AU2011221387B2

AU2011221387B2 - Pd-containing coating for low chlorine overvoltage

Info

Publication number: AU2011221387B2
Application number: AU2011221387A
Authority: AU
Inventors: Dino F. Difranco; Kenneth L. Hardee
Original assignee: Eltech Systems Corp
Current assignee: Eltech Systems Corp
Priority date: 2004-09-01
Filing date: 2011-09-07
Publication date: 2012-04-19
Anticipated expiration: 2024-09-01
Also published as: AU2011221387A1

Abstract

The present invention relates to an electrocatalytic coating and an electrode having the coating thereon, wherein the coating is a mixed metal oxide coating, preferably 5 platinum group metal oxides with or without valve metal oxides, and containing a transition metal component such as palladium, rhodium or cobalt. The electrocatalytic coating can be used especially as an anode component of an electrolysis cell for the electrolysis of a halogencontaining solution wherein the palladium component reduces the operating potential of the anode and eliminates the 10 necessity of a "break-in" period to obtain the lowest anode potential. 07/09/11. va 19447 abstract, 2

Description

AUSTRALIA Patents Act 1990 ORIGINAL COMPLETE SPECIFICATION INVENTION TITLE: PD-CONTAINIG COATING FOR LOW CHLORINE OVERVOLTAGE The following statement is a full description of this invention, including the best method of performing it known to us:- 2 PD-CONTAINING COATING FOR LOW CHLORINE OVERVOLTAGE BACKGROUND OF THE INVENTION The present application is a divisional application of Australian Patent 5 Application No. 2004323018, the disclosures of which are herein incorporated by reference. Field of the Invention The invention is directed to an electrode and an electrocatalytic coating thereon for use in aqueous halogen-containing solutions which provides a lower 10 start-up and overall operating voltage. Description Electrodes for use in electrolytic processes have been known which have a base or core metal bearing a layer or coating of metal oxides. The core meta of the electrode may be a valve metal such as titanium, tantalum, zirconium, niobium or 15 tungsten. Where the coating is an oxide mixture, an oxide of the core or substrate can contribute to the mixture. Such mixture can include an oxide of the substrate metal plus at least one oxide of a metal such as platinum, iridium, rhodium, palladium, ruthenium and osmium. Such electrodes are known in the art and generally referred to as "dimensionally stable". 20 An inherent drawback of these coatings in a chlorine/chlorate production environment, however, is the detrimental effect on chlorine evolution potential, leading to a higher operating potential and the necessity for a voltage "break-in" period during which the anode operates at a higher potential for up to several months. Attempts to overcome the disadvantage associated with chlorine evolution 25 potential have been addressed in U.S. Patent 4,233,340 in which there is provided an insoluble electrode having a coating containing a baked slurry of palladium oxide containing a platinum compound which can be thermally decomposed to form platinum metal. The coating contains 99 to 5 mol% palladium oxide and I to 95 mol% platinum metal. In U.S. Patent 4,443,317 there is taught an electrode for 30 electrolysis having a coating consisting of 40 to 90 mol% palladium oxide, 0.1 to 20 mol% platinum and 5 to 50 mol% (RUTiN)) 2 07/09/1 1,va 19447 speci.2 3 Therefore, it would be advantageous to provide an electrode having a coating thereon which would eliminate the necessity for a voltage "break-in" period and provide an overall lower operating potential. It would be further desirable for such an electrode and coating to prevent or eliminate an escalation in voltage following 5 postbaking of the coating. SUMMARY OF THE INVENTION There has now been found an electrode having an electrocatalytic coating thereon which provides a reduction in the operating potential of the electrode in 10 electrochemical cells for the oxidation of chloride to chlorine. The coating further allows for the elimination of the voltage "break-in" period necessary to obtain the lowest anode potential, and elimination of the anode potential escalation observed after postbake/creep steps. 15 In one aspect, the present invention provides a method for the production of an electrode for use in the electrolysis of a halogen-containing solution whereby said electrode provides reduced operating potential during said electrolysis, the method including the steps of: a) providing a valve metal substrate having an intermediate 20 electrocatalytic coating layer thereon; b) coating said valve metal substrate with a topcoating layer of a mixture including at least one transition metal oxide selected from the group including: palladium, rhodium or cobalt oxides, said mixture providing from 0.1 mole % up to 10 mole % of the total transition metal oxide content of the coating. 25 DESCRIPTION OF EMBODIMENTS OF THE INVENTION According to the present invention, an electrode encompassing an electrocatalytic coating having a lower operating potential and elimination of a voltage "break-in" period is provided. The electrode of the invention is particularly useful in the electrolytic production of chlorine and alkali metal hydroxides in 30 membrane cells, the electrolytic production of chlorates and hypochlorites. 