INSOLUBLE ELECTRODE COMPRISING AN ELECTRODEPOSITATED RUTHENIUM-IRIDIUM ALLOY

Abstract: Insoluble electrodes which are especially useful in the electrowinning of nickel in particular comprising an electri­ cally conducting substrate, a barrier layer on the substrate, an electrodeposited ruthenium-iridium intermediate layer which is partially oxidized and an outer layer containing ruthenium dioxide. The ruthenium-iridium layer can usefully be elec­ trodeposited from an aqueous bath containing a soluble ruthenium compound, a soluble iridium compound, a soluble fluorborate salt and fluorboric acid. A preferred iridium com­ pound for use in the bath is one prepared by refluxing a diammonium hexahalo salt of iridium and sulphamic acid in aqueous solution.

Description: Insoluble electrodes incorporating a precious metal alloy layer and baths and bath oonstituents for the electmxiscsition of precious metal alloys This invention relates to insoluble electrodes and also to processes for the production of ruthenium-iridium electrodeposits which are particularly useful in the production of the electrodes. The electrodes of the present invention are particularly, but not exclusively, suited for use as insoluble anodes in the electrowinning of nickel and the description below is mainly concerned with such a process. However, the electrodes may also be employed for the electrowinning of other metals, e.g., copper, zinc, manganese, cobalt, cadmium, gallium, indium, and alloys thereof, e.g., nickelcabalt alloys, and for other processes, e.g., for the electrolytic production of chlorine from brines, the dissociation of water, cathodic protection (e.g., in seawater or underground) and for battery electrodes. For environmental reasons there has been much interest in using electrochemical techniques for extracting metals from ores. However one of the major problems associated with the electrowinning of metals concerns the development of satisfactory anodes. They must be good electrical conductors and resistant to chemical attack in the environment in which they are used; in addition they must be sufficiently strong to withstand normal handling in commercial use, and they must be effective for the desired reactions at the anode without interfering with the activity at the cathode. Economic factors such as the cost of the anodes, their durability and the power requirements associated with their use must also be considered. In a typical nickel electrowinning process using insoluble anodes described by J.R. Boldt in "The Winning of Nickel", pp. 362-374 (1967), the electrolyte used is a purified leach liquor, which is essentially an aqueous solution of nickel sulphate, sodium sulphate and boric acid, and the anodes are made of rolled sheets of pure lead. The principal cathodic reaction is: EMI2.1 The principal anodic reaction, leading to the release of oxygen, is: EMI2.2 Lead and lead alloys have also been used as anode materials for electrowinning of metals other than nickel, e.g., copper and zinc. However lead has not been an entirely satisfactory anode material although lead alloys are often mechanically stronger and more resistant to certain corrosive -environments used in electrowinning processes than pure lead; their operating potential is substantially higher than that of precious metal coated titanium anodes, and there is the ever present possibility of cathode lead contamination, because at open circuit lead dissolves and can then be deposited at the cathode. Overall, very few material may be used effectively as anodes, especially in oxygen producing environments, because of the severe conditions. Graphite has been used - and its limitations are well known. In recent years there has been considerable interest in replacing graphite electrodes used in the electrolytic production of chlorine from brines with platinum group metal-coated anodes. In general anodes of this type comprise metal substrates which are corrosion resistant and ;which possess high melting points and good electrical conductivity and which passivate in that they form protective surface films in certain electrolytes (sometimes known as "valve metals") bearing a coating containing at least one platinum group metal or platinum group metal oxide. The oxides are preferred because they are less corrosive than the elemental metals in the chloride and because there is reduced tendency to shorting in cells such as mercury cells. Particularly preferred are anodes having coatings comprised of a platinum group metal oxide and a base metal oxide. Such coatings have been characterised by terms such as mixed crystals, solid solutions, ceramic semi-conductors, etc. Examples of coatings are those containing RuO2 alone or RuO2 together with IrO2, and/or Ir, as well as a valve metal oxide such as TiO2. Many techniques are known for preparing coatings containing platinum group metals. These include "painting" a RuCl3 layer on to, for example, a titanium substrate and heating in air at a temperature of from 200 to 7000C as well as preparing RuO2 coated electrodes by thermal oxidation of electrodeposited ruthenium. However it has been reported that such electrodeposited coatings are unsatisfactory from the point of oxygen potential and corrosion, the corrosion being evidenced by the appearance of a yellow colour in the solution, which is probably due to the formation of the yellow, volatile tetroxide, RuO4 that is thought to be formed by the dissolution of ruthenium in acidic solution. The platinum group metals do not all exhibit the same properties when used in electrolytic processes. Their behaviour will vary with electrolytic conditions and the reactions which occur. It has been found, for example, that anodes having an outer coating containing oxides of a platinum group metal e.g. RuO2 and TiO2, and a valve metal, which are commonly used in the production of chlorine, have a short life in electrowinning processes in which oxygen is produced at the anode. One major problem is that the electrode itself is passivated, and according to one theory :the passivation is caused by penetration of oxygen through the outer coating into the conductive substrate, e.g., a ingvalee metal. Electrodes with barrier coatings between the tractive surface coating and the substrate conductors have been proposed but none is entirely satisfactory. There is therefore a need for an insoluble electrode which can generally operate in a satisfactory manner in oxygen producing environments and which can therefore be employed in a variety of electrowinning operations including nickel electrowinning as well as in a variety of other applications. One aspect of the invention satisfies this need in general by providing an additional layer between a barrier layer on a substrate and a ruthenium dioxide outer layer. An insoluble electrode according to this aspect of the invention comprises an electrically conducting substrate, a barrier layer on the substrate and an outer surfs layer containing ruthenium dioxide, characterised in that the outer surface layer is non-electroplated and an intermediate layer comprising a ruthenium-iridium electrodeposit which is at least partially oxidised is interposed between the barrier layer and the outer surface layer. This electrode has been found to be especially useful for electrowinning, particularly nickel, where oxygen is evolved at the anode and highly acidic concentrations and elevated temperatures are encountered. The substrate which must be electroconductive, should be of a material which will be resistant to the environment in which it is used. The substrate tay be, for -exaplea valve metal or graphite. As stated above, the term "valve metal" (as applied to electrode materials) is defined as being high melting, corrosion resistant, electrically conductive metals which passivate, i.e., form protective films in certain electrolytes, for example, titanium, tantalum, niobium, zirconium, hafnium, molybdenum, tungsten, aluminium and alloys thereof. Titaniun is a preferred substrate material because of its electrical and chemical properties, its availability,and, its cost relative to other materials with comparable properties. The configuration of the substrate is not critical. It is well known to use electrodes of varying shape and size, e.g., sheet, mesh, expanded metal, tubes, rods, etc. The substrate, for example titanium, may be if desired, a sheath on a more conductive metal such as copper, iron, steel, or aluminium, or combinations thereof. In constructing the