1911 Encyclopædia Britannica/Electroplating

ELECTROPLATING, the art of depositing metals by the electric current. In the article Electrolysis it is shown how the passage of an electric current through a solution containing metallic ions involves the deposition of the metal on the cathode. Sometimes the metal is deposited in a pulverulent form, at others as a firm tenacious film, the nature of the deposit being dependent upon the particular metal, the concentration of the solution, the difference of potential between the electrodes, and other experimental conditions. As the durability of the electro-deposited coat on plated wares of all kinds is of the utmost importance, the greatest care must be taken to ensure its complete adhesion. This can only be effected if the surface of the metal on which the deposit is to be made is chemically clean. Grease must be removed by potash, whiting or other means, and tarnish by an acid or potassium cyanide, washing in plenty of water being resorted to after each operation. The vats for depositing may be of enamelled iron, slate, glazed earthenware, glass, lead-lined wood, &c. The current densities and potential differences frequently used for some of the commoner metals are given in the following table, taken from M‘Millan’s Treatise on Electrometallurgy. It must be remembered, however, that variations in conditions modify the electromotive force required for any given process. For example, a rise in temperature of the bath causes an increase in its conductivity, so that a lower E.M.F. will suffice to give the required current density; on the other hand, an abnormally great distance between the electrodes, or a diminution in acidity of an acid bath, or in the strength of the solution used, will increase the resistance, and so require the application of a higher E.M.F.

Metal.	Amperes.		Volts between Anode and Cathode.
	Per sq. decimetre of Cathode Surface.	Per sq. in. of Cathode Surface.
Antimony	0.4-0.5	0.02-0.03	1.0-1.2
Brass	0.5-0.8	0.03-0.05	3.0-4.0
Copper, acid bath	1.0-1.5	0.065-0.10	0.5-1.5
Copper, alkaline bath	0.3-0.5	0.02-0.03	3.0-5.0
Gold	0.1	0.006	0.5-4.0
Iron	0.5	0.03	1.0
Nickel, at first	1.4-1.5	0.09-0.10	5.0
Nickel, after	0.2-0.3	0.015-0.02	1.5-2.0
Nickel, on zinc	0.4	0.025	4.0-5.0
Silver	0.2-0.5	0.015-0.03	0.75-1.0
Zinc	0.3-0.6	0.02-0.04	2.5-3.0

Large objects are suspended in the tanks by hooks or wires, care being taken to shift their position and so avoid wire-marks. Small objects are often heaped together in perforated trays or ladles, the cathode connecting-rod being buried in the midst of them. These require constant shifting because the objects are in contact at many points, and because the top ones shield those below from the depositing action of the current. Hence processes have been patented in which the objects to be plated are suspended in revolving drums between the anodes, the rotation of the drum causing the constant renewal of surfaces and affording a burnishing action at the same time. Care must be taken not to expose goods in the plating-bath to too high a current density, else they may be “burnt”; they must never be exposed one at a time to the full anode surface, with the current flowing in an empty bath, but either one piece at a time should be replaced, or some of the anodes should be transferred temporarily to the place of the cathodes, in order to distribute the current over a sufficient cathode-area. Burnt deposits are dark-coloured, or even pulverulent and useless. The strength of the current may also be regulated by introducing lengths of German silver or iron wire, carbon rod, or other inferior conductors in the path of the current, and a series of such resistances should always be provided close to the tanks. Ammeters to measure the volume, and voltmeters to determine the pressure of current supplied to the baths, should also be provided. Very irregular surfaces may require the use of specially shaped anodes in order that the distance between the electrodes may be fairly uniform, otherwise the portion of the cathode lying nearest to the anode may receive an undue share of the current, and therefore a greater thickness of coat. Supplementary anodes are sometimes used in difficult cases of this kind. Large metallic surfaces (especially external surfaces) are sometimes plated by means of a “doctor,” which, in its simplest form, is a brush constantly wetted with the electrolyte, with a wire anode buried amid the hairs or bristles; this brush is painted slowly over the surface of the metal to be coated, which must be connected to the negative terminal of the electrical generator. Under these conditions electrolysis of the solution in the brush takes place. Iron ships’ plates have recently been coated with copper in sections (to prevent the adhesion of barnacles), by building up a temporary trough against the side of the ship, making the thoroughly cleansed plate act both as cathode and as one side of the trough. Decorative plating-work in several colours (e.g. “parcel-gilding”) is effected by painting a portion of an object with a stopping-out (i.e. a non-conducting) varnish, such as copal varnish, so that this portion is not coated. The varnish is then removed, a different design stopped out, and another metal deposited. By varying this process, designs in metals of different colours may readily be obtained.