07/09/1 ,va 19447 speci,3 4 The electrode used in the present invention comprises an electrocatalytically active film on a conductive substrate. The metals for the electrode are broadly contemplated to be any coatable metal. For the particular application of an electrocatalytic coating, the metal might be such as nickel or manganese, but will 5 most often be a "film-forming" metal. By "film 07/09/1Iva 19447 speci,4 5 forming metal" it is meant a metal or alloy which has the property that when connected as an anode in the electrolyte in which the coated anode is subsequently to operate, there rapidly forms a passivating oxide film which protects the underlying metal from corrosion by electrolyte, i.e., those metals 5 and alloys which are frequently referred to as "valve metals". Such valve metals include titanium, tantalum, zirconium, niobium, tungsten and silicon, and alloys containing one or more of these metals, as well as metal alloys and intermetallic mixtures, ceramics and cermets containing valve metal, (e.g., Ti Ni, Ti-Co, Ti-Fe and Ti-Cu). More specifically, grade 5 titanium may include 10 up to 6.75 weight percent aluminum and 4.5 weight percent vanadium, grade 6 up to 6 percent aluminum and 3 percent tin, grade 7 up to 0.25 weight percent palladium, grade 10 from 10 to 13 weight percent plus 4.5 to 7.5 weight percent zirconium, and.so on. Of particular interest for its ruggedness, corrosion resistance and availability is titanium. 15 By use of elemental metals, it is most particularly meant the metals in their normally available condition, i.e., having minor amounts of impurities. Thus, for the metal of particular interest, i.e., titanium, various grades of the metal are available including those in which other constituents may be alloys 20 or alloy plus impurities. Grades of titanium have been more specifically set forth in the standard specifications for titanium detailed in ASTM B 265-79. Plates, rods, tubes, wires or knitted wires and expanded meshes of titanium or other film-forming metals can be used as the electrode base. 25 Titanium or other film-forming metal clad on a conducting core can also be used. Regardless of the metal selected and the form of the anode base member, the surface of such substrate member advantageously is a cleaned 30 surface. This may be obtained by any of the known treatments to achieve a clean metal surface, including mechanical cleaning. The usual cleaning procedures of degreasing, either chemical or electrolytic, or other chemical cleaning operation may also be used to advantage. Where the base 6 preparation includes annealing, and the metal is grade 1 titanium, the titanium can be annealed at a temperature of at least about 450 0 C for a time of at least about 15 minutes, but most often a more elevated annealing temperature, e.g., 6000C to 8750C is advantageous. 5 When a cleaned surface, or prepared and cleaned surface has been obtained, and particularly for applying the necessary multiple coating layers which will be on the valve metal base, the base surface may be further treated to enhance adhesion such as of the electrocatalytic coating layers to the valve 10 metal. This will be achieved by means which include intergranular etching of the substrate metal, sharp grit blasting of the metal surface, peening, abrading, plasma spraying or combinations thereof, followed by optional surface treatment to remove embedded grit. 15 To prepare a metal such as titanium for etching, it can be most useful to condition the metal, as by annealing, to diffuse impurities to the grain boundaries. Thus, by way of example, proper annealing of grade 1 titanium will enhance the concentration of the iron impurity at grain boundaries. Also for the aspect of etching, it can be desirable to combine a metal surface 20 having a correct grain boundary metallurgy with an advantageous grain size. Again, referring to titanium as exemplary, at least a substantial amount of the grains having grain size number within a range of from about 3 to about 7 is advantageous. Grain size number as referred to herein is in accordance with the designation. provided in ASTM E 112-84. A serviceable metal substrate of 25 this condition has been disclosed in U.S. Patent 5,167,788. A suitably roughened metal surface can be obtained by special grit blasting with sharp grit, optionally followed by removal of surface embedded grit. The grit, which will usually contain angular particles, will cut the metal 30 surface as opposed to peening the surface. Serviceable grit for such purpose can include sand, aluminum oxide, steel and silicon carbide 7 Etching, or other treatment such as water blasting, following grit blasting can be used to remove embedded grit and/or clean the surface. Etching will be with a sufficiently active etch solution, typically an acid solution, to develop a surface roughness and/or surface morphology, 5 including possible aggressive grain boundary attack. These can be provided by hydrochloric, sulfuric, perchloric, nitric, oxalic, tartaric, and phosphoric acids as well as mixtures thereof, e.g., aqua regia. Other etchants that may be utilized include caustic etchants such as a solution of potassium hydroxide with potassium nitrate. Following etching, the etched metal surface can then 10 be subjected to rinsing and drying steps. The electrode having the electrocatalytic coating described herein will virtually always find service as an anode. Thus, the word "anode" is often used herein when referring to the electrode, but this is simply for convenience 15 and should not be construed as limiting the invention. In plasma spraying for a suitably roughened metal surface, the material will be applied in particulate form such as droplets of molten metal. In this plasma spraying, such as it would apply to spraying of a metal, the metal is 20 melted and sprayed in a plasma stream generated by heating with an electric arc to high temperatures in inert gas, such as argon or nitrogen, optionally containing a minor amount of hydrogen. It is to be understood by the use herein of the term plasma spraying" that although plasma spraying is preferred the term is meant to include generally thermal spraying such as 25 magnetohydrodynamic spraying, flame spraying and arc spraying, so that the spraying may simply be referred to as "melt spraying" or "thermal spraying". The particulate material employed may be a valve metal or oxides thereof, e.g., titanium oxide, tantalum oxide and niobium oxide. It is also 30 contemplated to melt spray titanates, spinels, magnetite, tin oxide, lead oxide, manganese oxide and perovskites. It is also contemplated that the oxide being sprayed can be doped with various additives Including dopants in ion form such as of niobium or tin or Indium.