electrode, the substrate should be treated to clean, and preferably to roughen, the surface before any coasting is applied. Cleaning includes, for example, removal of grease and dirt and also removal of any oxide skin that may have formed on the substrate. RougXen- ing the surface of the substrate can be effected, for ex¯ple, by etching or grit blasting and a particularly suitable technique is to grit blast using silica sand. The barrier layer deposited on the substrate improves the durability of the electrode. It is believed to serve as an oxygen diffusion barrier for the substrate and/or to behave as a current carrying layer and/or to serve as a support layer to improve the quality and adherence of the electrodeposited layer. A principal function of the barrier layer is to preserve the current carrying capacity of the electrode in the presence of released oxygen. The barrier layer composition is advantageously one of the platinum group metals and gold or alloys, mixtures, intermetallics and oxides thereof. Preferably the barrier layer contains at least one of the platinum group metals palladium, platinum, iridium and rhodium. Palladium and iridium are preferred because they are effective in preserving the current capacity of the electrodes, possibly as barriers to oxygen transport, without any special treatment. Platinum is effective but requires an additional oxidising treatment, e.g., by soaking in an oxidising medium such as in concentrated HN03 or 0.1N KMnO4. The use of rhodium, however, is not recommended because of its high cost. It has also been found that silicides, nitrides and carbides of at least one component of the substrate are suitable as barrier layers. Standard techniques may be usewdeto deposit such coatings on the substrate. These coatings tend to be orders of magnitude greater in thickness than the:latinum group metal barrier layers. For example, a nitriae coating may usefully be about 2 r thick and a silicide -layer may be about 250 rm thick. a a a preferred embodiment the electrode contains a palladium- or iridium-containing barrier layer adjacent to a valve metal substrate. The palladium layer also promotes adherence of the ruthenium-iridium intermediate eledtrodeposited layer to the substrate. The palladium or iridium can be deposited in any manner, e.g., by chemical or thermal decomposition from a solution or slurry deposited on the substrate, or by electroplating, electro phoresis, etc. Electroplating is preferred because it is convenient, inexpendive, rapid and neither labour nor-time intensive compared to thermal decomposition, and it is easily controlled compared to, e.g., electrophoresis or chemical or vapour deposition. The palladium layer shout be at least about 0.05 r in thickness and the optimum thickness is about 0.2 pm. Generally, what is sought is sufficient metal to coat the substrate substantially completely. It has been found, for example, that a palladium deposit of 0.25 mg/cm2 is a sufficient deposit to coat completely a sandblasted or otherwise roughened surface of the substrate. Iridium is more difficult to plate than palladium and it is more expensive. However, a flash coating of iridium serves as an effective barrier. The outer surface layer of ruthenium dioxide developed from a non-electrolytically deposited source is to ensure that even initially there is no loss of ruthenium anodically in use. Ruthenium dioxide is known to have a low oxygen over-potential, and its presence at the surface as an additional layer will also optimize the effectiveness of the material as an oxygen electrode. This in turn will enable the use of the electrode at a suffciently low potential to minimize the possibility of initial dissolution of ruthenium. Other non-electrolyti cally active components may be present in the outer surface layer, e.g., for a adherence, e.g., an oxide of substrate components such as TiO2, Ta2O5 and the like. In a preferred embodiment of the invention the outer surface layer contains at least about 80% Ru02. In the embodime: in which a non-active component is present the outer surface layer contains about 80% to about 99% ruthenium dioxide and about 1% to about 20% of the non-active component, e.g., titanium dioxide. Equitable outer layers may contain for example, 80% Ru02-20% TiO2, 85% Ru02-15t TiO2, 90% Ru02-10% TiO2, 80% RuO2-10% TiO2-10% Ta205. It is believed, however, that the requirement for a nonactive component such as a valve metal oxide is less critical and may even be eliminated in the present electrodes. The reason for this is that the thickness requirements of the outer (non-electrolytic) RuO2 deposit is not as critical in the present electrodes as in conventional electrodes' made entirely of a paint-type deposit. Conventional paint-type electrodes require a thickness build-up in sequential deposits that may be as high as eight coatings and higher each with individual with firing steps. Since the Ru02 (non-electrolytically deposited) layer can be thinner in the present electrodes, with no more than, for example, 1 or 2 coatings, the requirement for additional binders is lowered. Indeed durable anodes have been made using as the outer surface layer and a Ru-Ir layer, a RuO2 developed from paints without any additional oxide component. Where resinates, or the like are used, some oxides may be derived from the usual commercial formulations, but such paint formula tions can be applied without any additional oxides added. Any non-electrolytic technique can be used for producing the ruthenium dioxide containing outer surface layer. Many methods are known, for example, for developing ruthenium dioxide coatings from aqueous or organic vehicles containing ruthenium values. For example, the ruthenium may be preset as a compound such as a halide or resinate, which oxidises to ruthenium dioxide when subjected to a heat treatment in an oxidising atmosphere. Alternatively, ruthenium chloride 'in solution can be applied as a paint and the coating,pf ruthenium dioxide is formed by dechlorination and oxidation of the ruthenium chloride. For example, a solution of RRC13.3H20 in a suitable carrier may be applied on a previously coated and treated composite by brushing, spraying or dipping. A sufficient number of coats are applied to provide a ruthenium content of at least about 0.1 mg/cm2 of electrode surface area. The coatings may be fired individually or each may be allowed to dry and the final coating fired. Firing is carried out, e.g. in air, at a temperature of about 315 0C to about 455 0C, e.g., for about 15 to about 60 minutes. Titanium or other nonactive components may be co-deposited with the ruthenium using conventional techniques. Typically the initial loading (i.e. prior to build-up in use) of the RuO - containing outer layer is at least-about 0.1 mg/cm. Preferably, the initial loading is about 0.3 to about 1 mg/cm2 in thickness. Since there is usually a build-up of Rut2 during use in the cell, the initial thickness. of RuO2 is to ensure that precious metals of the intermediate layer do not dissolve before the proper build-up of RuO2 can occur and to ensure a low oxygen overpotential.in the cell. In this way precious metal loss is minimized. The ruthenium-iridium layer must be deposited in the metallic state by an electrodeposition technique. This is particularly advantageous because a metallic coating of suitable thickness can be deposited in one operation, a layer of uniform composition can be formed, and the deposit can be formed rapidly, in a manner which is neither time nor labour intensive compared to chemical or thermal decomposition techniques. Although it is possible to deposit separate layers of a ruthenium and iridium using individual plating baths and diffuse them thermally, it is preferred to co-deposit the ruthenium and iridium. While this invention is not confined to any particular electroplating method for producing the co-deposit, a second aspect of the invention is concerned with a method of producing. ruthenium-iridiuj electrodeposits which can be used to produce the electrodes of this invention in particular but can also-be rsed-to produce ruthenium-iridium coatings for any other use especially for a variety of decorative or functional purposes including the production of other electrodes In accordance with this aspect of the invention, a process is provided in which a ruthenium-iridium alloy is electrodeposited from a bath comprising an aqueous solution containing a soluble ruthenium compound, a soluble iridium compound, a soluble fluoborate salt and fluoboric acid. It has in general been found that a bath containing controlled amounts of both a soluble fluoborate and fluoboric acid can be usefully employed to form adherent, coherent, reproducible ruthenium and iridium alloy co-eposits- containing controlled amounts of iridium. Such baths are generally long lasting and stable over a wide ratio of ruthenium-iridium compositions and deposits can be formed which are substantially crack-free on visual examination and at a magnification of 500X at deposit thickness equivalent in a loading of up to at least about 2 mg/cm2 The baths are aqueous solutions of the soluble ruthenium and iridium components and a soluble fluoborate salt, fluoboric acid, and the bath can also optional contain sulphamic acid. In general, the baths can conveniently contain: Ingredient g/l Ru 1 - 12 Ir 1 - 12 NaBF4 * 10 - 200 HBF4 1 - 100 NH2 SO 3H O to 2 times the Ru+Ir Conc.