Platinised platinum

Impressed current ( power impressed ) Impressed currents using transformer-rectifiers, or any other d.c. source Carbon, silicon-iron, lead-platinum, platinised titanium, platinised Source of low-voltage d.c. This may be generated or drawn from transformer-rectifier fed from main supplies More complex Very significant especially in built-up areas... 

This electrode, shown diagrammatically in Figure 4.4, is assigned zero potential when hydrogen gas at one atmosphere bubbles over platinised platinum in a solution of hydrogen ions of concentration 1 mol 1 (strictly, at unit activity). 

Pla.tinum, Platinum plating has found appHcation in the production of platinised titanium, niobium, or tantalum anodes which are used as insoluble anodes in many other plating solutions (see Metalanodes). Plating solutions were often based on platinum "P" salt, which is diamminedinitroplatiniim (IT). A dinitroplatinite sulfate—sulfuric acid bath has been used to plate direcdy onto titanium (129). This bath contains 5 g/L of the platinum salt, pH adjusted to 2.0 with sulfuric acid. The bath is operated at 40°C at 10—100 A/m. Other baths based on chloroplatinic acid have been used in both acid and alkaline formulations the acid bath uses 20 g/L of the platinum salt and 300 g/L hydrochloric acid at 65° C and 10—200 A/m. The alkaline bath uses 10 g/L of the platinum salt, 60 g/L of ammonium phosphate and ammonium hydroxide to give a pH of 2.5—9.0. The alkaline bath can be plated directly onto nickel-base alloys acid baths require a gold strike on most metals. 

Cathodic protection applications in fresh water include use of ferrite-coated niobium , and the more usual platinum-coated niobium . Platinised niobium anodes have been used in seawater, underground and in deep wells " and niobium connectors have been used for joining current leads Excellent service has been reported in open-seawater, where anodic potentials of up to 120V are not deleterious, but crevice corrosion can occur at 20 to 40V due to local surface damage, impurities such as copper and iron, and under deposits or in mud ... 

In aqueous chloride where it is necessary to use platinised titanium anodes coated over only part of their surface, e.g. titanium rod tipped with a thin platinum film, it may be necessary to limit the applied voltage to 12 V. 

Certain organic compounds form complexes with platinum, and this accounts for the fact that the thin coating of platinum on titanium is rapidly corroded when platinised titanium is used as an anode in plating baths containing organic addition agents. 

The anodic behaviour of platinum and certain of its alloys is of considerable technical importance, since they can be employed under a wide range of conditions without appreciable corrosion, and often in circumstances where no other metal can be used. Their use industrially has recently been extended by applying them as thin coatings to a substrate of a passive metal such as tantalum or, more commonly nowadays, titanium, to reduce the cost. Platinised titanium anodes are discussed in detail in Section 11.3. 

Precious metals and oxides platinised titanium, platinised niobium, platinised tantalum, platinised silver, solid platinum metals, mixed metal oxide-coated titanium, titanium oxide-based ceramics. 

It is a valve metal and when made anodic in a chloride-containing solution it forms an anodic oxide film of TiOj (rutile form), that thickens with an increase in voltage up to 8-12 V, when localised film breakdown occurs with subsequent pitting. The TiOj film has a high electrical resistivity, and this coupled with the fact that breakdown can occur at the e.m.f. s produced by the transformer rectifiers used in cathodic protection makes it unsuitable for use as an anode material. Nevertheless, it forms a most valuable substrate for platinum, which may be applied to titanium in the form of a thin coating. The composite anode is characterised by the fact that the titanium exposed at discontinuities is protected by the anodically formed dielectric Ti02 film. Platinised titanium therefore provides an economical method of utilising the inertness and electronic conductivity of platinum on a relatively inexpensive, yet inert substrate. 

Early failures of platinised titanium anodes have been found to occur for reasons other than increased consumption of platinum or attack on the titanium substrate caused by voltages incompatible with a particular electrolyte. The following are examples ... 

The superimposition of a.c. ripple on the d.c. output from a transformer rectifier can under certain circumstances lead to increased platinum consumption rates and has been the subject of considerable researchIndeed, when platinised titanium anodes were first used it was recommended that the a.c. component was limited to 5% of the d.c. voltage . 

