US2872405A - Lead dioxide electrode - Google Patents
Lead dioxide electrode Download PDFInfo
- Publication number
- US2872405A US2872405A US552968A US55296855A US2872405A US 2872405 A US2872405 A US 2872405A US 552968 A US552968 A US 552968A US 55296855 A US55296855 A US 55296855A US 2872405 A US2872405 A US 2872405A
- Authority
- US
- United States
- Prior art keywords
- lead
- bath
- lead dioxide
- screen
- 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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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
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
Definitions
- chlorate such as the alkali metal chlorates
- common practice is to electrolyze sodium chlorate to form sodium perchlorate, treat the sodium perchlorate with potassium chloride to precipitate potassium perchlorate and return sodium chloride to the chlorate cells.
- the literature on the electrolytic production of perchlorates indicates a unanimous acceptance of platinum as the only suitable anode material. In spite of the high capital investment involved and the significant replacementcosts due to electrochemical attack and mechanical disintegration, platinum is still used as anode in the major perchlorate installations.
- Lead dioxide has also been suggested for use as anode material in the electrolytic oxidation of chlorates and other materials.
- the lead dioxide has been electroplated onto iron, steel, copper or nickel metal bases.
- the lead dioxide especially in massive form, has a very low rate of erosion itself in the chlorateperchlorate system, the base metals onto which it is deposited are rapidly eroded since the electrolyte gains access thereto through pinholes in the lead dioxide coating. This leads to breakdown of the anode itself. In addition it also results in the contamination of the perchlorate product which, at least in some applications, is considered highly undesirable.
- the metal base onto which the lead dioxide has been deposited has been in the form of rods, hollow cylinders, sheets, blocks, and the like. It was found Unite States Patent 'ice that there was a marked tendency for the lead dioxide to crack or break away from the base metal during normal handling or machining operations due to the natural brittleness of the lead dioxide and its poor adhesion to the metal base body and to stresses set up through expansion and contraction differentials during changes in temperature.
- Another object of the present invention is to provide a novel lead dioxide-containing anode which is markedly less susceptible to breakdown during operation than prior lead dioxide-containing anodes and which imparts less contamination to the chlorate-perchlorate solution than do prior lead dioxide-containing anodes.
- Still another object of the present invention is to provide a novel lead dioxide-coated metal base anode which possesses a greater mechanical strength and less tendency to crack or break during handling than do prior lead dioxide-containing anodes.
- a further object of the present invention is to provide a novel method for making a lead dioxide-containing electrode having the above-discussed characteristics.
- the novel electrode of the present invention comprises a fine metal screen having a large surface relative to its volume having a coating of lead dioxide electrodeposited thereon.
- the electrode is prepared by anodically electrodepositing lead dioxide from an aqueous solution of a lead salt onto a fine metal screen having a large surface area relative to its volume.
- the metal screen is removed leaving a body consisting essentially of lead dioxide for use as electrode.
- the electrode of the present invention overcomes or eliminates many of the above-mentioned limitations and disadvantages of prior lead dioxide-containing electrodes.
- massive layers of lead dioxide can be electrodeposited onto a very fine metal screen which presents a high surface area relative to its volume.
- the metal screen becomes heavily coated and the interstices completely filled in so that the resulting product consists principally of the lead dioxide, and the removal of the metal, as by dissolution, has little effect upon the mechanical strength of the lead dioxide structure.
- the lead dioxide fills the interstices of the screen so that the resulting lead dioxide body is in effect a solid body of lead dioxide containing a thin fine network of line metal members, which, upon dissolution, leaves a thin network of very fine channels which do not affect significantly the mechanical strength of the remaining lead dioxide body.
- the metal base prior to dissolution of the metal base or its removal by other means, it may serve to some extent as reinforcement for the assembly during handling, and with certain metals, principally tantalum, the metal base will not become dissolved during use.
- the removal of the base metal before or during use, and the elimination of contamination will be discussed more indetail hereinconsists substantially entirely of lead dioxide, and the.-
- lead dioxide is bonded to itself through the interstices 3 of the screen, the fact that the lead dioxide bonds poorly to the metal itself is immaterial.