8 It is also contemplated that such plasma spray application may be used in combination with etching of the substrate metal surface. Or the electrode base may be first prepared by grit blasting, as discussed hereinabove, which 5 may or may not be followed by etching. It will be understood from the foregoing that the surface may then proceed through various operations, providing a pretreatment before coating, e.g., the above-described plasma spraying of a valve metal oxide coating. 10 Other pretreatments may also be useful. For example, it is contemplated that the surface be subjected to a hydriding or nitriding treatment. Prior to coating with an electrochemically active material, it has been proposed to provide an oxide layer by heating the substrate in air or by anodic oxidation of the substrate as described in U.S. Patent 3,234,110. Various proposals have 15 also been made in which an outer layer of electrochemically active material is deposited on a sublayer, which primarily serves as a protective and conductive intermediate. Various tin oxide based underlayers are disclosed in U.S. Patent Nos. 4,272,354, 3,882,002 and 3,950,240. It is also contemplated that the surface may be prepared as with an antipassivation 20 layer. Following surface preparation, which might include providing a pretreatment layer such as described above, an electrochemically active coating layer can be applied to the substrate member. As is typically 25 representative of the electrochemically active coatings that are often applied, are those provided from active oxide coatings such as platinum group metal oxides, magnetite, ferrite, cobalt spinel or mixed metal oxide coatings. They may be water based, such as aqueous solutions, or solvent based, e.g., using alcohol solvent. However, it has been found that for the electrode of the 30 present invention, an important aspect of the preferred coating composition solutions are those containing a transition metal oxide comprising one or more of palladium, rhodium or cobalt, with palladium being preferred. The coating compositions will contain PdCl 2 , RhCI 3 or CoC1 2 and hydrochloric acid or in 9 alcohol solution. The metal salts can be utilized in a form such as PdCl 2 xH 2 0, RhCI 3 xH 2 0, and COC12 xH 2 0. For convenience, such forms will generally be referred to herein simply as PdCl 2 , RhCl 3 or CoCl 3 . Generally, the metal chloride will be dissolved in an alcohol such as either Isopropanol or 5 butanol, all combined with or with out small additions of hydrochloric acid, with n-butanol being preferred. In each embodiment of the present invention, as described further hereinbelow, the coating compositions will contain the transition metal 10 constituent in an amount from about 0.1 mole % up to about 10 mole %, basis 100 mole % of the total platinum group metal oxide content of the coating, with a preferred range being from about 0.4 mole % up to about 6 mole %. It will be understood that the constituents are substantially present as their oxides, and the reference to the metals is for convenience, particularly when 15 referring to proportions. It was unexpected that the use of such small amounts of the transition metal constituent in the coating compositions of the present invention would provide a reduction in the operating potential for electrolysis of halogen 20 containing solutions of from about 10 millivolts (mV) up to about 100 mV, depending on the potential value of the coating without the transition metal constituent. Previous coatings, as described hereinabove, have utilized large amounts of palladium oxide of upwards of 40% or more or In combination with other metals. Thus, it was not expected to achieve a desirable coating 25 composition as disclosed in the present invention with a more simplistic coating composition as described. In a first embodiment of the present invention, as is described in PCT Patent Appin. Ser. No PCT/USO4/14357, which is fully incorporated by 30 reference herein, the coating composition will contain, in addition to the Pd constituent as described hereinabove, an element of ruthenium oxide in combination with titanium oxide and antimony or tin oxides. It is contemplated that the coating