Swansea copper furnacesFig.304.is the section of the roasting furnace lengthwise;fig.303.the ground plan; in whichais the fire-door;bthe grate;cthe fore-bridge;dthe chimney;e eworking apertures on each of the long sides of the furnace, through which the ore is introduced, spread, and turned over;f fcast-iron hoppers;g gopenings in the vaulted roof;hthe hearth-sole;i iholes in this;ka vaulted space under the hearth. The hearth has a suitable oval shape, and is covered with a flat arch. Its length is 16 feet, breadth 131⁄2, mean height 2 feet.Melting furnaceFig.305.is a longitudinal section of the melting furnace;fig.306.the ground plan in whichais the fire door;bthe grate;cthe fire bridge;dthe chimney;ethe side openings;fthe working doors;gthe raking-out hole;hiron spouts, which conduct the melted metal into pits filled with water.The melting furnace is altogether smaller; but its firing hearth is considerably largerthan in the roasting furnace. The long axis of the oval hearth is 14 feet; its short axis 10 feet; its mean height 2 feet.The principal ore smelted at Chessy is the azure copper, which was discovered by accident in 1812. Red copper ore, also, has come into operation there since 1825. The average metallic contents of the richest azure ore are from 33 to 36 per cent.; of the poorer, from 20 to 24. The red ore contains from 40 to 67 parts in 100. The ore is sorted, so that the mean contents of metal may be 27 per cent., to which 20 per cent. of limestone are added; whence the cinder will amount to 50 per cent. of the ore. A few per cents. of red copper slag, with some quicklime andgahrslag, are added to each charge, which consists of 200 pounds of the above mixture, and 150 pounds of coke. When the furnace (fourneau à manche, see theScotch smelting hearth, underLead), is in good action, from 10 to 14 such charges are worked in 12 hours. When the crucible is full of metal at the end of this period, during which the cinder has been frequently raked off, the blast is stopped, and themattfloating over the metal being sprinkled with water and taken off, leaves the black copper to be treated in a similar way, and converted intorosettes. The refining of this black copper is performed in a kind of reverberatory furnace.The cinders produced in this reduction process are either vitreous and light blue, which are most abundant; cellular, black, imperfectly fused from excess of lime; or, lastly, red, dense, blistery, from defect of lime, from too much heat, and the passage of protoxide into the cinders. They consist of silicate of alumina, of lime, protoxide of iron; the red contain some silicate of copper.Split hearthThe copper-refining furnace at Chessy, near Lyons, is of the kind calledSpleiss-ofen(split hearths) by the Germans.Fig.307.is a section lengthwise in the dotted lineA Boffig.308., which is the ground plan.Split hearthThe foundation-walls are made of gneiss; the arch, the fire-bridge, and the chimney, of fire-bricks. The hearth,a, is formed of a dense mixture of coal-dust, upon a bottom of well-beat clayb, which reposes upon a bed of brickworkc. Beneath this there is a slag bottomd;eis the upper, andfthe under discharge hole. The hearth is egg-shaped; the longer axis being 8 feet, the shorter 61⁄2feet: in the middle it is 10 inches deep, and furnished with the outletsg g, which lead to each of theSpleiss-hearthsh h,fig.308.These outlets are contracted with fire-bricksi i, till the proper period of the discharge. The two hearths are placed in communication by a canalh; they are 31⁄2feet in diameter, 16 inches deep; are floored with well-beat coal ashes, and receive about 27 cwt. for a charge.lis the grate;m, the fire-bridge;n, the boshes in which thetuyèreslie;o, the chimney;p, the working door through which the slags may be drawn off. Above this is a small chimney, to carry off the flame and smoke whenever the door is opened.The smeltingpostor charge, to be purified at once, consists of 60 cwt. of black copper, to which a little granular copper and copper of cementation is added; theconsumption of pit-coal amounts to 36 cwt. As soon as the copper is melted, the bellows are set a-going, and the surface of the metal gets soon covered with a moderately thick layer of cinder, which is drawn off. This is the first skimming ordecrassage. By and by, a second layer of cinder forms, which is in like manner removed; and this skimming is repeated, to allow the blast to act upon fresh metallic surfaces. After 4 or 5 hours, no more slag appears, and then the fire is increased. The melted mass now begins to boil or work (travailler), and continues so to do, for about3⁄4of an hour, or an hour, after which the motion ceases, though the fire be kept up. Thegahrproofis now taken; but the metal is seldom fine in less than3⁄4of an hour after the boil is over. Whenever the metal is run off by the tap-hole into the two basinsi i, calledSPLIT-HEARTHS, a reddish vapour or mist rises from its surface, composed of an infinite number of minute globules, which revolve with astonishing velocity upon their axes, constituting what the Germans calledspratzen(crackling) of the copper. They are composed of a nucleus of metal, covered with a film of protoxide, and are used as sand for strewing upon manuscript. The copper is separated, as usual, by sprinkling water upon the surface of the melted metal, in the state ofrosettes, which are immediately immersed in a stream of water. This refining process lasts about 16 or 17 hours; the skimmings weigh about 50 cwt.; the refuse is from 15 to 17 per cent.; the loss from 2 to 3 per cent. Thegahrslagamounts to 11 cwt.KupfergahrheerdThe refining of the eliquated copper (calleddarrlinge) from which the silver has been sweated out by the intervention of lead, can be performed only in small hearths. The following is the representation of such a furnace, called, in German,Kupfergahrheerd.Fig.309.is the section lengthwise;fig.310.is the section across; andfig.311.is the ground plan, in whichais the hearth-hollow;b, a massive wall;c, the mass out of which the hearth is formed;d, cast-iron plates covering the hearth;e, opening forrunning off the liquid slag;f, a small wall;g, iron curb for keeping the coals together.The hearth being heated with a bed of charcoal,3⁄4cwt. ofdarrlingeare laid over it, and covered with more fuel: whenever this charge is melted, another layer of the coal anddarrlingeis introduced, and thus in succession till the hearth become full, or contain from 21⁄4to 21⁄2cwt. In Neustadt 71⁄2cwt. ofdarrlingehave been refined in one furnace, from which 5 cwt. ofgahrcopperhas been obtained. The blast oxidizes the foreign metals, namely, the lead, nickel, cobalt, and iron, with a little copper, forming thegahrslag; which is, at first, rich in lead oxide, and poor in copper oxide; but, at the end, this order is reversed. The slag, at first blackish, assumes progressively a copper red tint. The slag flows off spontaneously along the channele, from the surface of the hearth. Thegahreis tested by means of a proof rod of iron, calledgahr-eisen, thrust through thetuyèreinto the melted copper, then drawn out and plunged in cold water. As soon as thegahrspan(scale of copper) appears brownish red on the outside, and copper red within, so thin that it seems like a net-work, and so deficient in tenacity that it cannot be bent without breaking, the refining is finished. The blast is then stopped; the coals covering the surface, as also the cinders must be raked off the copper, after being left to cool a little; the surface is now cooled by sprinkling water upon it, and the thick cake of congealed metal (rondelle) is lifted off with tongs, a process calledschleissen(slicing), orsheibenreissen(shaving), which is continued till the last convex cake at the bottom of the furnace, styled thekingspiece, is withdrawn. Theserondellesare immediately immersed in cold water, to prevent the oxidation of the copper; whereupon the metal becomes of a cochineal red colour, and gets covered with a thin film of protoxide. Its under surface is studded over with points and hooks, the result of tearing the congealed disc from the liquid metal. Such cakes are calledrosettecopper. When the metal is very pure and free from protoxide, these cakes may be obtained very thin, one 24th of an inch for example.The refining of two cwts. and a half ofdarrlingetakes three quarters of an hour, and yields one cwt. and a half ofgahr copperin 36 rosettes, as also somegahrslag. Gahr copper generally contains from 11⁄2to 21⁄2per cent. of lead, along with a little nickel, silver, iron, and aluminum.Smelting of the Mansfeldt copper schist, or bituminous Mergelschiefer.—The cupreous ore is first roasted in large heaps, of 2000 cwts., interstratified with brush-wood, and with some slates rich in bituminous matter, mixed with the others. These heaps are 3 ells high, and go on burning 15 weeks in fair and 20 in rainy weather. The bitumen is decomposed; the sulphur is dissipated chiefly in the form of sulphurous acid; the metal gets partially oxidized, particularly the iron, which is a very desirable circumstance towards the production of a good smelting slag. The calcined ore is diminished one-tenth in bulk, and one-eighth in weight; becoming of a friable texture and a dirty yellow gray colour. The smelting furnaces are cupolas (schachtofen), 14 to 18 feet high; the fuel is partly wood charcoal, partly coke from the Berlin gas-works, and Silesia. The blast is given by cylinder bellows, recently substituted for the old barbarousBlasebälgen, or wooden bellows of the household form.The cupreous slate is sorted, according to its composition, into slate of lime, clay, iron, &c., by a mixture of which the smelting is facilitated. For example, 1 post or charge may consist of 20 cwt. of the ferruginous slate, 14 of the calcareous, 6 of the argillaceous, with 3 of fluor spar, 3 of rich copper slags, and other refuse matters. The nozzle at thetuyèreis lengthened 6 or 8 inches, to place the melting heat near the centre of the furnace. In 15 hours 1 fodder of 48 cwts. of the above mixture may be smelted, whereby 4 to 5 cwts. ofmatte(crude copper, calledKupfersteinin Germany) and a large body of slags are obtained. Themattecontains from 30 to 40 per cent. of copper, and from 2 to 4loths(1 to 2 oz.) of silver. The slags contain at times one-tenth their weight of copper.Thematteis composed of the sulphurets of copper, iron, silver, zinc, along with some arsenical cobalt and nickel. The slaty slag is raked off the surface of the meltedmattefrom time to time. The former is either after being roasted six successive times, smelted into black copper; or it is subjected to the following concentration process. It is broken to pieces, roasted by brushwood and coals three several times in brick-walled kilns, containing 60 cwts., and turned over after every calcination; a process of four weeks’ duration. The thrice roasted mass, calledspurrost, being melted in the cupolafig.313.with ore-cinder, yields thespurstein, or concentratedmatte. From 30 to 40 cwts. of spurrost are smelted in 24 hours; and from 48 to 60 per cent. ofspursteinare obtained, the slag from the slate smelting being employed as a flux. The spurstein contains from 50 to 60 per cent. of copper, combined with the sulphurets of copper, of iron, and silver.The spurstein is now mixed withdünnstein(a sulphuret of copper and iron produced in the original smeltings) roasted six successive times, in a quantity of 60 cwts., withbrushwood and charcoal; a process which requires from 7 to 8 weeks. The product of this six-fold calcination is theGahrrostof the Germans (done and purified); it has a colour like red copper ore, varying from blue gray into cochineal red; a granular fracture; it contains a little of the metal, and may be immediately reduced into metallic copper, calledkupfermachen. But before smelting the mass, it is lixiviated with water, to extract from it the soluble sulphate, which is concentrated in lead pans, and crystallized.The lixiviatedgahröstemixed with from1⁄4to1⁄5of the lixiviateddünnsteinrost, and1⁄6to1⁄10of the copper slate slag, are smelted with charcoal or coke fuel in the course of 24 hours, in a mass of 60 or 80 cwts. The product is black copper, to the amount of about1⁄4the weight, and1⁄6ofdünnstein, orthin matte. This black copper contains in the cwt. from 12 to 20 loths (6 to 10 oz.) of silver. Thedünnsteinconsists of from 60 to 70 per cent. of copper combined with sulphur, sulphuret of iron and arsenic; and when thrice roasted, yields a portion of metal. The black copper lies undermost in the crucible of the furnace, above it is thedünnstein, covered with the stone slag, or copper cinder, resulting from the slate-smelting. The slags being raked off, and the crucible sufficiently full, the eye or nozzle hole is shut, thedünnsteinremoved by cooling the surface, and breaking the crust, which is about1⁄4to1⁄2inch thick. The same method is adopted for taking out the black copper in successive layers. For the de-silvering of this, and similar black coppers, seeSilver.Form or tuyèreFig.312.is a vertical section through the form ortuyèrein the dotted lineA Boffig.314.Fig.313.is a vertical section in the dotted lineC Doffig.315.ais the