Reference must be made to the textbooks (see Electrochemistry) for a fuller account of the very varied solutions and methods employed for electroplating with silver, gold, copper, iron and nickel. It should be mentioned here, however, that solutions which would deposit their metal on any object by simple immersion should not be generally used for electroplating that object, as the resulting deposit is usually non-adhesive. For this reason the acid copper-bath is not used for iron or zinc objects, a bath containing copper cyanide or oxide dissolved in potassium cyanide being substituted. This solution, being an inferior conductor of electricity, requires a much higher electromotive force to drive the current through it, and is therefore more costly in use. It is, however, commonly employed hot, whereby its resistance is reduced. Zinc is commonly deposited by electrolysis on iron or steel goods which would ordinarily be “galvanized,” but which for any reason may not conveniently be treated by the method of immersion in fused zinc. The zinc cyanide bath may be used for small objects, but for heavy goods the sulphate bath is employed. Sherard Cowper-Coles patented a process in which, working with a high current density, a lead anode is used, and powdered zinc is kept suspended in the solution to maintain the proportion of zinc in the electrolyte, and so to guard against the gradual acidification of the bath. Cobalt is deposited by a method analogous to that used for its sister-metal nickel. Platinum, palladium and tin are occasionally deposited for special purposes. In the deposition of gold the colour of the deposit is influenced by the presence of impurities in the solution; when copper is present, some is deposited with the gold, imparting to it a reddish colour, whilst a little silver gives it a greenish shade. Thus so-called coloured-gold deposits may be produced by the judicious introduction of suitable impurities. Even pure gold, it may be noted, is darker or lighter in colour according as a stronger or a weaker current is used. The electro-deposition of brass—mainly on iron ware, such as bedstead tubes—is now very widely practised, the bath employed being a mixture of copper, zinc and potassium cyanides, the proportions of which vary according to the character of the brass required, and to the mode of treatment. The colour depends in part upon the proportion of copper and zinc, and in part upon the current density, weaker currents tending to produce a redder or yellower metal. Other alloys may be produced, such as bronze, or German silver, by selecting solutions (usually cyanides) from which the current is able to deposit the constituent metals simultaneously.

Electrolysis has in a few instances been applied to processes of manufacture. For example, Wilde produced copper printing surfaces for calico printing-rollers and the like by immersing rotating iron cylinders as cathodes in a copper bath. Elmore, Dumoulin, Cowper-Coles and others have prepared copper cylinders and plates by depositing copper on rotating mandrels with special arrangements. Others have arranged a means of obtaining high conductivity wire from cathode-copper without fusion, by depositing the metal in the form of a spiral strip on a cylinder, the strip being subsequently drawn down in the usual way; at present, however, the ordinary methods of wire production are found to be cheaper. J. W. Swan (Journ. Inst. Elec. Eng., 1898, vol. xxvii. p. 16) also worked out, but did not proceed with, a process in which a copper wire whilst receiving a deposit of copper was continuously passed through the draw-plate, and thus indefinitely extended in length. Cowper-Coles (Journ. Inst. Elec. Eng., 1898, 27, p. 99) very successfully produced true parabolic reflectors for projectors, by depositing copper upon carefully ground and polished glass surfaces rendered conductive by a film of deposited silver.