composition may optionally contain iridium oxide. The coating 10 compositions of the first embodiment, then, are those comprised of RuC 3 , TiC1 3 , SbCI 3 , and hydrochloric acid, all in aqueous solution. It has been found that, for the electrochemically active coating of the first embodiment, it is preferred that the coating formulation is prepared using a water base, as 5 opposed to an alcohol base. The coating composition of the first embodiment will contain sufficient ruthenium constituent to provide at least about 10 mole percent up to about 30 mole percent, and preferably from about 15 mole percent up to about 25 10 mole percent, basis 100 mole percent of the metal content of the coating. It will be understood that the constituents are substantially present as their oxides, and the reference to the metals is for convenience, particularly when referring to proportions. 15 A valve metal component will be included in the coating composition of the first embodiment. Various valve metals can be utilized including titanium, tantalum, niobium, zirconium, hafnium, vanadium, molybdenum, and tungsten, with titanium being preferred. Salts of the dissolved metal are utilized, and suitable inorganic substituents can include chlorides, iodides, 20 bromides, sulfates, borates, carbonates, acetates, and citrates, e.g., TiCl or, TiCl 4 , in acid solutions. Such coating composition will contain sufficient Ti constituent to provide at least about 50 mole percent up to about 85 mole percent and preferably from about 60 mole percent up to about 75 mole percent, basis 100 mole percent of the metal content of the coating. 25 Where the coating composition of the first embodiment will contain iridium oxide, suitable precursor substituents can include IrCI 3 or H 2 IrCI 6 . The iridium oxide will be present in an amount from about 1% mole percent up to about 25 mole percent, basis 100 mole percent of the metal content of the 30 coating. A preferred first embodiment coating composition will contain antimony oxide. Suitable precursor substituents can include SbCI 3 , SbCls, or other 11 inorganic antimony salts. The antimony oxide will generally be present in an amount from about 5 mole percent up to about 20 mole percent and preferably from about 10 mole percent up to about 15 mole percent, basis 100 mole percent of the metal content of the coating. 5. As mentioned hereinbefore, it is also contemplated that the first embodiment electrocatalytic coating can contain a tin oxide in place of or in addition to antimony oxide. Where tin oxide is the desired constituent, suitable precursor substituents can include SnCl 2 , SnSO4, or other inorganic 10 tin salts. Where tin oxide is utilized, it will generally be present in an amount from about 2 mole percent up to about 20 mole percent and preferably from about 3 mole percent up to about 15 mole percent, basis 100 mole percent of the metal content of the coating. 15 In the coating composition of the first embodiment, the ratio of ruthenium to antimony or tin will generally be from about 2:1 to about 0.1:1, and preferably about 1.5:1, with the ratio of titanium to antimony or tin being from about 19:1 to 1:1, and preferably about 5.7:1. Where the optional Iridium component is utilized, the ratio of ruthenium to iridium will generally be from 20 about 1:1 to about 99:1. In a second embodiment of the present invention, as is described in U.S. Pat. Appin. Ser No. 10/395939, which is fully incorporated herein by reference, the preferred coating composition solutions are typically those 25 consisting of RuCI 3 and IrC1l and hydrochloric acid, all in alcohol solution, with or without the presence of a valve metal component. It is also contemplated to utilize chloriridic acid, H 2 1rCI 6 . It will be understood that the RuCI 3 may be utilized in a form such as RuC1 3 xH 2 0 and lrC1 3 xH 2 0 can be similarly utilized. For convenience, such forms will generally be referred to herein simply as 30 RuCI 3 and IrCl3. Generally, the ruthenium chloride will be dissolved along with the iridium chloride in an alcohol such as either isopropanol or butanol, all combined with or with out small additions of hydrochloric acid, with n-butanol being preferred.

