1911 Encyclopædia Britannica/Gem, Artificial
GEM, ARTIFICIAL. The term “Artificial Gems” does not mean imitations of real gems, but the actual formation by artificial means of the real precious stone, so that the product is identical, chemically, physically and optically, with the one found in nature. For instance, in chemical composition the lustrous diamond is nothing but crystallized carbon. Could we take black amorphous carbon in the form of charcoal or lampblack and dissolve it in a liquid, and by the slow evaporation of that liquid allow the dissolved carbon to separate out, it would probably crystallize in the transparent form of diamond. This would be a true synthesis of diamond, and the product would be just as much entitled to the name as the choicest products of Kimberley or Golconda. But this is a very different thing from the imitation diamond so common in shop windows. Here the chemist has only succeeded in making a paste or glass having limpidity and a somewhat high refractivity, but wanting the hardness and “fire” of the real stone.
The Diamond.—Within recent years chemists have actually succeeded in making the real diamond by artificial means, and although the largest yet made is not more than one-fiftieth of an inch across, the process itself and the train of reasoning leading up to such an achievement are sufficiently interesting to warrant a somewhat full description. Attempts to make diamonds artificially have been numerous, but, with the sole exception of those of Henri Moissan, all have resulted in failure. The nearest approach to success was attained by J. B. Hannay in 1880 and R. S. Marsden in 1881; but their results have not been verified by others who have tried to repeat them, and the probability is that what was then thought to be diamond was in reality carborundum or carbide of silicon.
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. Near the centre, where most of the fragments have been found, is a crater with raised edges, three-quarters of a mile in diameter and 600 ft. deep, bearing just the appearance which would be produced had a mighty mass of iron—a falling star—struck the ground, scattered it in all directions, and buried itself deeply under the surface, fragments eroded from the surface forming the pieces now met with. Altogether ten tons of this iron have been collected, and specimens of the Canyon Diablo meteorite are in most collectors' cabinets. Dr A. E. Foote, a mineralogist, when cutting a section of this meteorite, found the tools injured by something vastly harder than metallic iron, and an emery wheel used for grinding it was ruined. He attacked the specimen chemically, and soon afterwards announced to the scientific world that the Canyon Diablo meteorite contained diamonds, both black and transparent. This startling discovery was subsequently verified by Professors C. Friedel and H. Moissan, and also by Sir W. Crookes.
The Ruby.—It is evident that of the other precious stones only the most prized are worth producing artificially. Apart from their inferior hardness and colour, the demand for what are known as "semi-precious stones" would not pay for the necessarily great expenses of the factory. Moreover, were it to be known that they were being produced artificially the demand—never very great—would almost cease. The only other gems, therefore, which need be mentioned in connexion with their artificial formation are those of the corundum or sapphire class, which include all the most highly prized gems, rivalling, and sometimes exceeding, the diamond in value. Here a remarkable and little-known fact deserves notice. Excepting the diamond and sapphire, each of the precious stones—the emerald, the topaz and amethyst—possesses a more noble, a harder, and more highly-prized counterpart of itself, alike in colour, but superior in brilliancy and hardness; still more strange, the precious stone to which its special name is usually attached is the variety the least prized. The ruby itself might almost be included in the same category. The true ruby consists of the earth alumina, in a clear, crystalline form, having a minute quantity of the element chromium as the colouring matter. It is often called the "Oriental Ruby," or red sapphire, and when of a paler colour, the "Pink Sapphire." But the ruby as met with in jewellers' shops of inferior standing is usually no true ruby, but a "spinel ruby" or "balas ruby," sometimes very beautiful in colour, but softer than the Oriental ruby, and different in chemical composition, consisting essentially of alumina and magnesia and a little silica, with the colouring matter chromium. The colourless basis of the true Oriental precious stones being taken as crystallized alumina or white sapphire, when the colouring matter is red the stone is called ruby, when blue sapphire, when green Oriental emerald, when orange-yellow Oriental topaz, and when violet Oriental amethyst. Clear colourless crystals are known as white sapphire, and are very valuable. It is evident, therefore, that whosoever succeeds in making artificially clear crystals of white sapphire has the power, by introducing appropriate colouring matter, to make the Oriental ruby, sapphire, emerald, topaz and amethyst. All of these stones, even when of small size, are costly and readily saleable, while when they are of fine quality and large size they are highly prized, a ruby of fine colour, and free from flaws, a few carats in weight, being of more value than a diamond of the same weight.