- the metal screen employed in accordance with the present invention may be selected from a wide variety of metals including tantalum, steel, nickel, Monel metal, tin, magnesium, aluminum, copper, and the like. Screens may be prepared by weaving individual wires crosswise or by stamping closely spaced holes in a metal sheet in either of which case a reticulated or foraminous network is provided and all of which are referred to herein as screen.
- the size of the openings in the screen and of the wires from wl ic-h they are made, or of the crossing elements in the case of a stamped screen may vary somewhat.
- the wire size may range from about 0.08" in diameter down to about 0.003" in diameter, or even finer, preferably 0.03 in diameter or finer.
- the Wire size of the screen may be somewhat finer than when plating on a single Wire because of the strengthening effect of the interlacin" of the wires in the screen.
- the number of openings per linear inch which may in turn depend upon the wire size, may range between about and about 50 mesh. Examples of materials of this type are: 50 mesh surgical tantalum gauze made of 0.003" wire; 14 mesh tantalum screen made of 0.025 wire; 16 mesh'nickel screen made of 0.012" wire; 14 mesh steel screen made of 0.020 wire; and the like.
- the stamped screens employed will be of comparable mesh and crossing element sizes.
- the metal screen onto which the lead dioxide is deposited will have a high surface area relative to its volume.
- the ratio of surface area (e. g. in square inches) to volume (e. g. in cubic inches) for a 0.08 diameter is 50. This ratio increases as the wire diameter decreases until it reaches 1330 for a 0.003" wire.
- the metal screen therefore, will have a ratio of at least 50 square units per cubic unit.
- any lead dioxide plating bath may be employed.
- the conventional lead dioxide plating baths generally fall within one of three principal systems: (1) alkaline aqueous solutions of lead tartrate; (2) non-alkaline aqueous solutions of lead perchlorate; and (3) acid aqueous solutions of lead nitrate.
- lead tartrate itself may be added to water along with a suitable base, or lead tartrate may be formed in situ in the bath.
- This latter embodiment is the preferred method of preparing the lead tartrate bath, and comprises mixing in water a soluble tartrate other than lead tartrate, such as an alkali metal tartrate, like sodium potassium tartrate, a base and lead oxide (PbO).
- the lead oxide dissolves in the alkaline tartrate solution forming lead tartrate in solution.
- sodium potassium tartrate (NaKCJ-LO AH O) between about 1 and about 1.5 parts, by weight, prefer- 4 ably between about 1.1 and about 1.25 parts, by weight, thereof p'er'part of lead oxide may beused.
- the lead. tartrate bath will be alkaline and hence a soluble base, preferably an alkali metal hydroxide, including ammonium hydroxide, is employed. Sodium hydroxide and potassium hydroxide are preferred with the former being particularly advantageous.
- the amount of base present in the alkaline lead tartrate bath that is to say the alkalinity of the bath, may vary somewhat. it has been suggested that as little as 2.7 moles of alkali hydroxide may be present per mole of lead tartrate.
- the anodic electrodeposition of leaddioxide from a lead tartratc bath in which the amount of total alkali hydroxide pres ent in the bath provides a mole ratio thereof to lead tartrate of at least about 4.5 to l, and the amount of alkali hydroxide may be such as to provide a mole ratio thereof to lead tartrate of as high as about 8 to l, or higher.
- the pH of the alkaline tartrate bath should be relatively high, pI-ls of above about 12 being particularly satisfactory.
- concentration of the main materials of the lead tartrate bath at the beginning of deposition may vary widely, although excessively high concentrations may lead to precipitation and to low quality deposits.
- concentration of lead in the bath is generally not in excess of about 8% (about 93 grams per liter).
- concentration of lead may be substantially below this, and it may be as low as about 1-2% (about 10 to 20 grams per liter).
- concentration of lead in the bath ranges between about 3 and about 5% (between about 32 and about 55 grams per liter).
- the lead perchlorate bath for electrodepositing lead dioxide is essentially an aqueous solution of lead perchlorate having a pH ranging from neutral to acid, preferably acid.