12 Such second embodiment coating composition will contain sufficient ruthenium constituent to provide at least about 5 mole percent, up to about 50 mole percent of ruthenium metal, basis 100 mole percent of the metal content 5 of the coating, with a preferred range being from about 15 mole percent to up to about 35 mole percent of ruthenium. It will be understood that the constituents are substantially present as their oxides, and the reference to the metals is for convenience, particularly when referring to proportions. 10 The coating composition of the second embodiment will contain sufficient Ir constituent to provide at least about 50 mole percent up to about 95 mole percent iridium metal, basis 100 mole percent of iridium and ruthenium metals, with a preferred range being from about 50 mole percent up to about 75 mole percent iridium. For best coating characteristics, then, 15 the molar ratio of Ru:lr will be from about 1:1 to about 1:4 with a preferred ratio being about 1:1.6. A valve metal component may optionally be included in the second embodiment coating composition in order to further stabilize the coating 20 and/or alter the anode efficiency As set forth hereinabove with reference to the invention first embodiment, various valve metals can be utilized including titanium, tantalum, niobium, zirconium, hafnium, vanadium, molybdenum, and tungsten. The valve metal component can be formed from a valve metal alchoxide in an alcohol solvent, with or without the presence of an acid. Such 25 valve metal alchoxides which are contemplated for use in the present invention include methoxides, ethoxides, isopropoxides and butoxides. For example, titanium ethoxide, titanium propoxide, titanium butoxide, tantalum ethoxide, tantalum isopropoxide or tantalum butoxide may be useful. 30 When the valve metal component is present in the second embodiment composition, the coating will contain from about 0.1 mole percent up to not greater than 25 mole percent basis 100 mole percent of the metal content of 13 the coating, with the preferred composition containing from about 5 mole percent up to about 15 mole percent. In a third embodiment, as is described in U.S. Patent 5,230,780, which 5 is fully incorporated herein by reference, the coating composition will consist of, in addition to the transition metal constituent, a solution of iridium, ruthenium, and titanium oxides. Usually, each precursor constituent will be a metal salt that most often is a halide salt and preferably for economy coupled efficiency of solution preparation such will all be the chloride salt. However, 10 other useful salts include iodides, bromides and ammonium chloro salts such as ammonium hexachloro iridate or ruthenate. The coating composition applied to the metal substrate will be aqueous, which will most always be simply water without any blending with further liquid. Preferably, deionized or distilled water is used to avoid inorganic impurities. 15 In the individual or combination solutions of the third embodiment, in addition to the suitable precursor substituent, most always with only one exception no further solution ingredients will be present. Such exception will virtually always be the presence of inorganic acid. For example, a solution of 20 iridium trichloride can further contain strong acid, most always hydrochloric acid, which will usually be present in an amount to supply about 5 to about 20 weight percent acid. Typically, the individual or combination solutions will have a pH of less than 1, such as within, the range of from about 0.2 to about 0.8. 25 The coating composition, then, of the third embodiment, will contain at least about 15, but less than 25 mole percent of the iridium constituent, from about 35 to about 50 mole percent of the ruthenium constituent, and at least about 30, but less than 45 mole percent of the titanium constituent, basis 100 30 mole percent of these constituents. For best coating characteristics, the molar ratio of ruthenium oxide to Iridium oxide in the resulting coating will be from greater than about 1.5:1 up to about 3:1.The resulting coating will 14 furthermore have a molar ratio of titanium oxide to the total of the oxides of iridium plus ruthenium of less than about 1:1, but most always above 0.5:1. In a fourth embodiment of the present invention, the preferred coating 5 compositions are those containing ruthenium, iridium and titanium oxides. As described hereinabove, suitable precursor constituents will include RuC1 3 , 1r03, and ortho butyl titanate, in alcohol solution. The coating composition, then, of the fourth embodiment, will contain from about 2 to about 20 mole percent of the iridium constituent, from about 10 to about 30 mole percent of 10 the ruthenium constituent, and from about 50 to about 85 mole percent of the titanium constituent, basis 100 mole percent of these constituents in the coating. In each of the foregoing embodiments, there has been described a 15 coating composition containing the transition metal oxide in combination with a mixed metal oxide coating as the electrochemically active coating layer. In a fifth embodiment of the present invention, it is contemplated that a topcoating layer of a transition metal comprising one or more of palladium, rhodium or cobalt, with palladium being preferred, can be applied over an 20 intermediate layer of an electrochemically active coating layer. The topcoating layer can be formed from a dilute solution of the transition metal in alcohol or water, with or without the presence of acid. Generally, the transition metal component will be present in an amount from about 0.2 to about 10 g/l of metal. The preferred topcoating layer will be formed from 25 PdC 2 in hydrochloric acid. Any of the foregoing coating compositions can be applied to the metal substrate by any of those means typically utilized for applying a liquid coating composition to a metal substrate. Such methods of application include dip 30 spin and dip drain techniques, brush application, roller coating and spray application such as electrostatic spray. Moreover, spray application and combination techniques, e.g., dip drain with spray application can be utilized. Spray application can be either conventional compressed gas or can be 15 electrostatic spray application. With the above-mentioned coating compositions for providing an electrochemically active coating, a roller coating operation can be most serviceable. 5 Regardless of the method of application of the coating, conventionally, a coating procedure is repeated to provide a uniform, more elevated coating weight than achieved by just one coating. However, the amount of coating applied will be sufficient to provide in the range of from about 0.1 g/m 2 (gram per square meter) total metals to about 20 g/m 2 , and preferably, from about 3 10 g/m 2 to about 12 g/m 2 . Following application of the coating, the applied composition will be heated to prepare the resulting mixed oxide coating by thermal decomposition of the precursors present in the coating composition. This prepares the mixed 15 oxide coating containing the mixed oxides in the molar proportions, basis the metals of the oxides, as above discussed. Such heating for the thermal decomposition will be conducted at a temperature of at least about 350*C for a time of at least about 3 minutes. More typically, the applied coating will be heated at a more elevated temperature of up to about 5500C for a time of not 20 more than about 20 minutes. Suitable conditions can include heating in air or oxygen. In general, the heating technique employed can be any of those that may be used for curing a coating on a metal substrate. Thus, oven coating, including conveyor ovens may be utilized. Moreover, infrared cure techniques can be useful. Following such heating, and before additional coating as 25 where an additional application of the coating composition will be applied, the heated and coated substrate will usually be permitted to cool to at least substantially ambient temperature. Particularly after all applications of the coating composition are completed, postbaking can be employed. Typical postbake conditions for coatings can include temperatures of from about 30 4000C up to about 5500C. Baking times may vary from about 10 minutes, up to as long as about 300 minutes.