- (*or equivalent fluoborate salt) The bath may additionally contain other additives well known in the art: for example boric acid and/or doping agents. Boric acid is known to prevent hydrolysis of HBF to HF. Advantageously, the baths can be designed to give the desired levels of iridium in the alloy deposited, ranging from very small but effect amounts, e.g. to improve the quality of the deposits and/or corrosion resistance up to about 36 weight percent. The fluoborate salt and the fluoboric acid are major factors in controlling the level of iridium in the deposit and in controlling the quality of the deposit. The concentrations of such components used for such control are interrelat'ed to each other and to the precious metal concentrations in the bath. The fluoborate salt functions at least as a current carrier in the bath and it can be used to regulate the viscosity of the bath. It also affects the quality of the deposit, as will be shown below. The fluoborate salt can be, e.g, an alkali metal or ammonium fluoborate. Preferably, for reasons of cost, sodium fluoborate is used. Based on sodium fluoborate, the concentration of fluoborate salt is equivalent to about 10 g/l to about 200 g/l sodium fluoborate, preferable amounts will depent on the compositional design of the bath, but in general the bath will preferably contain at least about 25 g/l equivalent of fluoborate salt. For a bath depositing about 2-4 weight percent iridium in the alloy, the bath will preferably contain about 25 to about 150 g/l, e.g., about 100 g/l. Suitably, the bath will have a density of about 1.043 to 1.038 g/cm3 (6 to 8 Be ). The fluoboric acid level can be used to control the level of iridium in the deposit. Its presence also improves the quality of the deposits. Without fluoboric acid deposits are severely cracked. When added the cracks are reduced materially. In general fluoboric acid is present in an amount of about 1 to about 100 g/l. Preferable amounts will depend on the design of the bath for a particular deposit. To obtain 2-4 weight percent iridium in the deposit, the bath will preferably contain, at least about 5 g/l, e.g., about 5 to about 50 g/l, more preferably about 10 to 40 g/l fluoboric acid. Generally, ruthenium is present as a soluble compound, and preferably a salt containing ruthenium in the form of a complex anion [Ru2N(H2O)2Y8]3- (often referred to as RuNC) e.g., the ammonium salt, flu2N(H20)28 (NH4 )3' wherein Y = either a chloro or bromo group, is @ employed. Examples of other ruthenium salts that may be useda-rSe halides and sulphamates. Generally, iridium is present as a soluble compound. In accordance with a third aspect of the invention, a novel iridium compound is provided which is prepared by reflexing a diammonium hexahalo salt of iridium and sulphamic acid in an aqueous environment for a period of time sufficient to permit, after distillation and cooling of the refluxing product, the formation of a precipitate. Use of (NH4)2IrC16 in particular generally requires a refluxing time of at least 30 hours, for example, at least about 50 hours or above 70 hours following which an olive green precipitate is formed after distillation and cooling. The precipitate is preferably washed throughout, for example until it is substantially uniformly green in colour. The iridium product is soluble in water to some extent and to minimise dissolution the washing is preferably carried out below room temperature, for example between O and 50C. The iridium product has a melting point above 350 C. Differential thermogravimetric analysis (DTG) in air shows that the product has a weight loss of about 46% from room temperature to 600 C. DTG analysis on (NH4)2IrC16 shows about a 61% weight loss under the same conditions. This particular product has been found to be especially useful in the ruthenium-iridium plating baths discussed above. Examples of other iridium compounds that may alternatively be employed in the baths are iridium sulphamates and iridium halides. While the bath may contain relatively large amounts of ruthenium and iridium, it is preferred to keep the precious metal content of the bath at a low level. This will prevent the loss of metal due to drag out and in addition it is less costly teo operate with lower precious metal inventories. In preferred baths, the ruthenium and iridium contents are less than 12 g/l, respectively, and preferably about 3 to 10 g/l, respectively. The ratio of ruthenium to iridium in the bath, surprisingly, can be varied widely without affecting the ratio of iridium in the deposit. Since the ruthenium is deposited at a faster rate than iridium, this permits the bath to be usable for a particular alloy composition even though the bath composition is changing. In general, however, the initial bath can usefully contain ruthenium and iridium in approximately a 1:1 weight ratio. The electrolyte can be replenished as necessary by adding a solution with ruthenium and iridium in concentrations equivalent to the composition of the deposit. Sulphamic acid serves as a stress reliever of the deposit. It is optional, but preferably present in the bath in a ratio of about 0.1:1 up to about 2:1 of sulphamic acid: total weight Ru+Ir and preferably this ratio is about 0.5:1. The electrodeposition process can be carried out at a temperature in the range of about room temperature up to about 95 0C, preferably about 50 to 700C and at a cathode current density of about 5 to 120 mA/cm2, preferably about 20 to 100 mA/cm2. The pH of the bath is important. If it is not maintained within certain tolerable limits, iridium will not co-deposit. The optimum pH range is about 0.3 to about 1.5, preferably about 0.9 to about 1.3. The pH is maintained, advantageously, with fluoboric acid or sulphamic acid. The electrodeposition process can be operated at such conditions to co-deposit iridium and ruthenium containing about 0.1 to 36% iridium. As indicated above, the bath can be designed to provide a specific iridium content in the deposited alloy. Major advantages of the process are that reproducible coatings can be deposited over wide ranges of Ru:Ir ratios in the bath, the baths can be operated for a longer period of time without adJustment, the iridium level can be controlled at a low but effective level for a desired effects and that iridium can be co-deposited with ruthenium. Moreover, adherent and coherent ruthenium-iridium alloys can be deposited. When the electrodeposition process is used in the manufacture of the nsoluble electrodes in accordance with the first aspect of the invention, the ruthenium-iridi deposits usefully have a thickness of about 0.1 to about 4 or 5 m, preferably 0.5 to 2 m and an optimum thickness of about 1 gm. Thicknesses below about 0.1 m tend not to be continuous and too much of the substrate is exposed. As noted above, electroplated ruthenium per se will corrode rapidly at the anode at potentials for oxygen evolution, passing into the acid solution in the octavalent state at potentials greater than about 1.1 V (measured against a saturated calomel electrode). This is both costly - in terms of loss of expensive precious metal and a hazard in that there is a potential for vaporization of RuO4. It has been found that the iridium addition in the electrodeposited intermediate layer suppresses the dissolution of ruthenium. The level of iridium addition which is effective depends on the conditions under which the anode is used. Very small additions of iridium have a marked effect in suppressing the ruthenium dissolution. For exemple, in an accelerated life test in