Patent GB-1159241-A (GB)
Title: Improvements in or relating to Electrodeposition of Lead Dioxide
Inventor: GIBSON FRED DANIEL JUNIOR
IPC: C25B11/04
Filed: 1966-07-19
Abstract: 1,159,241. Electro-depositing lead dioxide; anodizing; producing chlorine, producing bromine- and iodine-compounds; chrome plating. F. D. GIBSON, B. B. HALKER and R. L. THAYER. July 19, 1966 [July 22, 1965; Jan. 13, 1966], No. 32298/ 66. Heading C7B. PbO 2  is electro-deposited as a coating on a substrate using an electrolyte containing Pb(NO 3 ) 2  (e.g. 50-200 g/1) and HNO 3  (e.g. 5-20 g/1) (e.g. at 73-92‹ C. ) with the Fe content of the electrolyte arranged to be in the range of from 0 to 0À02 g/1 of electrolyte calculated as free Fe at least at the start of the electro-deposition. The electrolyte may contain NaF. Both copper nitrate and nickel nitrate may be substantially absent from the electrolyte. Details are given for removing Fe and chlorides from the electrolyte. The process may be operated continuously with effluent electrolyte from the electrolytic cell being replenished with PbO and returned to the cell through a continuous circuit. At repeated intervals, samples of the electrolyte may be tested to determine the amount of Fe and chlorides present. Whenever either is found to be in excess of predetermined limits a portion of the electrolyte is withdrawn from the continuous circuit, transferred to a treatment tank and after treatment to remove the excess is returned to the plating cell, the coating process being uninterrupted. Organic impurities may also be removed. The electrolyte is agitated during electrolysis. The PbO 2  may be deposited on graphite, Ti, Ta, Zr, Hf or Nb substrates. Specified cathodes are of stainless steel, graphite, Cu or Ti. A tightly adherent PbO a  coating may be produced to provide anodes for use in other processes  (see below) or a coating may be produced which is subsequently stripped and comminuted to produce powder. Tightly adherent PbO 2  coatings are produced using continuous current but the current density may be reduced in one or two steps. Prior to deposition, graphite anodes may be planed and Ti, Ta, Zr, Hf and Nb anodes may be sandblasted. The anodes may be plates, rods or tubes. If they are tubes, they may be filled with sand. In order to prevent curling of a Ti, Ta, Zr, Hf or Nb plate during deposition of PbO 2 , the PbO 2  may be deposited only on separated discrete areas of the plate. This may be achieved by anodizing the plate and then removing the anodized coating only from the areas to be coated with PbO 2 . Anodizing may be in an electrolyte containing NaC1 and sodium chromate at #H 5-6 using an increasing voltage to keep current density constant. Removal of the anodized coating may be by sand blasting. A substrate may be coated with PbO 2  on only one side so as to produce an electrode which may be subsequently used as a bi-polar electrode. In producing powdered PbO 2 , a Ti, Ta, Zr, Hf or Nb anode is first abraded with a wire brush, a thin coating of PbO 2  is plated thereon, the anode is washed and further PbO 2  is deposited. This aids stripping of PbO 2  from the anode. Substrates with tightly adherent PbO 2  coatings produced by the process may be used as anodes in the electrolytic production of sodium chlorate; sodium perchlorate; chlorine; alkali earth hypochlorites, chlorates and perchlorates; sodium hypochlorite; sodium bromate, iodate, periodate; potassium chlorate and perchlorate; iodic acid; periodic acid; potassium bromates, iodates, and periodates and as an inert anode in chrome plating solutions.