- the bath may be prepared by adding lead perchlorate itself in water, or the lead perchlorate may be formed in situ in the bath.
- This latter embodiment is the preferred means of preparing the lead perchlorate bath, and comprises adding lead oxide (Pl- 0) to an aqueous solution of perchloric acid.
- the amount of perchloric acid employed willbe at least that theoretically required to combine with the lead oxide to provide lead perchlo rate, and preferably excess perchloric acid is employed so that the pH of the solution is acid.
- acid pH conditions are preferred, as stated, preferably within the range of about 0.8 to about 5.
- concentration of lead perchlorate in the bath at the beginning of deposition may vary widely, although concentrations at or near the saturation point under the conditions encountered during operation and shutdown are highly desirable. Generally, the concentration of lead perchlorate may range between about 50 and about 500 grams per liter, preferably between about and about 350 grams liter.
- the lead nitrate bath is essentially an aqueous acid solution of lead nitrate.
- lead nitrate itself may be added to water, or the lead nitrate may be formed in situ in the bath, as by mixing lead oxide (.PbO) with aqueous nitric acid.
- lead oxide aqueous nitric acid
- the more acid the bath, the better its operation, and pHs as low as about 0.8 may be employed. At acidities appreciably greater than this, acid fuming from the bath becomes excessive, especially at elevated operating temperatures.
- the exact acidity of the bath may depend on the nature of the metal screen onto which the lead dioxide is to be deposited. For example, tantalum is not attacked at the lower end of the pH range whereas some of the other metals, such as steel, are. With metals that are readily attacked, higher acid pHs may be employed, such as pHs in the neighborhood of 'about4, or evenhigher.
- the bath initially made up and at the time operation commences may have a pH somewhat higher than the above figures, since, once operation has started, the pH drops to the desired level due to depletion of lead and release of nitric acid. r
- the concentration of lead nitrate in the bath may vary widely.
- the concentration of the lead nitrate in the bath may range from as low as about 50 grams per liter to as high as the maximum solubility thereof in the bath at operating temperature, which may be as high as about 700 grams perliter.
- concentrations above the lowerend of the range such as at least about 250 grams per liter and especially at least about 300 grams per liter are preferred.
- the concentration of the lead nitrate in order to facilitate handling of the bath during shutdown periods and during continuous replenishing procedures, when the bath may be at or near room temperature, it is also preferable that the concentration of the lead nitrate not be substantially in excess of its solubility at these lower temperatures, which may be in the neighborhood of about 400 grams .per liter. For optimum commercial operation, the concentration of the lead nitrate 1 will not exceed about 350 grams per liter.
- a small amount of copper nitrate may be included to prevent deposition of lead on the cathode.
- the amount of copper nitrate may vary widely, and may run as high as about 30 grams per liter, although it has been found that amounts as low as about 0.5 gram per liter provide significant results.
- any of those baths may be operated at temperatures ranging from about room temperature up to the boiling point of the bath.
- the exact optimum operating temperature will, of course depend upon the particular bath system selected. In genreal, however, it has been found that with any of the baths, moderately elevated temperatures, such as between about 60 and about 75 C., are preferred.
- the metal screen is immersed as anode, in the desired bath, and is connected tea-suitable source of current. Because with very fine screens kinking or bending thereof may be encountered, it may be desirable to weight the metal base so that itwill remain straight and perpendicular during the plating ope'ration.
- a weight such as asman glass bulb filled with mercury, may be attached to the end of a fine screen.
- Portions of the screen on which it is not desired to plate lead dioxide may be coated with a stop-off lacquer or paint.
- appropriate shielding such as that disclosed and claimed in copending application Serial No. 534,618, filed September 15, 1955, the deposition of lead dioxide at selected portions of the metal base can be controlled.
- the metal screen should be substantially free of oxide film which will hinder the anodic plating of the lead dioxide thereon. Any such oxide film may readily -be removed by chemical or mechanical means well known in the artand as dictated by the nature of the metal member.
- a cathode is also provided.
- the cathode material may be selected from a Wide variety of conducting materials, including lead itself, carbon, and the like.