This being the case, it is not surprising that repeated attempts have been made to effect the crystallization of alumina. This is not a matter of difficulty, but unfortunately the crystals generally form thin plates, of good colour, but too thin to be useful as gems; In 1837 M. A. A. Gaudin made true rubies, of microscopic size, by fusing alum in a carbon crucible at a very high temperature, and adding a little chromium as colouring matter. In 1847 J. J. Ebelmen produced the white sapphire and rose-coloured spinel by fusing the constituents at a high temperature in boracic acid. Shortly afterwards he produced the ruby by employing borax as the solvent. The boracic acid was found to be too volatile to allow the alumina to crystallize, but the use of borax made the necessary difference. But it was not till about the year 1877 that E. Frémy and C. Feil first published a method whereby it was possible to produce a crystallized alumina from which small stones could be cut. They first formed lead aluminate by the fusion together of lead oxide and alumina. This was kept in a state of fusion in a fireclay crucible (in the composition of which silica enters largely). Under the influence of the high temperature the silica of the crucible gradually decomposes the lead aluminate, forming lead silicate, which remains in the liquid state, and alumina, which crystallizes as white sapphire. By the admixture of 2 or 3% of a chromium compound with original materials the resulting white sapphire became ruby. More recently Edmond Frémy and A. Verneuil obtained artificial rubies by reacting at a red heat with barium fluoride on amorphous alumina containing a small quantity of chromium. The rubies obtained in this manner are thus described by Frémy and Verneuil: "Their crystalline form is regular; their lustre is adamantine; they present the beautiful colour of the ruby; they are perfectly transparent, have the hardness of the ruby, and easily scratch topaz. They resemble the natural ruby in becoming dark when heated, resuming their rose-colour on cooling." Des Cloizeaux says of them that "under the microscope some of the crystals show bubbles. In converging polarized light the coloured rings and the negative black cross are of a remarkable regularity."
Other experimentalists have attacked the problem in other directions. Besides those already mentioned, L. Eisner, H. H. De Senarmont, Sainte-Claire Deville, and H Caron and H. Debray have succeeded with more or less success in producing rubies. The general plan adopted has been to form a mixture of salts fusible at a red heat, forming a liquid in Which alumina will dissolve. Alumina is now added till the fused mass will take up no more, and the crucible is left in the furnace for a long time, sometimes extending over weeks. The solvent slowly volatilizes, and the alumina is deposited in crystals, coloured by whatever colouring oxide has been added.
Mention has been made above of a stone frequently substituted for the true ruby, called the "spinel" or "balas" ruby. The spinel and ruby occur together in nature, stones from Burma being as often spinel as true Oriental ruby. In the artificial production of the ruby it sometimes happens that spinel crystallizes out when true Oriental ruby is expected. The fusion bath is so arranged that only red-coloured alumina shall crystallize out, but it is difficult to have all the materials of such purity as to ensure the complete absence of silica and magnesia. In this case, when these impurities have accumulated to a certain point they unite with the alumina, and spinel then separates, as it crystallizes more easily than ruby. When all the magnesia and silica have been eliminated in this way the bath resumes its deposition of crystalline ruby. Rubies of fine colour and of considerable size have been shown in London, made on the Continent by a secret process. The writer has seen several cut stones so made weighing over a carat each, the uncut crystals measuring half an inch along a crystal edge, and weighing over 70 grains, and a clear plate of ruby cut from a single crystal weighing over 10 grains. Ruby has been made by Sir W. Roberts-Austen as a by-product in the production of metallic chromium. Oxide of chromium and aluminium powder are intimately mixed together in a refractory crucible, and the mixture is ignited at the upper part. The aluminium and chromium oxide react with evolution of so much heat that the reduced chromium is melted. Such is the intensity of the reaction that the resulting alumina is also completely fused,floating as a liquid on the molten chromium. Sometimes the alumina takes up the right amount of chromium to enable it to assume the ruby colour. On cooling the melted alumina crystallizes in large flakes, which on examination by transmitted light are seen to be true ruby. The development of the red colour is said by C. Greville-Williams only to take place at a white heat. It is not due to the presence of chromic acid, but to a reaction between alumina and chromic oxide, which requires an elevated temperature.
Artificially made but real rubies have been put on the market, prepared by a process of fusion by A. Verneuil. He finds that certain conditions have to be fulfilled in order to get the alumina in a transparent form. The temperature must not be higher than is absolutely necessary for fusion. The melted product must always be in the same part of the oxyhydrogen flame, and the point of contact between the melted product and the support should be reduced to as small an area as possible. M. Verneuil uses a vertical blowpipe flame directed on a support capable of movement up and down by means of a screw, so that the fused product may be removed from the zone of fusion as it gets higher by addition of fresh material. The material employed is either composed of small, valueless rubies, or alumina coloured with the right amount of chromium. It is very finely powdered and fed in through the blowpipe orifice, whence it is blown in a highly heated condition into the zone of fusion. The support is a small cylinder of alumina placed in the axis of the blowpipe. As the operation proceeds the fine grains of powder driven on to the support in the zone of fusion form a cone which gradually rises and broadens out until it becomes of sufficient size to be used for cutting. Rubies prepared in this way have the same specific gravity and hardness as the natural ruby, and they are also dichroic, and in the vacuum tube under the influence of the cathode stream they phosphoresce with a discontinuous spectrum showing the strong alumina line in the red. When properly cut and mounted it is almost impossible to distinguish them from natural stones.
