブ、酸化タンタル及び酸化ジルコニウム
より選ばれる少なくとも1種の金属酸化物5〜95モル
%、好ましくは20〜80モル%
とから構成される外層を設ける。この外層において、(
i)の酸化イリジウムの割合が5モル%より少ないと、
得られる電極の酸素過電圧が高くなる傾向がみられ、一
方、95モル%を超えると電極の消耗が大きくなりやす
い。On the intermediate layer composed of platinum and intermediate oxide dispersed and coated as described above, there is further added: (i) 5 to 95 mol%, preferably 20 to 80 mol% of iridium oxide; ) An outer layer composed of 5 to 95 mol %, preferably 20 to 80 mol % of at least one metal oxide selected from niobium oxide, tantalum oxide and zirconium oxide is provided. In this outer layer, (
When the proportion of iridium oxide in i) is less than 5 mol%,
There is a tendency for the oxygen overvoltage of the resulting electrode to become high, and on the other hand, if it exceeds 95 mol %, the electrode tends to suffer from large wear.
また、中間酸化物として酸化イリジウムと、酸化ニオブ
、酸化タンタル及び酸化ジルコニウムより選ばれる少な
くとも1種の金属酸化物からなる混合金属酸化物を使用
する場合、外層における酸化イリジウムの含有量(X)
は、中間酸化物における酸化イリジウムの含有量(Y)
よりも多いことが望ましく、前者の含有量(Xモル%)
と後者の含有量(Yモル%)の差(X −Y)は通常、
5〜95、好ましくは20〜95の範囲内にあることが
好都合である。In addition, when using a mixed metal oxide consisting of iridium oxide and at least one metal oxide selected from niobium oxide, tantalum oxide, and zirconium oxide as the intermediate oxide, the content of iridium oxide in the outer layer (X)
is the content of iridium oxide in the intermediate oxide (Y)
It is desirable that the content of the former is greater than (X mol%)
The difference (X − Y) between the content (Y mol%) of the latter and the latter content (Y mol%) is usually
It is conveniently within the range 5-95, preferably 20-95.
上記の成分・組成よりなる外層は、中間酸化物の形成法
と同様にして行なうことができる。外層の被覆量は一般
に1〜1007/m”、好ましくは5〜50jJ/m”
の範囲内になるようにするのが適当である。The outer layer consisting of the above components and composition can be formed in the same manner as the method for forming the intermediate oxide. The coverage of the outer layer is generally 1 to 1007/m", preferably 5 to 50jJ/m"
It is appropriate to keep it within the range of .
以上に述べた本発明の電極は、高電流密度下でも長寿命
化を図ることができ、省資源化につながることはもちろ
ん、装置のメンテナンスが容易になる等の種々のメリッ
トがある。The electrode of the present invention described above can have a long life even under high current density, and has various advantages such as resource saving and easy maintenance of the device.
また、本発明の電極は、卑な電位環境下でも電極の安定
化を図ることができ、通電停止下での電極の劣化がほと
んどなくなり、通電の開閉操作が多い電解でも長寿命化
が図れる。In addition, the electrode of the present invention can stabilize the electrode even in a base potential environment, almost eliminates deterioration of the electrode when energization is stopped, and extends the life of the electrode even in electrolysis that requires many switching operations.
更に、本発明の電極は、金属の表面処理に有用な交流電
解やパルス電解にも利用することができる。Furthermore, the electrode of the present invention can also be used in AC electrolysis and pulsed electrolysis, which are useful for surface treatment of metals.
次に実施例を掲げて本発明をさらに具体的に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例1
JIS2種担当チタン板素材(LO,5X’l OX”
lOmm)をトリクロルエチレンで脱脂洗浄した後、2
0°Cの8重量%HF水溶液で2分間処理し、次いで1
20°Cの601を量%H,SO,溶液中で3分間処理
した。次いでチタン基体を硫酸溶液から取り出し、窒素
雰囲気中で冷水を噴霧し、急冷した。更に20℃の0.
