EP0087186B1 - Elektrode mit Bleibasis und Verfahren zu ihrer Herstellung - Google Patents

Elektrode mit Bleibasis und Verfahren zu ihrer Herstellung Download PDF

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Publication number
EP0087186B1
EP0087186B1 EP83200195A EP83200195A EP0087186B1 EP 0087186 B1 EP0087186 B1 EP 0087186B1 EP 83200195 A EP83200195 A EP 83200195A EP 83200195 A EP83200195 A EP 83200195A EP 0087186 B1 EP0087186 B1 EP 0087186B1
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EP
European Patent Office
Prior art keywords
particles
lead
anode
titanium
activated
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
Application number
EP83200195A
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English (en)
French (fr)
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EP0087186A1 (de
Inventor
Henri Bernard Beer
Michael Katz
Jean Hinden
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Eltech Systems Corp
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Eltech Systems Corp
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Priority to AT83200195T priority Critical patent/ATE24553T1/de
Publication of EP0087186A1 publication Critical patent/EP0087186A1/de
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Publication of EP0087186B1 publication Critical patent/EP0087186B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof

Definitions

  • the present invention relates to dimensionally stable electrodes, and more particularly to anodes for oxygen evolution in an acid electrolyte, such as are used e.g. in processes for electrowinning metals from acid electrolytes.
  • Lead or lead alloy anodes have been widely used in processes for electrowinning metals from sulphate solutions. They nevertheless have important limitations, such as a high oxygen overvoltage and loss of the anode material lead- ting to contamination of the electrolyte, as well as the metal product obtained on the cathode.
  • Anodes of lead-silver alloy provide a certain decrease of the oxygen overvoltage and improvement of the current efficiency, but they still have the said limitations as a whole.
  • Metal electrowinning cells generally require a large anode surface and operate at a low current density in order to ensure an even electrodeposition of metal on the cathode, so that the cost of using a titanium base becomes relatively important and must also be taken into account.
  • EP-A-0 046 727 discloses an anode for metal electrowinning comprising lead or lead alloy substrate with an active electrocatalytic layer of titanium powder pressed into the lead substrate.
  • the titanium powder in the active layer is impregnated with at least one platinum group metal oxide as electro- catalyst.
  • the valve metal particles used are simply applied over the lead base and pressed into its surface.
  • EP-A-0 046 447 discloses an electrode with valve metal substrate and an electrocatalytic layer wherein the electrocatalytic layer is formed by a surface treatment of the substrate with solution of a thermodecomposable platinum group metal compound and a halide agent.
  • the halide agent attacks the valve metal substrate and converts metal from the substrate into ions which are further converted into an oxide of the valve metal during heating.
  • DE-A-2 948 565 discloses a composite electrode comprising an inner layer of an electrically conductive material such as carbon, Fe, Cu, Ni, and Mn and two layers of pressed and sintered titanium powder.
  • the first powder layer being non-porous and the second layer of sintered powder titanium having porosity between 30 and 90%. Both layers are metallurgically bonded to the carbon of stainless steel inner layer.
  • DE-A-2 652 152 discloses an electrode comprising a conductive substrate onto which at least one metal or metal oxide has been formed or deposited under such conditions that at least one solid is codeposited by occlusion in the coating.
  • the conductive substrates disclosed are Ni, Ti, Al, Fe, etc. and the codeposited solids are NiO, Ti0 2 , Fe 2 0 3 , Zr0 2 , etc.
  • An object of the invention is to provide an improved anode for evolving oxygen in an acid electrolyte.
  • Another object of the invention is to provide an anode with a base of lead or lead alloy with improved electrochemical performance for anodically evolving oxygen in an acid electrolyte, so as to be able to substantially avoid loss of the anode material, whereby to avoid said limitations of conventional lead or lead alloy anodes.
