Electrometallurgy
ELECTROMETALLURGY. The present article, as explained under Electrochemistry , treats only of those processes in which electricity is applied to the production of chemical reactions or molecular changes at furnace temperatures. In many of these the application of heat is necessary to bring the substances used into the liquid state for the purpose of electrolysis, aqueous solutions being unsuitable. Among the earliest experiments in this branch of the subject were those of Sir H. Davy, who in 1807 (Phil. Trans., 1808, p. 1), produced the alkali metals by passing an intense current of electricity from a platinum wire to a platinum dish, through a mass of fused caustic alkali. The action was started in the cold, the alkali being slightly moistened to render it a conductor; then, as the current passed, heat was produced and the alkali fused, the metal being deposited in the liquid condition. Later, A. Matthiessen (Quarterly Journ. Chem. Soc. viii. 30) obtained potassium by the electrolysis of a mixture of potassium and calcium chlorides fused over a lamp. There are here foreshadowed two types of electrolytic furnace-operations: (a) those in which external heating maintains the electrolyte in the fused condition, and (b) those in which a current-density is applied sufficiently high to develop the heat necessary to effect this object unaided. Much of the earlier electro-metallurgical work was done with furnaces of the (a) type, while nearly all the later developments have been with those of class (b). There is a third class of operations, exemplified by the manufacture of calcium carbide, in which electricity is employed solely as a heating agent; these are termed electrothermal, as distinguished from electrolytic. In certain electrothermal processes (e.g. calcium carbide production) the heat from the current is employed in raising mixtures of substances to the temperature at which a desired chemical reaction will take place between them, while in others (e.g. the production of graphite from coke or gas-carbon) the heat is applied solely to the production of molecular or physical changes. In ordinary electrolytic work only the continuous current may of course be used, but in electrothermal work an alternating current is equally available.
Electric Furnaces. - Independently of the question of the application of external heating, the furnaces used in electrometallurgy may be broadly classified into (i.) arc furnaces, in which the intense heat of the electric arc is utilized, and (ii.) resistance and incandescence furnaces, in which the heat is generated by an electric current overcoming the resistance of an inferior conductor.
Excepting such experimental arrangements as that of C.M. Despretz (C.R., 1849, 29) for use on a small scale in the laboratory, Pichou in France and J.H. Johnson in England appear, in 1853, to have introduced the earliest practical form of furnace. In these arrangements, which were similar if not identical, the furnace charge was crushed to a fine powder and passed through two or more electric arcs in succession. When used for ore smelting, the reduced metal and the accompanying slag were to be caught, after leaving the arc and while still liquid, in a hearth fired with ordinary fuel. Although this primitive furnace could be made to act, its efficiency was low, and the use of a separate fire was disadvantageous. In 1878 Sir William Siemens patented a form of furnace [1] which is the type of a very large number of those designed by later inventors.
In the best-known form a plumbago crucible was used with a hole cut in the bottom to receive a carbon rod, which was ground in so as to make a tight joint. This rod was connected with the positive pole of the dynamo or electric generator. The crucible was fitted with a cover in which were two holes; one at the side to serve at once as sight-hole and charging door, the other in the centre to allow a second carbon rod to pass freely (without touching) into the interior. This rod was connected with the negative pole of the generator, and was suspended from one arm of a balance-beam, while from the other end of the beam was suspended a vertical hollow iron cylinder, which could be moved into or out of a wire coil or solenoid joined as a shunt across the two carbon rods of the furnace. The solenoid was above the iron cylinder, the supporting rod of which passed through it as a core. When the furnace with this well-known regulating device was to be used, say, for the melting of metals or other conductors of electricity, the fragments of metal were placed in the crucible and the positive electrode was brought near them. Immediately the current passed through the solenoid it caused the iron cylinder to rise, and, by means of its supporting rod, forced the end of the balance beam upwards, so depressing the other end that the negative carbon rod was forced downwards into contact with the metal in the crucible. This action completed the furnace-circuit, and current passed freely from the positive carbon through the fragments of metal to the negative carbon, thereby reducing the current through the shunt. At once the attractive force of the solenoid on the iron cylinder was automatically reduced, and the falling of the latter caused the negative carbon to rise, starting an arc between it and the metal in the crucible. A counterpoise was placed on the solenoid end of the balance beam to act against the attraction of the solenoid, the position of the counterpoise determining the length of the arc in the crucible. Any change in the resistance of the arc, either by lengthening, due to the sinking of the charge in the crucible, or by the burning of the carbon, affected the proportion of current flowing in the two shunt circuits, and so altered the position of the iron cylinder in the solenoid that the length of arc was, within limits, automatically regulated. Were it not for the use of some such device the arc would be liable to constant fluctuation and to frequent extinction. The crucible was surrounded with a bad conductor of heat to minimize loss by radiation. The positive carbon was in some cases replaced by a water-cooled metal tube, or ferrule, closed, of course, at the end inserted in the crucible. Several modifications were proposed, in one of which, intended for the heating of non-conducting substances, the electrodes were passed horizontally through perforations in the upper part of the crucible walls, and the charge in the lower part of the crucible was heated by radiation.