3重量%HF水溶液中に2分間浸漬した後水洗した。Example 1 JIS Class 2 titanium plate material (LO, 5X'l OX"
After degreasing and cleaning the 10mm) with trichlorethylene, 2
treated with 8 wt% aqueous HF at 0 °C for 2 min, then 1
601 at 20° C. was treated in a solution containing % H, SO for 3 minutes. The titanium substrate was then removed from the sulfuric acid solution and quenched by spraying with cold water in a nitrogen atmosphere. Furthermore, 0.
It was immersed in a 3% by weight aqueous HF solution for 2 minutes and then washed with water.
水洗後ジニトロジアミノ白金を硫酸溶液に溶解してpt
含有量5I/12、pH舛2.50°Cに調整した状態
の白金メツキ浴中で15mA/cm”で約50秒間のメ
ツキを行なって、Ptを分散析出させた。分散被覆量は
197m2であった。まt;この時のチタン基体への白
金の被覆率は約40%であった。After washing with water, dinitrodiaminoplatinum was dissolved in a sulfuric acid solution and pt
Pt was dispersed and precipitated by plating at 15 mA/cm'' for about 50 seconds in a platinum plating bath with a content of 5 I/12 and a pH adjusted to 2.50°C.The dispersed coating amount was 197 m2. The platinum coverage on the titanium substrate at this time was about 40%.
このようにして、分散被覆した白金をチタン基体を40
0°Cの大気中で1時間加熱処理した。In this way, the dispersion-coated platinum was applied to the titanium substrate for 40 minutes.
Heat treatment was performed in the atmosphere at 0°C for 1 hour.
次いで、塩化イリジウム酸のブタノール溶液と塩化タン
タルのエタノール溶液を混会し、■r5.9:j/Q及
びTa50jl/Q(金属換算)を含有する塗布液を調
製した後、マイクロピペットで1cm”当り2.7μQ
秤量し、それを上記基体に塗布した後、室温で30分間
真空乾燥させ、更に500℃の大気中で10分間焼成し
た。この工程を2回繰り返した。Next, a butanol solution of chloroiridic acid and an ethanol solution of tantalum chloride were mixed to prepare a coating solution containing ■r5.9:j/Q and Ta50jl/Q (metal equivalent), and then a 1 cm" 2.7μQ per
After weighing and applying it to the above substrate, it was vacuum dried at room temperature for 30 minutes, and further baked in air at 500° C. for 10 minutes. This process was repeated twice.
次いで、外層を得るため塩化イリジウム酸のブタノール
溶液と塩化タンタルのエタノール溶液を混合し、Ir5
0j/Q及びTa201/I2 (金属換算)を含有す
る塗布液を調製した後、この塗布液を用いて前記と同様
の工程を8回繰り返して実施例電極−1を作成した。Then, to obtain the outer layer, a butanol solution of chloroiridic acid and an ethanol solution of tantalum chloride were mixed, and Ir5
After preparing a coating solution containing Oj/Q and Ta201/I2 (metal equivalent), the same steps as above were repeated eight times using this coating solution to create Example Electrode-1.
次に、上記実施例電極−1と同様の方法で酸化物の組成
をかえた実施例電極−2〜9を作製した。Next, Example electrodes 2 to 9 with different oxide compositions were prepared in the same manner as Example electrode 1.
更に、上記実施例と同様にして、チタン基体を処理した
後400°Cの大気中で1時間加熱処理し、更に上記実
施例電極−1の製造と同様の工程で酸化物をコーティン
グした比較例電極−1と外層酸化物だけをコーティング
した比較例電極−2を作製した。さらに表−1に示す酸
化物の組成をもつ比較例電極−3,4も作製した。この
ようにして得られた各電極を次の条件下で電解した時の
電極寿命を表1に示す。Furthermore, a comparative example was prepared in which a titanium substrate was treated in the same manner as in the above example, then heat treated in the atmosphere at 400°C for 1 hour, and further coated with an oxide in the same process as in the production of Example Electrode-1. Comparative Example Electrode-2 was prepared by coating only Electrode-1 and outer layer oxide. Furthermore, comparative electrodes 3 and 4 having the oxide compositions shown in Table 1 were also produced. Table 1 shows the electrode life when each electrode thus obtained was electrolyzed under the following conditions.