- thecathode is a. material non-reactive with the bath during shutdown, such as carbon.
- lead dioxide begins to deposit at the anode, and the flow of current may be continued until the desired deposit has been built up.
- the lead dioxide is deposited in a relatively massive layer, that is, in layers of at least thick and upwards of 1" thick or more.
- the lead dioxide will make up the preponderant portion in terms of volume and weight, and the interstices of the screen are completely filled in and the lead dioxide has the appearance of being a solid, continuous plate or block.
- the metal base may be removed before using the electrode in the contemplated electrochemical procedure to provide an electrode material consisting entirely of lead dioxide.
- Chemical dissolving means may be employed.
- the metal base may be dissolved out in a pre-electrolysis using a sodium chlorate or other suitable electrolyte.
- any of the various baths removes lead therefrom.
- the bath may be replenished periodically or continuously.
- PbO lead dioxide
- some nitric acid is also lost during operation of the bath so that it may be also necessary to add further nitric acid as the bath is replenished in order to maintain the desired pH.
- the resulting product may thus be used as electrode in electrochemical procedures in accordance with technique conventional therein.
- One of the principal uses of the present electrode is as anode in'the electrolytic oxidation of chlorate to perchlorate.
- the product may also be used as anode in the electrolytic oxidation of chromic sulfate to chromic acid and of sulfate to persulfate and in the electrolysis of sodium chloride to sodium per-'
- the metal base is of a type which will' chlorate. become dissolved during the contemplated electrochemical reaction and it is not removed before use, means may be provided to eliminate the possible contamination of the electrolyte by the dissolved metal where such contamination would be undesirable.
- a chlorate cell may be operated under slightly alkaline or neutral conditions when the metal body is nickel or iron. As the metal dissolves it in part precipitates as the hydroxide and in part plates at the cathode.
- precipitate can be removed leaving the final solution free of contamination by the metal.
- the final electrolyte can be treated, as by making it alkaline, to precipitate the metal which can then be removed.
- An acid lead nitrate bath is prepared by dissolving leadoxide (PbO) in sufficient aqueous nitric acid to provide a concentration of lead nitrate of 350 grams per liter and a pH of l-2.2.
- PbO leadoxide
- a 14 mesh tantalum screen of 0.025 Wire and having dimensions of 3 x 18" is immersed in the bath to a depth of 14%.
- the screen is attached as anode to a suitable source of current.
- a carbon rod is also immersed in the bath and attached as cathode to the same source of current.
- Plastic shields are immersed in the bath at the edges of the screen and at the bottom thereof to prevent serious treeing of lead dioxide at these points.
- Suitable shielding means form the subject matter of copending application Serial No. 534,618, filed September 15, 1955.
- the bath is heated to 70 C., and the circuit is completed.
- the anode current density is 15 amperes per square foot.
- the lead dioxide deposit After 143 hours of plating, the lead dioxide deposit has a thickness of /8, and weighs 4,900 grams.
- a sprayed copper over silver current contact is formed on the, top 3" of the electrode prepared as described above.
- This copper over silver current contact is disclosed and claimed in copending application Serial No. 534,617, filed September 15, 1955, now U. S. Patent No. 2,824,027.
- the electrode is then operated as anode in the electrolysis of a 600 gram per liter sodium chlorate solution.
- the cell operated for 860 hours at 100 amperes without any noticeable erosion of the lead dioxide anode.
- Example II In this example the bath employed in Example I is also used. A 16 mesh nickel screen of 0.012" Wire and a width of 3" and a length of 20" is immersed in the bath to a depth of The screen is attached as anode to a suitable source of current. Carbon cathodes are also employed, and attached to the same source of current. The anode current density is amperes per square foot.
- a hard, dense lead dioxide deposit is plated onv the nickel screen. After 138 hours of platingthe lead dioxide has a thickness of /s" and weighs 6,900 grams.
- Example III talum gauze. After 117 hours of plating, the lead dioxide deposit is /4" thick and weighs 788 grams.
- a current contact is formed on the top 2" of this electrode by casting a block of Woods metal alloy about this portion of the electrode.
