iron metal copper cobalt acid process solution oxide pure
NICKEL, a chemical term, designating a metallic element which was discovered by Cronsted in 1751. In 1754 he succeeded in isolating it (in an impure state), and found it to be a "halbmetall" (semi-metal). Afterwards finding it to be present largely in " kupfer-nickel,"1 he borrowed from that mineral the name for his- new element.
Nickel (Ni) is one of the less abundant of elements. It is contained in the sun's atmosphere and in all meteoric iron. Of nickel minerals the following are of metallurgic importance: - nickel-blende, NS; arsenical nickel glance, Ni(As . S)2; niccolo-cobaltic pyrites, (Ni, Co, Fe),Sc, garnierite, 5(Ni, Mg)0 . 4SiO2 + H2O.. Almost invarilarge proportions of copper, iron, and other foreign metallic ores and gangue. The metallurgy of nickel accordingly is a complex subject which cannot be fully treated here.
As an example of a sulphureous ore may be quoted that niccolocupreous pyrites which is being worked at Dillenburg in Nassau. The process employed is closely analogous to the old process of copper-smelting as explained in METALLURGY (vol. xvi. p. 61). The fully refined mat (" Concentrations-Stein ") consists of 35 per cent. of nickel, 43 of copper, 2 of iron, and 20 of sulphur. The article METALLURGY (ut sup.), under arsenides, describes a process which, when applied to arseniferous cobalt and nickel ores, yields the cobalt as smalt, the nickel as part of a "speis" (an alloy of arsenides). The same process serves occasionally for (so to say) collecting small proportions of nickel diffused throughout oxidized ores, the arsenic requisite being introduced in the form of native arsenide of iron.
If an arseniferous ore contains copper, the process sometimes is modified by addition of iron pyrites or some other su]phurcous material, and so conducted that-, in addition to a nickelous speis, a cnpreous mat is produced. The speis and mat do not mix, but form separate layers, the mat, as the lighter of the two, going to the top. .
All sulphureous, arsenical, or poor oxidized nickel ores are being wrought by methods analogous to the above, in so far at least as they all aim, in the first instance, at the production of a speis or mat from which the metal has to be extracted by subsequent operations. Direct methods are being used only in conjunction with one kind of ore, namely, that rich oxidized nickel ore which was discovered in New Caledonia about 1875, and has since been imported into Europe in large and yearly increasing quantities. It occurs in veins within serpentine, and consists of garnierite mixed with more or less of oxide of iron, chrome-iron ore, and a little black oxide of cobalt. It is valuable chiefly through its absolute freedom from arsenic and sulphides. Most of the ore goes to France, where it is worked chiefly by two firms. Christofle at St Denis treats the ore with hydrochloric acid, and from the solution recovers the metal by methods analogous to those customarily employed in connexion with speis and mats. Gamier, at the Septemes Works near Marseilles, makes straight for the metal. The powdered ore, after mechanical purification (by such methods as are explained in METALLURGY, vol. xvi. p. 59), is mixed with charcoal and fluorspar (or other flux) and worked into a paste with coal-tar, which is then shaped into bricks or walnut-sized stones. The ore thus prepared is then manipulated pretty much in the same way as an iron ore is for the production of pig-iron. The furnaces used are about 13 feet high, and worked with cold wind. Gamier in this manner produces three kinds of metal : - (1) an almost pure carbide of nickel, which needs only be decarbonized to be converted into pure metal ; (2) an alloy of the carbides of nickel and iron ; and (3), from mixtures of nickel and iron ore, a nickeliferous pig-iron which, when refined and piddled, yields ❑ very superior kind of wrought iron, harder and less liable to oxidation than the ordinary metal.
Extraction of Metal front Mats and Speises. - The first step as a rule is a roasting process, which, in the case of a speis, yields an arse niferons mixture of oxides ; a mat, in general, passes into a mixture of oxide, sulphate, and unchanged sulphide. Either roasted material is easily disintegrated by being treated with aqueous muriatic or sulphuric acid, with formation of a solution of nickel-salt, contaminated, in general, with arsenic, antimony, bismuth, copper, iron, cobalt, and zinc, which must be removed by suitable analytical methods. But, as we have no space to consider this problem in its general form, we will assume antimony, bismuth, and zinc to be absent. If, in this case, the iron predominates sufficiently over the arsenic, these two can both be removed at one stroke by evaporating the solution to dryness and calcining the residue at the lowest sufficient temperature ; the iron-salt only is reduced to an insoluble basic salt (of Fe203), which includes all the arsenic, so that by redissolving in water and passing the liquor through a filter press we obtain a solution which, by theory, is free of iron and arsenic. Practically, however, a trace of iron remains, and must be removed by precipitation with carbonate of lime in the cold and filtration. A repetition of the same process at about 60° C. eliminates the copper, so that only the cobalt is left, which, however, is no impurity metallurgically, and consequently may be suffered to remain, hut, if present in sufficient quantity, must be recovered for its own sake. This is effected by addition of bleaching powder and gentle heating. If care be taken to let a little of the cobalt escape, the rest goes down as black peroxide, Co203, sufficiently pure for its ordinary applications. From the filtered nickel solution the metal is precipitated, by addition of milk-of-lime, as a green hydrated oxide, which is collected and washed in a filter press. The precipitate, being inconveniently gelatinous and bulky, is next rendered compact by a gentle calcination, and, if it is, as usual, contaminated with sulphate of lime, is freed from this impurity by judicious washing with highly dilute muriatic acid or otherwise. The purified oxide then, either by mere pressure or with the help of starch or other plastifying material, is shaped into little cubes of about one centimetre's side, embedded in charcoal dust within graphite or fire-clay crucibles and heated in a fire. A dull red heat suffices for the mere reduction of the oxide to metal ; but a strong red heat is applied in order to cause the nickel cubes to sinter together and become fast and compact. No degree of red heat will fuse them unless they are contaminated with copper. There is no need to explain how, with cupriferons leys, the process has to be modified to lead ultimately to a fused regulus of copper-nickel available for the preparation of german silver. From a copper-free liquor, provided only it contains its iron all as ferric salt, a pure nickel precipitate can be obtained at once by addition of oxalic acid. The (green) oxalate of nickel precipitate need only be washed, dried, and ignited to be converted into a pure (but partially oxidized) metal. This process has actually been applied, at least experimentally, in the working of the New Caledonian ore, with this modification, however, that the oxalic acid was recovered by boiling the oxalate of nickel with carbonate of potash, and precipitating the acid by milk-of-lime from the alkaline solution.
