Lead alloys anodes

Anodes. Lead—antimony (6—10 wt %) alloys containing 0.5—1.0 wt % arsenic have been used widely as anodes in copper, nickel, and chromium electrowinning and metal plating processes. Lead—antimony anodes have high strength and develop a corrosion-resistant protective layer of lead dioxide during use. Lead—antimony anodes are resistant to passivation when the current is frequendy intermpted. 

Wrought lead—calcium—tin anodes have replaced many cast lead—calcium anodes (14). Superior mechanical properties, uniform grain stmcture, low corrosion rates, and lack of casting defects result in increased life for wrought lead—calcium—tin anodes compared to other lead alloy anodes. 

Copper-containing lead alloys undergo less corrosion in sulfuric acid or sulfate solutions than pure lead or other lead alloys. The uniformly dispersed copper particles give rise to local cells in which lead forms the anode and copper forms the cathode. Through this anodic corrosion of the lead, an insoluble film of lead sulfate forms on the surface of the lead, passivating it and preventing further corrosion. The film, if damaged, rapidly reforms. 

The electrolysis is conducted at 90—95°C and an anode current density of about 50 120 A/m when using lead alloy anodes and lead cathodes. Using graphite electrodes, the current density is from 70 100 A/m using titanium anodes and graphite cathodes, the current density is 50 80 A/m (82). 

Asahi also reports an undivided cell process employing a lead alloy cathode, a nickel—steel anode, and an electrolyte composed of an emulsion of 20 wt % of an oil phase and 80 wt % of an aqueous phase (125). The aqueous phase is 10 wt % K HPO, 3 wt % K B O, and 2 wt % (C2H (C4H )2N)2HP04. The oil phase is about 28 wt % acrylonitrile and 50 wt % adiponitrile. The balance of the oil phase consists of by-products and water. The cell operates at a current density of 20 A/dm at 50°C. Circulated across the cathode surface at a superficial velocity of 1.5 m/s is the electrolyte. A 91% selectivity to adiponitrile is claimed at a current efficiency of 90%. The respective anode and cathode corrosion rates are about mg/(Ah). Asahi s improved EHD process is reported to have been commercialized in 1987. 

Finally it must be remembered with these anodes that Pb02 film, which acts to provide the current leakage, can be detached even when no current is flowing. With renewed anodic loading, the film has to be reformed, which leads to a corresponding consumption of anode material. The anodes should therefore be operated as continuously as possible with a basic load. An exhaustive treatment of the composition and behavior of lead alloy anodes can be found in Ref. 13. 

Besides Type A lead, nine lead alloys are specified in British Standards for various purposes. Their compositions and impurity limits are given in Table 4.13. In addition, alloys for batteries and for anodes are of importance. In due course it is likely that European standards will supersede the current national ones... 

Morgan, J. FI. Lead Alloy Anode for Cathodic Protection , Corr. Tech. 10/12. 348-352 (1958)... 

For long lengths of anode it is sometimes necessary to extrude one material over another to improve a particular characteristic. Thus titanium may be extruded over a copper rod to improve the longitudinal conductivity and current attenuation characteristics of the former lead alloys may be treated similarly to compensate for their poor mechanical properties. It should he noted that these anodes have the disadvantage that, should the core metal be exposed to the electrolyte by damage to the surrounding metal, rapid corrosion of the former will occur. 

If a lead alloy is used as a ship s hull anode, consideration should be given both to the make-up of the water in which the anode is initially passivated and that in which it will normally operate. The same consideration will apply for static structures in estuarine waters. 

A typical anode for practical use would be in the order of 25 to 48 mm in diameter, with hard platinum alloy pins of 0-50 mm diameter by 10 mm length, spaced every 150 to 300 mm and progressively positioned around the circumferenceThe pins are a press fit into holes in the lead or lead alloy (approximately 01 mm diametric interference) and lie flush with the surface. The lead is peened around the pins to improve the mechanical and electrical contact. 

This group includes platinised-titanium, platinised-niobium, lead alloys and lead-platinum anodes, which are used for immersed structures, e.g. jetties, sheet piling and power stations. 

Metal oxide coatings Commercial lead dioxide coatings, for example, on titanium, have a higher stability compared with lead or lead alloy anodes with their in situ formed oxide layer. A secure contact between Pb02 and titanium has to be guaranteed, for example, by a platinum layer or at least by a sufficiently large number of platinum crystallites. 