shaft of the furnace,bthe rest,c cthe forms;dthe sole or hearth-stone, which has a slope of 3 inches towards the front wall;e e, &c. casing walls of fire bricks;f f, &c. filling up walls built of rubbish stones;g ga mass through which the heat is slowly conducted;h hthe two holes through one or other of which alternately the product of the smelting process is run off into the fore-hearth. Beneath the hearth-sole there is a solid body of loam; and the fore-hearth is formed with a mixture of coal-dust and clay;kis the discharge outlet.Fig.314.is a horizontal section of the furnace through the hole or eye in the dotted lineE Foffig.312.;fig.315.a horizontal section of the shaft of the furnace through the form in the dotted lineG Hoffigs.312 and 313. The height of the shaft, from the lineE Fto the top, is 14 feet; fromEtoG, 25 inches; fromcto the line belowb, 2 feet; from that line to the line oppositeg g, 2 feet. The width at the lineg gis 3 feet 3 inches, and atc26 inches. The basinsi i,fig.314., are 3 feet diameter, and 20 inches deep.The refining of copper is said to be well executed at Seville, in Spain; and, therefore, some account of the mode of operating there may be acceptable to the reader.The first object is to evaporate in a reverberatory furnace all the volatile substances, such as sulphur, arsenic, antimony, &c., which may be associated with the sulphur; and the second, to oxidize and to convert into scoriæ the fixed substances, such as iron, lead, &c., with the least possible expense and waste. The minute quantities of gold and silver which resist oxidation cannot be in any way injurious to the copper. The hearth is usually made of a refractory sand and clay with ground charcoal, each mixed in equal volumes, and worked up into a doughy consistence with water. This composition is beat firmly into the furnace bottom. But a quartzose hearth is found to answer better, and to be far more durable; such as a bed of fire-sandstone.Before kindling the furnace, its inner surface is smeared over with a cream-consistenced mixture of fire-clay and water.The cast pigs, or blocks of black or crude copper, are piled upon the hearth, each successive layer crossing at right angles the layer beneath it, in order that the flame mayhave access to play upon the surface of the hearth, and to heat it to a proper pitch for making the metal flow.The weight of the charge should be proportional to the capacity of the furnace, and such that the level of the metallic bath may be about an inch above the nozzle of the bellows; for, were it higher, it would obstruct its operation, and were it too low, the stream of air would strike but imperfectly the surface of the metal, and would fail to effect, or would retard at least, the refining process, by leaving the oxidation and volatilization of the foreign metals incomplete.As the scoriæ form upon the surface, they are drawn off with an iron rabble fixed to the end of a wooden rod.Soon after the copper is melted, charcoal is to be kindled in three iron basins lined with loam, placed alongside the furnace, to prepare them for receiving their charge of copper, which is to be converted in them, intorosettes.The bellows are not long in action before the evaporation of the mineral substances is so copious, as to give the bath a boiling appearance; some drops rise up to the roof of the reverberatory, others escape by the door, and fall in a shower of minute spherical globules. This phenomenon proves that the process is going on well; and, when it ceases, the operation is nearly completed. A small proof of copper, of the form of a watch-case, and therefore calledmontre, is taken out from time to time, upon the round end of a polished iron rod, previously heated. This rod is dipped two or three inches into the bath, then withdrawn and immersed in cold water. The copper cap is detached from the iron rod, by a few blows of a hammer; and a judgment is formed from its thickness, colour, and polish, as to the degree of purity which the copper has acquired. But thesewatchesneed not be drawn till the small rain, above spoken of, has ceased to fall. At the end of about 11 hours of firing, the numerous small holes observable in the firstwatchsamples begin to disappear; the outer surface passes from a bright red to a darker hue, the inner one becomes of a more uniform colour, and always less and less marked with yellowish spots. It will have acquired the greatest pitch of purity that the process can bestow, when thewatchesbecome of a dark crimson colour.Care must be taken to stop this refining process at the proper time; for, by prolonging it unduly, a small quantity of cupreous oxide would be formed, which, finding no oxygen to reduce it, would render the whole body of copper hard, brittle, and incapable of lamination.The basins must now be emptied of their burning charcoal, the opening of thetuyèremust be closed, and the melted copper allowed to flow into them through the tap-hole, which is then closed with loam. Whenever the surface is covered with a solid crust, it is bedewed with water; and as soon as the crust is about 11⁄2inch thick it is raised upon hooks above the basin, to drain off any drops, and then carried away from the furnace. If these cakes, or rosettes, be suddenly cooled by plunging them immediately in water, they will assume a fine red colour, from the formation of a film of oxide.Each refining operation produces, in about 12 hours, 17⁄10tons of copper, with the consumption of about4⁄5of a ton of dry wood.Care should be taken that the copper cake orrosettebe all solidified before plunging it into water, otherwise a very dangerous explosion might ensue, in consequence of the sudden extrication of oxygen from the liquid metal, in the act of condensation. On the other hand, the cake should not be allowed to cool too long in the air, lest it get peroxidized upon the surface, and lose those fine red, purple, and yellow shades, due to a film of the protoxide, which many dealers admire.When a little oxide of antimony and oxide of copper are combined with copper, they occasion the appearance of micaceous scales in the fractured faces. Such metal is hard, brittle, yellowish within, and can be neither laminated nor wire-drawn. These defects are not owing to arsenic, as was formerly imagined; but, most probably, to antimony in the lead, which is sometimes used in refining copper. They are more easily prevented than remedied.According to M. Frèrejean, proprietor of the great copper works of Vienne, in Dauphiny, too low a temperature or too much charcoal, gives to the metal a cubical structure, or that of divergent rays; in either of which states it wants tenacity. Too high a temperature, or too rapid a supply of oxygen, gives it a brick red colour, a radiated crystallization without lustre, or a very fine grain of indeterminate form; the last structure being unsuitable for copper that is to be worked under the hammer or in the rolling-press. The form which indicates most tenacity is radiated with minute fibres glistening in mass. Melted copper will sometimes pass successively through these three states in the space of ten minutes.Roasting moundFig.316.represents aroasting moundof copper pyrites in the Lower Hartz, near Goslar, where a portion of the sulphur is collected. It is a vertical section of a truncated quadrangular pyramid. A layer of wooden billets is arranged at the base of the pyramid in the linea a.C, a wooden chimney which stands in the centre of the mound with a small pile of charcoal at its bottom,c;d dare large lumps of ore surrounded by smaller pieces;f f, are rubbish and earth to form a covering. A current of air is admitted under the billets by an opening, in the middle of each of the four sides of the basea a, so that two principal currents of air cross under the vertical axisCof the truncated pyramid, as indicated in the figure.The fire is applied through the chimneyC; the charcoal at its bottomc, and the pilea aare kindled. The sulphureous oresd,f, are raised to such a high temperature as to expel the sulphur in the state of vapour.In the Lower Hartz a roasting mound continues burning during four months. Some days after it is kindled the sulphur begins to exhale, and is condensed by the air at the upper surface of the pyramid. When this seems impregnated with it, small basins l l are excavated, in which some liquid sulphur collects; it is removed from time to time with iron ladles, and thrown into water, where it solidifies. It is then refined and cast into roll brimstone.A similar roasting mound contains, in the Lower Hartz, from 100 to 110 tons of ore and 730 cubic feet of wood. It yields in four months about one ton and a half of sulphur from copper pyrites. Lead ore is treated in the same way, but it furnishes less sulphur.There are usually from 12 to 15 roasting heaps in action at once for three smelting works of the Lower Hartz. After the first roasting two heaps are united to form a third, which is calcined anew, but under a shed; the ores are then stirred up and roasted for the third time, whence a crude mixture is procured for the smelting-house.The most favourable seasons for roasting in the open air are spring and autumn; the best weather is a light wind accompanied with gentle rain. When the wind or rain obstruct the operation, this inconvenience is remedied by planks distributed round the upper surface of the truncated pyramid over the sulphur basins.Manufacturing assays of copper.—The first thing is to make such a sample as will represent the whole mass to be valued; with which view, fragments must be taken from different spots, mixed, weighed, and ground together. A portion of this mixture being tried by the blow-pipe, will show, by the garlic or sulphurous smell of its fumes, whether arsenic, sulphur, or both, be the mineralizers. In the latter case, which often occurs, 100 gr. or 1000 gr. of the ore are to be mixed with one half its weight of saw-dust, then imbued with oil, and heated moderately in a crucible till all the arsenical fumes be dissipated. The residuum being cooled and triturated, is to be exposed in a shallow earthen cup to a slow roasting heat, till the sulphur and charcoal be burned away. What remains being ground and mixed with half its weight of calcined borax, one-twelfth its weight of lamp black, next made into a dough with a few drops of oil, is to be pressed down into a crucible, which is to be covered with a luted lid, and to be subjected, in a powerful air furnace, first to a dull red heat, and then to vivid ignition for 20 minutes. On cooling and breaking the crucible, a button of metallic copper will be obtained. Its colour and malleability indicate pretty well the quality, as does its weight, the relative value of the ore. It should be cupelled with lead, to ascertain if it contains silver or gold. SeeAssay, andSilver.If the blow-pipe trial showed no arsenic, the first calcination may be omitted; and if neither sulphur nor arsenic, a portion of the ground ore should be dried, and treated directly with borax, lamp black and oil. It is very common to make a dry assay of copper ores, by one roasting and one fusion along with 3 parts of black flux; from the weight of the metallic button the richness of the ore is inferred.The humid assay is more exact, but it requires more skill and time.The sulphur and the silica are easily got rid of, by the acids which do not dissolve them, but only the metallic oxides and the other earths. These oxides may then be thrown down by their appropriate reagents, the copper being precipitated in the state of either the black oxide, or pure metal. 