16 As has been discussed hereinbefore, the coating of the present invention is particularly serviceable for an anode in an electrolytic process for the manufacture of chlorate and alkali metal hydroxides. However, it is also contemplated that these electrodes may find use in other processes, such as 5 the manufacture of chlorine and hypochlorites. EXAMPLE 1 Flat, titanium plates of unalloyed grade 1 titanium were etched in a 90 10 950C solution of 18-20% hydrochloric acid for 25 minutes to roughen the surfaces for coating application. 15 Table 1 Gn.umwa Aa n SEP @50 C 300gi Ia Sciulion SAert i Ir S, Sn TI Ta Pd Ri h O 0 Tep/Tnm siteTenpiThe akAmng 266kMrn 2ASkftg A t 25 13 13 428 4490C/36 d 4 90nie .195 1.140 &+ Vbte* 24.5 19.3 19.3 4?8 9.8 1.105n~~e 1.CI0rfr8a IM B~~~~M t~vzs 1. 2 .w 4153 1.135 B 1O.4 2 1 428 4M9C/36nhIdes 470C/90mnutes un 14 1.077 B. WAad ?AS19.3 428 . 4 1.1 1.0 114 C0 2a g 19 49 1.3 460490C/36nindMes 515C/12ninues 18 1 0 V1bt*O 14.415.7 a 480BDC/3u~mdes 52CI18Dmmks 1.30 1.93 1. M WmO14 S7 8 1.6 4C n 12C17 nue E M*wioI U. 10 1 .7 4W4/.1f~ 45/~fW 37 1.19 1.108 E+ 440d /33 10 1.7 n8 13n0 45C/1 inues F WitmftO 24.5 19. 19-3 428 1.131 1.13 1.1 F+ Witana 24.5 19.3 13 428 08 41.149C/36MIe " 1.08 1.0 G a a 39 9 49 464C36nidA 1.125 1.101 1.58 Go- BAn 29 M9 4a9 1.3 A14 1.079 1.071 H Want49 14.4 15.7 8 46 0C/36.Ies N'A1 196 H. Vfa1*O 144 15.7 8 1.6 . 1.03 1.075 1.067 S a 3 10 1.7 46.49C/36n es5 1.112 1.07 I. B.a-- 3 3 10 1.7 9.8 t&.45/Srfne tNVA 1.07 J2 Vlea1O25 1M.3 19.3 428 1.3 1 46490C/36nides .171 1.144 1.Cnu L+ WitO 24.5 19.3 19.3 428 1.3 460OC/36ninges OA 1.113 1.04 1.03 M+ WImM3n 24.5 1S3 1M3 428 1.3 1.120 1.09 1.07 Coating compositions as set forth in Table 1 were applied. Coating solutions were prepared by adding the metals listed (as chloride salts) to 20 either a butanol or a water/HCI solvent. After mixing to dissolve all of the salts, the solutions were applied to individual samples of prepared titanium plates. The coatings were applied in layers, with each coat being applied separately and allowed to dry at room temperature, followed by heating in air 17 to the listed curing conditions. After application of the final coat, some of the samples were further baked in air at the temperature/time conditions listed in the postbake column of the table. 5 Standard Electrode Potentials (vs. SCE) were measured at 50 degrees Celsius in a 300 gpl NaCl solution on the coated samples. Table 1 shows the measured values and shows that for all the coatings listed, the presence of palladium in the formulation lowers the SEP value with and without the presence of a postbake operation. 10 EXAMPLE 2 Three samples of production made coatings were obtained from storage. The composition of the coatings and substrate type are shown in 15 Table 2.