The furnace used by Henri Moissan in his experiments on reactions at high temperatures, on the fusion and volatilization of refractory materials, and on the formation of carbides, silicides and borides of various metals, consisted, in its simplest form, of two superposed blocks of lime or of limestone with a central cavity cut in the lower block, and with a corresponding but much shallower inverted cavity in the upper block, which thus formed the lid of the furnace. Horizontal channels were cut on opposite walls, through which the carbon poles or electrodes were passed into the upper part of the cavity. Such a furnace, to take a current of 4 H.P. (say, of 60 amperes and 50 volts), measured externally about 6 by 6 by 7 in., and the electrodes were about 0.4 in. in diameter, while for a current of 100 H.P. (say, of 746 amperes and 100 volts) it measured about 14 by 12 by 14 in., and the electrodes were about 1.5 in. in diameter. In the latter case the crucible, which was placed in the cavity immediately beneath the arc, was about 3 in. in diameter (internally), and about 3 in. in height. The fact that energy is being used at so high a rate as 100 H.P. on so small a charge of material sufficiently indicates that the furnace is only used for experimental work, or for the fusion of metals which, like tungsten or chromium, can only be melted at temperatures attainable by electrical means. Moissan succeeded in fusing about lb of either of these metals in 5 or 6 minutes in a furnace similar to that last described. He also arranged an experimental tube-furnace by passing a carbon tube horizontally beneath the arc in the cavity of the lime blocks. When prolonged heating is required at very high temperatures it is found necessary to line the furnace-cavity with alternate layers of magnesia and carbon, taking care that the lamina next to the lime is of magnesia; if this were not done the lime in contact with the carbon crucible would form calcium carbide and would slag down, but magnesia does not yield a carbide in this way. Chaplet has patented a muffle or tube furnace, similar in principle, for use on a larger scale, with a number of electrodes placed above and below the muffle-tube. The arc furnaces now widely used in the manufacture of calcium carbide on a large scale are chiefly developments of the Siemens furnace. But whereas, from its construction, the Siemens furnace was intermittent in operation, necessitating stoppage of the current while the contents of the crucible were poured out, many of the newer forms are specially designed either to minimize the time required in effecting the withdrawal of one charge and the introduction of the next, or to ensure absolute continuity of action, raw material being constantly charged in at the top and the finished substance and by-products (slag, etc.) withdrawn either continuously or at intervals, as sufficient quantity shall have accumulated. In the King furnace, for example, the crucible, or lowest part of the furnace, is made detachable, so that when full it may be removed and an empty crucible substituted. In the United States a revolving furnace is used which is quite continuous in action.
Incandescence furnaces
The class of furnaces heated by electrically incandescent materials has been divided by Borchers into two groups: (1) those in which the substance is heated by contact with a substance offering a high resistance to the current passing through it, and (2) those in which the substance to be heated itself affords the resistance to the passage of the current whereby electric energy is converted into heat. Practically the first of these furnaces was that of Despretz, in which the mixture to be heated was placed in a carbon tube rendered incandescent by the passage of a current through its substance from end to end. In 1880 W. Borchers introduced his resistance-furnace, which, in one sense, is the converse of the Despretz apparatus. A thin carbon pencil, forming a bridge between two stout carbon rods, is set in the midst of the mixture to be heated. On passing a current through the carbon the small rod is heated to incandescence, and imparts heat to the surrounding mass. On a larger scale several pencils are used to make the connexions between carbon blocks which form the end walls of the furnace, while the side walls are of fire-brick laid upon one another without mortar. Many of the furnaces now in constant use depend mainly on this principle, a core of granular carbon fragments stamped together in the direct line between the electrodes, as in Acheson's carborundum furnace, being substituted for the carbon pencils. In other cases carbon fragments are mixed throughout the charge, as in E.H. and A.H. Cowles's zinc-smelting retort. In practice, in these furnaces, it is possible for small local arcs to be temporarily set up by the shifting of the charge, and these would contribute to the heating of the mass. In the remaining class of furnace, in which the electrical resistance of the charge itself is utilized, are the continuous-current furnaces, such as are used for the smelting of aluminium, and those alternating-current furnaces, (e.g. for the production of calcium carbide) in which a portion of the charge is first actually fused, and then maintained in the molten condition by the current passing through it, while the reaction between further portions of the charge is proceeding.