Ordinary cube-nickel contains from 94 to 99 per cent. of real nickel. The purest commercial metal is that extracted has no information regarding the mechanical characters of such highly-refined Now Caledonian metal. The best commercial cube-nickel (although it may contain less than 1 per cent. of impurities) is always utterly devoid of plasticity ; it breaks under the hammer, although the pure metal, as was shown as early as 1804 by Richter, and malleability of the best wrought iron combined with gravity is 8'279 for ingot, and 8.666 (Richter) for the forged metal. It can be welded at a red heat like wrought iron, which it exceeds in relative infusibility. It does not tarnish even on long exposure to the air. Sulphuretted hydrogen does not blacken it. Liquid water, even in the presence of air, has no action upon it. Aqueous non-oxidizing acids act upon it as they do on iron, but more slowly. Nitric acid and aqua regia dissolve it as nitrate Ni(NO3)2 and chloride NiC12 respectively. When heated strongly in air it is gradually oxidized ; it decomposes steam, slowly, at a red heat. In brief, it unites in itself all the virtues of iron with some of the characteristics of the noble metals, and yet its application in the mechanical arts was never thought of until Fleitmann in 1879 made a most remarkable observation. Finding that even the purest nickel which he could produce on a manufacturing scale was brittle, he attributed this defect not to the traces of metallic impurities still present in it but to occluded carbonic oxide, and tried to remove this by addition of magnesium to the molten metal. He succeeded beyond expectation : one-eighth of a per cent. of magnesium added to the metal (in an atmosphere of carbonic acid) before pouring imparted to it all the plasticity of the pure metal.' Fleitmann also found that the thus purified nickel could be permanently welded on wrought iron, and that a combination plate thus produced could be rolled out into the thinnest sheet without breach of continuity. Since that time his firm (Fleitmann Witte of Iserlohn) have made a business of the manufacture of cooking utensils and other useful articles out of such nickel-plated iron. Physiological experiments on a dog, instituted at the instance of the firm, showed that the metal is innocuous. Cobalt, as Fleitmann found, behaves in every respect like nickel, and even exceeds it in whiteness and brilliancy.2 The writer has for more than a year been in the habit of using a nickel basin (supplied by Messrs Johnson & Matthey of London) for operations with caustic-alkali lye, and finds it to work admirably - better, in fact, than a silver one.
Nickel Electroplating. - This art, invented by BOttcher about 1848, has developed into an important industry, especially in the United States. The best kind of solution to use is one of the double sulphate of nickel and ammonia, which should be saturated at 25° and used in conjunction with a plate of nickel as positive electrode.
Alloys. - Nickel alloys were used practically long before Crousted's discovery of the metal. GERMAN SILVER (q.v.), long known to the Chinese as " Pack Tong," i.e., " white copper," consists of nickel, copper, and zinc united in varying proportions,-3 of copper, 1 of zinc, and 1 of nickel is said to give the most silver-like alloy. An alloy of "german " with real silver has lately been introduced as " tiers-argent" ; it consists of silver 27.6, copper 59'0, zinc 9.6, nickel 3.4 per cent. In the United States, in Belgium, and in Germany, an alloy of 1 of nickel with 3 of copper serves for the making of minor coins. All these alloys are non-magnetic.
Salts. - For nickel salts see CHEMISTRY and chemical handbooks.
Analysis. - Nickel-salts, as a rule, and their solutions more generally, exhibit a green colour. Sulpliuretted hydrogen does not precipitate the metal from solutions containing free mineral acid. Sulphide of ammonium, from neutral or alkaline solutions, precipitates a black sulphide which, like sulphide of cobalt, when once produced is almost insoluble in dilute cold hydrochloric acid, and has the specific property of being very appreciably soluble in a mixture of yellow (i.e., ordinary) sulphide of ammonium and free ammonia, forming a dark coffee-brown solution. Unlike iron-salts, nickel-salts are not oxidized into sesquioxide (analogous to Fe202) salts by nitric acid or chlorine. Carbonate of baryta, which readily precipitates oxide of iron (Fe203) and alumina, does not precipitate nickel from its solutions in the cold. By means of these reactions nickel is easily distinguished and separated from all other metals except cobalt. To test a nickel solution for cobalt, add excess of nitrite of potassium and acidify with acetic acid. Cobalt, if present, comes down gradually as " Fischer's salt," a double nitrite of Co203 and K.20 .
The atomic weight of nickel, according to the latest determinations, is identical with that of cobalt : - Ni( - Co) 58'6, 0 being 16.
Karmarsch and Heeren's Technisches Worterbuch gives a very full account of the metallurgy of nickel, quite up to date (1883). (W. 1).)