105 parts of black oxide represent 100 of copper. Before entering upon the complete analysis of an ore, preliminary trials should be made, to ascertain what are its chief constituents. If it be sulphuret of copper, or copper pyrites, without silver or lead, 100 grains exactly of its average powder may be weighed out, treated in a matras with boiling muriatic acid for some time, gradually adding a few drops of nitric acid, till all action ceases, or till the ore be all dissolved. The insoluble matter found floating in the liquid contains most of the sulphur; it may be separated upon a filter, washed, dried, and weighed; then verified by burning away. The incombustible residuum, treated by muriatic acid, may leave an insoluble deposit, which is to be added to the former. To the whole of the filtered solutions carbonate of potash isto be added; and the resulting precipitate, being washed, and digested repeatedly in water of ammonia, all its cupric oxide will have been dissolved, whenever the ammonia is no longer rendered blue.Caustic potash, boiled with the ammoniacal solution, will separate the copper in the state of black oxide; which is to be thrown upon a filter, washed, dried, and weighed. The matter left undissolved by the ammonia, consists of oxide of iron, with probably a little alumina. The latter being separated by caustic potash, the iron oxide may be also washed, dried, and weighed. The powder which originally resisted the muriatic acid, is silica.Assay of copper ores, which contain iron, sulphur, silver, lead, and antimony.100 grains of these ores, previously sampled, and pulverized, are to be boiled with nitric acid, adding fresh portions of it from time to time, till no more of the matter be dissolved. The whole liquors which have been successively digested and decanted off, are to be filtered and treated with common salt, to precipitate the silver in the state of a chloride.The nitric acid, by its reaction upon the sulphur, having generated sulphuric acid, this will combine with the lead oxidized at the same time, constituting insoluble sulphate of lead, which will remain mixed with the gangue. Should a little nitrate of lead remain in the liquid, it may be thrown down by sulphate of soda, after the silver has been separated. The dilute liquid being concentrated by evaporation, is to be mixed with ammonia in such excess as to dissolve all the cupric oxide, while it throws down all the oxide of iron and alumina; which two may be separated, as usual, by a little caustic potash. The portion of ore insoluble in the nitric acid, being digested in muriatic acid, every thing will be dissolved except the sulphur and silica. These being collected upon a filter, and dried, the sulphur may be burned away, whereby the proportion of each is determined.Ores of theoxideof copper, are easily analyzed by solution in nitric acid, the addition of ammonia, to separate the other metals, and precipitation by potash. Thenative carbonateis analyzed by calcining 100 grains; when the loss of weight will shew the amount of water and carbonic acid; then that of the latter may be found, by expelling it from another 100 grains, by digestion in a given weight of sulphuric acid. The copper is, finally, obtained in a metallic state by plunging bars of zinc into the solution of the sulphate.Thenative arseniates of copperare analyzed by drying them first at a moderate heat; after which they are to be dissolved in nitric acid. To this solution, one of nitrate of lead is to be added, as long as it occasions a precipitate; the deposit is to be drained upon a filter, and the clear liquid which passes through, being evaporated nearly to dryness, is to be digested in hot alcohol, which will dissolve every thing except a little arseniate of lead. This being added to the arseniate first obtained, from the weight of the whole, the arsenic acid, constituting 35 per cent., is directly inferred. The alcoholic solution being now evaporated to dryness, the residue is to be digested in water of ammonia, when the cupric oxide will be dissolved, and the oxide of iron will remain. The copper is procured, in the state of black oxide, by boiling the filtered ammoniacal solution with the proper quantity of potash.The analysis of muriate of copper—atacamite—is an easy process. The ore being dissolved in nitric acid, a solution of nitrate silver is added, and from the weight of the chloride precipitated, the equivalent amount of muriate or chloride of copper is given; for 100 of chloride of silver represent 93 of chloride of copper, and 43·8 of its metallic basis. This calculation may be verified by precipitating the copper of the muriate from its solution in dilute sulphuric acid, by plates of zinc.The phosphate of coppermay be analyzed either by solution in nitric acid, and precipitation by potash; or by precipitating the phosphoric acid present, by means of acetate of lead. The phosphate of lead thus obtained, after being washed, is to be decomposed by dilute sulphuric acid. The insoluble sulphate of lead being washed, dried, and weighed, indicates by its equivalent the proportion of phosphate of lead, as also of phosphate of copper; for 100 of sulphate of lead correspond to 92·25 phosphate of lead, and 89·5 phosphate of copper; and this again to 52·7 of the black oxide.Copper forms the basis of a greater number of importantALLOYSthan any other metal. With zinc it formsBrassin all its varieties; which see.BronzeandBell Metalare alloys of copper and tin. This compound is prepared in crucibles when only small quantities are required; but in reverberatory hearths, when statues, bells, or cannons are to be cast. The metals must be protected as much as possible during their combination from contact of air by a layer of pounded charcoal, otherwise two evils would result, waste of the copper by combustion, and a rapid oxidizement of the tin, so as to change the proportions and alter the properties of the alloy. The fused materials ought to be well mixed by stirring, to give uniformity to the compound. SeeBronze.An alloy of 100 of copper and 4·17 of tin has been proposed by M. Chaudet for the ready manufacture ofmedals. After melting this alloy he casts it in moulds made of such bone-ash as is used for cupels. The medals are afterwards subjected to the action of the coining press, not for striking them, for the mould furnishes perfect impressions, but for finishing and polishing them.By a recent analysis of M. Berthier, the bells of thependules, or ornamental clocks, made in Paris, are found to be composed, of copper 72·00, tin 26·56, iron 1·44, in 100 parts.An alloy of 100 of copper and 14 of tin is said by M. Dussaussy to furnish tools, which hardened and sharpened in the manner of the ancients, afford an edge nearly equal to that of steel.Cymbals, gongs, and thetamtamof the Chinese are made of an alloy of 100 of copper with about 25 of tin. To give this compound the sonorous property in the highest degree it must be subjected to sudden refrigeration. M. D’Arcet, to whom this discovery is due, recommends to ignite the piece after it is cast, and to plunge it immediately into cold water. The sudden cooling gives the particles of the alloy such a disposition that, with a regulated pressure by skilful hammering, they may be made to slide over each other, and remain permanently in their new position. When by this means the instrument has received its intended form, it is to be heated and allowed to cool slowly in the air. The particles now take a different arrangement from what they would have done by sudden refrigeration; for instead of being ductile they possess such an elasticity, that on being displaced by a slight compression, they return to their primary position after a series of extremely rapid vibrations; whence a very powerful sound is emitted. Bronze, bell-metal, and probably all the other alloys of tin with copper present the same peculiarities.The alloy of 100 of copper with from 60 to 33 of tin forms commonbell-metal. It is yellowish or whitish gray, brittle, and sonorous, but not so much so as the preceding. The metal of house-clock bells contain a little more tin than that of church-bells, and the bell of a repeater contains a little zinc in addition to the other ingredients.The bronze-founder should study to obtain a rapid fusion, in order to avoid the causes of waste indicated above. Reverberatory furnaces have been long adopted for this operation; and among these, the elliptical are the best. The furnaces with spheroidal domes are used by the bell-founders, because their alloy being more fusible, a more moderate melting heat is required; however, as the rapidity of the process is always a matter of consequence, they also would find advantage in employing the elliptical hearths (see theform of the melting furnace, as figured under Smelting of copper ores.) Coal is now universally preferred for fuel.The alloy of 100 of copper with 50 of tin, or more exactly of 32 of the former with 141⁄2of the latter, constitutesspeculummetal, for making mirrors of reflecting telescopes. This compound is nearly white, very brittle, and susceptible of a fine polish with a brilliant surface. The following compound is much esteemed in France for making specula. Melt 2 parts of pure copper and 1 of grain-tin in separate crucibles, incorporate thoroughly with a wooden spatula, and then run the metal into moulds. The lower surface is the one that should be worked into a mirror.Mr. Edwards, in the Nautical Almanack for 1787, gave the following instructions for making speculum metal.The quality of the copper is to be tried by making a series of alloys with tin, in the proportion of 100 of the former to 47, to 48, to 49, and to 50 of the latter metal; whence the proportions of the whitest compound may be ascertained. Beyond the last proportion, the alloy begins to lose in brilliancy of fracture, and to take a bluish tint. Having determined this point, take 32 parts of the copper, melt, and add one part of brass and as much silver, covering the surface of the mixture with a little black flux; when the whole is melted, stir with a wooden rod, and pour in from 15 to 16 parts of melted tin (as indicated by the preparatory trials), stir the mixture again, and immediately pour it out into cold water. Then melt again at the lowest heat, adding for every 16 parts of the compound 1 part of white arsenic, wrapped in paper, so that it may be thrust down to the bottom of the crucible. Stir with a wooden rod as long as arsenical fumes rise, and then pour it into a sand mould. While still red hot, lay the metal in a pot full of very hot embers, that it may cool very slowly, whereby the danger of its cracking or flying into splinters is prevented.Having described the different alloys of copper and tin, I shall now treat of the method of separating these metals from each other as they exist in old cannons, damaged bells, &c. The process employed on a very great scale in France during the Revolution, for obtaining copper from bells, was contrived by Fourcroy; founded upon the chemical fact that tin is more fusible and oxidizable than copper.1. A certain quantity of bell metal was completely oxidized by calcination in a reverberatory furnace; the oxide was raked out, and reduced to a fine powder.2. Into the same furnace a fresh quantity of the same metal was introduced; it wasmelted, and there was added to it one half of its weight of the oxide formed in the first operation. The temperature was increased, and the mixture well incorporated; at the end of a few hours, there was obtained on the one hand copper almost pure, which subsided in a liquid state, and spread itself upon the sole of the hearth, while a compound of oxide of tin, oxide of copper, with some of the earthy matters of the furnace collected on the surface of the metallic bath in a pasty form. These scoriæ were removed with a rake, and as soon as the surface of the melted copper was laid bare, it was run out. The scoriæ were levigated, and the particles of metallic copper were obtained after elutriation. By this process, from 100 pounds of bell metal, about 50 pounds of copper were extracted, containing only oneper cent.of foreign matters.3. The washed scoriæ were mixed with1⁄8their weight of pulverised charcoal; the mixture was triturated to effect a more intimate distribution of the charcoal; and it was then put into a reverberatory hearth, in which, by aid of a high heat, a second reduction was effected, yielding a fluid alloy consisting of about 60 parts of copper and 20 of tin; while the surface of the bath got covered with new scoriæ containing a larger proportion of tin than the first.4. The alloy of 60 of copper with 40 of tin was next calcined in the same reverberatory furnace, but with stirring of the mass. The air in sweeping across the surface of the bath, oxidized the tin more rapidly than the copper; whence proceeded crusts of oxide that were skimmed off from time to time. This process was continued till the metallic alloy was brought to the same standard as bell metal, when it was run out to be subjected to the same operations as the metal of No. 1.The layers of oxide successively removed in this way were mixed with charcoal, and reduced in afourneau à manche, or Scotch lead smelting furnace.I shall not prosecute any further the details of this complicated process of Fourcroy; because it has been superseded by a much better one contrived by M. Bréant. He employed a much larger quantity of charcoal to reduce the scoriæ rich in tin; and increased the fusibility by adding crushed oyster-shells, bottle glass, or even vitrified scoriæ, according to the nature of the substance to be reduced; and he treated them directly in a reverberatory furnace.The metal, thus procured, was very rich in tin. He exposed it in masses on a sloping hearth of a reverberatory furnace, where, by a heat regulated according to the proportions of the two metals in the alloy, he occasioned an eliquation or sweating out of the tin. Metallic drops were seen to transpire round the alloyed blocks or pigs, and, falling like rain, flowed down the sloping floor of the furnace; on whose concave bottom the metal collected, and was ladled out into moulds. When the alloy, thus treated, contained lead, this metal was found in the first portions that sweated out. The purest tin next came forth, while the last portions held more or less copper in solution. By fractioning the products, therefore, there was procured:1. Tin with lead.2. Tin nearly pure.3. Tin alloyed with a little copper.A spongy mass remained, exhibiting sometimes beautiful crystallizations; this mass, commonly too rich in copper to afford tin by liquation, was treated by oxidizement. In this manner, M. Bréant diminished greatly the reductions and oxidations; and therefore incurred in a far less degree the enormous waste of tin, which