sulphuric acid at a current density of 500 mA/cm2 and ambient temperature, roughly 1 weight % iridium addition increased the anode life from 1 hour (without iridium addition) to at least 11 hours, and even as high as 95 hours, and similarly 2 weight % iridium further increased the anode life. The iridium content of the intermediate layer is typically in the range of0.1%.e.g.from about 1%up to about 36%. For reasons of cost, it is peferable to keep the iridium level as low as possible consistent with achieving optimum life for the electrode. For electrowinning of nidkel, e.g. at current densities of the order of 30 to 50 mA/cm2 and temperatures of about 550 to 800C, very small additions of iridium are effective. In an advantageous embodiment of the invention 2 for use at current densities up to about 50 mA/sm2, the level of iridium in the electrodeposited layer is at least about and preferably greater than about 18 e.g.; about 2% or 4%. For example, in anodes having an outer layer of non-electroplated Ru02, there is no db&num;uneble dissolution of ruthenium with an iridium level of about 4 weight %. When used for current densities greater than about 50 mA/cm2, the iridium level is preferably at least about 2%. Without the R 2 outer layer it would appear that more than 4% iridium is required e.g., 7%, to prevent ruthenium dissolution. Even at the higher levels of iridium, e.g., 7%, the metallic electrodeposited layer must be subjected to an oxidixing treatment to oxidise the surface at least partially. In general, where more severe electrolysis conditions are used, a greater amount of iridium may be necessary to suppress ruthenium dissolution. It was noted that even with the anodes where the iridium content was not sufficiently high for ruthenium dissolution to occur initially, in use anodically an oxide coating builds up which eventually protects the coating and prevents further dissolution of the ruthenium. However, to avoid the initial dissolution and to avoid the hazard of Ru04 formation, a ruthenium dioxide-containing coating - formed by a non-electrolytic treatment - must be provided on the surface of the electrode. Before depositing the outer surface layer on the ruthenium-iridium intermediate layer, however, the ruthenium-iridium layer is treated in air so that the surface of the intermediate layer is at least partially oxidized. By this is meant the surface of the intermediate layer can be partially or whollyroxidized with or without partial or whole oxidation beneath the surface to any depth in the intermediate layer. Surface oxidation can be carried out at a temperature about 400 C to about 9000C in an atmosphere which is oxidizing toSthe deposit. Air is preferred. Preferably,heat treatment of the intermediate layer is carried out at about 4000C to about 7000C, e.g., about 5930C for about 5 to about 60 minutes, e.g., about 15 minutes. Surface oxidation need only be carried out to provide an observable colour change of metallic to violet. This is an evidence of surface oxidation. It is known that various oxides will develop at least at the surface of ruthenium and iridium when subjected to such oxidation treatment. The ruthenium-iridium electrodeposited layer clearly oxidizes at least at the surface. A predominant phase present is RuO2, which may be in solid solution with other oxides which develop at the surface. By way of example to demonstrate the use of electrodes of the invention in the electrowinning of nickel in particular, such electrowinning commonly uses electrolytes containing about 40 to 100 g/l nickel, 50 to 100 g/l sodium sulphate and up to 40 g/l boric acid in sulphuric acid to maintain a pH in the range of about 0 to 5.5. In one specific electrowinning process the anode is bagged, and the anolyte is a sulphate solution containing about 40 to 70 g/l nickel (as nickel sulphate), 40 g/l sulphuric acid, 100 g/l sodium sulphate, 40 g/l boric acid, and the anolyte is maintained at a pH of about 0. Electrowinning is carried out advantageously a± a temperature of about 500 to 700C and at an anode current density of about 30-50 mA/cm2. The following examples are intended to give those skilled in the art a better appreciate of the invention. In all the tests, anode potentials are measured in volts vs. a saturated calomel electrode (SCE) and H/Tis an abbreviation.to denote the conditioning of the layer of a composite sample, namely the temperature, time, and atmosphere. Loadings, e.g. of precious metals or their oxides, alloys, etc. in various layers are given as nominal values. Some examples are now given to illustrate each of the three aspects of the invention; Example 1 relates to the third aspect of the invention and describes the product ion of the novel iridium compound , Examples 2 to 8 relate to the second aspect of the invention, ie the process of electrodepositing ruthenium-iridium alloy and Examples 9 to 16 relate to the third aspect of the invention, ie the insoluble anodes and their manufacture and use in particular. EXAMPLE 1 A. 25 gof (NH4)21rC16 and 60 gof NH2SO3H were 3 dissolved in 600 Cm of distilled water. The solution was 3 refluxed continuously for 71 hours. Then 550 cm of the refluxed solution was distilled off; The distillate was a clear, colourless solution which gave a positive test for Cl ion when AgN03 was added. The remainder of the solution was dark murky green, which upon cooling produced a thick precipitate, which was collected on filter paper and washed several times with ice water. After air drying, it was transferred to a desiccator to dry and resulted in approximately 11 g of an olive green salt. The filtrate and rinse water will yield more of this green salt, but only after considerable standing or by reduction of the volume by another distillation The iridium contents of two different preparations were 44.4% and 45.1%. X-ray diffraction analysis of these salts gave µ similar pattern, which was different to that of (NH4) 2IrCl6, the starting material. It appears from the infrared spectrograph of the green salt that H20 is present, but no Ir-N-Ir bridge. Chemical analysis shows it to contain 44.4% Ir, 41.1% C1, 5.3% N, 5.18 0, 4.12% NH4, 0.71% H20, and the presence of H. No S is present. Its melting point is above 3500C. B. The above procedure was repeated except that the solution of diammonium hexahalo iridium (IV) in sulphamic acid was refluxed for only 30 hours. X-ray diffraction analysis on a black precipitate obtained after distillation and filtration showed it to be the diammino iridium salt, ie the diammonium iridium salt did not react in this time peric EXAMPLE 2 This example illustrates the effect of iridium additions to a ruthenium sulphamate bath. To an aqueous bath containing 2 to 3 g/l of 5Ru2.N(H20)2 cl & 7 (NH4)3 (known as Ru NC) the reaction product of the refluxed diammonium hexachloro iridium IV salt, as prepared in Example 1, was added in amounts to make up baths containing approximately 10%, 20%, 30%, 40%, 50%, 70% and 90%, by weight of iridium. At a plating temperature of 550 C, and a current density of 20 mA/cm2 it was found that at a concentration of about 45% iridium in the bath, the level of iridium in the alloy deposit reached a maximum of about 15% by weight. Thereafter, the percentage of iridium in the deposit levelled off. Increasing the amount of iridium over 45 weight percent in the bath tested, did not therefore increase the amount of iridium in the deposit. EXAMPLE 3 This example illustrates the relationship between the iridium, fluoborate, and fluoboric acid contents of the baths and the level of iridium in the deposited alloys. A series of plating baths were prepared as aqueous solutions containing ruthenium, iridium, sodium fluoborate, fluoboric acid and sulphamic acid. All baths were prepared using the iridium salt made as described in Example 1 and ZRu2 N(H2O)2 C18¯7 (NH4)3, to give a 1 to 1 weight ratio of ruthenium and iridium in the baths; the sulphamic acid concentration in each bathos 6 to 7 g/l but the other bath components were varied relative to each other. The baths had an initial pH of from about 1.2 to 0.5 and deposits of ruthenium-iridium alloys were produced at 550-600C and 20 mA/cm2 on a copper substrate using a platinum anode. The deposited alloys were analyzed for iridium content by x-ray fluorescence. The results are tabulated in Tables I and II. Table I shows the effect of variations in iridium and fluoboric acid concentrations in baths containing 25 g/l NaBF4. Table II shows the effect of variations