- Anode current density 10 amperes per square decimeter.
- Example IV In this example the bath employed in Example I is used. A 14 mesh steel screen of 0.020" wire and a width of 3 and a length of 18" is immersed in the bath to a depth of 14". The screen is attached as anode to a suitable source of current. Carbon cathodes are also employed, and attached to the same source of current. The anode current density is 20 amperes per square foot.
- Plastic shield of the type disclosed and claimed in said copending application Serial No. 534,618 are immersed in the bath at the. edges of the screen and at the bottom to prevent serious treeing of lead dioxide at these points.
- a hard, dense deposit of lead dioxide is formed on the steel screen. After 113 hours of plating, the lead dioxide deposit is /s" thick and Weighs 4,715 grams.
- An electrode for electrochemical processes comprising a metal screen presenting a large surface area relative to its volume having a coating of lead dioxide electrodeposited thereon, said electrodeposited lead dioxide completely filling the interstices of said screen.
- the electrode of claim 1 wherein the metal screen has a surface area to volume ratio of at least about 50 square units per cubic unit.
- An electrode for electrochemical processes comprising a metal screen presenting a large surface area relative to its mass having a coating of at least & thick of lead dioxide electrodeposited thereon, said electrodeposited lead dioxide completely filling the interstices of said screen.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US552968A US2872405A (en) | 1955-12-14 | 1955-12-14 | Lead dioxide electrode |
GB37937/56A GB850380A (en) | 1955-12-14 | 1956-12-12 | Improvements in lead dioxide-coated electrodes |
GB37935/56A GB850379A (en) | 1955-12-14 | 1956-12-12 | Improvements in lead dioxide electrodes |
FR1168150D FR1168150A (fr) | 1955-12-14 | 1956-12-13 | Perfectionnements apportés aux électrodes contenant du bioxyde de plomb |
FR1168152D FR1168152A (fr) | 1955-12-14 | 1956-12-13 | Perfectionnements aux électrodes contenant du bioxyde de plomb |
DEP17606A DE1094245B (de) | 1955-12-14 | 1956-12-14 | Bleidioxyd-Elektrode zur Verwendung bei elektrochemischen Verfahren |
DEP17604A DE1105854B (de) | 1955-12-14 | 1956-12-14 | Bleidioxyd-Elektrode fuer elektrolytische Verfahren |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US552968A US2872405A (en) | 1955-12-14 | 1955-12-14 | Lead dioxide electrode |
Publications (1)
Publication Number | Publication Date |
---|---|
US2872405A true US2872405A (en) | 1959-02-03 |
Family
ID=24207574
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US552968A Expired - Lifetime US2872405A (en) | 1955-12-14 | 1955-12-14 | Lead dioxide electrode |
Country Status (4)
Country | Link |
---|---|
US (1) | US2872405A (de) |
DE (2) | DE1105854B (de) |
FR (2) | FR1168152A (de) |
GB (2) | GB850379A (de) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2945791A (en) * | 1958-03-05 | 1960-07-19 | Jr Fred D Gibson | Inert lead dioxide anode and process of production |
US3058895A (en) * | 1958-11-10 | 1962-10-16 | Anocut Eng Co | Electrolytic shaping |
US3087870A (en) * | 1959-06-22 | 1963-04-30 | Union Carbide Corp | Process for plating adherent lead dioxide |
US3109790A (en) * | 1960-07-27 | 1963-11-05 | Hooker Chemical Corp | Method of preparing phosphine |
US3213004A (en) * | 1961-03-08 | 1965-10-19 | American Potash & Chem Corp | Surface preparation of platinum group metals for electrodeposition |
US3250691A (en) * | 1962-05-28 | 1966-05-10 | Pittsburgh Plate Glass Co | Electrolytic process of decomposing an alkali metal chloride |