flies off with the draught of air in high and long continued heats. He also consumed less fuel as well as labour, and obtained purer products of known composition, ready to be applied directly in many arts.He treated advantageously in this manner more than a million of kilogrammes (1000 tons) of scoriæ, for every 2 cwts. of which he paid 40centimes(four-pence), while several million kilogrammes of much richer scoriæ had been previously sold to other refiners at 5centimesor onesous.I have said that the ancients made their tools and military weapons of bronze. Several of these have been analyzed, and the results are interesting.An antique sword found in 1799, in the peat moss of the Somme, consisted of copper 87·47; tin 12·53, in 100 parts.The bronze springs for the balistæ, according to Philo of Byzantium, were made of copper 97, tin 3.Hard and brittle nails afforded by analysis, 92 of copper, and 8 of tin.Of three antique swords found in the environs of Abbeville, one was found to consist of 85 of copper to 15 of tin. The nails of the handle of this sword were flexible; they were composed of copper 95, tin 5.Another of the swords consisted of 90 of copper and 10 of tin; and the third, of 96 copper, with 4 tin.A fragment of an ancient scythe afforded to analysis 92·6 copper, and 7·4 tin.The process of coating copper with tin, exemplifies the strong affinity between the two metals. The copper surface to be tinned is first cleared up with a smooth sandstone;then it is heated and rubbed over with a little sal ammoniac, till it be perfectly clean and bright: the tin, along with some pounded rosin, is now placed on the copper, which is made so hot as to melt the tin, and allow of its being spread over the surface with a dossil or pad of tow. The layer thus fixed on the copper is exceedingly thin; Bayen found that a copper pan, 9 inches in diameter and 31⁄4inches deep, being weighed immediately before and after tinning, became only 21 grains heavier. Now as the area tinned, including the bottom, amounted to 155 square inches, 1 grain of tin had been spread over nearly 71⁄2square inches; or only 20 grains over every square foot.Copper and Arsenicform a white-coloured alloy, sometimes used for the scales of thermometers and barometers; for dials, candlesticks, &c. To form this compound, successive layers of copper clippings and white arsenic are put into an earthen crucible; which is then covered with sea salt, closed with a lid, and gradually heated to redness. If 2 parts of arsenic have been used with 5 of copper, the resulting compound commonly contains one tenth of its weight of metallic arsenic. It is white, slightly ductile, denser, and more fusible than copper, and without action on oxygen at ordinary temperatures; but, at higher heats, it is decomposed with the exhalation of arsenious acid. The white copper of the Chinese consists of 40·4 copper; 31·6 nickel; 25·4 zinc; and 2·6 iron. This alloy is nearly silver white; it is very sonorous, well polished, malleable at common temperatures, and even at a cherry red, but very brittle at a red-white heat. When heated with contact of air, it oxidizes, burning with a white flame. Its specific gravity was 8·432. When worked with great care, it may be reduced to thin leaves, and to wires as small as a needle. SeeGerman Silver,infra.Tutenag, formerly confounded with white copper, is a different composition from the above. Keir says it is composed of copper, zinc, and iron; and Dick describes it as a short metal, of a grayish colour, and scarcely sonorous. The Chinese export it, in large quantities, to India.Copper, White, orGerman silver. M. Gersdorf, of Vienna, states, that the proportions of the metals in this alloy should vary according to the uses for which it is destined. When intended as a substitute for silver, it should be composed of 25 parts of nickel, 25 of zinc, and 50 of copper. An alloy better adapted for rolling, consists of 25 of nickel, 20 of zinc, and 60 of copper. Castings, such as candlesticks, bells, &c., may be made of an alloy, consisting of 20 of nickel, 20 of zinc, and 60 of copper; to which 3 of lead are added. The addition of 2 or 21⁄2of iron (in the shape of tin plate?) renders the packfong much whiter but, at the same time, harder and more brittle.Keferstein has given the following analysis of the genuine German silver, as made from the original ore found in Hildburghausen, near Suhl, in Henneberg:—Copper40·4Nickel31·6Zinc25·4Iron2·6100·0Chinese packfong, according to the same authority, consists of 5 parts of copper, alloyed with 7 parts of nickel, and 7 parts of zinc.The best alloy for making plummer blocks, bushes, and steps for the steel or iron gudgeons, and pivots of machinery to run in, is said to consist of 90 parts of copper, 5 of zinc, and 5 of antimony.A factitious protoxide of copper, of a fine red colour, may be made by melting together, with a gentle heat, 100 parts of sulphate of copper, and 59 of carbonate of soda in crystals, and continuing the heat till the mass become solid. This being pulverized, and mixed exactly with 15 parts of copper filings, the mixture is to be heated to whiteness, in a crucible, during the space of 20 minutes. The mass, when cold, is to be reduced to powder, and washed. A beautiful metallic pigment may be thus prepared, at the cost of 2s.a pound.All the oxides and salts of copper are poisonous; they are best counteracted by administering a large quantity of sugar, and sulphuretted hydrogen water.The following scientific summary of copper ores in alphabetical order may prove acceptable to many readers, amid the present perplexing distribution of the native metallic compounds in mineralogical systems.1.Arseniate of Copper.A.Erinite, rhomboidal arseniate of copper, micaceous copper,kupferglimmer. Emerald green; specific gravity 4·043; scratches calc-spar; yields water by heat; fusible at the blowpipe, and reducible into a white metallic globule. Soluble in nitric acid; the solution throws down copper by iron. It consists of arsenic acid 33·78; oxide of copper 59·24; water 5; alumina 1·77. It is found in Cornwall, Ireland, Hungary.B.Liroconite; octahedral arseniate of copper; lens ore, so called from the flatnessof the crystal. Blue; specific gravity 2·88; scratches calc-spar. It consists of arsenic acid 14; oxide of copper 49; water 35. It is found in Huel-Mutrel, Huel-Gorland, Huel-Unity, mines in Cornwall.C.Olivenite; right prismatic arseniate of copper; olive-ore. Dull green; specific gravity 4·28; scratches fluor; yields no water by heat; fusible at the blowpipe into a glassy bead, enclosing a white metallic grain. It consists of arsenic acid 45, oxide of copper 50·62. It affords indications of phosphoric acid, which the analysts seem to have overlooked. It occurs in the above and many other mines in Cornwall.D.Aphanese.Trihedral arseniate of copper. Bluish green, becoming gray upon the surface; specific gravity 4·28; scarcely scratches calc-spar; yields water with heat; and traces of phosphoric acid.The fibrous varieties called wood copper, contain water, and resemble the last species in composition.2.Carbonate of Copper.A.Azurite; kupferlazur. Blue. Crystallizes in oblique rhomboidal prisms; specific gravity 3 to 3·83; scratches calc-spar, is scratched by fluor; yields water with heat, and blackens. Its constituents are, carbonic acid 25·5; oxide of copper 69·1; water 5·4. The Chessy and Banat azurite is most profitably employed to make sulphate of copper.B.Malachite; green carbonate or mountain green. Crystallizes in right rhomboidal prisms; specific gravity 3·5; affords water with heat, and blackens. It consists of carbonic acid 18·5; oxide of copper 72·2; water 9·3.C.Mysorine; anhydrous carbonate of copper. Dark brown generally stained green or red; conchoidal fracture; soft, sectile; specific gravity 2·62. It consists of carbonic acid 16·7; oxide of copper 60·75; peroxide of iron 19·5; silica 2·10. This is a rare mineral found in the Mysore.3.Chromate of Copper and Lead; vauquelinite. Green of various shades; specific gravity 6·8 to 7·2; brittle; scratched by fluor; fusible at the blowpipe with froth and the production of a leaden bead. It consists of chromic acid 28·33; oxide of lead 60·87; oxide of copper 10·8. It occurs at Berezof in Siberia along with chromate of lead.4.Dioptase; silicate of copper; emerald copper. Specific gravity 3·3; scratches glass with difficulty; affords water with heat, and blackens; infusible at the blowpipe. It consists of silica 43·18; oxide of copper 45·46; water 11·36. This rare substance comes from the government of Kirgis.The silicate of Dillenberg is similar in composition.5. Gray copper ore called Panabase, from the number of metallic bases which it contains; and Fahlerz. Steel gray; specific gravity 4·79 to 5·10; crystallizes in regular tetrahedrons; fusible at the blowpipe, with disengagement of fumes of antimony and occasionally of arsenic; swells up and scorifies, affording copper with soda flux. Is acted upon by nitric acid with precipitation of antimony; becomes blue with ammonia; yields a blue precipitate with ferrocyanide of potassium; as also indications frequently of zinc, mercury, silver, &c. Its composition which is very complex is as follows: sulphur 26·83; antimony 12·46; arsenic 10·19; copper 40·60; iron 4·66; zinc 3·69; silver 0·60. Some specimens contain from 5 to 31 per cent. of silver. The gray copper ores are very common; in Saxony; the Hartz; Cornwall; at Dillenberg; in Mexico; Peru, &c. They are important on account both of their copper and silver.Tennantiteis a variety of Fahlerz. It occurs in Cornwall. Its constituents are, sulphur 28·74; arsenic 11·84; copper 45·32; iron 9·26.6.Hydrated silicate of Copper; or Chrysocolla. Green or bluish green; specific gravity 2·03 to 2·16; scratched by steel; very brittle; affords water with heat, and blackens; is acted upon by acids, and leaves a siliceous residuum. Solution becomes blue with ammonia. Its constituents are silica 26; oxide of copper 50; water 17; carbonic acid 7.7.Muriate of Copper.Atakamite; green; crystallizes in prisms; specific gravity 4·43. Its constituents are, chlorine 15·90; copper 14·22; oxide of copper 54·22; water 14·16; oxide of iron 1·50. The green sand of Peru, collected by the inhabitants of Atakama, is this substance in a decomposed state.8.Oxide of Copper.A. Black, or Melaconise; a black earthy looking substance found at Chessy and other places. It is deutoxide of copper.B. Protoxide or red oxide of copper; ziegelerz. Crystallizes in the regular octahedron; specific gravity 5·69; scratches calc-spar; fusible at the blowpipe into the black oxide; and reducible in the smoke of the flame to copper; acted upon by nitric acid with disengagement of nitrous gas; solution is rendered blue by ammonia. Its constituents are oxygen 11·22; copper 88·78. It occurs near Chessy, and upon the eastern slope of the Altai mountains.9.Phosphate of Copper.Dark green; crystallizes in octahedrons; specific gravity 3·6 to 3·8; scratches calc-spar; yields water with heat; and affords metallic copperwith soda flux; acted on by nitric acid. Its constituents are, phosphoric acid 28·7; oxide of copper 63·9; water 7·4. It occurs at the mines of Libethen in Hungary.10.Pyritous Copper; Kupferkies; a metallic looking substance, of a bronze-yellow colour, crystallizing in octahedrons which pass into tetrahedrons; specific gravity 4·16; fusible at the blowpipe into beads attractable by the magnet, and which afterwards afford copper with a soda flux; soluble in nitric acid; solution is rendered blue by ammonia, and affords an abundant precipitate of iron. Its composition is, sulphur 36; copper 34·5; iron 30·5; being a combined sulphuret of these two metals. This is the most important metallurgic species of copper ores. It occurs chiefly in primitive formations, as among gneiss and mica slate, in veins or more frequently masses in very many parts of the world—Cornwall, Anglesea, Wicklow, &c. It is found among the early secondary rocks, in Shetland, Yorkshire, Mansfeldt, &c. The finest crystallized specimens come from Cornwall, Derbyshire, Freyberg, and Saint Marie-aux-Mines in France.11.Seleniate of Copper; Berzeline. Is of metallic aspect; silver white; ductile; fusible at the blowpipe into a gray bead, somewhat malleable; is acted upon by nitric acid; consists of selenium 40; copper 64.12.Sulphate of Copper; Cyanose. Blue; soluble, &c. like the artificialsulphates, which see.Brochantiteis a subsulphate of copper observed in small crystals at Ekaterinenbourg in Siberia.13.Sulphuret of Copper; Kupferglanz. Of a steel gray metallic aspect; crystallizes in rhomboids; specific gravity 5·69; somewhat sectile, yet brittle; fusible with intumescence at the blowpipe, and yields a copper bead with soda; soluble in nitric acid; becomes blue with ammonia, but lets fall scarcely any oxide of iron. Its constituents are, sulphur 19; copper 79·5; iron 0·75; silica 1·00. It occurs in small quantities in Cornwall, &c.The chemical preparations of copper which constitute distinct manufactures are, Blue or Roman vitriol; for which seeSulphate of Copper;Scheele’s greenandSchweinurth green,Verditer, andVerdigris. See these articles in their alphabetical places.