18 09 M Cc 0 ) a , ie 05 4) - 19 In order to remove any surface contamination, the coated substrates #1-3 were heated in an oven to 450-470'C for approximately 5 minutes. SEP measurements were then made on the samples and are shown in Table 2. It can be noted from the data that sample #1 was previously postbaked and as such had 5 elevated SEP values. A solution of 0.7 g/l Pd (as PdCl 2 ) in 18 Wt% HCI was prepared and one coat of this solution was applied to samples 1-3 to create samples 4-6. The coating was allowed to air dry and the samples were placed in an oven at 460-490'C for 3-6 10 minutes in order to cure the coat. After removal from the oven and a subsequent cooling period, SEP measurements were again made on the samples. The data in Table 2 shows that sample 4 no longer had an elevated SEP and this is attributable to the topcoat of palladium solution applied. 15 The three samples 4-6 were subsequently postbaked at 470'C for 90 minutes to create samples 7-9 and the SEP's were again recorded. The data in Table 2 shows that none of the SEP's increased after the postbaking operation and this is attributable to the topcoat of palladium solution applied. 20 While in accordance with the patent statutes the best mode and preferred embodiments have been set forth, the scope of the invention is not limited thereto, but rather by the scope of the attached claims. Throughout this specification and the claims which follow, unless the 25 context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. 30 The reference to any prior art in this specification is not and should not be taken as an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge. 07/09/I 1,va 19447 speci.19