〈電解条件〉
電解液 : IMH2Son−IMNazsOt電流密
度’ 4 A / (mz
対極 二Pt
極間距離:10mm
表−1
注、)
上表のNo、2〜9.12の電極は白金を1.?/ m
!分散被覆した電極である。<Electrolytic conditions> Electrolyte: IMH2Son-IMNazsOt Current density' 4 A / (mz Counter electrode 2 Pt Distance between electrodes: 10 mm Table 1 Note) The electrodes No. 2 to 9.12 in the above table are platinum 1. ? / m
! It is a dispersion coated electrode.
注2)塩化白金酸と塩化タンタルを含む塗布液を塗布し
熱分解により得られた中間層である。Note 2) An intermediate layer obtained by applying a coating solution containing chloroplatinic acid and tantalum chloride and thermally decomposing it.
実施例2
前記実施例1に記載したと同様の方法でチタン板上に白
金を12/m’分散析出させ、それを400°Cの大気
中で1時間加熱処理した。Example 2 Platinum was dispersed and precipitated at 12/m' on a titanium plate in the same manner as described in Example 1, and then heat-treated in the atmosphere at 400°C for 1 hour.
次いで、塩化イリジウム酸のブタノール溶液と塩化タン
タルのエタノール液を混合し、Ir13ン/α及びT
a 50fl/Q (金属換算)を含有する塗布液を
調製した後、マイクロピペットで1 cm”当り2.7
μα秤量し、それを上記基体に塗布した後室温で30分
間真空乾燥させ、更に500°Cの大気中で10分間焼
成した。この工程を2回繰り返した。Next, a butanol solution of chloroiridic acid and an ethanol solution of tantalum chloride were mixed, and Ir13/α and T
a After preparing a coating solution containing 50 fl/Q (metal equivalent), apply 2.7 fl/Q per 1 cm with a micropipette.
μα was weighed, applied to the substrate, vacuum dried at room temperature for 30 minutes, and further baked in air at 500° C. for 10 minutes. This process was repeated twice.
次いで、外層を得るため塩化イリジウム酸のブタノール
溶液と塩化タンタルのエタノール溶液を混合し、Ir5
0j’/ff及びTa2O&/R(金属換算)を含有す
る塗布液を調製した後、この塗布液を用いて前記と同様
の工程を12回繰り返して、実施例電極−1Oを作製し
た。Then, to obtain the outer layer, a butanol solution of chloroiridic acid and an ethanol solution of tantalum chloride were mixed, and Ir5
After preparing a coating solution containing 0j'/ff and Ta2O&/R (metal equivalent), the same steps as above were repeated 12 times using this coating solution to produce Example Electrode-1O.
比較のため、上記実施例−1Oと同様の方法でチタン基
体を処理した後32I/m”の白金を電気メツキしくこ
の時の白金の被覆率は99%以上)、この白金被覆チタ
ン板を400°Cの大気中で1時間加熱処理し、次いで
外層を得るため前記実施例電極−10と同様の工程を繰
り返して比較例電極=5.6を作製した。For comparison, a titanium substrate was treated in the same manner as in Example 1O above, and then electroplated with 32 I/m'' of platinum (platinum coverage at this time was over 99%), and this platinum-coated titanium plate was coated with 400 A comparative example electrode 5.6 was prepared by heat-treating in the atmosphere at °C for 1 hour, and then repeating the same steps as for Example electrode-10 to obtain an outer layer.
