Page:EB1911 - Volume 11.djvu/590

 Attempts have been made by two methods to make carbon crystallize in the transparent form. One is to crystallize it slowly from a solution in which it has been dissolved. The difficulty is to find a solvent. Many organic and some inorganic bodies hold carbon so loosely combined that it can be separated out under the influence of chemical action, heat or electricity, but invariably the carbon assumes the black amorphous form. The other method is to try to fuse the carbon by fierce heat, when from analogy it is argued that on cooling it will solidify to a clear limpid crystal. The progress of science in other directions has now made it pretty certain that the true mode of making diamond artificially is by a combination of these two methods. Until recently it was assumed that carbon was non-volatile at any attainable temperature, but it is now known that at a temperature of about 3600° C. it volatilizes readily, passing without liquefying directly from the solid to the gaseous state. Very few bodies act in this manner, the great majority when heated at atmospheric pressure to a sufficient temperature passing through the intermediate condition of liquidity. Some few, however, which when heated at atmospheric pressure do not liquefy, when heated at higher pressures in closed vessels obey the common rule and first become liquid and then volatilize. Sir James Dewar found the critical pressure of carbon to be about 15 tons on the sq. in.; that is to say, if heated to its critical temperature (3600° C.), and at the same time subjected to a pressure of 15 tons to the sq. in., it will assume the liquid form. Enormous as such pressures and temperatures may appear to be, they have been exceeded in some of Sir Andrew Noble’s and Sir F. Abel’s researches; in their investigations on the gases from gunpowder and cordite fired in closed steel chambers, these chemists obtained pressures as great as 95 tons to the sq. in., and temperatures as high as 4000° C. Here then, if the observations are correct, we have sufficient temperature and enough pressure to liquefy carbon; and, were there only sufficient time for these to act on the carbon, there is little doubt that the artificial formation of diamonds would soon pass from the microscopic stage to a scale more likely to satisfy the requirements of science, if not those of personal adornment.

It has long been known that the metal iron in a molten state dissolves carbon and deposits it on cooling as black opaque graphite. Moissan carried out a laborious and systematic series of experiments on the solubility of carbon in iron and other metals, and came to the conclusion that whereas at ordinary pressures the carbon separates from the solidifying iron in the form of graphite, if the pressure be greatly increased the carbon on separation will form liquid drops, which on solidifying will assume the crystalline shape and become true diamond. Many other metals dissolve carbon, but molten iron has been found to be the best solvent. The quantity entering into solution increases with the temperature of the metal. But temperature alone is not enough; pressure must be superadded. Here Moissan ingeniously made use of a property which molten iron possesses in common with some few other liquids—water, for instance—of increasing in volume in the act of passing from the liquid to the solid state. Pure iron is mixed with carbon obtained from the calcination of sugar, and the whole is rapidly heated in a carbon crucible in an electric furnace, using a current of 700 amperes and 40 volts. The iron melts like wax and saturates itself with carbon. After a few minutes’ heating to a temperature above 4000° C.—a temperature at which the lime furnace begins to melt and the iron volatilizes in clouds—the dazzling, fiery crucible is lifted out and plunged beneath the surface of cold water, where it is held till it sinks below a red heat. The sudden cooling solidifies the outer skin of molten metal and holds the inner liquid mass in an iron grip. The expansion of the inner liquid on solidifying produces enormous pressure, and under this stress the dissolved carbon separates out in a hard, transparent, dense form—in fact, as diamond. The succeeding operations are long and tedious. The metallic ingot is attacked with hot aqua regia till no iron is left undissolved. The bulky residue consists chiefly of graphite, together with translucent flakes of chestnut-coloured carbon, hard black opaque carbon of a density of from 3.0 to 3.5, black diamonds—carbonado, in fact—and a small quantity of transparent colourless diamonds showing crystalline structure. Besides these there may be corundum and carbide of silicon, arising from impurities in the materials employed. Heating with strong sulphuric acid, with hydrofluoric acid, with nitric acid and potassium chlorate, and fusing with potassium fluoride—operations repeated over and over again—at last eliminate the graphite and impurities and leave the true diamond untouched. The precious residue on microscopic examination shows many pieces of black diamond, and other colourless transparent pieces, some amorphous, others crystalline. Although many fragments of crystals are seen, the writer has scarcely ever met with a complete crystal. All appear broken up, as if, on being liberated from the intense pressure under which they were formed, they burst asunder. Direct evidence of this phenomenon has been seen. A very fine piece of diamond, prepared in the way just described and carefully mounted on a microscopic slide, exploded during the night and covered the slide with fragments. This bursting paroxysm is not unknown at the Kimberley mines.

Sir William Crookes in 1906 communicated to the Royal Society a paper on a new formation of diamond. Sir Andrew Noble has shown that in the explosion of cordite in closed steel cylinders pressures of over 50 tons to the sq. in. and a temperature probably reaching 5400° were obtained. Here then we have conditions favourable for the liquefaction of carbon, and if the time of explosion were sufficient to allow the reactions to take place we should expect to get liquid carbon solidified in the crystalline state. Experiment proved the truth of these anticipations. Working with specially prepared explosive containing a little excess of carbon Sir Andrew Noble collected the residue left in the steel cylinder. This residue was submitted by Sir William Crookes to the lengthy operations already described in the account of H. Moissan’s fused iron experiment. Finally, minute crystals were obtained which showed octahedral planes with dark boundaries due to high refracting index. The position and angles of their faces, and cleavages, the absence of birefringence, and their high refractive index all showed that the crystals were true diamond.

The artificial diamonds, so far, have not been larger than microscopic specimens, and none has measured more than about half a millimetre across. That, however, is quite enough to show the correctness of the train of reasoning leading up to the achievement, and there is no reason to doubt that, working on a larger scale, larger diamonds will result. Diamonds so made burn in the air when heated to a high temperature, with formation of carbonic acid; and in lustre, crystalline form, optical properties, density and hardness, they are identical with the natural stone.

It having been shown that diamond is formed by the separation of carbon from molten iron under pressure, it became of interest to see if in some large metallurgical operations similar conditions might not prevail. A special form of steel is made at some large establishments by cooling the molten metal under intense hydraulic pressure. In some samples of the steel so made Professor Rosel, of the university of Bern, has found microscopic diamonds. The higher the temperature at which the steel has been melted the more diamonds it contains, and it has even been suggested that the hardness of steel in some measure may be due to the carbon distributed throughout its mass being in this adamantine form. The largest artificial diamond yet formed was found in a block of steel and slag from a furnace in Luxembourg; it is clear and crystalline, and measures about one-fiftieth of an inch across.

A striking confirmation of the theory that natural diamonds have been produced from their solution in masses of molten iron, the metal from which has gradually oxidized and been washed away under cycles of atmospheric influences, is afforded by the occurrence of diamonds in a meteorite. On a broad open plain in Arizona, over an area of about 5 m. in diameter, lie scattered thousands of masses of metallic iron, the fragments varying in weight from half a ton to a fraction of an ounce. There is little doubt that these fragments formed part of a meteoric shower, although no record exists as to when the fall took place.