The Story of Electricity

by John Munro

CHAPTER XL

ELECTRO-CHEMISTRY AND ELECTRO-METALLURGY.

In no department of the application of electricity to practical work has there been a greater development than in electro- metallurgy and electro-chemistry. To-day there are vast industries depending upon electrical processes and the developments of a quarter of a century have been truly remarkable. Already more than one-half of the copper used in the arts is derived by electrolytic refining. The production of aluminum depends entirely on electricity, the electric furnace as a possible rival to the blast furnace for the production of iron and steel is being seriously considered, and many other metallurgical processes are being undertaken on a large scale. We have seen in our chapter on Electrolysis how a metal may be deposited from a solution of its salt and how this process could be used for deriving a pure metal or for plating or coating with the desired metal the surface of another metal or one covered with graphite. In the following pages it is intended to take up some of the more notable accomplishments in this field achieved by electricity, which have been developed to a state of commercial importance.

The electric arc not only supplies light, but heat of great intensity which the electrical engineer as well as the pure scientist has found so valuable for many practical operations. It is of course obvious that for most chemical operations, and especially in the field of metallurgy, heat is required for the separation of combinations of various elements, for their purification, as well as for the combination with other elements into alloys or compounds of direct utility. The usual method of generating heat is by the combustion of some fuel, such as coal, coke, gas or oil, and this has been utilized for hundreds of years in smelting metals and ores and in refining the material from a crude state. Now it may happen that a nation or region may be rich in metalliferous ores, but possess few, if any, coal deposits. Accordingly the ore must be mined and transported considerable distances for treatment and the advantages of manufacturing industries are lost to the neighborhood of its original production. But if water power is available, as it is in many mountainous countries where various ores are found, then this power can be transformed into electricity which is available as power not only in various manufacturing operations, but for primary metallurgical work in smelting the ores and obtaining the metal therefrom. A striking instance of this is the kingdom of Sweden, which contains but little coal, yet is rich in minerals and in water power, so that its waterfalls have been picturesquely alluded to as the country's "white coal." Likewise, at Niagara Falls a portion of the vast water power developed there has been used in the manufacture of aluminum, calcium carbide, carborundum, and other materials, while at other points in the United States and Canada, not to mention Europe, large industries where electricity is used for metallurgical or chemical work are carried on and the erection of new plants is contemplated.

The application of electricity to metallurgical and chemical work has been, in nearly all cases, the result of scientific research, and elaborate experimental laboratories are maintained by the various corporations interested in the present or future use of electrical processes. It is recognized by many of the older workers in this field that electrical developments are bound to come in the near future, and while they have not installed such appliances in their works yet they are keeping close watch of present developments, and in many cases experimental investigation and research is being carried on where electrical methods have not yet been introduced generally into the plant.

Prior to 1886 the refining of copper was the only electro- metallurgical industry and at that time it was carried on on a very limited scale. To-day the production of electrolytic copper as an industry is second in importance only to the actual production of that metal. From the small refinery started by James Elkington at Pembury in South Wales, a vast industry has developed in which there has been a change in the size of operations and in the details of methods rather than in the fundamental process. For a solution of copper sulphate is employed as the electrolyte, blocks of raw copper as the anodes, and thin sheets of pure copper as the cathodes. The passage of the electric current, as we have seen on page 79, in the chapter on Electrolysis, is able to decompose the copper in the electrolyte and to precipitate chemically pure copper on the cathode, the copper of the solution being replenished from the raw material used as the anode by which the current is passed into the bath. At this Welsh factory 250 tons yearly were produced, and small earthenware pots sufficed for the electrolyte. Thirty years later one American factory alone was able to produce at least 350 tons of electrolytic copper in twenty-four hours, and over 400,000 tons is the aggregate output of the refineries of the world, which is about 53 per cent, of the total raw copper production. Of this amount 85 per cent, comes from American refineries, whose output has more than doubled since 1900.

The chief reason for this increased output of electrolytic copper has been the great demand for its use in the electrical industries where not only a vast amount is consumed, but where copper of high purity, to give the maximum conductivity required by the electrical engineer, is demanded. When it is realized that every dynamo is wound with copper wire and that the same material is used for the trolley wire and for the distribution wires in electric lighting, it will be apparent how the demand for copper has increased in the last quarter of a century. Electrolytic methods not only supply a purer article and are economical to operate, especially if there is water power in the vicinity, but the copper ores contain varying amounts of silver and gold which can be recovered from the slimes obtained in the electrolytic process. Wherever possible machinery has been substituted for hand labor, the raw copper anodes have been cast, and the charging and discharging of the vats is carried on by the most modern mechanical methods in which efficiency and economy are secured. On the chemical side of the process attempts have been made to improve the electrolyte, notably by the addition of a small amount of hydrochloric acid to prevent the loss of silver in the slimes, and this part of the work is watched with quite as much care as the other stages. Electric furnaces have also been constructed for smelting copper ores, but these have not found wide application, and the problem is one of the future. For the most part the copper electrically refined is produced in an ordinary smelter. The mints of the United States are now all equipped with electrolytic refining plants to produce the pure metal needed for coinage and they have proved most satisfactory and economical.