このようにして得られt;各電極を次の条件下で電解し
た時の触媒の消耗の経時変化を添付の第1図に示す。The time course of the consumption of the catalyst thus obtained was shown in the attached FIG. 1 when each electrode was electrolyzed under the following conditions.
電解液 : I MH!S 04−IMN a zs
O+電流波形: +l A / c m ”で80秒間
電解後0 、 l A / c m ”で20秒間電解
の繰り返し
対極 :Pt
第1図より実施例電極−10は、卑な電位環境下にさら
されても、安定な電極であることがわかる。Electrolyte: I MH! S 04-IMN azs
O + current waveform: After electrolysis for 80 seconds at +lA/cm'', electrolysis was repeated for 20 seconds at 0 and lA/cm''. Counter electrode: Pt From FIG. It can be seen that the electrode is stable even when
実施例3
前記実施例1に記載したと同様の方法で、外層の酸化物
組成だけを変えた表−2に示す実施例電極−11〜13
と比較例電極−8及びチタン板上に322/m”のPt
をメツキした比較例電極−9を作製した。Example 3 Example electrodes-11 to 13 shown in Table-2 were prepared in the same manner as described in Example 1, but only the oxide composition of the outer layer was changed.
and comparative example electrode-8 and 322/m” Pt on the titanium plate.
Comparative Example Electrode-9 was prepared by plating.
これらの電極の液温60°Cのlμ/aの硫酸水溶液中
での電位−電流特性を添付の第2図に示す。The potential-current characteristics of these electrodes in a lμ/a sulfuric acid aqueous solution at a liquid temperature of 60°C are shown in the attached FIG. 2.
第2図より、実施例電極は酸素過電圧が低いことがわか
る。From FIG. 2, it can be seen that the electrode of the example has a low oxygen overvoltage.
第1図は実施例2で作製した電極の触媒の消耗経時変化
を示すグラフであり、
第2図は実施例3で作製した電極の硫酸水溶液中での電
位−電流特性を示すグラフである。
第1図
時間 (時間)
実施例電極−10ニア0モル%Ir0z−30モル%T
ag、/Pt−(20モル%IrOx 80モル%T
a0x)/Ti[x/Ti
比較例ti−5ニア0モル%Ir0z30モル%T a
OX/ P t /TLOX/TL
比較例電極−6ニア0モル%Ir0h30モル%TaO
*/20モル%Ir0z−80モル%Ta0X/p t
/TiOx/TiFIG. 1 is a graph showing changes over time in catalyst consumption of the electrode prepared in Example 2, and FIG. 2 is a graph showing potential-current characteristics of the electrode prepared in Example 3 in an aqueous sulfuric acid solution. Figure 1 Time (hours) Example electrode-10nia 0 mol%Ir0z-30 mol%T
ag, /Pt-(20 mol% IrOx 80 mol% T
a0x)/Ti[x/Ti Comparative Example ti-5 Near 0 mol% Ir0z 30 mol% Ta
OX/ P t /TLOX/TL Comparative Example Electrode-6 Near 0 mol% Ir0h30 mol% TaO
*/20 mol% Ir0z-80 mol% Ta0X/pt
/TiOx/Ti
Claims (1)
た白金と、少なくとも基体表面の露出部分を被覆する酸
化イリジウム、酸化マンガン、酸化コバルト、酸化スズ
及び酸化アンチモンより選ばれる少なくとも1種の金属
酸化物0〜20モル%と酸化ニオブ、酸化タンタル及び
酸化ジルコニウムより選ばれる少なくとも1種の金属酸
化物80〜100モル%からなる複合金属酸化物又は混
合金属酸化物又は単一金属酸化物とから構成される中間
層と、 (b)酸化イリジウム5〜95モル%と、酸化ニオブ、
酸化タンタル及び酸化ジルコニウムより選ばれる少なく
とも1種の金属酸化物5〜95モル%からなる混合金属
酸化物から構成される外層 を設けてなることを特徴とする電解用電極。 2、中間層における白金の被覆率が10〜80%である
請求項1記載の電解用電極。 3、中間層が、基体表面が部分的に露出する程度に分散
被覆された白金と、酸化イリジウム5〜15モル%と酸
化ニオブ、酸化タンタル及び酸化ジルコニウムより選ば
れる少なくとも1種の金属酸化物85〜95モル%から
なる混合金属酸化物とから構成される請求項1又は2記
載の電解用電極。 4、中間層の混合金属酸化物における酸化イシリジウム
の含有量が外層における混合金属酸化物における酸化イ
リジウムの含有量よりも少ない請求項3の電解用電極。[Claims] 1. On an electrode base made of titanium or a titanium alloy, (a) platinum dispersed and coated to such an extent that the base surface is partially exposed, and iridium oxide covering at least the exposed portion of the base surface; , 0 to 20 mol % of at least one metal oxide selected from manganese oxide, cobalt oxide, tin oxide, and antimony oxide, and 80 to 100 mol % of at least one metal oxide selected from niobium oxide, tantalum oxide, and zirconium oxide. (b) 5 to 95 mol% of iridium oxide, niobium oxide,