in iridium and fluoboric acid concentrations in the baths at various levels of NaBF4. TABLE I @ @ NaBF@ = 25 g/l Ru:Ir = 1:1 Bath Deposit Ir/HBF@ Ir in Alloy Test Weight Ratio w/o A 3.08 4.65 16.6 .66 B 3.08 0.29 4.0 10.46 C 6.16 0.59 9.4 10.46 D 6.16 0.30 2.1 20.3 TABLE II Bath Deposit Ir/HBF@ NaBF@ Ir in Alloy Test Weight Ratio g/L w/o A 3.08 4.65 25 16.6 0.66 B 3.08 0.29 25 4.0 10.46 E 3.08 0.93 50 14.8 3.31 F 3.08 0.23 50 6.8 13.11 G 3.08 0.14 50 3.4 21.46 H 3.08 0.70 75 23.2 4.39 I 3.08 0.22 75 8.1 14.0 J 3.08 0.09 75 6.0 33.50 K 3.08 9.29 100 17.4 0.33 L 3.08 0.32 100 5.4 9.60 M 3.08 0.08 100 1.8 39.02 The data in Tables I and II show the interrelationship of the concentrations of Ir, NaBF4 and HBF4, and from such data a bath composition can be optimized to give the desired deposit for a particular application. EXAMPLE 4 Plating baths were prepared using ruthenium and iridium components prepared as described in Example 2, and with the ruthenium and iridium in a weight ration of 1 to 1, to give ruthenium-iridium deposits containing various amounts ofiridium. Typical baths and plating conditions are shown in Table III. TABLE III Bath I II III IV A COMPOSITION, (g/l) Ru 8-9 8-9 3-4 3-4 Ir 8-9 8-9 3-4 3-4 NaBF4 100 100 75 75 HBF4 30 20 14 4 NH2 SO 3H 7 7 6-7 5-7 B PLATING CONDITIONS current 30 30 20 20 density (mA/cm2) T (OC) 70 70 60 60 pH 0.9 0.8 0.9 1.2 C Ir IN DEPOSIT w/o 3-4 5-6 8-9 23-24 EXAMPLE 5 This Example illustrates the effect of current density and temperature on the iridium content of the deposit. Using a bath of the following composition Ingredients g/l Ru 1-2 Ir 1-2 NaBF4 100 HBF4 10 NH2S03H 7 the plating conditions were varied, eg: A at a temperature of 600C and pH of 1.0, varying the cathode current density from 1-100 mA/cm2 B at a cathode current density of 30 mA/cm2, varying the temperature from 20 to 70 C. Results, tabulated in Tables IV and V show that the % iridium deposited increases with both increase in temperature and increase in current density, respectively. TABLE IV Current Density (mA/cm2) Iridium in Deposit (w/o 10 0.7 20 1.1 30 1.6 40 1.8 50 2.2 60 2.7 70 3.0 80 3.7 90 3.8 100 4.7 Temperature ( C) Iridium in Deposit (w/o) room temperature < 0.1 38 0.1 46 1.1 56 2.5 70 6.6 EXAMPLE 6 This example illustrates the use of various ruthenium and iridium salts as components of the bath. In the tests outlined below the specific ruthenium and iridium salts used to prepare the bath, the bath com- position and plating conditions are given. All deposits are on a copper substrate. In all test samples the ruthen- ium-iridium alloy deposit is heat treated in air for 15 minutes at 593 C before use in an accelerated life test. The results include the concentration of iridium in the ruthenium-iridium alloy deposit and observations on the quality of the deposits. "cd" is the current density and "ALTC" refers to accelerated life test which is carried out at 500 mA/cm2 at ambient temperature in 1N H2SO4. The life is based on hours to 10 v cell voltage and the results given related to the precious metals loading. 1 Salts: RuCl3.3H2O and (NH4)2IrCl6 A Bath Composition Ru = 3-4 g/l Ir = 3-4 g/l NaBF4 = 100 g/l HBF4 = 10 g/l NH2SO3H = 6-7 g/l B. Plating Conditions cd = 20 mA/cm2 T = 600C pH = 0.5 C. Results 1. [Ir], in alloy = 7.0% 2. The deposit was not adherent 2. Salts: RuC1,.3H2O and IrCl, A. Bath Composition Ru = 3-4 g/l Ir = 3-4 g/l NaBF4 = 100 g/l HBF4 = 10 g/l @ NH2SO3H = 6-7 g/l B. Plating Conditions cd = 20 mA/cm2 T = 600C pH = 0.7 C. Results 1. [Ir], in alloy = 26-1/2% 2. Light, very shiny deposit, finely cracked at 500X at 1.4 mg/cm2 loading. 3. ALTC: 55 hr/mg. A. Bath Composition Ru = 3-4 g/l Ir = 3-4 g/l NaBF4 r 100 g/l HBF4 = 10 g/l NH2SO3H = 6-7 g/l B. Plating Conditions cd = 20 mA/cm2 T = 600C pH = 0.9 C. Results 1. [Ir], in alloy = 21.3% 2. Matte-grey deposit, under 500X, nodular in appearance. 3. ALTC: 426 hrs/mg. 4. Salts: RuNC and (NH4)2IrCl6 A. Bath Composition Ru = 3-4 g/l Ir = 3-4 g/l NaBF4 = 100 g/l HBF4 = 10 g/l NH2SO3H = 6-7 g/l B. Plating Conditions cd = 20 mA/cm2 T = 600C pH = 0.9 C. Results 1. [Ir], in alloy - 1.7%' 2. Deposit metallic 3. White turned light violet when treated 4. ALTC: 25 hrs/mg. The results are included merely to indicate that iridium does plate out with ruthenium using a variety of compounds of iridium and ruthenium. However, it should be noted that the examples do not represent optimized baths. EXAMPLE 7 Baths were prepared and deposits made substantially as described in Example 3, except that the deposits are made on titanium. The composite Ru-Ir on Ti materials were treated at 5930C in air for 15 minutes and then subjected to a screening test (ALTC) in 1N H2S04 at ambient tem 2 perature and an anode current density of 500 mA/cm Results are tabulated in Table VI, which gives variations in compositions of the baths, w/o iridium in the deposits and the hours to 10 volts cell voltage in the screening test. TABLE VI Bath Deposit Performance Ir/HBF4 NaBF4 Ir in Alloy ALTC Test Weight Ratio g/l t/o Hours to 10 Volts N 3.08 0.33 0 7.8 15 9.27 0 3.08 0.29 25 4.0 91 10.46 P 3.08 0.23 50 6.8 90 3.11 Q 3.08 0.22 75 8.1 112 14.10 S 1.38 0.14 150 11.0 178 9.8 T 1.38 0.14 200 12.0 27 9.8 Generally, for every given Ir/HBF4 ratio, as the concentration of NaBF4 increases the w/o Ir in the alloy deposit increases. However, the performance of deposits as anodes goes through a maximum at about 100 g/l NaBF4. This suggests that the level of NaBF4 in the bath should be controlled, eg at about 100 g/l, for optimum performance when the deposit from the bath is to be used as an anode material in particular. EXAMPLE 8 A titanium substrate was sandblasted with No2 sand to roughen the surface and to prime the surface with embedded silica. The sandblasted substrate was brushed with pumice, rinsed, cathodically cleaned in 0.5 M Na2C03 to remove dirt and adhering pumice particles, rinsed, dried and weighed. Before plating the surface was water-rinsed and placed in the following plating bath prepared using the ruthenium and iridium components described in Example 2: Ingredients g/l Ru 3-4 Ir 3-4 NaBF 25 HBF4 10 NH2S03H 6-7 H 3B03 10 Plating was carried out at a temperature of 600C, pH = 1, 2 and a current density of 20 mA/cm to form a coherent, adherent co-deposit of ruthenium and iridium as an alloy containing 12 weight percent iridium and having a loading of about 1 mg/cm2. The deposit was bright metallic. The Ru-Ir coated titanium was heat treated in air for 15 minutes at 5930C to oxidize at least the surface of the co-deposit. This initial oxidation was evidenced by a colour change from metallic to light violet. After oxidation the electrode was tested at conditions which simulate nickel electrowinning at high temperature. The electrolyte wes made up of 60 to 80 gl nickel (as nickel sulphate), 40 g/l sulphuric acid, 100 g/l sodium sulphate and 10 g/l boric acid. With the electrolyte temperature at 70 C, the pH of about 0 to 0.5 and at an 2 anode current density of about 30 mA/cm2, the life of the electrode was over 3600 hours at a working potential of 1.27-1.31 volts/SCE. EXAMPLE 9 This example illustrates the preparation of typical electrodes of the invention, in which the barrier layer is palladium, and the activity of such electrodes when used as anodes for the electrowinning of nickel. Surface roughened titanium sheet was cleaned and plated with a thin coating of a precious metal as a barrier layer. To roughen and clean the titanium it was sandblasted with SiO2-sand, brushed with pumice, rinsed, cathodically cleaned in 0.5 M Na2CO3 to remove dirt and the remaining pumice particles then rinsed and dried. Thereafter, the cleaned substrate was plated with a thin deposit of palladium, the amount varying from about 0.1 to about 0.6yam, using known electroplating baths. In some of the samples the palladium deposit is subjected to special treatment. For example, the palladium coated-titanium in some samples was subjected to a temperature of 593 C for 1 hour in an atmosphere of 5% H2-95 % N2. However, it was found during the course of investigating the materials that such treatment could be eliminated without noticeable harmful effects to the electrode life or performance. A ruthenium-iridium intermediate, eg of about 0.5 to about 4pm thickness, was plated on the palladium layer from a sulphamate bath of the type described in Example 2 to give a deposit containing about 4% iridium and the balance ruthenium. The bath was maintained at a pH of 0.9 and a temperature of 57 C and