As the electrolytic production of copper is an industry of great present importance, so the production of iron and steel by electricity promises to be of the greatest future importance. Electric furnaces for making steel are now maintained, and the industry has passed beyond an experimental condition. But it has not reached the point where it is competing with the Bessemer or the open hearth process of the manufacture of steel, while for the smelting of iron ores the electric furnace has not yet been found practical from an economic standpoint. Before 1880 Sir William Siemens showed that an electric arc could be used to melt iron or steel in a crucible, and he patented an electric crucible furnace which was the first attempt to use electricity in iron and steel manufacture. He stated that the process would not be too costly and that it had a great future before it. This was an application of the intense heat of the arc, which supplies a higher temperature than any source known except that of the sun. This heat is used to melt the metal, in which condition various impurities can be removed and necessary ingredients added. Siemens' furnace did not find extensive application, largely on account of the great metallurgical developments then taking place in the iron industry and the thorough knowledge of metallurgical processes as carried on, possessed by metallurgical engineers. But the idea by no means languished, and in 1899 Paul Heroult and other electro-metallurgists were active in developing a practical electric furnace for iron and steel work. The Swedish engineer, F. A. Kjellin, was also active and as the result of the efforts of these and other workers, by 1909 electric furnaces were employed, not only in the manufacture of special steels whose composition and making were attended with special care, but for rails and structural material. There were reported to be between thirty and forty electric steel plants in various countries, and the outlook for the future was distinctly bright. The application of electro- metallurgy at this time was confined to the manufacture of steel, as the smelting of iron had not emerged from the experimental stage of its development, though extensive trials on a large scale of various furnaces have been undertaken in Europe and by the Canadian government at Sault Ste. Marie, where the Heroult furnace, soon to be described, was employed. Electro-metallurgy of steel, as in all utilization of electrical power, depends upon obtaining electricity at a reasonable cost, and then utilizing the heat of the arc or of the current in the most practical and economical form. One of the pioneer furnaces for this purpose which has seen considerable development and practical application is the Heroult furnace, which is a tilting furnace of the crucible type, whose operation depends upon both the heat of the arc and on the heat produced by the resistance of the molten material. In the Heroult process the impurities of the molten iron are washed out by treatment with suitable slags. The furnace consists of a crucible in the form of a closed shallow iron tank, thickly lined with dolomite and magnazite brick, with a hearth of crushed dolomite. The electric current enters the crucible through two massive electrodes of solid carbon, 70 inches in length and 14 inches in diameter, so mounted that they can be moved either vertically or horizontally by the electrician in charge. These electrodes are water-jacketed to reduce the rate of consumption. The furnace contains an inlet for an air blast and openings in its covering for charging the material and for the escape of the gases. The actual process of steel-making consists of charging the crucible with steel scrap, pig iron, iron ore, and lime of the proper quality and in the right proportions, placing this material on the hearth of the furnace. Combined arc and resistance heating is applied to raise the charge to the melting point. The current is of 120 volts or the same as that used in an ordinary incandescent lighting circuit, but is alternating and of 4,000 amperes. This is for a three-ton furnace. As the material melts the lime and silicates form a slag which fuses rapidly and covers the iron and steel in the crucible, so that the molten bath is protected from the action of the gases which are liberated and the oxygen in the atmosphere. The next step in the process is to lower the electrodes until they just touch beneath the surface of the molten slag so that subsequent heating is due not to the effect of the arc but to the resistance which the bath offers to the passage of the current.

Air from an air blast is introduced into the crucible to oxidize the impurities of the metal, particularly the sulphur and the phosphorus which are carried into the slag and this is removed by the tilting of the furnace. Fresh quantities of lime, etc., are added, and the operation is repeated until a comparatively pure metal remains, when an alloy high in carbon is added and whatever other constituents are desired for the finished steel. The charge is then tipped into the casting ladle and the part of the electric furnace is finished. For three tons of steel eight to ten hours are required in the Heroult crucible furnace.