1. An electrolytic electrode comprising an outer layer made of a mixed metal oxide containing 5 to 95 mol% of at least one metal oxide selected from tantalum oxide and zirconium oxide. 2. The electrode for electrolysis according to claim 1, wherein the platinum coverage in the intermediate layer is 10 to 80%. 3. The intermediate layer includes platinum dispersed and coated to such an extent that the substrate surface is partially exposed, 5 to 15 mol% of iridium oxide, and at least one metal oxide selected from niobium oxide, tantalum oxide, and zirconium oxide 85 The electrode for electrolysis according to claim 1 or 2, comprising a mixed metal oxide comprising 95 mol%. 4. The electrode for electrolysis according to claim 3, wherein the content of isridium oxide in the mixed metal oxide of the intermediate layer is lower than the content of iridium oxide in the mixed metal oxide of the outer layer.
Priority Applications (1)
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JP1008578A JP2505560B2 (en) | 1989-01-19 | 1989-01-19 | Electrode for electrolysis |
Applications Claiming Priority (1)
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JP1008578A JP2505560B2 (en) | 1989-01-19 | 1989-01-19 | Electrode for electrolysis |
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JPH02190491A true JPH02190491A (en) | 1990-07-26 |
JP2505560B2 JP2505560B2 (en) | 1996-06-12 |
Family
ID=11696903
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JP1008578A Expired - Fee Related JP2505560B2 (en) | 1989-01-19 | 1989-01-19 | Electrode for electrolysis |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02200790A (en) * | 1989-01-30 | 1990-08-09 | Ishifuku Kinzoku Kogyo Kk | Electrode for electrolysis |
JPH05148675A (en) * | 1991-11-28 | 1993-06-15 | Permelec Electrode Ltd | Electrolytic electrode base body, electrolytic electrode and production thereof |
US5294317A (en) * | 1992-03-11 | 1994-03-15 | Tdk Corporation | Oxygen generating electrode |
JPH06146052A (en) * | 1992-11-11 | 1994-05-27 | Permelec Electrode Ltd | Production of metallic foil by electrolysis |
JPH06146051A (en) * | 1992-11-06 | 1994-05-27 | Permelec Electrode Ltd | Production of metallic foil by electrolysis |
JPH07331494A (en) * | 1994-04-04 | 1995-12-19 | Furukawa Electric Co Ltd:The | Oxygen generating electrode and its production |
US20150292106A1 (en) * | 2012-11-29 | 2015-10-15 | Industrie De Nora S.P.A. | Electrode for oxygen evolution in industrial electrochemical processes |
JP2017533344A (en) * | 2014-10-21 | 2017-11-09 | エヴォクア ウォーター テクノロジーズ エルエルシーEvoqua Water Technologies LLC | Electrode with two-layer coating, method of use and manufacturing |
JP2018111874A (en) * | 2017-01-13 | 2018-07-19 | カイゲンファーマ株式会社 | Electrode for electrolysis |
CN113337845A (en) * | 2020-02-17 | 2021-09-03 | 马赫内托特殊阳极(苏州)有限公司 | Electrode capable of reversing polarity and application thereof |