operated at a current density of 20 mA/cm2. The ruthenium iridium deposit was treated in air at a temperature of about 500 to 6000C for about 10 to 20 minutes to oxidize the surface. A surface RuO2 layer was applied to each sample by painting the composite with 2 coats of a solution of RuCl3.3H2O in n-butanol. After each application the electrode was dried under a heat lamp (about 65-93 C) to 2 obtain a ruthenium chloride loading of about 1 rng/cm , and then the composite was heat treated in air for 60 minutes at about 4500C to about 6000C in order to convert the chloride to the dioxide of ruthenium. A uniform, blue-black coating resulted which was adherent when finger rubbed, but not completely adherent when subjected to a tape test involving firmly applying a strip of tape to the coating and rapidly stripping it and ascertaining whether any of the coating had been pulled off. The samples were tested as anodes under conditions which simulated the anolyte in a bagged-anode nickel electrowinning, viz. an aqueous electrolyte composed of 70 g/l nickel (as nickel sulphate), 40 g/l sulphuric acid, 100 g/l sodium sulphate, and 10 g/l boric acid. The bath was maintained at a temperature of 700C, a pH of 0 to 0.5, 2 and an anode current density of 30 mA/cm . The tests were arbitrarily tDsdnated when the anode potential reaches 2 volts (vs. SCE). Life of typical samples are given in Table VII, with variations in preparation of the sample noted. The data in Table VII show that anodes of the present invention are effective for electrowinning nickel, and further that current densities of 30 mA/cm2 the anodes operate at very stable potentials in the neighbourhood of about 1.19 to 1.4 volts/CSE. EXAMPLE '10 This example illustrates the effect of various treatment conditions on the outer coating and on the intermediate layer of composite anodes. The anodes are not in accordance with the invention because of the absence of a barrier layer but the results are useful in determining factors involved in the outer and intermediate layers of anodes of the invention. TABLE VII Sample Barrier Layer Intermediate Layer Surface Layer Anode Potential and I.D. Conditioning Conditioning Conditioning Life to 2 Volts vs. SCE 1 0.1 m Pd 0.5 m Ru-Ir 0.7 mg/cm2 RuO2 1.19-1.37V up to 4000 Hours * 593 C-15 m-air 455 C-60 m-air 2V at 4200 Hours 2 0.1 m Pd 1 m Ru-Ir 0.5 mg/cm2 RuO2 1.16-1.36V up to 9330 Hours - 593 C-15 m-air 453 C-30 m-air ** 3 0.1 m Pd 2 m Ru-Ir 0.5 mg/cm2 RuO2 1.16-1.38V up to 9640 Hours - 593 C-15 m-air 453 C-30 m-air ** 4 0.5 m Pd 0.6 m Ru-Ir 0.5 mg/cm2 RuO2 1.19-1.38V up to 3850 Hours * 593 C-15 m-air 453 C-30 m-air 2V at 4180 Hours 5 0.5 m Pd 1.3 m Ru-Ir 0.6 mg/cm2 RuO2 1.22-1.38V up to 6520 Hours - 593 C-15 m-air 453 C-30 m-air 2V at 6860 Hours - - no conditioning treatment. * - heat treated at 593 C for 1 hour in 5% H2/N2. ** - still in test. SCE - Saturated Calomel Electrode. A Effect on Outer Layer Composite samples without barxieK layers Are prepared in a similar manner to that shown in EXAMPLE 9 except that the final heat treatment in air of the RuC13.3H20 deposit was varied with respect to time and temperature. The samples were allowed to stand in 1N H2SO4, at temperatures up to 70 C. Tables VIII-A shows the effect of variations in heat treatment of the Ru02 layer on the anode. TABLE VIII-A Treatment Temperature, C Time, min Effect 260 15-60 Dissolution 315 30 Stable 370 30 Stable 425 15-60 Stable 455 30 Stable The results show that at a temperature-time cycle which does not convert the ruthenium chloride deposit to the oxide, the coating will dissolve immediately on contact with the acid. Coating adherence improves with higher heat treatment temperatures, at 455 C, the adherence being demonstrably better than at 315 C. The optimum time of heat treatment, as determined by tape tests, was about 30-60 minutes. B Effect of Temperature-Time on Intermediate Layer Samples were prepared by plating a Ru-4%Ir alloy deposit on to a sandblasted, pumiced and cathodically cleaned titanium substrate. The ruthenium-iridium layer was subjected to various temperature-time cycles in air. Thereafter the composites were tested as anodes in 1N H2504 as electrolyte, ambient temperature and at an anode 2 current density of 5000 A/m . TABLE VIII-B shows the effects of heat treatment conditions on the anode. TLE VII I-B Heat Treatment Time in Hours to Cell Conditions 'rotential 'o 10 olts 426 0C- 1 hr -air 3 5930C-15 min-air 150 5930C-30 min-air 144 704 0C- 1 hr -air 36 The results in Table VIII show the preferred temperaturetime cycle for heating the alloy is that equivalent to 593 C for 15 to 30 minutes. At 704 C for 1 hour the integrity of the co-deposit was damaged and the substrate was unduly oxidized. At 426 0C for 1 hour insufficient oxide was formed. C Effect of Atmosphere on Alloy Layer Samples were prepared in a similar manner to those prepared in part B of this example except that the atmosphere of the heat treatment of the ruthenium-4 weight % iridium alloy layer was varied. The composites were used as anodes in a simulated nickel electrowinning bath, substantially as described in EXAMPLE 9, except that the bath was maintained at 550C. TABLE VIII-C gives a comparison of an electrode prepared by heat treating the alloy layer in an atmosphere of essentially pure 02 with one treated in air. TABLE VIIT-C Time in Hours to Anode Heat Treatment Potential of '2 Volts 5930C-15 min-02 3200 5930C-15 min-air 4200 EXAMPLE 11 This example illustrates the effect of the addition of titanium to the ruthenium oxide outer layer. A composite was prepared in a similar manner to that shown in Example 9, except that titanium chloride in the amount of 15 weight %, based on the weight of titanium, was added to the RuC13.3H20 solution, and the ruthenium coating solution was made with methanol rather than butanol. The ruthenium chloride solutLon used to deposit the outer layer was prepared by dissolving RuC13 3H20 and an acqueous solution of TiC13 (20%) in methanol such that the ruthenium to titanium weight ratio was 85:15. The titanium was oxidized to the titanic (+4) state by the addition of H202. The resultant ruthenium- and titanium-containing solution was applied to the oxidized ruthenium-iridium alloy layer by applying several coats until the loading averaged 2 1.2 mg/cm . Each coat was allowed to dry under a heat lamp (65-930C) before the next was applied. After applying the final coat the electrode was heated in air for 30 minutes at 454 0C. The resultant material had a blue-black outer layer that had good adherence, showing only slight coating lift-off in a tape test. Data for the tests are shown in Table IX. When tested in a simulated nickel electrowinning recovery cell, anodes of this type showed an initial anodic potential substantially equivalent to that shown by coatings having a surface layer developed from a RuC13.3H20 paint containing no TiC13. The life in Table IX was shorter than the life for comparable electrodes without TiO2 in Table VII. Possibly the coating technique must be improved. EXAMPLE 12 This example illustrates the effect of a palladium barrier layer and a ruthenium-iridium intermediate layer, in accordance with the present invention, as oxygen electrodes in various tests. Composite samples were prepared on roughened and cleaned titanium with layers deposited essentially as described in Example 9, except that samples were prepared with and without a palladium layer and with and without a ruthenium-iridium layer. One sample was prepared with an electrodeposited ruthenium intermediate layer. Part A In the tests recorded in Table X-A, Samples 7 and 8 had a thin electroplated deposit of palladium of O.lWm thickness, heat treated at 5930C for 1 hour in 5% H2/ N2. TABLE IX Samples Barrier Layer Intermediate Layer Surface Layer I.D. Conditioning Conditioning Conditioning Performance III-1 0.2 m Pd 0.5 m Ru-Ir 0.7 mg/cm2 RuO2/TiO2 1.25-1.38V to 3350 Hours 593 C-1 Hr-5%H2-N2 593 C-15 m-air 453 C-30 m-air 2V at 3500 Hours III-2 0.1 m Pd 1.0 m Ru-Ir 0.8 mg/cm2 RuO2/TiO2 1.28-1.32V to 5600 Hours 593 C-1 Hr-5%H2-N2 593 C-15 m-air 453 C-30 m-air 1.37-1.68V to 8000 Hours 2V at 8500 Hours Samples 6, 7 and 8 had a surface coating of Ru02 formed from a ruthenium trichloride-containing paint deposit heat treated at 454 C for 30 min. in air. The RuO2 loading was 3 0.5 mg/cm . Sample 8 had an intermediate layer between the palladium layer and Ru02 layer of electrodeposited ruthenium4% iridium. The ruthenium-iridium layer, which is 0.5 m