Swansea copper furnaces
Fig.304.is the section of the roasting furnace lengthwise;fig.303.the ground plan; in whichais the fire-door;bthe grate;cthe fore-bridge;dthe chimney;e eworking apertures on each of the long sides of the furnace, through which the ore is introduced, spread, and turned over;f fcast-iron hoppers;g gopenings in the vaulted roof;hthe hearth-sole;i iholes in this;ka vaulted space under the hearth. The hearth has a suitable oval shape, and is covered with a flat arch. Its length is 16 feet, breadth 131⁄2, mean height 2 feet.
Melting furnace
Fig.305.is a longitudinal section of the melting furnace;fig.306.the ground plan in whichais the fire door;bthe grate;cthe fire bridge;dthe chimney;ethe side openings;fthe working doors;gthe raking-out hole;hiron spouts, which conduct the melted metal into pits filled with water.
The melting furnace is altogether smaller; but its firing hearth is considerably largerthan in the roasting furnace. The long axis of the oval hearth is 14 feet; its short axis 10 feet; its mean height 2 feet.
The principal ore smelted at Chessy is the azure copper, which was discovered by accident in 1812. Red copper ore, also, has come into operation there since 1825. The average metallic contents of the richest azure ore are from 33 to 36 per cent.; of the poorer, from 20 to 24. The red ore contains from 40 to 67 parts in 100. The ore is sorted, so that the mean contents of metal may be 27 per cent., to which 20 per cent. of limestone are added; whence the cinder will amount to 50 per cent. of the ore. A few per cents. of red copper slag, with some quicklime andgahrslag, are added to each charge, which consists of 200 pounds of the above mixture, and 150 pounds of coke. When the furnace (fourneau à manche, see theScotch smelting hearth, underLead), is in good action, from 10 to 14 such charges are worked in 12 hours. When the crucible is full of metal at the end of this period, during which the cinder has been frequently raked off, the blast is stopped, and themattfloating over the metal being sprinkled with water and taken off, leaves the black copper to be treated in a similar way, and converted intorosettes. The refining of this black copper is performed in a kind of reverberatory furnace.
The cinders produced in this reduction process are either vitreous and light blue, which are most abundant; cellular, black, imperfectly fused from excess of lime; or, lastly, red, dense, blistery, from defect of lime, from too much heat, and the passage of protoxide into the cinders. They consist of silicate of alumina, of lime, protoxide of iron; the red contain some silicate of copper.
Split hearth
The copper-refining furnace at Chessy, near Lyons, is of the kind calledSpleiss-ofen(split hearths) by the Germans.Fig.307.is a section lengthwise in the dotted lineA Boffig.308., which is the ground plan.
Split hearth
The foundation-walls are made of gneiss; the arch, the fire-bridge, and the chimney, of fire-bricks. The hearth,a, is formed of a dense mixture of coal-dust, upon a bottom of well-beat clayb, which reposes upon a bed of brickworkc. Beneath this there is a slag bottomd;eis the upper, andfthe under discharge hole. The hearth is egg-shaped; the longer axis being 8 feet, the shorter 61⁄2feet: in the middle it is 10 inches deep, and furnished with the outletsg g, which lead to each of theSpleiss-hearthsh h,fig.308.These outlets are contracted with fire-bricksi i, till the proper period of the discharge. The two hearths are placed in communication by a canalh; they are 31⁄2feet in diameter, 16 inches deep; are floored with well-beat coal ashes, and receive about 27 cwt. for a charge.
lis the grate;m, the fire-bridge;n, the boshes in which thetuyèreslie;o, the chimney;p, the working door through which the slags may be drawn off. Above this is a small chimney, to carry off the flame and smoke whenever the door is opened.
The smeltingpostor charge, to be purified at once, consists of 60 cwt. of black copper, to which a little granular copper and copper of cementation is added; theconsumption of pit-coal amounts to 36 cwt. As soon as the copper is melted, the bellows are set a-going, and the surface of the metal gets soon covered with a moderately thick layer of cinder, which is drawn off. This is the first skimming ordecrassage. By and by, a second layer of cinder forms, which is in like manner removed; and this skimming is repeated, to allow the blast to act upon fresh metallic surfaces. After 4 or 5 hours, no more slag appears, and then the fire is increased. The melted mass now begins to boil or work (travailler), and continues so to do, for about3⁄4of an hour, or an hour, after which the motion ceases, though the fire be kept up. Thegahrproofis now taken; but the metal is seldom fine in less than3⁄4of an hour after the boil is over. Whenever the metal is run off by the tap-hole into the two basinsi i, calledSPLIT-HEARTHS, a reddish vapour or mist rises from its surface, composed of an infinite number of minute globules, which revolve with astonishing velocity upon their axes, constituting what the Germans calledspratzen(crackling) of the copper. They are composed of a nucleus of metal, covered with a film of protoxide, and are used as sand for strewing upon manuscript. The copper is separated, as usual, by sprinkling water upon the surface of the melted metal, in the state ofrosettes, which are immediately immersed in a stream of water. This refining process lasts about 16 or 17 hours; the skimmings weigh about 50 cwt.; the refuse is from 15 to 17 per cent.; the loss from 2 to 3 per cent. Thegahrslagamounts to 11 cwt.
Kupfergahrheerd
The refining of the eliquated copper (calleddarrlinge) from which the silver has been sweated out by the intervention of lead, can be performed only in small hearths. The following is the representation of such a furnace, called, in German,Kupfergahrheerd.Fig.309.is the section lengthwise;fig.310.is the section across; andfig.311.is the ground plan, in whichais the hearth-hollow;b, a massive wall;c, the mass out of which the hearth is formed;d, cast-iron plates covering the hearth;e, opening forrunning off the liquid slag;f, a small wall;g, iron curb for keeping the coals together.
The hearth being heated with a bed of charcoal,3⁄4cwt. ofdarrlingeare laid over it, and covered with more fuel: whenever this charge is melted, another layer of the coal anddarrlingeis introduced, and thus in succession till the hearth become full, or contain from 21⁄4to 21⁄2cwt. In Neustadt 71⁄2cwt. ofdarrlingehave been refined in one furnace, from which 5 cwt. ofgahrcopperhas been obtained. The blast oxidizes the foreign metals, namely, the lead, nickel, cobalt, and iron, with a little copper, forming thegahrslag; which is, at first, rich in lead oxide, and poor in copper oxide; but, at the end, this order is reversed. The slag, at first blackish, assumes progressively a copper red tint. The slag flows off spontaneously along the channele, from the surface of the hearth. Thegahreis tested by means of a proof rod of iron, calledgahr-eisen, thrust through thetuyèreinto the melted copper, then drawn out and plunged in cold water. As soon as thegahrspan(scale of copper) appears brownish red on the outside, and copper red within, so thin that it seems like a net-work, and so deficient in tenacity that it cannot be bent without breaking, the refining is finished. The blast is then stopped; the coals covering the surface, as also the cinders must be raked off the copper, after being left to cool a little; the surface is now cooled by sprinkling water upon it, and the thick cake of congealed metal (rondelle) is lifted off with tongs, a process calledschleissen(slicing), orsheibenreissen(shaving), which is continued till the last convex cake at the bottom of the furnace, styled thekingspiece, is withdrawn. Theserondellesare immediately immersed in cold water, to prevent the oxidation of the copper; whereupon the metal becomes of a cochineal red colour, and gets covered with a thin film of protoxide. Its under surface is studded over with points and hooks, the result of tearing the congealed disc from the liquid metal. Such cakes are calledrosettecopper. When the metal is very pure and free from protoxide, these cakes may be obtained very thin, one 24th of an inch for example.
The refining of two cwts. and a half ofdarrlingetakes three quarters of an hour, and yields one cwt. and a half ofgahr copperin 36 rosettes, as also somegahrslag. Gahr copper generally contains from 11⁄2to 21⁄2per cent. of lead, along with a little nickel, silver, iron, and aluminum.
Smelting of the Mansfeldt copper schist, or bituminous Mergelschiefer.—The cupreous ore is first roasted in large heaps, of 2000 cwts., interstratified with brush-wood, and with some slates rich in bituminous matter, mixed with the others. These heaps are 3 ells high, and go on burning 15 weeks in fair and 20 in rainy weather. The bitumen is decomposed; the sulphur is dissipated chiefly in the form of sulphurous acid; the metal gets partially oxidized, particularly the iron, which is a very desirable circumstance towards the production of a good smelting slag. The calcined ore is diminished one-tenth in bulk, and one-eighth in weight; becoming of a friable texture and a dirty yellow gray colour. The smelting furnaces are cupolas (schachtofen), 14 to 18 feet high; the fuel is partly wood charcoal, partly coke from the Berlin gas-works, and Silesia. The blast is given by cylinder bellows, recently substituted for the old barbarousBlasebälgen, or wooden bellows of the household form.
The cupreous slate is sorted, according to its composition, into slate of lime, clay, iron, &c., by a mixture of which the smelting is facilitated. For example, 1 post or charge may consist of 20 cwt. of the ferruginous slate, 14 of the calcareous, 6 of the argillaceous, with 3 of fluor spar, 3 of rich copper slags, and other refuse matters. The nozzle at thetuyèreis lengthened 6 or 8 inches, to place the melting heat near the centre of the furnace. In 15 hours 1 fodder of 48 cwts. of the above mixture may be smelted, whereby 4 to 5 cwts. ofmatte(crude copper, calledKupfersteinin Germany) and a large body of slags are obtained. Themattecontains from 30 to 40 per cent. of copper, and from 2 to 4loths(1 to 2 oz.) of silver. The slags contain at times one-tenth their weight of copper.
Thematteis composed of the sulphurets of copper, iron, silver, zinc, along with some arsenical cobalt and nickel. The slaty slag is raked off the surface of the meltedmattefrom time to time. The former is either after being roasted six successive times, smelted into black copper; or it is subjected to the following concentration process. It is broken to pieces, roasted by brushwood and coals three several times in brick-walled kilns, containing 60 cwts., and turned over after every calcination; a process of four weeks’ duration. The thrice roasted mass, calledspurrost, being melted in the cupolafig.313.with ore-cinder, yields thespurstein, or concentratedmatte. From 30 to 40 cwts. of spurrost are smelted in 24 hours; and from 48 to 60 per cent. ofspursteinare obtained, the slag from the slate smelting being employed as a flux. The spurstein contains from 50 to 60 per cent. of copper, combined with the sulphurets of copper, of iron, and silver.
The spurstein is now mixed withdünnstein(a sulphuret of copper and iron produced in the original smeltings) roasted six successive times, in a quantity of 60 cwts., withbrushwood and charcoal; a process which requires from 7 to 8 weeks. The product of this six-fold calcination is theGahrrostof the Germans (done and purified); it has a colour like red copper ore, varying from blue gray into cochineal red; a granular fracture; it contains a little of the metal, and may be immediately reduced into metallic copper, calledkupfermachen. But before smelting the mass, it is lixiviated with water, to extract from it the soluble sulphate, which is concentrated in lead pans, and crystallized.
The lixiviatedgahröstemixed with from1⁄4to1⁄5of the lixiviateddünnsteinrost, and1⁄6to1⁄10of the copper slate slag, are smelted with charcoal or coke fuel in the course of 24 hours, in a mass of 60 or 80 cwts. The product is black copper, to the amount of about1⁄4the weight, and1⁄6ofdünnstein, orthin matte. This black copper contains in the cwt. from 12 to 20 loths (6 to 10 oz.) of silver. Thedünnsteinconsists of from 60 to 70 per cent. of copper combined with sulphur, sulphuret of iron and arsenic; and when thrice roasted, yields a portion of metal. The black copper lies undermost in the crucible of the furnace, above it is thedünnstein, covered with the stone slag, or copper cinder, resulting from the slate-smelting. The slags being raked off, and the crucible sufficiently full, the eye or nozzle hole is shut, thedünnsteinremoved by cooling the surface, and breaking the crust, which is about1⁄4to1⁄2inch thick. The same method is adopted for taking out the black copper in successive layers. For the de-silvering of this, and similar black coppers, seeSilver.