Furnaces of an altogether different type are those employing an alternating current, such as the Kjellin and Rochling furnaces, where the metal to be heated really forms the secondary circuit of a large and novel form of transformer which in principle is analogous to the familiar transformer seen to step down the potential of alternating current as for house lighting. For such a transformer the primary coil is formed of heavy wire and the secondary circuit is the molten metal which is contained in an annular channel. The current obtained in the metal is of considerable intensity, but at lower potential than that in the primary coil, and roughly is equal to that of the primary multiplied by the number of turns in the coil. The condition is similar to that in the ordinary induction coil where the current from a battery at low potential flows around a coil of a few turns and is surrounded by a second coil with a large number of turns of fine wire in which current of small intensity but of high potential is generated. In the induction furnace the reverse takes place and the current flowing in the metal derived from that of the heavy coil in the primary is of great intensity. For this type of furnace molten metal is required and the furnace is never entirely emptied, so that its process is continuous. The temperature attained is not as high as in the arc furnace, so that the raw materials used have to be of a high degree of purity, and this has proved a restriction of the field of usefulness of this type of furnace in many cases. It, however, has been improved recently and two rings of molten metal employed instead of one so that a wide centre trough is obtained in which the metal is subjected to ordinary resistance heat by direct or alternating currents. This furnace permits of various metallurgical operations and the elimination of impurities as in the Heroult type.

A third type of furnace that is meeting with some extensive use is the Giroud, which, like the Heroult furnace, is based on the arc and resistance in principle, but in its construction has a number of different features. As the current passes horizontally from the upper electrodes through the slag and molten metal in the furnace chamber to the base electrodes of the furnace, it permits of the easy regulation of the arcs and the use of lower electromotive force, while there is only one arc in the path of the current instead of two as in the Heroult type.

Sufficient quantities of steel have been made in electric furnaces to permit of the determination of the quality of the product as well as the economy of the process. It has been found in Germany that rail steel made in the induction furnace has a much higher bending and breaking limit than ordinary Bessemer or Thomas rail steel, and in Germany in 1908 rails so made commanded a considerably higher price per ton than those of ordinary rail steel. After trial orders had proved satisfactory, in 1908 5,000 tons of rails were ordered for the Italian and Swiss governments at a German works, where furnaces of eight tons capacity had been installed. In the United States only a few electric steel furnaces are in operation, and these, for the most part, for purposes of demonstration and experiment. But in Europe the industry is well established, and while at present small, is constantly growing and possesses an assured future.

In addition to the manufacture of steel, the application of the electric furnace for producing what are known as ferro-alloys, or alloys of iron, silicon, chromium, manganese, tungsten and vanadium, is now a large and important industry. Special steels have their uses in different mechanical applications and the advantage of alloying them with the rarer metals has been demonstrated for several important purposes, as for example, the use of chrome steel for armor plate, and steel containing vanadium for parts of motor cars. These industries for the most part contain electric arc furnaces and have, as their object, the manufacture of ferro-alloys, which are introduced into the steel, it having been found advantageous to use the rare metals in this form rather than in their crude state.

There is one electro-metallurgical process that has made possible the production in commercial form and for ordinary use of a metal that once was little more than a chemical curiosity. In 1885 there were produced 3.12 tons of aluminum, and its value was roughly estimated at about $12 a pound. By 1908 America alone produced over 9,000 tons valued at over $500,000,000, while European manufacturers were also large producers. In 1888 the electrolytic manufacture of aluminum was commenced in America and in the following year it was begun in Switzerland. Aluminum is formed by the electrolysis of the aluminum oxide in a fused bath of cryolite and fluorspar. The aluminum may be obtained in the form of bauxite, and is produced in large rectangular iron pots with a thick carbon lining. The pot itself is the cathode, while large graphite rods suspended in the bath serve as the anodes. After the arc is formed and the heat of the bath rises to a sufficient degree the material is decomposed and the metal is separated out so that it can be removed by ladling or with a siphon. The application of heat to obtain this metal previous to the invention of the electric furnace could only be considered a laboratory problem and the expense involved did not permit of commercial application. Now, however, aluminum is universally available and with the expiration of certain patents, the material has sold as low as 25 cents a pound.

Electrolytic methods serve also for the refining of nickel and for the production of lead, and as in other fields of metallurgy, these processes are attracting the attention of chemists and of engineers. While tin as yet has not yielded to electrolytic or electro-thermal methods with any success, the removal of tin from tin scraps and cuttings has been carried on with considerable success. With zinc the electrolytic and electro-thermal processes have not been able yet to compete with the older metallurgical method of distillation, but an important industry is electro- galvanizing, where a solution of zinc sulphate is deposited on iron and gives a protective coating. Experimental methods with the use of electricity in extracting zinc from its ores are being tested at various European plants, but the matter has not yet reached a commercial scale.