Platinised-titanium installations have now been in use for 30 years for jetties, ships and submarines and for internal protection, particularly of cooling-water systems . For the protection of heat exchangers an extruded anode of approximately 6 mm in diameter (copper-cored titanium-platinum) has shown a reduction in current requirement (together with improved longitudinal current spread) over cantilever anodes of some 30% . This continuous or coaxial anode is usually fitted around the water box periphery a few centimetres away from the tubeplate. 

Furthermore, the restrictions on operating voltage that apply to titanium in a marine enviroment are not always relevant to titanium in soils free of chloride contamination. Coke breeze is, however, an integral part of the groundbed construction and ensures a lower platinum consumption rate. However, for some borehole groundbeds, platinised niobium is preferred, particularly in the absence of carbonaceous backfill or in situations where the water chemistry within a borehole can be complex and may, in certain circumstances, contain contaminants which favour breakdown of the anodic Ti02 film on titanium. In particular, the pH of a chloride solution in a confined space will tend to decrease owing to the formation of HOCl and HCl, and this will result in an increase in the corrosion rate of the platinum. 

Platinum electrodeposition on to tantalum had been carried out as early as 1913 and the use of platinised tantalum as an anode suggested in 1922 , whilst platinum electrodeposition on to niobium was first successfully carried out in 1950 . 

The insertion of platinum microelectrodes into the surface of lead and some lead alloys has been found to promote the formation of lead dioxide in chloride solutions" " . Experiments with silver and titanium microelectrodes have shown that these do not result in this improvement". Similar results to those when using platinum have been found with graphite and iridium, and although only a very small total surface area of microelectrodes is required to achieve benefit, the larger the ratio of platinum to lead surface, the faster the passivation". Platinised titanium microelectrodes have also been utilised. 

Platinised tantalum Platinised niobium Platinised titanium Platinum Thermally deposited noble metal oxide on titanium High- silicon/ chromium iron... 

Platinised-titanium, platinised-niobium, lead and lead-platinum anodes used for submerged structures, ships and power stations. 

Platinised titanium These anodes are usually in the form of titanium rod, tube or wire with a coating of platinum 2-5 to 5-0 tm thick. Diameters are generally in the range 3 to 25 mm. In order to reduce the voltage drop in very long anodes, a copper cored variety is available. Platinised titanium anodes may also be used in mesh or plain sheet form and can be fabricated to suit particular applications. 

Platinum Platinum-coated titanium is the most important anode material for impressed-current cathodic protection in seawater. In electrolysis cells, platinum is attacked if the current waveform varies, if oxygen and chlorine are evolved simultaneously, or if some organic substances are present Nevertheless, platinised titanium is employed in tinplate production in Japan s. Although ruthenium dioxide is the most usual coating for dimensionally stable anodes, platinum/iridium, also deposited by thermal decomposition of a metallo-organic paint, is used in sodium chlorate manufacture. Platinum/ruthenium, applied by an immersion process, is recommended for the cathodes of membrane electrolysis cells. ... 

Fig. 19.16 Schematic E — I diagrams of local cell action on stainless steel in CUSO4 + H2SO4 solution showing the effect of metallic copper on corrosion rate. C and A are the open-circuit potentials of the local cathodic and anodic areas and / is the corrosion current. The electrode potentials of a platinised-platinum electrode and metallic copper immersed in the same solution as the stainless steel are indicated by arrows, (a) represents the corrosion of stainless steel in CUSO4 -I- H2 SO4, (b) the rate when copper is introduced into the acid, but is not in contact with the steel, and (c) the rate when copper is in contact with the stainless steel...

The hydrogen electrode consists of an electrode of platinum foil (approximately 1 X 1 X 0-002 cm) welded to a platinum wire which is fused into a glass tube. In order to increase its catalytic activity it is platinised by making it cathodic in a solution of chloroplatinic acid (2% chloroplatinic acid in 2 N HCl) frequently lead acetate is added to the solution (0-02%) and this appears to facilitate the deposition of an even and very finely divided layer... 

The nature and the physical state of the metal employed for the electrodes. The fact that reactions involving gas evolution usually require less overpotential at platinised than at polished platinum electrodes is due to the much larger effective area of the platinised electrode and thus the smaller current density at a given electrolysis current. 

Walton DJ, Burke LD, Murphy MM (1996) Sonoelectrochemistry chlorine, hydrogen and oxygen evolution at platinised platinum. Electrochim Acta 41 2747-2751... 

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