Form or tuyère
Fig.312.is a vertical section through the form ortuyèrein the dotted lineA Boffig.314.Fig.313.is a vertical section in the dotted lineC Doffig.315.ais the shaft of the furnace,bthe rest,c cthe forms;dthe sole or hearth-stone, which has a slope of 3 inches towards the front wall;e e, &c. casing walls of fire bricks;f f, &c. filling up walls built of rubbish stones;g ga mass through which the heat is slowly conducted;h hthe two holes through one or other of which alternately the product of the smelting process is run off into the fore-hearth. Beneath the hearth-sole there is a solid body of loam; and the fore-hearth is formed with a mixture of coal-dust and clay;kis the discharge outlet.Fig.314.is a horizontal section of the furnace through the hole or eye in the dotted lineE Foffig.312.;fig.315.a horizontal section of the shaft of the furnace through the form in the dotted lineG Hoffigs.312 and 313. The height of the shaft, from the lineE Fto the top, is 14 feet; fromEtoG, 25 inches; fromcto the line belowb, 2 feet; from that line to the line oppositeg g, 2 feet. The width at the lineg gis 3 feet 3 inches, and atc26 inches. The basinsi i,fig.314., are 3 feet diameter, and 20 inches deep.
The refining of copper is said to be well executed at Seville, in Spain; and, therefore, some account of the mode of operating there may be acceptable to the reader.
The first object is to evaporate in a reverberatory furnace all the volatile substances, such as sulphur, arsenic, antimony, &c., which may be associated with the sulphur; and the second, to oxidize and to convert into scoriæ the fixed substances, such as iron, lead, &c., with the least possible expense and waste. The minute quantities of gold and silver which resist oxidation cannot be in any way injurious to the copper. The hearth is usually made of a refractory sand and clay with ground charcoal, each mixed in equal volumes, and worked up into a doughy consistence with water. This composition is beat firmly into the furnace bottom. But a quartzose hearth is found to answer better, and to be far more durable; such as a bed of fire-sandstone.
Before kindling the furnace, its inner surface is smeared over with a cream-consistenced mixture of fire-clay and water.
The cast pigs, or blocks of black or crude copper, are piled upon the hearth, each successive layer crossing at right angles the layer beneath it, in order that the flame mayhave access to play upon the surface of the hearth, and to heat it to a proper pitch for making the metal flow.
The weight of the charge should be proportional to the capacity of the furnace, and such that the level of the metallic bath may be about an inch above the nozzle of the bellows; for, were it higher, it would obstruct its operation, and were it too low, the stream of air would strike but imperfectly the surface of the metal, and would fail to effect, or would retard at least, the refining process, by leaving the oxidation and volatilization of the foreign metals incomplete.
As the scoriæ form upon the surface, they are drawn off with an iron rabble fixed to the end of a wooden rod.
Soon after the copper is melted, charcoal is to be kindled in three iron basins lined with loam, placed alongside the furnace, to prepare them for receiving their charge of copper, which is to be converted in them, intorosettes.
The bellows are not long in action before the evaporation of the mineral substances is so copious, as to give the bath a boiling appearance; some drops rise up to the roof of the reverberatory, others escape by the door, and fall in a shower of minute spherical globules. This phenomenon proves that the process is going on well; and, when it ceases, the operation is nearly completed. A small proof of copper, of the form of a watch-case, and therefore calledmontre, is taken out from time to time, upon the round end of a polished iron rod, previously heated. This rod is dipped two or three inches into the bath, then withdrawn and immersed in cold water. The copper cap is detached from the iron rod, by a few blows of a hammer; and a judgment is formed from its thickness, colour, and polish, as to the degree of purity which the copper has acquired. But thesewatchesneed not be drawn till the small rain, above spoken of, has ceased to fall. At the end of about 11 hours of firing, the numerous small holes observable in the firstwatchsamples begin to disappear; the outer surface passes from a bright red to a darker hue, the inner one becomes of a more uniform colour, and always less and less marked with yellowish spots. It will have acquired the greatest pitch of purity that the process can bestow, when thewatchesbecome of a dark crimson colour.
Care must be taken to stop this refining process at the proper time; for, by prolonging it unduly, a small quantity of cupreous oxide would be formed, which, finding no oxygen to reduce it, would render the whole body of copper hard, brittle, and incapable of lamination.
The basins must now be emptied of their burning charcoal, the opening of thetuyèremust be closed, and the melted copper allowed to flow into them through the tap-hole, which is then closed with loam. Whenever the surface is covered with a solid crust, it is bedewed with water; and as soon as the crust is about 11⁄2inch thick it is raised upon hooks above the basin, to drain off any drops, and then carried away from the furnace. If these cakes, or rosettes, be suddenly cooled by plunging them immediately in water, they will assume a fine red colour, from the formation of a film of oxide.
Each refining operation produces, in about 12 hours, 17⁄10tons of copper, with the consumption of about4⁄5of a ton of dry wood.
Care should be taken that the copper cake orrosettebe all solidified before plunging it into water, otherwise a very dangerous explosion might ensue, in consequence of the sudden extrication of oxygen from the liquid metal, in the act of condensation. On the other hand, the cake should not be allowed to cool too long in the air, lest it get peroxidized upon the surface, and lose those fine red, purple, and yellow shades, due to a film of the protoxide, which many dealers admire.
When a little oxide of antimony and oxide of copper are combined with copper, they occasion the appearance of micaceous scales in the fractured faces. Such metal is hard, brittle, yellowish within, and can be neither laminated nor wire-drawn. These defects are not owing to arsenic, as was formerly imagined; but, most probably, to antimony in the lead, which is sometimes used in refining copper. They are more easily prevented than remedied.
According to M. Frèrejean, proprietor of the great copper works of Vienne, in Dauphiny, too low a temperature or too much charcoal, gives to the metal a cubical structure, or that of divergent rays; in either of which states it wants tenacity. Too high a temperature, or too rapid a supply of oxygen, gives it a brick red colour, a radiated crystallization without lustre, or a very fine grain of indeterminate form; the last structure being unsuitable for copper that is to be worked under the hammer or in the rolling-press. The form which indicates most tenacity is radiated with minute fibres glistening in mass. Melted copper will sometimes pass successively through these three states in the space of ten minutes.
Roasting mound
Fig.316.represents aroasting moundof copper pyrites in the Lower Hartz, near Goslar, where a portion of the sulphur is collected. It is a vertical section of a truncated quadrangular pyramid. A layer of wooden billets is arranged at the base of the pyramid in the linea a.
C, a wooden chimney which stands in the centre of the mound with a small pile of charcoal at its bottom,c;d dare large lumps of ore surrounded by smaller pieces;f f, are rubbish and earth to form a covering. A current of air is admitted under the billets by an opening, in the middle of each of the four sides of the basea a, so that two principal currents of air cross under the vertical axisCof the truncated pyramid, as indicated in the figure.
The fire is applied through the chimneyC; the charcoal at its bottomc, and the pilea aare kindled. The sulphureous oresd,f, are raised to such a high temperature as to expel the sulphur in the state of vapour.
In the Lower Hartz a roasting mound continues burning during four months. Some days after it is kindled the sulphur begins to exhale, and is condensed by the air at the upper surface of the pyramid. When this seems impregnated with it, small basins l l are excavated, in which some liquid sulphur collects; it is removed from time to time with iron ladles, and thrown into water, where it solidifies. It is then refined and cast into roll brimstone.
A similar roasting mound contains, in the Lower Hartz, from 100 to 110 tons of ore and 730 cubic feet of wood. It yields in four months about one ton and a half of sulphur from copper pyrites. Lead ore is treated in the same way, but it furnishes less sulphur.
There are usually from 12 to 15 roasting heaps in action at once for three smelting works of the Lower Hartz. After the first roasting two heaps are united to form a third, which is calcined anew, but under a shed; the ores are then stirred up and roasted for the third time, whence a crude mixture is procured for the smelting-house.
The most favourable seasons for roasting in the open air are spring and autumn; the best weather is a light wind accompanied with gentle rain. When the wind or rain obstruct the operation, this inconvenience is remedied by planks distributed round the upper surface of the truncated pyramid over the sulphur basins.
Manufacturing assays of copper.—The first thing is to make such a sample as will represent the whole mass to be valued; with which view, fragments must be taken from different spots, mixed, weighed, and ground together. A portion of this mixture being tried by the blow-pipe, will show, by the garlic or sulphurous smell of its fumes, whether arsenic, sulphur, or both, be the mineralizers. In the latter case, which often occurs, 100 gr. or 1000 gr. of the ore are to be mixed with one half its weight of saw-dust, then imbued with oil, and heated moderately in a crucible till all the arsenical fumes be dissipated. The residuum being cooled and triturated, is to be exposed in a shallow earthen cup to a slow roasting heat, till the sulphur and charcoal be burned away. What remains being ground and mixed with half its weight of calcined borax, one-twelfth its weight of lamp black, next made into a dough with a few drops of oil, is to be pressed down into a crucible, which is to be covered with a luted lid, and to be subjected, in a powerful air furnace, first to a dull red heat, and then to vivid ignition for 20 minutes. On cooling and breaking the crucible, a button of metallic copper will be obtained. Its colour and malleability indicate pretty well the quality, as does its weight, the relative value of the ore. It should be cupelled with lead, to ascertain if it contains silver or gold. SeeAssay, andSilver.
If the blow-pipe trial showed no arsenic, the first calcination may be omitted; and if neither sulphur nor arsenic, a portion of the ground ore should be dried, and treated directly with borax, lamp black and oil. It is very common to make a dry assay of copper ores, by one roasting and one fusion along with 3 parts of black flux; from the weight of the metallic button the richness of the ore is inferred.
The humid assay is more exact, but it requires more skill and time.
The sulphur and the silica are easily got rid of, by the acids which do not dissolve them, but only the metallic oxides and the other earths. These oxides may then be thrown down by their appropriate reagents, the copper being precipitated in the state of either the black oxide, or pure metal. 105 parts of black oxide represent 100 of copper. Before entering upon the complete analysis of an ore, preliminary trials should be made, to ascertain what are its chief constituents. If it be sulphuret of copper, or copper pyrites, without silver or lead, 100 grains exactly of its average powder may be weighed out, treated in a matras with boiling muriatic acid for some time, gradually adding a few drops of nitric acid, till all action ceases, or till the ore be all dissolved. The insoluble matter found floating in the liquid contains most of the sulphur; it may be separated upon a filter, washed, dried, and weighed; then verified by burning away. The incombustible residuum, treated by muriatic acid, may leave an insoluble deposit, which is to be added to the former. To the whole of the filtered solutions carbonate of potash isto be added; and the resulting precipitate, being washed, and digested repeatedly in water of ammonia, all its cupric oxide will have been dissolved, whenever the ammonia is no longer rendered blue.
Caustic potash, boiled with the ammoniacal solution, will separate the copper in the state of black oxide; which is to be thrown upon a filter, washed, dried, and weighed. The matter left undissolved by the ammonia, consists of oxide of iron, with probably a little alumina. The latter being separated by caustic potash, the iron oxide may be also washed, dried, and weighed. The powder which originally resisted the muriatic acid, is silica.
Assay of copper ores, which contain iron, sulphur, silver, lead, and antimony.
100 grains of these ores, previously sampled, and pulverized, are to be boiled with nitric acid, adding fresh portions of it from time to time, till no more of the matter be dissolved. The whole liquors which have been successively digested and decanted off, are to be filtered and treated with common salt, to precipitate the silver in the state of a chloride.