CN114351179A (en) * | 2021-12-02 | 2022-04-15 | 江苏友诺环保科技有限公司 | Iridium tantalum manganese coating titanium anode plate with intermediate layer and preparation method thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JPWO2022065455A1 (en) * | 2020-09-24 | 2022-03-31 |
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JPS5310556A (en) * | 1976-07-15 | 1978-01-31 | Toshiba Corp | Waste water treating system |
JPS5325838A (en) * | 1976-08-23 | 1978-03-10 | Matsushita Electric Ind Co Ltd | Storage battery electrode plate |
JPS5940914A (en) * | 1982-08-31 | 1984-03-06 | Mazda Motor Corp | Vehicle attitude control device |
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Patent Citations (3)
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JPS5310556A (en) * | 1976-07-15 | 1978-01-31 | Toshiba Corp | Waste water treating system |
JPS5325838A (en) * | 1976-08-23 | 1978-03-10 | Matsushita Electric Ind Co Ltd | Storage battery electrode plate |
JPS5940914A (en) * | 1982-08-31 | 1984-03-06 | Mazda Motor Corp | Vehicle attitude control device |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02200790A (en) * | 1989-01-30 | 1990-08-09 | Ishifuku Kinzoku Kogyo Kk | Electrode for electrolysis |
JPH05148675A (en) * | 1991-11-28 | 1993-06-15 | Permelec Electrode Ltd | Electrolytic electrode base body, electrolytic electrode and production thereof |
EP0699780A1 (en) | 1992-03-11 | 1996-03-06 | TDK Corporation | Oxygen generating electrode |
US5294317A (en) * | 1992-03-11 | 1994-03-15 | Tdk Corporation | Oxygen generating electrode |
JPH06146051A (en) * | 1992-11-06 | 1994-05-27 | Permelec Electrode Ltd | Production of metallic foil by electrolysis |
JPH06146052A (en) * | 1992-11-11 | 1994-05-27 | Permelec Electrode Ltd | Production of metallic foil by electrolysis |
JPH07331494A (en) * | 1994-04-04 | 1995-12-19 | Furukawa Electric Co Ltd:The | Oxygen generating electrode and its production |
US20150292106A1 (en) * | 2012-11-29 | 2015-10-15 | Industrie De Nora S.P.A. | Electrode for oxygen evolution in industrial electrochemical processes |
US11098415B2 (en) * | 2012-11-29 | 2021-08-24 | Industrie De Nora S.P.A. | Electrode for oxygen evolution in industrial electrochemical processes |
US11643746B2 (en) | 2012-11-29 | 2023-05-09 | Industrie De Nora S.P.A. | Electrode for oxygen evolution in industrial electrochemical processes |
JP2017533344A (en) * | 2014-10-21 | 2017-11-09 | エヴォクア ウォーター テクノロジーズ エルエルシーEvoqua Water Technologies LLC | Electrode with two-layer coating, method of use and manufacturing |
JP2018111874A (en) * | 2017-01-13 | 2018-07-19 | カイゲンファーマ株式会社 | Electrode for electrolysis |
CN113337845A (en) * | 2020-02-17 | 2021-09-03 | 马赫内托特殊阳极(苏州)有限公司 | Electrode capable of reversing polarity and application thereof |
CN113337845B (en) * | 2020-02-17 | 2024-02-09 | 马赫内托特殊阳极(苏州)有限公司 | Electrode capable of reversing polarity and application thereof |
CN114351179A (en) * | 2021-12-02 | 2022-04-15 | 江苏友诺环保科技有限公司 | Iridium tantalum manganese coating titanium anode plate with intermediate layer and preparation method thereof |
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