Uses and advantages
For ordinary metallurgical work the electric furnace, requiring as it does (excepting where waterfalls or other cheap sources of power are available) the intervention of the boiler and steam-engine, or of the gas or oil engine, with a consequent loss of energy, has not usually proved so economical as an ordinary direct fired furnace. But in some cases in which the current is used for electrolysis and for the production of extremely high temperatures, for which the calorific intensity of ordinary fuel is insufficient, the electric furnace is employed with advantage. The temperature of the electric furnace, whether of the arc or incandescence type, is practically limited to that at which the least easily vaporized material available for electrodes is converted into vapour. This material is carbon, and as its vaporizing point is (estimated at) over 3500° C., and less than 4000° C., the temperature of the electric furnace cannot rise much above 3500° C. (6330° F.); but H. Moissan showed that at this temperature the most stable of mineral combinations are dissociated, and the most refractory elements are converted into vapour, only certain borides, silicides and metallic carbides having been found to resist the action of the heat. It is not necessary that all electric furnaces shall be run at these high temperatures; obviously, those of the incandescence or resistance type may be worked at any convenient temperature below the maximum. The electric furnace has several advantages as compared with some of the ordinary types of furnace, arising from the fact that the heat is generated from within the mass of material operated upon, and (unlike the blast-furnace, which presents the same advantage) without a large volume of gaseous products of combustion and atmospheric nitrogen being passed through it. In ordinary reverberatory and other heating furnaces the burning fuel is without the mass, so that the vessel containing the charge, and other parts of the plant, are raised to a higher temperature than would otherwise be necessary, in order to compensate for losses by radiation, convection and conduction. This advantage is especially observed in some cases in which the charge of the furnace is liable to attack the containing vessel at high temperatures, as it is often possible to maintain the outer walls of the electric furnace relatively cool, and even to keep them lined with a protecting crust of unfused charge. Again, the construction of electric furnaces may often be exceedingly crude and simple; in the carborundum furnace, for example, the outer walls are of loosely piled bricks, and in one type of furnace the charge is simply heaped on the ground around the carbon resistance used for heating, without containing-walls of any kind. There is, however, one (not insuperable) drawback in the use of the electric furnace for the smelting of pure metals. Ordinarily carbon is used as the electrode material, but when carbon comes in contact at high temperatures with any metal that is capable of forming a carbide a certain amount of combination between them is inevitable, and the carbon thus introduced impairs the mechanical properties of the ultimate metallic product. Aluminium, iron, platinum and many other metals may thus take up so much carbon as to become brittle and unforgeable. It is for this reason that Siemens, Borchers and others substituted a hollow water-cooled metal block for the carbon cathode upon which the melted metal rests while in the furnace. Liquid metal coming in contact with such a surface forms a crust of solidified metal over it, and this crust thickens up to a certain point, namely, until the heat from within the furnace just overbalances that lost by conduction through the solidified crust and the cathode material to the flowing water. In such an arrangement, after the first instant, the melted metal in the furnace does not come in contact with the cathode material.