The nitric acid, by its reaction upon the sulphur, having generated sulphuric acid, this will combine with the lead oxidized at the same time, constituting insoluble sulphate of lead, which will remain mixed with the gangue. Should a little nitrate of lead remain in the liquid, it may be thrown down by sulphate of soda, after the silver has been separated. The dilute liquid being concentrated by evaporation, is to be mixed with ammonia in such excess as to dissolve all the cupric oxide, while it throws down all the oxide of iron and alumina; which two may be separated, as usual, by a little caustic potash. The portion of ore insoluble in the nitric acid, being digested in muriatic acid, every thing will be dissolved except the sulphur and silica. These being collected upon a filter, and dried, the sulphur may be burned away, whereby the proportion of each is determined.
Ores of theoxideof copper, are easily analyzed by solution in nitric acid, the addition of ammonia, to separate the other metals, and precipitation by potash. Thenative carbonateis analyzed by calcining 100 grains; when the loss of weight will shew the amount of water and carbonic acid; then that of the latter may be found, by expelling it from another 100 grains, by digestion in a given weight of sulphuric acid. The copper is, finally, obtained in a metallic state by plunging bars of zinc into the solution of the sulphate.
Thenative arseniates of copperare analyzed by drying them first at a moderate heat; after which they are to be dissolved in nitric acid. To this solution, one of nitrate of lead is to be added, as long as it occasions a precipitate; the deposit is to be drained upon a filter, and the clear liquid which passes through, being evaporated nearly to dryness, is to be digested in hot alcohol, which will dissolve every thing except a little arseniate of lead. This being added to the arseniate first obtained, from the weight of the whole, the arsenic acid, constituting 35 per cent., is directly inferred. The alcoholic solution being now evaporated to dryness, the residue is to be digested in water of ammonia, when the cupric oxide will be dissolved, and the oxide of iron will remain. The copper is procured, in the state of black oxide, by boiling the filtered ammoniacal solution with the proper quantity of potash.
The analysis of muriate of copper—atacamite—is an easy process. The ore being dissolved in nitric acid, a solution of nitrate silver is added, and from the weight of the chloride precipitated, the equivalent amount of muriate or chloride of copper is given; for 100 of chloride of silver represent 93 of chloride of copper, and 43·8 of its metallic basis. This calculation may be verified by precipitating the copper of the muriate from its solution in dilute sulphuric acid, by plates of zinc.
The phosphate of coppermay be analyzed either by solution in nitric acid, and precipitation by potash; or by precipitating the phosphoric acid present, by means of acetate of lead. The phosphate of lead thus obtained, after being washed, is to be decomposed by dilute sulphuric acid. The insoluble sulphate of lead being washed, dried, and weighed, indicates by its equivalent the proportion of phosphate of lead, as also of phosphate of copper; for 100 of sulphate of lead correspond to 92·25 phosphate of lead, and 89·5 phosphate of copper; and this again to 52·7 of the black oxide.
Copper forms the basis of a greater number of importantALLOYSthan any other metal. With zinc it formsBrassin all its varieties; which see.
BronzeandBell Metalare alloys of copper and tin. This compound is prepared in crucibles when only small quantities are required; but in reverberatory hearths, when statues, bells, or cannons are to be cast. The metals must be protected as much as possible during their combination from contact of air by a layer of pounded charcoal, otherwise two evils would result, waste of the copper by combustion, and a rapid oxidizement of the tin, so as to change the proportions and alter the properties of the alloy. The fused materials ought to be well mixed by stirring, to give uniformity to the compound. SeeBronze.
An alloy of 100 of copper and 4·17 of tin has been proposed by M. Chaudet for the ready manufacture ofmedals. After melting this alloy he casts it in moulds made of such bone-ash as is used for cupels. The medals are afterwards subjected to the action of the coining press, not for striking them, for the mould furnishes perfect impressions, but for finishing and polishing them.
By a recent analysis of M. Berthier, the bells of thependules, or ornamental clocks, made in Paris, are found to be composed, of copper 72·00, tin 26·56, iron 1·44, in 100 parts.
An alloy of 100 of copper and 14 of tin is said by M. Dussaussy to furnish tools, which hardened and sharpened in the manner of the ancients, afford an edge nearly equal to that of steel.
Cymbals, gongs, and thetamtamof the Chinese are made of an alloy of 100 of copper with about 25 of tin. To give this compound the sonorous property in the highest degree it must be subjected to sudden refrigeration. M. D’Arcet, to whom this discovery is due, recommends to ignite the piece after it is cast, and to plunge it immediately into cold water. The sudden cooling gives the particles of the alloy such a disposition that, with a regulated pressure by skilful hammering, they may be made to slide over each other, and remain permanently in their new position. When by this means the instrument has received its intended form, it is to be heated and allowed to cool slowly in the air. The particles now take a different arrangement from what they would have done by sudden refrigeration; for instead of being ductile they possess such an elasticity, that on being displaced by a slight compression, they return to their primary position after a series of extremely rapid vibrations; whence a very powerful sound is emitted. Bronze, bell-metal, and probably all the other alloys of tin with copper present the same peculiarities.
The alloy of 100 of copper with from 60 to 33 of tin forms commonbell-metal. It is yellowish or whitish gray, brittle, and sonorous, but not so much so as the preceding. The metal of house-clock bells contain a little more tin than that of church-bells, and the bell of a repeater contains a little zinc in addition to the other ingredients.
The bronze-founder should study to obtain a rapid fusion, in order to avoid the causes of waste indicated above. Reverberatory furnaces have been long adopted for this operation; and among these, the elliptical are the best. The furnaces with spheroidal domes are used by the bell-founders, because their alloy being more fusible, a more moderate melting heat is required; however, as the rapidity of the process is always a matter of consequence, they also would find advantage in employing the elliptical hearths (see theform of the melting furnace, as figured under Smelting of copper ores.) Coal is now universally preferred for fuel.
The alloy of 100 of copper with 50 of tin, or more exactly of 32 of the former with 141⁄2of the latter, constitutesspeculummetal, for making mirrors of reflecting telescopes. This compound is nearly white, very brittle, and susceptible of a fine polish with a brilliant surface. The following compound is much esteemed in France for making specula. Melt 2 parts of pure copper and 1 of grain-tin in separate crucibles, incorporate thoroughly with a wooden spatula, and then run the metal into moulds. The lower surface is the one that should be worked into a mirror.
Mr. Edwards, in the Nautical Almanack for 1787, gave the following instructions for making speculum metal.
The quality of the copper is to be tried by making a series of alloys with tin, in the proportion of 100 of the former to 47, to 48, to 49, and to 50 of the latter metal; whence the proportions of the whitest compound may be ascertained. Beyond the last proportion, the alloy begins to lose in brilliancy of fracture, and to take a bluish tint. Having determined this point, take 32 parts of the copper, melt, and add one part of brass and as much silver, covering the surface of the mixture with a little black flux; when the whole is melted, stir with a wooden rod, and pour in from 15 to 16 parts of melted tin (as indicated by the preparatory trials), stir the mixture again, and immediately pour it out into cold water. Then melt again at the lowest heat, adding for every 16 parts of the compound 1 part of white arsenic, wrapped in paper, so that it may be thrust down to the bottom of the crucible. Stir with a wooden rod as long as arsenical fumes rise, and then pour it into a sand mould. While still red hot, lay the metal in a pot full of very hot embers, that it may cool very slowly, whereby the danger of its cracking or flying into splinters is prevented.
Having described the different alloys of copper and tin, I shall now treat of the method of separating these metals from each other as they exist in old cannons, damaged bells, &c. The process employed on a very great scale in France during the Revolution, for obtaining copper from bells, was contrived by Fourcroy; founded upon the chemical fact that tin is more fusible and oxidizable than copper.
1. A certain quantity of bell metal was completely oxidized by calcination in a reverberatory furnace; the oxide was raked out, and reduced to a fine powder.
2. Into the same furnace a fresh quantity of the same metal was introduced; it wasmelted, and there was added to it one half of its weight of the oxide formed in the first operation. The temperature was increased, and the mixture well incorporated; at the end of a few hours, there was obtained on the one hand copper almost pure, which subsided in a liquid state, and spread itself upon the sole of the hearth, while a compound of oxide of tin, oxide of copper, with some of the earthy matters of the furnace collected on the surface of the metallic bath in a pasty form. These scoriæ were removed with a rake, and as soon as the surface of the melted copper was laid bare, it was run out. The scoriæ were levigated, and the particles of metallic copper were obtained after elutriation. By this process, from 100 pounds of bell metal, about 50 pounds of copper were extracted, containing only oneper cent.of foreign matters.
3. The washed scoriæ were mixed with1⁄8their weight of pulverised charcoal; the mixture was triturated to effect a more intimate distribution of the charcoal; and it was then put into a reverberatory hearth, in which, by aid of a high heat, a second reduction was effected, yielding a fluid alloy consisting of about 60 parts of copper and 20 of tin; while the surface of the bath got covered with new scoriæ containing a larger proportion of tin than the first.
4. The alloy of 60 of copper with 40 of tin was next calcined in the same reverberatory furnace, but with stirring of the mass. The air in sweeping across the surface of the bath, oxidized the tin more rapidly than the copper; whence proceeded crusts of oxide that were skimmed off from time to time. This process was continued till the metallic alloy was brought to the same standard as bell metal, when it was run out to be subjected to the same operations as the metal of No. 1.
The layers of oxide successively removed in this way were mixed with charcoal, and reduced in afourneau à manche, or Scotch lead smelting furnace.
I shall not prosecute any further the details of this complicated process of Fourcroy; because it has been superseded by a much better one contrived by M. Bréant. He employed a much larger quantity of charcoal to reduce the scoriæ rich in tin; and increased the fusibility by adding crushed oyster-shells, bottle glass, or even vitrified scoriæ, according to the nature of the substance to be reduced; and he treated them directly in a reverberatory furnace.
The metal, thus procured, was very rich in tin. He exposed it in masses on a sloping hearth of a reverberatory furnace, where, by a heat regulated according to the proportions of the two metals in the alloy, he occasioned an eliquation or sweating out of the tin. Metallic drops were seen to transpire round the alloyed blocks or pigs, and, falling like rain, flowed down the sloping floor of the furnace; on whose concave bottom the metal collected, and was ladled out into moulds. When the alloy, thus treated, contained lead, this metal was found in the first portions that sweated out. The purest tin next came forth, while the last portions held more or less copper in solution. By fractioning the products, therefore, there was procured:
A spongy mass remained, exhibiting sometimes beautiful crystallizations; this mass, commonly too rich in copper to afford tin by liquation, was treated by oxidizement. In this manner, M. Bréant diminished greatly the reductions and oxidations; and therefore incurred in a far less degree the enormous waste of tin, which flies off with the draught of air in high and long continued heats. He also consumed less fuel as well as labour, and obtained purer products of known composition, ready to be applied directly in many arts.
He treated advantageously in this manner more than a million of kilogrammes (1000 tons) of scoriæ, for every 2 cwts. of which he paid 40centimes(four-pence), while several million kilogrammes of much richer scoriæ had been previously sold to other refiners at 5centimesor onesous.
I have said that the ancients made their tools and military weapons of bronze. Several of these have been analyzed, and the results are interesting.
An antique sword found in 1799, in the peat moss of the Somme, consisted of copper 87·47; tin 12·53, in 100 parts.
The bronze springs for the balistæ, according to Philo of Byzantium, were made of copper 97, tin 3.
Hard and brittle nails afforded by analysis, 92 of copper, and 8 of tin.
Of three antique swords found in the environs of Abbeville, one was found to consist of 85 of copper to 15 of tin. The nails of the handle of this sword were flexible; they were composed of copper 95, tin 5.