  • a further object of the invention is to provide a simple method of making such an electrode with improved performance.
  • the electrochemical performance of the anode is improved in accordance with the invention by providing the anode with titanium particles which are catalytically activated by means of ruthenium and manganese in oxide form and are partly embedded at the surface of the anode base of lead or lead alloy, so that they are firmly anchored and electrically connected to the base.
  • the remaining, non-embedded part of said catalytic particles thus projects from said surface of the anode base, and thereby can present a surface for oxygen evolution which can be considerably larger than the underlying surface of the anode base of lead or lead alloy.
  • Said partly embedded catalytic particles are preferably arranged according to the invention, so that they substantially cover the entire surface of the lead or lead alloy base, present a maximum surface for oxygen evolution, and thereby more especially provide a substantially uniform distribution of the anode current density.
  • ruthenium and manganese to catalytically activate titanium particles in accordance with the invention is particularly advantageous since ruthenium can provide an excellent electro- catalyst for oxygen evolution at a relatively low cost with respect to other metals of the platinum group.
  • the catalytic particles applied according to the invention advantageously consist of titanium sponge and may have a size lying in the range between 150 and 1250 ⁇ m and preferably in the range of about 300-1000 ⁇ m.
  • the amount or loading of said catalytic particles applied according to the invention per unit area of the anode base should generally be adequate to substantially cover the anode base.
  • the catalytic particles advantageously comprise a minimum amount of ruthenium, corresponding to at most 6% by weight of the titanium of said particles, evenly distributed on a very large surface.
  • This improved electrocatalytic performance and stability of the Ru-Mn oxide system under the conditions of oxygen evolution in acid media constitutes a particularly advantageous feature of the catalytically activated titanium particles used on a lead base according to the present invention.
  • an additional pressing step to apply non-activated particles of a valve metal or a valve metal oxide, more particularly zirconium dioxide can further increase the stability of the activated particles. This is especially important in processes for electrowinning metals from electrolytes containing Mn 2+ ions, where the deposition of poorly conducting Mn0 2 can be detrimental for anode performance.
  • An activating solution was prepared by dissolving 0.57 g RuCl 3 . aq. and 1.33 g Mn(N03)2. aq. in 4 ml 1-butyl-alcohol. The solution was then diluted with six times its weight of 1-butyl-alcohol.
  • the same activating solution was used also on 4.9 g Ti sponge (particle size 315-630 pm).
  • the temperatures for drying and heating as well as the number of impregnations were identical to those applied to the larger particles. However, the duration of the heat treatment at 400°C was 12 minutes.
  • the Ru and Mn loadings in this case amounted to 27 mg Ru/g Ti sponge and 34 mg Mn/g Ti sponge.
  • the activated titanium sponge particles were then pressed onto a lead sheet coupon.
  • the larger particles size (greater than 630 ⁇ m) were pressed first at 290 kg/cm 2 to give Ti, Mn and Ru loadings per unit lead-sheet area of 322, 11.5 and 9.1 g/m 2 respectively.
  • smaller activated titanium particles (315-630 pm) were then pressed at 360 kg/cm 2 to give Ti, Mn and Ru loadings of 400, 13.7 and 10.8 g/m 2 respectively.
  • An electrode sample (L 62) was thus obtained with a lead base uniformly covered with Ru-Mn oxide activated titanium sponge. particles in an amount corresponding to 722 g/m 2 Ti sponge, 19.9 g/m 2 Ru and 25.2 g/m 2 Mn.
  • This electrode sample was tested as an oxygen evolving anode in H 2 SO 4 (150 gpl).
  • a further anode sample (L 76) was prepared like L 62 but the larger particles were only activated 4 times instead of 5.
  • the overall Ru and Mn loadings amounted in this case to 22.1 and 28.0 g/m 2 respectively.
  • the anode was tested under identical conditions and showed a potential of 1.5 vs NHE after 22 days and 1.8 V after 140 days of operation.
  • An anode sample (L 64) was prepared like L 62 of Example 1 but with higher Ru and Mn loadings of 23.1 and 29.3 g/m 2 respectively. The anode was tested in a Zn electrowinning solution containing Mn 2+ as a major impurity.