US3267009A (en) * | 1962-10-08 | 1966-08-16 | Engelhard Ind Inc | Electrodeposition of platinum containing minor amounts of bismuth |
US3282807A (en) * | 1962-03-30 | 1966-11-01 | Burnham John | Process for purifying electrode surfaces |
US3318794A (en) * | 1962-02-08 | 1967-05-09 | Isomura Sangyo Kaisha Ltd | Method of manufacturing lead dioxide electrode |
US3463707A (en) * | 1965-06-16 | 1969-08-26 | Pacific Eng & Production Co | Electrodeposition of lead dioxide |
US3493478A (en) * | 1966-12-02 | 1970-02-03 | Handady V K Udupa | Electrolytic preparation of perchlorates |
US4008144A (en) * | 1974-08-22 | 1977-02-15 | Agency Of Industrial Science & Technology | Method for manufacturing of electrode having porous ceramic substrate coated with electrodeposited lead dioxide and the electrode manufactured by said method |
US4013538A (en) * | 1971-12-22 | 1977-03-22 | General Electric Company | Deep submersible power electrode assembly for ground conduction of electricity |
US4026786A (en) * | 1975-07-31 | 1977-05-31 | The United States Of America As Represented By The Secretary Of The Interior | Preparation of PbO2 anode |
US4136235A (en) * | 1977-01-21 | 1979-01-23 | Diamond Shamrock Technologies S.A. | Secondary batteries |
US4173497A (en) * | 1977-08-26 | 1979-11-06 | Ametek, Inc. | Amorphous lead dioxide photovoltaic generator |
US4236978A (en) * | 1980-02-08 | 1980-12-02 | Rsr Corporation | Stable lead dioxide anode and method for production |
US4278522A (en) * | 1978-08-23 | 1981-07-14 | Bbc Brown Boveri & Company Limited | Apparatus for treating contaminated water |
US4415411A (en) * | 1980-03-04 | 1983-11-15 | The Japan Carlit Co., Ltd. | Anode coated with β-lead dioxide and method of producing same |
Citations (6)
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GB190624806A (en) * | 1905-11-09 | 1907-02-07 | Paul Ferchland | Improvements in and connected with Electrodes for Electrolytic Purposes |
FR371245A (fr) * | 1905-11-09 | 1907-03-02 | Paul Ferchland | électrodes pour opérations électrolytiques et leur fabrication |
US900502A (en) * | 1906-11-05 | 1908-10-06 | Paul Ferchland | Electrode for electrolytic purposes. |
US1423071A (en) * | 1921-09-17 | 1922-07-18 | Hidro Metalurgica Soc | Process for manufacturing electrodes |
US1706951A (en) * | 1924-06-28 | 1929-03-26 | Nat Carbon Co Inc | Electrolytic apparatus |
US2492206A (en) * | 1943-01-19 | 1949-12-27 | Joseph C White | Lead perchloric acid primary cell |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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DE140317C (de) * | ||||
DE117129C (de) * | 1899-04-20 | 1901-01-17 | Boehringer & Soehne Gmbh | Verfahren zur Aktivirung von elektrolytisch gewonnenem Sauerstoff |
DE325154C (de) * | 1919-09-22 | 1920-09-08 | Hans Bardt | Verfahren zur Herstellung von Bleisuperoxyd- oder Mangansuperoxydelektroden |
AT95048B (de) * | 1922-02-20 | 1923-11-26 | Siegwart Johann Benetter | Elektrode für elektrische Sammler. |
CH100171A (de) * | 1922-06-12 | 1923-07-16 | Chem Fab Weissenstein Ges M B | Anode zur Herstellung von Perverbindungen. |
NL88097C (de) * | 1951-12-31 |
-
1955
- 1955-12-14 US US552968A patent/US2872405A/en not_active Expired - Lifetime
-
1956
- 1956-12-12 GB GB37935/56A patent/GB850379A/en not_active Expired
- 1956-12-12 GB GB37937/56A patent/GB850380A/en not_active Expired
- 1956-12-13 FR FR1168152D patent/FR1168152A/fr not_active Expired
- 1956-12-13 FR FR1168150D patent/FR1168150A/fr not_active Expired