in 0 thickness was heated at 593 C for 15 minutes in air before the outer Ru02 layer was applied. Samples 6, 7 and 8 were used as anodes in a simulated nickel electrowinning anolyte, as described in Example 9. Data showing the time and anode potential for oxygen evolution are shown in Table X-A. TABLE X-A Anode Potentials in Simulated Ni Electrowinning Cell Operated at 300 A/m2 and 700C Time, Sample 6 ' Sample 7 Sample 8 hrs Ti/Ru02 .T i/Pd/Ru02 Ti/Pd/Ru-Ir/Ruo2 1 1.28 1.20 1.20 100 1.27 1.23 1.27 336 2.7 1.25 1.26 500 -- 1.26 1.25 672 -- 1.28 1.25 1000 -- 1.30 1.26 1164 -- +2.0V 1.27 2000 -- -- 1.27 3000 -- -- 1.29 4000 -- -- 1.37 4200 -- -- 2.0V The data in Table X-A showed: The electrode composed essentially of RuO2 on Ti (Sample 6) operated at a good potential, but it had a short life as an oxygen electrode. The electrodes having a Pd-barrier layer (Samples 7 and 8) had operating potentials comparable to the RuO2 working potential of SWnpe 6. The Ru-Ir intermediate layer increased the life of the oxygen electrode (Sample 8 vs. Sample 7), the potentials for Sample 8 being stabilized and low for about 4000 hours, which was roughly 4 times the life of Sample 7 without the Ru-Ir layer. It will be appreciated that, within certain limits, an increase in RuO2 loading in the surface coating (ie, the working layer) will increase the life of the electrode. The limits in thickness of the coating will be dictated largely by the technique for applying suitable Ru02 coating of the desired thickness and by considerations of cost. Part B In the tests recorded in Table X-B, Sample 9 was prepared with a Pd- barrier layer, an electrodeposited Ru-4%Ir intermediate layer and an RuO2surface layer. In Sample 10, the intermediate layer was electroplated Ru. Samples 9 and 10 were tests in a simulated nickel electrowinning anolyte essentially the same as described in Example 9, but operated at 550C. TABLE X-B Time in Hours to Anode Sample Anode Layers on Ti Potential of 2 Volts 9 O.lpm Pd(l) 0.SLlm Ru-Ir(2) > 8407 0.5 mg/cm2 Ru02(3) (Still in Test) 10 @ O.lpm Pd(l) -0.5um Ru(2) 264 0.5 mg/cm2 RuO2(3) (1) Electroplated Deposit H/T = 593 C - 1 hr - 5% H@/N@ (2) Electroplated Deposit H/T = 5930C - 15 min - ai (3) Paint Deposit H/T = 454 C - 30 min - air The data in Table X-B show that the addition of iridium in the intermediate layer increases the life of the anode markedly. Part C In tests recorded in Table X-C, Sample 11 which did not have a barrier layer was compared with Sample 12, having a barrier layer and therefore in accordance with the invention, TABLE XI Anode Time in Hours to Sample layers on Ti Anode Potential of 2 Volts V-1 0.1 m Pd(1) > 8000 1.0 m Ru-Ir(2) (Still in Test) V-2 0.1 m Pt(3) 2230 l.lFm Ru-Ir(2) V-3 0.1 m Pt(4) 4510 claim Ru-lr(2) V-4 0.07 mg/cm2 Ir (x) > 7410 l.OWm Ru-Ir (2) (Still in Test) V-5 None 2136 l.Oprn Ru-Ir(2) V-6 Flash Coating Au(x) ( > 213)* l.lpm Ru-Ir (2) V-7 None ( 114)* l.Opm Ru-Ir(2) Conditioning treatments: : (1) 593 C- 1 hr - 5% H2/N2 (2) 593 C-15 min-air (3) 593 C- 1 hr -N2 (4) 593 C- 1 hr -5% H2/N2 + 72 hours room temperature (x) No Treatment in conc. HNO3 (*) Under accelerated test in 1 N H2S04 at current density of 500 mA/cm2 and ambient temperature to 10 volts cell voltage The data shows that Ir and Pd are particularly suitable as barrier layers and that an oxidation treatment improved the effectiveness of the platinum barrier layer. It is noted that the Pd layer in Sample V-1 was treated in a reducing atmosphere; as noted previously this treatment is not necessary for an effective Pd barrier layer. However, platinum generally requires the treatment in an oxidizing medium to be effective. - Such platinum treatment is preferably carried out at room temperature. EXAMPLE 14 This example shows the effect of variations in thickness of the Ru-Ir and Pd layers. as an oxygen electrode under severe conditions, viz in 1N H2504 electrolyte at 5000 A/m2. TABLE X-C Time-in Hours to Cell Sample Anode Layers on Ti Potential of to Volts 11 O.Spm Ru-Ir(2) 1.1 mg/cm2 Ru02(3) 110 12 0.2pm Pd(l) 0.5 m Ru-Ir(2) 250 1.1 mg/cm2 Ru02(3) (1) Electroplated deposit (no H/T) (2) Electroplated deposit H/T = 593 C-15 min-air (3) Paint deposit H/T = 4540C-30 min-air The data in Table X-C shows that the palladium barrier layer increases the durability of the anode. EXAMPLE '13 This example illustrates variations in the barrier layer. Composite anode samples were prepared with a variety of metals electroplated on roughened and cleaned titanium sheet, followed by an electroplated layer of Ru-4%Ir. Data showing the results of tests using such composites as anodes in a simulated nickel electrowinning electrolyte, essentially as described in Example 9, are given in Table XI. The thickness of the various deposits and treatments to which the deposits were subjected (if any) are noted. Part A - Variations in Thickness of Ru-Ir Composite tri-layer samples, viz Pd/Ru-Ir/RuO2 on Ti, in accordance with the present invention, were prepared in essentially the same manner as described in Example 9, with variations in thickness in the Ru-Ir layer. In the samples prepared the Pd and RuO2 were constant, viz Pd = 0.1 m, H/T = 593 C - 1 hr 5* H2/N2 or no treatment 2 0 RUO2 = 0.5 mg/cm , H/T 454 C - 30 min in air. The data in Table XII records the hours to 2V when tested in the simulated nickel electrowinning anolyte using the conditions noted in Example 9. TABLE XII Time in Hours to Sample Intermediate Layer Anode Potential-of 2 Volts 13 Ru-4%Ir = 0.5 m, H/T-5930C-15 min-air 4200 14 Ru-4%Ir = 1 m, H/T-593 C-15 min-air > 9330 (Still in Test) 15 Ru-4%Ir = 2wn H/T-5930C-15 min-air > 9640 (Still in Test) 16 Ru-4%Ir = 4um H/T-5930C-15 min-air 2500 The data in Table XII show that electrodes of the present invention operate effectively with the variation in thickness of the Ru-4%Ir coating of -from 0.5-4 m, and the optimum thickness is in the range of about 1-3 m. Part B - Variation in Thickness of Pd Anode samples were prepared of electroplated palladium on roughened and cleaned titanium sheet, with the thickness of the Pd-deposit varying from about 0.05 to about lpm, ie, 2 up to about 1.3 mg/cm Pd. The samples were tested as oxygen electrodes in 1N H2SO at room temperature. A graph of potentials of the electrodes when operating at a constant current density of 2 mA/cm2 as a function of Pd-loading showed that at a Pd level greater than 0.2 mg/cm2, the surface behaved like pure Pd, an indication that the titanium surface was completely covered with palladium. Below about 0.2 mg/cm2 of palladium, the titanium substrate influence the potential, as evidenced by the rise in potential as the Pd loading decreased below about 0.2 mg/cm2. EXAMPLE 15 This example illustrates the effect of iridium, the effect of an oxidation treatment in the intermediate layer, and the contribution of the Ru02 layers of the present invention in tests as oxygen electrodes. Again, no barrier layer was present in the electrodes but the results are still useful. Composite samples were prepared, all having an electroplated ruthenium-containing layer with an iridium content varied from 0 up to about 12%. The electroplated layer was deposited directly on roughened and cleaned titanium. Each sample had an electrodeposit of about 1 mg/cm2 loading. Thereafter, with the exception of Samples 24 and 25, each sample was subjected to a treatment at 593 C in air for 15 minutes. Samples 18, 20 and 24 each had a further outer layer of RuO2 (0.8 mg/cm2) developed from a ruthenium-chloridecontaining paint, which was subjected to a heat treatment of 450 C for 30 hours in air. Sample 25 was comparable to Sample 21, except that it did not haveranioxidation treatment. The samples were used as anodes in-a IN H2 SO4 electrolyte operated at incremental current densities until a colour change in the electrolyte was observed. Whitë-Teflon (Trademark) tape inserted at the stopper for eat ttestwas removed and examined. Effluent gas from the test container was bubbled through a solution of 1:5 of H2S03:H20. No noticeable change occurred in the H2S03. The results in Table XIII showt 1) The presence of Ir suppressed the corrosion of Ru. As the iridium content increased from 0 to 3.9 to 9.4% the current density at which colouring of the electrolyte began TABLE XIII Deposit on Teflon Ru in Solution Sample Anode Layers % Ir Coated Stopper g/l (Approx.) Observations on Electrolyte 17 Ru 0 Black+ 0.18 Yellowing at 30 mA/cm2 18 Ru + RuO2 0 Brown-Black Smudge 0.043 Yellowing at 125 mA/cm2 19 Ru/Ir 3.9 Black 0.003 Yellowing at 50 mA/cm2 20 Ru/Ir + RuO2 3.9 None 0.003 Yellowing at 250 mA/cm2 21 Ru/Ir 6.8 Trace 0.003 Possibly More Red than Yellow at 250 mA/cm2 22 Ru/Ir 9.4 Trace 0.003 Pinking at 250 mA/cm2 23 Ru/Ir 11.3 Trace 0.003 Pinking at 250 mA/cm2 24 Ru/Ir*-RuO2 9.4 Trace 0.007 Yellowing at 30 mA/cm2 25 Ru/Ir* 6.8 Black-Brown 0.0064 Yellowing at 30 mA/cm2 *No oxidation treatment. Ru = an electroplated layer of Ru. Ru/Ir = an electroplated layer of Ru-4Ir. RuO2 = a layer developed from a RuCl,-containing paint. +x-ray fluorescence of a similarly formed deposit showed the presence of ruthenium. rising from 30 to 250 nA/cm , and the deposits of Ru02.2H20 on the tape decreased from black amounts to trace amounts (Cf Samples 17, 19, 22). 