  • Ti sponge (particle size 315-630 microns) was activated like in Example 1. It was then pressed onto lead at 270 kg/cm 2 to give a loading of Ti, Mn and Ru corresponding to 427, 15.1 and 11.9 g/m 2 respectively. Finally particulate Zr0 2 (particle size 150-500 ⁇ m) was pressed with a pressure of about 410 kg/cm2 on top of the Ti sponge to give a Zr0 2 loading corresponding to 248 g/ M 2.
  • the electrode sample thus obtained (L 82) was tested as an oxygen evolving anode in H 2 S0 4 (150 gpl).
  • the electrode potential at a current density of 500 A/m 2 amounted to 1.50 V vs NHE after 150 h of anodic operation. It amounted to 1.59 V after 293 days, and is still operating. This corresponds to a voltage saving of 410 mV with respect to pure, untreated lead.
  • Ti sponge (particle size 315-630 ⁇ m) was activated first with a Ru and Mn containing solution as described in Example 1. The activation method was also identical to the one described in
  • a top-coating was applied by impregnation with a solution containing Ti-butoxide which was prepared by diluting 1.78 g Ti-butoxide in 3.75 ml 1-butyl-alcohol and 0.25 ml HCI.
  • the impregnated sponge was dried at 100°C for about 1 h.
  • a heat treatment was then effected at 250°C for 12 minutes and finally at 400°C under an external air flow for about 12 minutes.
  • the resulting activated titanium particles were then pressed on lead at about 250 kg/cm 2 .
  • the electrode sample (L 84) was thus obtained with a lead base uniformly covered with Ru-Mn oxide activated titanium sponge particles "topcoated" with Ti-oxide in amounts corresponding to 13.3 g Ru/m 2 , 16.9 g Mn/m 2 , 5.8 g Ti/m 2 and 515 g Ti sponge/m 2 .
  • This electrode sample was tested as an oxygen evolving anode in H 2 S0 4 (150 gpl). Its potential at a current density of 500 A/m 2 amounted to 1.49 V vs NHE after 130 h of anodic operation. This corresponds to a 510 mV saving over untreated lead. The anode potential amounted to 1.64 V after 128 days, which corresponds to a 360 mV saving over untreated lead.
  • Example 2 An activating solution was prepared as described in Example 1, but instead of diluting it six times (example 1), it was diluted with only three times its amount of n-butyl-alcohol.
  • the activated titanium sponge particles were then pressed and partly embedded at the surface of a lead sheet coupon.
  • the larger particles (size greater than 630 ⁇ m) were pressed first at 240 kg/cm 2 to give Ti, Mn and Ru loadings per unit lead sheet area of 350, 10.5 and 8.3 g/m 2 respectively.
  • An electrode sample (L 95) was thus obtained with a lead base uniformly covered with Ru-Mn oxide activated titanium sponge particles in an amount corresponding to 760 g/m 2 Ti sponge, 23.2 g/m 2 Ru and 29.3 g/m 2 Mn.
  • This electrode sample was tested as an oxygen evolving anode in H 2 SO I (150 gpl).
  • the electrode potential, at a current density of 500 A/m 2 amounted to 1.65 V vs NHE after 287 days of anodic operation.
  • a further anode sample (L 92) was prepared like L 95 but the smaller particles (400-630 ⁇ m) were activated like in Example 1 (L 62).
  • the overall Ti, Mn and Ru loadings amounted in this case to 726, 22.5 and 17.7 g/m 2 respectively. Pressing of the larger particles and smaller particles was carried out at 290 kg/cm 2 and 410 kg/cm 2 respectively.
  • the anode has been tested under identical conditions and showed a potential of 1.78 V vs NHE after 289 days of operation.
  • Example 5 An activating solution was prepared as described in Example 5. 4,22 g of larger particles (particle size above 630 ⁇ m) was activated twice under the conditions specified in Example 7 to give 21.5 mg Ru/g Ti and 27.4 mg Mn/g Ti.
  • An anode sample (L 120) was prepared by pressing the larger particles first at 210 kg/cm 2 to give Ti, Mn and Ru loadings of 360, 9.8 and 7.7 g/m 2 respectively. Smaller activated titanium particles (400-630 pm) were then pressed at 320 kg/cm 2 to give Ti, Mn and Ru loadings of 420, 13.9 and 10.9 g/m 2 respectively. The overall Ti, Mn and Ru loadings thus obtained amounted to 780, 23.7 and 18.6 g/m 2 respectively.
  • the electrode sample was tested as an oxygen evolving anode in H I S0 4 (150 gpl).
  • the electrodes potential at a current density of 500 A/m 2 , amounted to 1.58 V vs NHE after 218 days of anodic operation.
  • Titanium sponge 400-630 pm was oxidized as follows, prior to activation with Ru-Mn oxide.