Another of the swords consisted of 90 of copper and 10 of tin; and the third, of 96 copper, with 4 tin.
A fragment of an ancient scythe afforded to analysis 92·6 copper, and 7·4 tin.
The process of coating copper with tin, exemplifies the strong affinity between the two metals. The copper surface to be tinned is first cleared up with a smooth sandstone;then it is heated and rubbed over with a little sal ammoniac, till it be perfectly clean and bright: the tin, along with some pounded rosin, is now placed on the copper, which is made so hot as to melt the tin, and allow of its being spread over the surface with a dossil or pad of tow. The layer thus fixed on the copper is exceedingly thin; Bayen found that a copper pan, 9 inches in diameter and 31⁄4inches deep, being weighed immediately before and after tinning, became only 21 grains heavier. Now as the area tinned, including the bottom, amounted to 155 square inches, 1 grain of tin had been spread over nearly 71⁄2square inches; or only 20 grains over every square foot.
Copper and Arsenicform a white-coloured alloy, sometimes used for the scales of thermometers and barometers; for dials, candlesticks, &c. To form this compound, successive layers of copper clippings and white arsenic are put into an earthen crucible; which is then covered with sea salt, closed with a lid, and gradually heated to redness. If 2 parts of arsenic have been used with 5 of copper, the resulting compound commonly contains one tenth of its weight of metallic arsenic. It is white, slightly ductile, denser, and more fusible than copper, and without action on oxygen at ordinary temperatures; but, at higher heats, it is decomposed with the exhalation of arsenious acid. The white copper of the Chinese consists of 40·4 copper; 31·6 nickel; 25·4 zinc; and 2·6 iron. This alloy is nearly silver white; it is very sonorous, well polished, malleable at common temperatures, and even at a cherry red, but very brittle at a red-white heat. When heated with contact of air, it oxidizes, burning with a white flame. Its specific gravity was 8·432. When worked with great care, it may be reduced to thin leaves, and to wires as small as a needle. SeeGerman Silver,infra.
Tutenag, formerly confounded with white copper, is a different composition from the above. Keir says it is composed of copper, zinc, and iron; and Dick describes it as a short metal, of a grayish colour, and scarcely sonorous. The Chinese export it, in large quantities, to India.
Copper, White, orGerman silver. M. Gersdorf, of Vienna, states, that the proportions of the metals in this alloy should vary according to the uses for which it is destined. When intended as a substitute for silver, it should be composed of 25 parts of nickel, 25 of zinc, and 50 of copper. An alloy better adapted for rolling, consists of 25 of nickel, 20 of zinc, and 60 of copper. Castings, such as candlesticks, bells, &c., may be made of an alloy, consisting of 20 of nickel, 20 of zinc, and 60 of copper; to which 3 of lead are added. The addition of 2 or 21⁄2of iron (in the shape of tin plate?) renders the packfong much whiter but, at the same time, harder and more brittle.
Keferstein has given the following analysis of the genuine German silver, as made from the original ore found in Hildburghausen, near Suhl, in Henneberg:—
Chinese packfong, according to the same authority, consists of 5 parts of copper, alloyed with 7 parts of nickel, and 7 parts of zinc.
The best alloy for making plummer blocks, bushes, and steps for the steel or iron gudgeons, and pivots of machinery to run in, is said to consist of 90 parts of copper, 5 of zinc, and 5 of antimony.
A factitious protoxide of copper, of a fine red colour, may be made by melting together, with a gentle heat, 100 parts of sulphate of copper, and 59 of carbonate of soda in crystals, and continuing the heat till the mass become solid. This being pulverized, and mixed exactly with 15 parts of copper filings, the mixture is to be heated to whiteness, in a crucible, during the space of 20 minutes. The mass, when cold, is to be reduced to powder, and washed. A beautiful metallic pigment may be thus prepared, at the cost of 2s.a pound.
All the oxides and salts of copper are poisonous; they are best counteracted by administering a large quantity of sugar, and sulphuretted hydrogen water.
The following scientific summary of copper ores in alphabetical order may prove acceptable to many readers, amid the present perplexing distribution of the native metallic compounds in mineralogical systems.
1.Arseniate of Copper.
A.Erinite, rhomboidal arseniate of copper, micaceous copper,kupferglimmer. Emerald green; specific gravity 4·043; scratches calc-spar; yields water by heat; fusible at the blowpipe, and reducible into a white metallic globule. Soluble in nitric acid; the solution throws down copper by iron. It consists of arsenic acid 33·78; oxide of copper 59·24; water 5; alumina 1·77. It is found in Cornwall, Ireland, Hungary.
B.Liroconite; octahedral arseniate of copper; lens ore, so called from the flatnessof the crystal. Blue; specific gravity 2·88; scratches calc-spar. It consists of arsenic acid 14; oxide of copper 49; water 35. It is found in Huel-Mutrel, Huel-Gorland, Huel-Unity, mines in Cornwall.
C.Olivenite; right prismatic arseniate of copper; olive-ore. Dull green; specific gravity 4·28; scratches fluor; yields no water by heat; fusible at the blowpipe into a glassy bead, enclosing a white metallic grain. It consists of arsenic acid 45, oxide of copper 50·62. It affords indications of phosphoric acid, which the analysts seem to have overlooked. It occurs in the above and many other mines in Cornwall.
D.Aphanese.Trihedral arseniate of copper. Bluish green, becoming gray upon the surface; specific gravity 4·28; scarcely scratches calc-spar; yields water with heat; and traces of phosphoric acid.
The fibrous varieties called wood copper, contain water, and resemble the last species in composition.
2.Carbonate of Copper.
A.Azurite; kupferlazur. Blue. Crystallizes in oblique rhomboidal prisms; specific gravity 3 to 3·83; scratches calc-spar, is scratched by fluor; yields water with heat, and blackens. Its constituents are, carbonic acid 25·5; oxide of copper 69·1; water 5·4. The Chessy and Banat azurite is most profitably employed to make sulphate of copper.
B.Malachite; green carbonate or mountain green. Crystallizes in right rhomboidal prisms; specific gravity 3·5; affords water with heat, and blackens. It consists of carbonic acid 18·5; oxide of copper 72·2; water 9·3.
C.Mysorine; anhydrous carbonate of copper. Dark brown generally stained green or red; conchoidal fracture; soft, sectile; specific gravity 2·62. It consists of carbonic acid 16·7; oxide of copper 60·75; peroxide of iron 19·5; silica 2·10. This is a rare mineral found in the Mysore.
3.Chromate of Copper and Lead; vauquelinite. Green of various shades; specific gravity 6·8 to 7·2; brittle; scratched by fluor; fusible at the blowpipe with froth and the production of a leaden bead. It consists of chromic acid 28·33; oxide of lead 60·87; oxide of copper 10·8. It occurs at Berezof in Siberia along with chromate of lead.
4.Dioptase; silicate of copper; emerald copper. Specific gravity 3·3; scratches glass with difficulty; affords water with heat, and blackens; infusible at the blowpipe. It consists of silica 43·18; oxide of copper 45·46; water 11·36. This rare substance comes from the government of Kirgis.
The silicate of Dillenberg is similar in composition.
5. Gray copper ore called Panabase, from the number of metallic bases which it contains; and Fahlerz. Steel gray; specific gravity 4·79 to 5·10; crystallizes in regular tetrahedrons; fusible at the blowpipe, with disengagement of fumes of antimony and occasionally of arsenic; swells up and scorifies, affording copper with soda flux. Is acted upon by nitric acid with precipitation of antimony; becomes blue with ammonia; yields a blue precipitate with ferrocyanide of potassium; as also indications frequently of zinc, mercury, silver, &c. Its composition which is very complex is as follows: sulphur 26·83; antimony 12·46; arsenic 10·19; copper 40·60; iron 4·66; zinc 3·69; silver 0·60. Some specimens contain from 5 to 31 per cent. of silver. The gray copper ores are very common; in Saxony; the Hartz; Cornwall; at Dillenberg; in Mexico; Peru, &c. They are important on account both of their copper and silver.Tennantiteis a variety of Fahlerz. It occurs in Cornwall. Its constituents are, sulphur 28·74; arsenic 11·84; copper 45·32; iron 9·26.
6.Hydrated silicate of Copper; or Chrysocolla. Green or bluish green; specific gravity 2·03 to 2·16; scratched by steel; very brittle; affords water with heat, and blackens; is acted upon by acids, and leaves a siliceous residuum. Solution becomes blue with ammonia. Its constituents are silica 26; oxide of copper 50; water 17; carbonic acid 7.
7.Muriate of Copper.Atakamite; green; crystallizes in prisms; specific gravity 4·43. Its constituents are, chlorine 15·90; copper 14·22; oxide of copper 54·22; water 14·16; oxide of iron 1·50. The green sand of Peru, collected by the inhabitants of Atakama, is this substance in a decomposed state.
8.Oxide of Copper.
A. Black, or Melaconise; a black earthy looking substance found at Chessy and other places. It is deutoxide of copper.
B. Protoxide or red oxide of copper; ziegelerz. Crystallizes in the regular octahedron; specific gravity 5·69; scratches calc-spar; fusible at the blowpipe into the black oxide; and reducible in the smoke of the flame to copper; acted upon by nitric acid with disengagement of nitrous gas; solution is rendered blue by ammonia. Its constituents are oxygen 11·22; copper 88·78. It occurs near Chessy, and upon the eastern slope of the Altai mountains.
9.Phosphate of Copper.Dark green; crystallizes in octahedrons; specific gravity 3·6 to 3·8; scratches calc-spar; yields water with heat; and affords metallic copperwith soda flux; acted on by nitric acid. Its constituents are, phosphoric acid 28·7; oxide of copper 63·9; water 7·4. It occurs at the mines of Libethen in Hungary.
10.Pyritous Copper; Kupferkies; a metallic looking substance, of a bronze-yellow colour, crystallizing in octahedrons which pass into tetrahedrons; specific gravity 4·16; fusible at the blowpipe into beads attractable by the magnet, and which afterwards afford copper with a soda flux; soluble in nitric acid; solution is rendered blue by ammonia, and affords an abundant precipitate of iron. Its composition is, sulphur 36; copper 34·5; iron 30·5; being a combined sulphuret of these two metals. This is the most important metallurgic species of copper ores. It occurs chiefly in primitive formations, as among gneiss and mica slate, in veins or more frequently masses in very many parts of the world—Cornwall, Anglesea, Wicklow, &c. It is found among the early secondary rocks, in Shetland, Yorkshire, Mansfeldt, &c. The finest crystallized specimens come from Cornwall, Derbyshire, Freyberg, and Saint Marie-aux-Mines in France.
11.Seleniate of Copper; Berzeline. Is of metallic aspect; silver white; ductile; fusible at the blowpipe into a gray bead, somewhat malleable; is acted upon by nitric acid; consists of selenium 40; copper 64.
12.Sulphate of Copper; Cyanose. Blue; soluble, &c. like the artificialsulphates, which see.
Brochantiteis a subsulphate of copper observed in small crystals at Ekaterinenbourg in Siberia.
13.Sulphuret of Copper; Kupferglanz. Of a steel gray metallic aspect; crystallizes in rhomboids; specific gravity 5·69; somewhat sectile, yet brittle; fusible with intumescence at the blowpipe, and yields a copper bead with soda; soluble in nitric acid; becomes blue with ammonia, but lets fall scarcely any oxide of iron. Its constituents are, sulphur 19; copper 79·5; iron 0·75; silica 1·00. It occurs in small quantities in Cornwall, &c.
The chemical preparations of copper which constitute distinct manufactures are, Blue or Roman vitriol; for which seeSulphate of Copper;Scheele’s greenandSchweinurth green,Verditer, andVerdigris. See these articles in their alphabetical places.