One of the earliest notable uses of the electric furnace in a large electro-chemical industry was for the production of carborundum, a carbide of silicon, which is remarkably useful as an abrasive, being available in the manufacture of grinding stones and other like purposes to replace emery and corundum. It is produced by the use of a simple electric furnace of the resistance type, where coke, sand, and sawdust are heated to a temperature of between 2000 degrees and 3000 degrees C. The chemical reaction involves the production of carbon monoxide, and gives a carbide of silicon, a crystalline solid which has the excellent abrasive properties mentioned. The manufacture was first started by its inventor, E. G. Acheson, about 1891 on a small scale, and in the following year 1,000 pounds of the material were produced at the Niagara Falls works. Within fifteen years its output had increased to well over six million pounds.

The electric furnaces at Niagara Falls have supplied many interesting electro-chemical processes. After making a carbide in the electric furnace it was found possible to decompose it by further increasing the heat to a point where the second element is volatilized and the pure carbon in the form of artificial graphite remains. In more recent work the carbide containing the silicon has been done away with and ordinary anthracite coal used as a charge from which the pure graphite is obtained. This graphite has been found especially useful in electrical work as for electrodes, while a more recent process enables a soft variety of graphite to be obtained which becomes a competitor of the natural material.

One of the most interesting of the many electro-chemical processes is the heating of lime and coke in the electric furnace so as to obtain a product in the form of calcium carbide, which, on solution in water, forms acetylene gas, a useful and valuable illuminant. This process dates from 1893 when T. L. Willson in the United States first started its manufacture on a large scale, and the great electrochemist, Henri Moissin, about the same time independently invented a similar process as a result of his notable work with the electric furnace. The process involves merely a transformation at a high temperature, a portion of the carbon in the form of coke, uniting with pulverized lime to give the calcium carbide or CaC2. Now this material, when water is added to it, decomposes, and acetylene or C2H2 is formed, which is a gas of high illuminating value as the carbon separates and glows brightly after being heated to incandescence in the flame.

The electric furnace at Niagara Falls has been able to produce still another combination in the form of siloxicon by heating carbon and silicon to a temperature slightly below that required to produce carborundum. This product is a highly refractory material and is valuable for the manufacture of crucibles, muffles, bricks, etc., for work where extreme temperatures are employed. The electric furnace enables various elements to be isolated, such. as silicon, sodium, and phosphorus, and when obtained in their pure state they find wide application.

The most important electro-chemical work of the future is to devise some means of obtaining nitrogen from the air. It is stated by scientists that the nitrogen of the soil is being exhausted and that at some future time the Earth may not be able to bear crops sufficient for the sustenance of man, unless some artificial means be found to replenish the nitrogen. Unlimited supplies of nitrogen exist in the air, but to fix it with other materials in such form that it will be useful as a fertilizer has been one of the problems to which the electro-chemists have recently devoted much attention. By the use of the electric arc and passing air through a furnace, various substances have been tried to take up the nitrogen of the air. Thus when calcium carbide is heated and brought into contact with nitrogen one atom of carbon is given up and two atoms of nitrogen take its place, resulting in the production of cyanamide.

Other important electro-chemical processes are involved in the electrolysis of the various alkaline salts to obtain metallic sodium and such products as chlorates. Thus by the electrolysis of sodium chloride metallic sodium and chlorine is obtained. From the metallic sodium solid caustic soda is then derived by a secondary reaction, while the chlorine is combined with lime to form chloride of lime or bleaching powder. In some processes the electrolysis affords directly an alkaline hypochlorite or a chlorate, the former being of wide commercial use as a bleaching agent in textile works and in the paper industry. The same process employed in the electrolysis of sodium salts is used in the case of magnesium and calcium.

Electrolysis is also made use of in the manufacture of chloroform and iodoform, as the chlorine or iodine which is produced in the electrolytic cell is allowed to act upon the alcohol or acetone under such conditions that chloroform or iodoform is produced.

Electro-chemistry plays an important part in many other industries whose omission from our description must not be considered as indicating any lack of their importance. New processes constantly are being discovered which may range all the way from the production of artificial gems to the wholesale production of the most common chemicals used in the arts. In many branches of chemical industry manufacturing processes have been completely changed, and from the research laboratories, which all large progressive manufacturers now maintain, as well as from workers in universities and scientific schools, new methods and discoveries are constantly forthcoming.