  • Example 2 3.5 g of the oxidized Ti sponge thus obtained was then activated as described in Example 1 with the only difference that an intermediate heat treatment was carried out at 250°C instead of 200°C after each activation.
  • the Mn and Ru loadings per g sponge amounted to 32.8 and 25.8 mg respectively.
  • the peroxidized and activated Ti sponge was then pressed in two steps, first at 230 kg/cm 2 and then at 290 kg/cm 2 to give Mn and Ru loadings of 21.1 and 16.6 g/m 2 respectively.
  • the loading of the oxidized Ti sponge amounted to 643 g/m 2 .
  • the overall Mn and Ru loadings amount to 25.3 and 19.9 g/m 2 respectively.
  • the electrode has been tested in 150 gpl H 2 SO 4 at 500 A/m 2 and its potential after 275 days of operation amounted to 1.65 V vs NHE.
  • the activated Ti sponge particles were then pressed onto a lead sheet coupon.
  • An electrode sample (L 164) was thus obtained with a lead base uniformly covered with Ru-Mn oxide activated titanium sponge particles in an amount corresponding to 848 g/m 2 Ti sponge, 20.8 g/m 2 Ru and 37.5 g/m 2 Mn.
  • This electrode sample was tested as an oxygen evolving anode in 150 gpl H 2 S0 4 . Its potential, at a current density of 500 A/m 2 , amounted to 1.50 V vs NHE after 36 days of anodic operation.
  • This electrode L 161 has been tested under identical conditions and showed a potential of 1.60 V vs NHE after 70 days of operation.
  • Ti sponge particles larger than 630 pm, activated as in Example 8 were pressed first at 230 kg/cm 2 to give Ti, Mn and Ru loadings per unit lead-sheet area of 428, 11.5 and 9.0 g/m 2 respectively.
  • Smaller activated titanium sponge particles (size 315-630 pm), obtained with activating solution B, were then pressed at 350 kg/cm 2 to give Ti, Mn and Ru loadings of 493, 48.0 and 9.8 g/m 2 respectively.
  • An electrode sample (L 163) was thus obtained with a lead base uniformly covered with Ru-Mn oxide activated titanium sponge particles in an amount corresponding to 921 g/m 2 Ti, 59.5 g/m 2 Mn and 18.8 g/m 2 Ru.
  • This electrode has been tested as an oxygen evolving anode in 150 gpl H 2 SO 4 at 500 A/m 2. Its potential after 33 days of operation amounted to 1.57 V vs NHE.
  • the electrode has been tested at 500 AI M 2 in 150 gpl H 2 S0 4 and shows a potential of 1.74 V vs NHE after 18 days (430 h) of operation under these conditions.
  • An activating solution was prepared by dissolving 0.44 g RuC1 3 aq (38 weight% Ru), 0.090 g SnCl 2 . 2H 2 0+0.52 g Mn (N0 3 ) 2 - 4H 2 0 in four ml of butyl-alcohol.
  • titanium sponge particle size 315-630 ⁇ m
  • this activating solution was impregnated with this activating solution in the following manner: 0.77 ml of solution was uniformly applied to the titanium sponge, dried at 140°C during 15 min., baked at 250°C for 10 min. and at 420°C for 10 min., all drying and baking steps in air. After cooling, the titanium sponge was activated twice again, each time with 0.5 ml of activating solution, dried and baked as mentioned above.
  • the activated titanium particles were pressed onto the surface of a lead-calcium, alloy (0.06% Ca) coupon at 250 kg/cm 2 so as to get the following respective loadings: Ti 700 g/m 2 , Ru 20 g/m 2 , Sn 5.8 g/m 2 and Mn 13.7 g/m 2 .
  • This electrode sample was tested as an oxygen evolving anode in H 2 SO 4 (150 gpl) of 500 A/m 2 .
  • the electrode potential amounted to 1.67 V vs NHE after 7 months of operation.
  • an anode according to the invention can be fabricated in a simple manner and be used for prolonged evolution of oxygen at a potential which is significantly lower than the anode potential corresponding to oxygen evolution on lead or lead alloy under otherwise similar operating conditions.
  • catalytic particles may be applied and anchored to the lead or lead alloy base of the anode, not only by means of a press as in the examples described above, but also by any other means such as pressure rollers for example, which may be suitable for providing the essential advantages of the invention.
  • Anodes according to the invention may be advantageously applied instead of currently used anodes of lead or lead alloy, in order to reduce the energy costs required for industrially electrowinning metals such as zinc, copper, cobalt, and nickel and to improve the purity of the metal produced on the cathode.
  • Such anodes may be usefully applied to various processes where oxygen evolution at a reduced overvoltage is required.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Catalysts (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Chemically Coating (AREA)
  • Inert Electrodes (AREA)