Electrothermal Processes. - In these processes the electric current is used solely to generate heat, either to induce chemical reactions between admixed substances, or to produce a physical (allotropic) modification of a given substance. Borchers predicted that, at the high temperatures available with the electric furnace, every oxide would prove to be reducible by the action of carbon, and this prediction has in most instances been justified. Alumina and lime, for example, which cannot be reduced at ordinary furnace temperatures, readily give up their oxygen to carbon in the electric furnace, and then combine with an excess of carbon to form metallic carbides. In 1885 the brothers Cowles patented a process for the electrothermal reduction of oxidized ores by exposure to an intense current of electricity when admixed with carbon in a retort. Later in that year they patented a process for the reduction of aluminium by carbon, and in 1886 an electric furnace with sliding carbon rods passed through the end walls to the centre of a rectangular furnace. The impossibility of working with just sufficient carbon to reduce the alumina, without using any excess which would be free to form at least so much carbide as would suffice, when diffused through the metal, to render it brittle, practically restricts the use of such processes to the production of aluminium alloys. Aluminium bronze (aluminium and copper) and ferro-aluminium (aluminium and iron) have been made in this way; the latter is the more satisfactory product, because a certain proportion of carbon is expected in an alloy of this character, as in ferromanganese and cast iron, and its presence is not objectionable. The furnace is built of fire-brick, and may measure (internally) 5 ft. in length by 1 ft. 8 in. in width, and 3 ft. in height. Into each end wall is built a short iron tube sloping downwards towards the centre, and through this is passed a bundle of five 3-in. carbon rods, bound together at the outer end by being cast into a head of cast iron for use with iron alloys, or of cast copper for aluminium bronze. This head slides freely in the cast iron tubes, and is connected by a copper rod with one of the terminals of the dynamo supplying the current. The carbons can thus, by the application of suitable mechanism, be withdrawn from or plunged into the furnace at will. In starting the furnace, the bottom is prepared by ramming it with charcoal-powder that has been soaked in milk of lime and dried, so that each particle is coated with a film of lime, which serves to reduce the loss of current by conduction through the lining when the furnace becomes hot. A sheet iron case is then placed within the furnace, and the space between it and the walls rammed with limed charcoal; the interior is filled with fragments of the iron or copper to be alloyed, mixed with alumina and coarse charcoal, broken pieces of carbon being placed in position to connect the electrodes. The iron case is then removed, the whole is covered with charcoal, and a cast iron cover with a central flue is placed above all. The current, either continuous or alternating, is then started, and continued for about 1 to 1 hours, until the operation is complete, the carbon rods being gradually withdrawn as the action proceeds. In such a furnace a continuous current, for example, of 3000 amperes, at 50 to 60 volts, may be used at first, increasing to 5000 amperes in about half an hour. The reduction is not due to electrolysis, but to the action of carbon on alumina, a part of the carbon in the charge being consumed and evolved as carbon monoxide gas, which burns at the orifice in the cover so long as reduction is taking place. The reduced aluminium alloys itself immediately with the fused globules of metal in its midst, and as the charge becomes reduced the globules of alloy unite until, in the end, they are run out of the tap-hole after the current has been diverted to another furnace. It was found in practice (in 1889) that the expenditure of energy per pound of reduced aluminium was about 23 H.P.-hours, a number considerably in excess of that required at the present time for the production of pure aluminium by the electrolytic process described in the article Aluminium. Calcium carbide, graphite (q.v.), phosphorus (q.v.) and carborundum (q.v.) are now extensively manufactured by the operations outlined above.
Electrolytic Processes. - The isolation of the metals sodium and potassium by Sir Humphry Davy in 1807 by the electrolysis of the fused hydroxides was one of the earliest applications of the electric current to the extraction of metals. This pioneering work showed little development until about the middle of the 19th century. In 1852 magnesium was isolated electrolytically by R. Bunsen, and this process subsequently received much attention at the hands of Moissan and Borchers. Two years later Bunsen and H.E. Sainte Claire Deville working independently obtained aluminium (q.v.) by the electrolysis of the fused double sodium aluminium chloride. Since that date other processes have been devised and the electrolytic processes have entirely replaced the older methods of reduction with sodium. Methods have also been discovered for the electrolytic manufacture of calcium (q.v.), which have had the effect of converting a laboratory curiosity into a product of commercial importance. Barium and strontium have also been produced by electro-metallurgical methods, but the processes have only a laboratory interest at present. Lead, zinc and other metals have also been reduced in this manner.
For further information the following books, in addition to those mentioned at the end of the article Electrochemistry , may be consulted: Borchers, Handbuch der Elektrochemie; Electric Furnaces (Eng. trans. by H.G. Solomon, 1908); Moissan, The Electric Furnace (1904); J. Escard, Fours électriques (1905); Les Industries électrochimiques (1907).
(W. G. M.)
[1] Cf. Siemens's account of the use of this furnace for experimental purposes in British Association Report for 1882.
Note - this article incorporates content from Encyclopaedia Britannica, Eleventh Edition, (1910-1911)