2) The presence of Ru02 developed on the surface from a non-electroplated deposit suppressed the formation of a enium-containing deposit believed to be RuO2.2H20 (via Ru04 formation) and the corrosion of Ru in all cases. With no Ir present, there was less of a deposit on the tape with a RuO2 surface layer than without it (cf Samples 17 and 18), and corrosion began at a higher current density. In Ru-Ir deposits not heat treated, the ruthenium-containing deposits on the tape were less when RuO2 was present, and the corrosion of Ru was also to a lesser amount (Cf Samples 25 and 24). When the Ru-Ir deposit was heat treated and RuO2 was present, no ruthenium-containing deposit was found at current densities 2 up to about 250 mA/cm (Cf Sample 20). 3) Further, the results showed oxidation of the Ru-Ir layer was necessary to form a protective oxide film. When Ru-Ir was not heat treated, corrosion of Ru began at 30 mA/cm and a black-brown deposit was present on the tape. When Ru-Ir was heat treated, corrosion began at much higher current densities, and the volatiles were reduced to trace amounts (Cf Samples 21 and 25). From the results it can be seen that the optimum amount of iridium in the Ru-Ir can be predetermined for given conditions of operation based upon, eg,corrosion and economics. For example, the Sample 20 containing:about 3.9% iridium and having an RuO2 outer coating may be used at current densities up to 250 mA/cm2 without noticeable dissolution of the ruthenium in the electrolyte. It appears±.from the data that less than 4% iridium may be used with-the'--RuO for lower current densities of the order of 30-50 mA/cmi, eg, 1% or 2% may be sufficient. EXAMPLE 16 This example illustrates the effect of the iridium level in a ruthenium-iridium layer. Again no barrier layer is present but the results are valid nevertheless. In the experiments of this example composite samples composed of a ruthenium-iridium electroplated deposit on roughened and cleaned titanium were tested in an accelerated life test. The ruthenium-iridium deposits contained various mounts from zero up to about 25% iridium (by weight). Results with typical samples prepared under comparable conditions are reported in Table XIV. TABLE XIV Time in Hours to Cell Sample ''% Ir Potential of 10 Volts 26 0 0.3 27 0.7 95 2s 2 105 29 3 110 30 6.1 114 31 6.3 120 32 8.1 112 33 9.4 118 34 11 179 35 21.3 426 It will be appreciated that the selected results reported in Table XIV are for rough screening tests. Some tests not reported in the table showed poor performance at high levels of iridium and good life at low levels of iridium. However, the life of the electrodes will vary markedly depending on such factors as the type of bath used, plating conditions, thickness of the coating, treatment conditions, integrity of the deposit, etc. It is believed, however, that the results tabulated are for relatively comparable samples and that in general the experiments showed a trend, as indicated. As noted previously the present anodes are particularly useful for lectrowinning nickel but may also be used for a variety of other purposes including recovering nickel-cobalt deposits from a suitable electrolyte under comparable conditions aid vith stably low anode potentials, eg of the order of about 1.15-1.3@@C@.

Claims: Claims 1. An insoluble electrode comprising an electrically conducting substrate, a barrier layer on the substrate and an outer surface layer containing ruthenium dioxide, characterised in that the outer surface layer is non-electroplated and an intermediate layer comprising a ruthenium-iridium electrodeposit which is at least partially oxidised is interposed between the barrier layer and the outer surface layer. 2. An electrode according to claim 1 characterised in that the substrate is a valve metal as herein defined. 3. An electrode according to claim 2 characterised in that the substrate is titanium. 4. An electrode according to any preceding claim characterised in that the barrier layer is one of the platinum group metals and gold or alloys, mixtures, intermetallics and oxides thereof. 5. An electrode according to any preceding claim characterised in that the outer surface layer contains at least 808 ruthenium dioxide. 6. An electrode according to any preceding claim characterised in that the ruthenium-iridium intermediate layer is produced by co-deposition. 7. An electrode according to claim 6 characterised in that the ruthenium-iridium layer is electrodeposited from a bath comprising an aqueous solution containing a soluble ruthenium compound, a soluble iridium compound, a soluble fluoborate salt and fluoboric acid. 8. An electrode according to claim 7 characterised in that the ruthenium compound of the bath is a salt containing ruthenium in the form of the complex anion LRu2 N(H20)2 Y J 3 wherein Y is C1 or Br. 9. An electrode according to claim 7 or claim 8 characterised in that the iridium compound of the bath is one prepared by refluxing a diammonium hexahalo salt of iridium and sulphamic acid in an aqueous environment for a period of time sufficient to permit, after distillation and cooling of the refluxing product, the formation of a precipitate. 10. An electrode according to any preceding claim characerised in that the ixldium content of the inteXmediate layer is from 0.1 to 368. 11. An electrode according to claim 10 characterised in that the iridium content of the intermediate layer is from 2 to 4%. 12. An electrode according to any preceding claim characterised in that the oxidation of the rutheniumiridium intermediate layer is effected at 400 to 900 C in an oxidising atmosphere. 13. A process in which a ruthenium-iridium alloy is electrodeposited from a bath comprising an aqueous solution containing a soluble ruthenium compound, a soluble iridium compound, a soluble fluoborate salt and fluoboric acid. 14. A process according to claim 13 characterised in that the ruthenium compound of the bath is a salt containing ruthenium in the form of the complex anion ZRu2 N(H20)2 Y J 3 wherein Y is C1 or Br. 15. A process according to claim 13 or claim 14 characterised in that the iridium compound of the bath is one prepared by refluxing a diammonium hexahalo salt of iridium and sulphamic acid in an aqueous environment for a period of time sufficient to permit, after distillation and cooling of the refluxing product, the formation of a precipitate. 16. A process according to any one of claims 13 to 15, characterised in that the bath contains at least--i g/l of fluoboric acid. 17. A process according to any one of claims 13 to 16, characterised in that the soluble fluoborate is sodium fluoborate present in an amount of at least 25 g/l. 18. A process according to any one of claims 13 to 17 characterised is that the bath additionally contains sulphamic acid. 19. A process according to any one of claims 13 to 18 characterised in that the pH of the bath is from 0.3 to 1.5. 20. A process according to any one of claims 13 to 19 characterised in that the bath additionally contains boric acid. 21. An iridium compound characterised in that it is prepared by refluxing a diammonium hexshalo salt of iridium and sulphamic acid in an aqueous environment for a period of time sufficient to permit, after distillation and cooling of the refluxing product, the formation of a precipitate. 22. An iridium compound according to claim 21 characterised in that its preparation includes refluxing for at least 30 hours. 23. The use of an electrode in accordance with any one of claims 1 to 12 in a metal electrowinning process.

Inventors: BORNER, WILLIAM GERRARD, MCEWEN, JAMES, SCARPELLINO JR., ANTHONY JOSEPH
Applicants: INCO EUROPE LIMITED
Application year: 1979
Main classification: C25C7
IPC codes: C01G55, C01B21, C25D3, C25C7, C25B11