Claims (9)

1. Verfahren zur Herstellung einer Sauerstoff entwickelnden Anode, die einen Kern aus Blei oder einer Bleilegierung und einen Katalysator aus Platingruppenmetall umfaßt, bei dem Titanschwammteilchen, die Ruthenium und Mangan in Oxidform enthalten, auf der Oberfläche des Kerns verteilt und teilweise in die Oberfläche eingebettet und in dem Kern aus Blei oder einer Bleilegierung verankert werden.
2. Verfahren nach Anspruch 1, bei dem die Ruthenium- und Mangan-oxide durch thermische Zersetzung von auf die Titanteilchen aufgebrachten Ruthenium- und Manganverbindungen erhalten werden.
3. Verfahren nach Anspruch 1 oder 2, bei dem die katalytisch aktivierten Titanschwammteilchen, die eine Teilchengröße von mehr als 600 Mikrometern haben, zuerst in die Oberfläche des Anodenkerns eingepreßt werden und die aktivierten Teilchen, die eine Teilchengröße von 300 bis 600 Mikrometern haben, anschließend in die Anodenkernoberfläche eingepreßt werden.
4. Verfahren nach Anspruch 3, bei dem die Teilchen, die eine Teilchengröße von 300 bis 600 Mikrometern haben, mit mehr Ruthenium versehen sind als die Teilchen mit einer Teilchengröße von mehr als 600 Mikrometern.
5. Verfahren nach Anspruch 1, bei dem die aktivierten Teilchen Titan in einer Menge enthalten, die mehr als 400 g je Quadratmeter der Oberfläche des Anodenkerns entspricht.
6. Verfahren nach Anspruch 1, bei dem weiterhin Titanoxid auf den katalytisch aktivierten Teilchen durch thermische Zersetzung einer Titanverbindung gebildet wird, die nach der Bildung des Rutheniums und Mangans in Oxidform auf die Teilchen aufgebracht wird.
7. Verfahren nach Anspruch 1, bei dem eine Schicht aus Ventilmetall- und/oder -methalloxidteilchen auf die Anode nach der Verankerung der Titanschwammteilchen aufgebracht wird.
8. Verfahren nach Anspruch 7, bei dem Teilchen aus Zirkondioxid auf den Anodenkern gepreßt werden, nachdem die katalytisch aktivierten Titanteilchen verankert worden sind.
9. Sauerstoff entwickelnde Anode, die einen Kern aus Blei oder einer Bleilegierung und eine darauf befindliche elektrochemisch aktive Schicht umfaßt, bei der die aktive Schicht Rutheniumoxid und Manganoxid enthaltende Titanschwammteilchen, die auf der Oberfläche des Kerns verankert sind, umfaßt.
EP83200195A 1982-02-18 1983-02-08 Elektrode mit Bleibasis und Verfahren zu ihrer Herstellung Expired EP0087186B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83200195T ATE24553T1 (de) 1982-02-18 1983-02-08 Elektrode mit bleibasis und verfahren zu ihrer herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP82810077 1982-02-18
EP82810077 1982-02-18