Claims

1. A method for the production of an electrode for use in the electrolysis of a halogen-containing solution whereby said electrode provides reduced operating 5 potential during said electrolysis, the method including the steps of: c) providing a valve metal substrate having an intermediate electrocatalytic coating layer thereon; d) coating said valve metal substrate with a topcoating layer of a mixture including at least one transition metal oxide selected from the group including: 10 palladium, rhodium or cobalt oxides, said mixture providing from 0.1 mole % up to 10 mole % of the total transition metal oxide content of the coating.

2. A method according to claim 1, wherein said valve metal substrate is one or more of a valve metal mesh, sheet, blade, tube, punched plate or wire member 15 and said valve metal is one or more of titanium, tantalum, aluminum, hafnium, niobium, zirconium, molybdenum or tungsten, their alloys and intermetallic mixtures thereof.

3. A method according to claim 2, wherein said wherein a surface of said 20 valve metal substrate is a roughened surface and said roughened surface is prepared by one or more of intergranular etching, grit blasting, peening, abrading or plasma spraying.

4. A method according to claim 3, wherein there is established a ceramic 25 oxide barrier layer as a pretreatment layer on said roughened surface.

5. A method according to claim 3, wherein said intermediate electrocatalytic coating includes a platinum group metal or metal oxides, magnetite, ferrite, cobalt oxide spinel, tin oxide, and antimony oxide, and/or contains a mixed 30 crystal material of at least one oxide of a valve metal and at least one oxide of a platinum group metal, and/or contains one or more of manganese dioxide, lead dioxide, palatinate substituent, nickel-nickel oxide or a mixture of nickel plus lanthanum oxides. 07/09/1 Iva 19447 speci,20 -21

6. A method according to claim 5, wherein said transition metal oxide of said topcoating layer is palladium oxide, and said palladium oxide is present in an amount from 0.4 mole % up to 6 mole %. 5

7. A method according to claim 1, wherein said method further includes the step of heating said topcoating and said heating is by baking at a temperature of from at least 350'C up to 550*C for a time of from at least 3 minutes up to 20 minutes. 10

8. A method according to claim 1, wherein said electrode is an anode in a process for the production of one or more of chlorine, chlorate or hypochlorite.

9. A method according to claim 1, wherein said electrode provides a reduction in the operating potential during said electrolysis in an amount from 10 15 millivolts to 100 millivolts.

10. A method according to claim 1, wherein said intermediate electrocatalytic coating layer and said topcoating layer are applied to said valve metal substrate by one or more of dip spin, dip drain, brush application, roller coating and 20 spray application.

11. An electrolytic cell for the electrolysis of a halogen-containing solution containing the electrode made by a method according to any one of claims I to 10. 25

12. A method according to claim 1, substantially as hereinbefore described.

13. An electrolytic cell according to claim 11, substantially as hereinbefore described. 30 07/09/1I,va 19447 speci,21