- 1956-12-14 DE DEP17604A patent/DE1105854B/de active Pending
- 1956-12-14 DE DEP17606A patent/DE1094245B/de active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB190624806A (en) * | 1905-11-09 | 1907-02-07 | Paul Ferchland | Improvements in and connected with Electrodes for Electrolytic Purposes |
FR371245A (fr) * | 1905-11-09 | 1907-03-02 | Paul Ferchland | électrodes pour opérations électrolytiques et leur fabrication |
US900502A (en) * | 1906-11-05 | 1908-10-06 | Paul Ferchland | Electrode for electrolytic purposes. |
US1423071A (en) * | 1921-09-17 | 1922-07-18 | Hidro Metalurgica Soc | Process for manufacturing electrodes |
US1706951A (en) * | 1924-06-28 | 1929-03-26 | Nat Carbon Co Inc | Electrolytic apparatus |
US2492206A (en) * | 1943-01-19 | 1949-12-27 | Joseph C White | Lead perchloric acid primary cell |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2945791A (en) * | 1958-03-05 | 1960-07-19 | Jr Fred D Gibson | Inert lead dioxide anode and process of production |
US3058895A (en) * | 1958-11-10 | 1962-10-16 | Anocut Eng Co | Electrolytic shaping |
US3087870A (en) * | 1959-06-22 | 1963-04-30 | Union Carbide Corp | Process for plating adherent lead dioxide |
US3109790A (en) * | 1960-07-27 | 1963-11-05 | Hooker Chemical Corp | Method of preparing phosphine |
US3213004A (en) * | 1961-03-08 | 1965-10-19 | American Potash & Chem Corp | Surface preparation of platinum group metals for electrodeposition |
US3318794A (en) * | 1962-02-08 | 1967-05-09 | Isomura Sangyo Kaisha Ltd | Method of manufacturing lead dioxide electrode |
US3282807A (en) * | 1962-03-30 | 1966-11-01 | Burnham John | Process for purifying electrode surfaces |
US3250691A (en) * | 1962-05-28 | 1966-05-10 | Pittsburgh Plate Glass Co | Electrolytic process of decomposing an alkali metal chloride |
US3267009A (en) * | 1962-10-08 | 1966-08-16 | Engelhard Ind Inc | Electrodeposition of platinum containing minor amounts of bismuth |
US3463707A (en) * | 1965-06-16 | 1969-08-26 | Pacific Eng & Production Co | Electrodeposition of lead dioxide |
US3493478A (en) * | 1966-12-02 | 1970-02-03 | Handady V K Udupa | Electrolytic preparation of perchlorates |
US4013538A (en) * | 1971-12-22 | 1977-03-22 | General Electric Company | Deep submersible power electrode assembly for ground conduction of electricity |
US4008144A (en) * | 1974-08-22 | 1977-02-15 | Agency Of Industrial Science & Technology | Method for manufacturing of electrode having porous ceramic substrate coated with electrodeposited lead dioxide and the electrode manufactured by said method |
US4026786A (en) * | 1975-07-31 | 1977-05-31 | The United States Of America As Represented By The Secretary Of The Interior | Preparation of PbO2 anode |
US4136235A (en) * | 1977-01-21 | 1979-01-23 | Diamond Shamrock Technologies S.A. | Secondary batteries |
US4173497A (en) * | 1977-08-26 | 1979-11-06 | Ametek, Inc. | Amorphous lead dioxide photovoltaic generator |
US4278522A (en) * | 1978-08-23 | 1981-07-14 | Bbc Brown Boveri & Company Limited | Apparatus for treating contaminated water |
US4236978A (en) * | 1980-02-08 | 1980-12-02 | Rsr Corporation | Stable lead dioxide anode and method for production |
US4415411A (en) * | 1980-03-04 | 1983-11-15 | The Japan Carlit Co., Ltd. | Anode coated with β-lead dioxide and method of producing same |
Also Published As
Publication number | Publication date |
---|---|
DE1094245B (de) | 1960-12-08 |
GB850379A (en) | 1960-10-05 |
GB850380A (en) | 1960-10-05 |
FR1168150A (fr) | 1958-12-04 |
DE1105854B (de) | 1961-05-04 |
FR1168152A (fr) | 1958-12-04 |
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