Publications (2)

Publication Number Publication Date
EP0087186A1 EP0087186A1 (de) 1983-08-31
EP0087186B1 true EP0087186B1 (de) 1986-12-30

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EP83200195A Expired EP0087186B1 (de) 1982-02-18 1983-02-08 Elektrode mit Bleibasis und Verfahren zu ihrer Herstellung

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EP (1) EP0087186B1 (de)
JP (1) JPS58161787A (de)
KR (1) KR890001132B1 (de)
AU (1) AU1145883A (de)
CA (1) CA1208601A (de)
DE (1) DE3368696D1 (de)
ES (1) ES519885A0 (de)
FI (1) FI830537L (de)
NO (1) NO830562L (de)
PL (1) PL240656A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3423605A1 (de) * 1984-06-27 1986-01-09 W.C. Heraeus Gmbh, 6450 Hanau Verbundelektrode, verfahren zu ihrer herstellung und ihre anwendung
KR101516812B1 (ko) 1998-02-16 2015-04-30 스미또모 가가꾸 가부시끼가이샤 염소의 제조방법
FI118159B (fi) 2005-10-21 2007-07-31 Outotec Oyj Menetelmä elektrokatalyyttisen pinnan muodostamiseksi elektrodiin ja elektrodi

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933616A (en) * 1967-02-10 1976-01-20 Chemnor Corporation Coating of protected electrocatalytic material on an electrode
US3840443A (en) * 1967-02-10 1974-10-08 Chemnor Corp Method of making an electrode having a coating comprising a platinum metal oxide
US4003817A (en) * 1967-12-14 1977-01-18 Diamond Shamrock Technologies, S.A. Valve metal electrode with valve metal oxide semi-conductive coating having a chlorine discharge in said coating
DE2035212C2 (de) * 1970-07-16 1987-11-12 Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach Metallanode für elektrolytische Prozesse
DE2652152A1 (de) * 1975-11-18 1977-09-15 Diamond Shamrock Techn Elektrode fuer elektrolytische reaktionen und verfahren zu deren herstellung
DD137365A5 (de) * 1976-03-31 1979-08-29 Diamond Shamrock Techn Elektrode
US4256810A (en) * 1978-12-04 1981-03-17 Gould Inc. High conductivity titanium electrode
GB2085031B (en) * 1980-08-18 1983-11-16 Diamond Shamrock Techn Modified lead electrode for electrowinning metals
CA1225066A (en) * 1980-08-18 1987-08-04 Jean M. Hinden Electrode with surface film of oxide of valve metal incorporating platinum group metal or oxide

Also Published As

Publication number Publication date
DE3368696D1 (en) 1987-02-05
PL240656A1 (en) 1984-03-26
NO830562L (no) 1983-08-19
ES8403532A1 (es) 1984-03-16
KR840003596A (ko) 1984-09-15
JPS6227160B2 (de) 1987-06-12
ES519885A0 (es) 1984-03-16
FI830537L (fi) 1983-08-19
CA1208601A (en) 1986-07-29
KR890001132B1 (ko) 1989-04-24
EP0087186A1 (de) 1983-08-31
JPS58161787A (ja) 1983-09-26
FI830537A0 (fi) 1983-02-17
AU1145883A (en) 1983-08-25

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