The Sapphire.—Auguste Daubrée has shown that when a full quantity of chromium is added to the bath from which white sapphire crystallizes the colour is that of ruby, but when much less chromium is added the colour is blue, forming the true Oriental sapphire. The real colouring matter of the Oriental sapphire is not definitely known, some chemists considering it to be chromium and others cobalt. Artificial sapphires have been made of a fair size and perfectly transparent by the addition of cobalt to the igneous bath of alumina, but the writer does not consider them equal in colour to true Oriental sapphire.
The Oriental Emerald.—The stone known as emerald consists chemically of silica, alumina and glucina. Like the ruby, it owes its colour to chromium, but in a different state of oxidation. As already mentioned, there is another stone which consists of crystallized alumina coloured with chromium, but holding the chromium in a different state of oxidation. This is called the Oriental emerald, and, owing to its beauty of colour, its hardness and rarity, it is more highly prized than the emerald itself and commands higher prices. The Oriental emerald has been produced artificially in the same way as the ruby, by adding a larger amount of chromium to the alumina bath and regulating the temperature.
The Oriental Amethyst.—The amethyst is rock crystal (quartz) of a bluish-violet colour. It is one of the least valuable of the precious stones. The sapphire, however, is found occasionally of a beautiful violet colour; it is then called the Oriental amethyst, and, on account of its beauty and rarity, is of great value. It is evident that if to the igneous bath of alumina some colouring matter, such as manganese, is added capable of communicating a violet colour to the crystals of alumina, the Oriental amethyst will be the result. Oriental amethyst has been so formed artificially, but the stone being known only as a curiosity to mineralogists and experts in precious stones, and the public not being able to discriminate between the violet sapphire and amethystine quartz, there is no demand for the artificial stone.
The Oriental Topaz.—The topaz is what is called a semi-precious stone. It occurs of many colours, from clear white to pink, orange, yellow and pale green. The usual colour is from straw-yellow to sherry colour. The exact composition of the colouring matter is not known; it is not entirely of mineral origin, as it changes colour and sometimes fades altogether on exposure to light. Chemically the topaz consists of alumina, silica and fluorine. It is not so hard as the sapphire. There is also a yellow variety of quartz, which is sometimes called "false topaz." The Oriental topaz, on the other hand, is a precious stone of great value. It consists of dear crystalline sapphire coloured with a small quantity of ferric oxide. It has been produced artificially by adding iron instead of chromium to the matrix from which the white sapphire crystallizes.
The Zircon.—The zircon is a very beautiful stone, varying in colour, like the topaz, from red and yellow to green and blue. It is sometimes met with colourless, and such are its refractive powers and brilliancy that it has been mistaken for diamond. It is a compound of silica and zirconia. H. Sainte-Claire Deville formed the zircon artificially by passing silicon fluoride at a red heat over the oxide zirconia in a porcelain tube. Octahedral crystals of zircon are then produced, which have the same crystalline form, appearance and optical qualities as the natural zircon.
Bibliography.—Sir William Crookes, "A New Formation of Diamond," Proc. Roy. Soc. vol. lxxvi. p. 458; "Diamonds," a lecture delivered before the British Association at Kimberley, South Africa, 5th September, 1905, Chemical News, vol. xcii. pp. 135, 147, 159; J. J. Ebelmen, "Sur la production artificielle des pierres dures, Comptes rendus, vol. xxv. p. 279; "Sur une nouvelle méthode pour obtenir, par la voie sèche, des combinations crystallisées, et sur ses applications à la réproduction de plusieurs espèces minérales," Comptes rendus, vol. xxv. p. 66; Edmond Frémy and C. Feil, "Sur la production artificielle du corindon, du rubis, et de différents silicates crystallisées," Comptes rendus, vol. lxxxv. p. 1029; C. Friedel, "Sur l'existence du diemant dans le fer météorique de Cañon Diablo," Comptes rendus, vol. cxv. p. 1037, vol. cxvi. p. 290; H. Moissan, "Etude de la météorite de Cañon Diablo," Comptes rendus, vol. cxvi. p. 288; "Expériences sur la rproduction du diemant," Comptes rendus, vol. cxviii. p. 320; "Sur quelques expériences relatives à la préparation du diemant," Comptes rendus, vol. cxxiii. p. 206; Le Four électrique (Paris, 1897); H. Sainte-Claire Deville and H. Caron, "Sur un nouveau mode de production à l'état cristallisé d'un certain nombre d'espèces chimiques et minéralogiques," Comptes rendus, vol. xlvi. p. 764; A. Verneuil, "Production artificielle des rubis par fusion," ibid. vol. cxxxv. p. 791; J. Boyer, La Synthèse des pierres précieuses (Paris, 1909). (W. C.)