In addition to reduction of its ores in furnaces, manganese can be produced by electrolysis. The electrolyte is manganese sulfate that is produced by treating ore with sulfuric acid, (TMnOj + 2HjSO —> 2MnSO + + 2H2O). The anode is lead alloy, and the cathode is... 

The most important use of barium is as a scavenger in electronic tubes. The metal, often in powder form or as an alloy with aluminum, is employed to remove the last traces of gases from vacuum and television picture tubes. Alloys of barium have numerous applications. It is incorporated to lead alloy grids of acid batteries for better performance and added to molten steel and metals in deoxidizing alloys to lower the oxygen content. Thin films of barium are used as lubricant suitable at high temperatures on the rotors of anodes in vacuum X-ray tubes and on alloys used for spark plugs. A few radioactive isotopes of this element find applications in nuclear reactions and spectrometry. 

Adding tellurium to lead and to lead alloyed with silver and arsenic improves the creep strength and the charging capacity of storage battery electrodes (see Batteries). These alloys have also been suggested for use as insoluble anodes in electrowinning. 

In C. E. Acker s process (1898), now abandoned,47 sodium chloride was electrolyzed in a cell in which molten lead was used as cathode, and a carbon rod as anode. During the electrolysis, the molten lead dissolved the sodium forming an alloy the chlorine was drawn off from the anodes. The alloy of lead and sodium was decomposed by steam to form hydrogen and sodium hydroxide. 

The electrolysis Of fused alkali salts.—Many attempts have been made to prepare sodium directly by the electrolysis of the fused chloride, since that salt is by far the most abundant and the cheapest source of the metal. The high fusion temp. the strongly corrosive action of the molten chloride and the difficulty of separating the anodic and cathodic products, are the main difficulties which have been encountered in the production of sodium by the electrolysis of fused sodium chloride. Attention has been previously directed to C. E. Acker s process for the preparation of sodium, or rather a sodium-lead alloy, by the electrolysis of fused sodium chloride whereby sodium is produced at one electrode, and chlorine at the other but the process does not appear to have been commercially successful. In E. A. Ashcroft s abandoned process the fused chloride is electrolyzed in a double cell with a carbon anode, and a molten lead cathode. The molten lead-sodium alloy was transported to a second chamber, where it was made the anode in a bath of molten sodium hydroxide whereby sodium was deposited at the cathode. A. Matthiessen 12 electrolyzed a mixture of sodium chloride with half its weight of calcium chloride the addition of the chloride of the alkaline earth, said L. Grabau, hinders the formation of a subchloride. J. Stoerck recommended the addition of... 

Asahi also reports an undivided cell process employing a lead alloy cathode, a nickel—steel anode, and an electrolyte composed of an emulsion of 20 wt % of an oil phase and 80 wt % of an aqueous phase (125). The aqueous phase is 10 wt % KjHPO 3 wt % and 2 wt %... 

Emulsion with aq. phosphate buffer, lead alloy, or steel anode/lead or cadmium cathode, 55°C Yield 90%... 

Sacrificial anode — is a piece of metal used as an anode in electrochemical processes where it is intended to be dissolved during the process. In -+ corrosion protection it is a piece of a non-noble metal or metal alloy (e.g., magnesium, aluminum, zinc) attached to the metal to be protected. Because of their relative -+ electrode potentials the latter is established as the -+ cathode und thus immune to corrosion. In -+ electroplating the metal used as anode may serve as a source for replenishing the electrolyte which is consumed by cathodic deposition. The sodium-lead alloy anode used in the electrochemical production of tetraethyl lead may also be considered as a sacrificial anode. 

A highly purified manganese sulfate solution (see Section 3.5.1.3.1) serves as the electrolyte. The cathodic electrolyte contains 30 to 40 g/L manganese sulfate and 125 to 150 g/L ammonium sulfate and the manganese depleted anodic electrolyte 10 to 20 g/L manganese sulfate, 25 to 40 g/L sulfuric acid and 125 to 150 g/L ammonium sulfate. The anodes consist of lead alloyed with 1% silver, the cathodes of stainless steel or Hastelloy, type 316. The cells are operated at 35 to 40°C, a cathodic current density of 2 to 5.5 A/dm and a potential of 5V. The yield ba.sed on electricity consumed is 50 to 70%. 

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