[30]There follow eight different methods of treating crude bullion or rich concentrates. In a general way three methods are involved,—1st, reduction with lead or antimony, and cupellation; 2nd, reduction with silver, and separation with nitric acid; 3rd, reduction with lead and silver, followed by cupellation and parting with nitric acid. The use of sulphur or antimony sulphide would tend to part out a certain amount of silver, and thus obtain fairly pure bullion upon cupellation. But the introduction of copper could only result deleteriously, except that it is usually accompanied by sulphur in some form, and would thus probably pass off harmlessly as a matte carrying silver. (Seenote 33 below.)[31]It is not very clear where this lead comes from. Should it be antimony? The German translation gives this as "silver."[Pg 398][32]These powders are described in Book VII., p.236. It is difficult to say which the second really is. There are numbers of such recipes in theProbierbüchlein(seeAppendix B), with which a portion of these are identical.[33]A variety of methods are involved in this paragraph: 1st, crude gold ore is smelted direct; 2nd, gold concentrates are smelted in a lead bath with some addition of iron—which would simply matte off—the lead bullion being cupelled; 3rd, roasted and unroasted pyrites andcadmia(probably blende, cobalt, arsenic, etc.) are melted into a matte; this matte is repeatedly roasted, and then re-melted in a lead bath; 4th, if the material "flies out of the furnace" it is briquetted with iron ore and lime, and the briquettes smelted with copper matte. Three products result: (a) slag; (b) matte; (c) copper-gold-silver alloy. The matte is roasted, re-smelted with lead, and no doubt a button obtained, and further matte. The process from this point is not clear. It appears that the copper bullion is melted with lead, and normally this product would be taken to the liquation furnace, but from the text it would appear that the lead-copper bullion was melted again with iron ore and pyrites, in which case some of the copper would be turned into the matte, and the lead alloy would be richer in gold and silver.[Pg 399]Historical Note on Gold.—There is ample evidence of gold being used for ornamental purposes prior to any human record. The occurrence of large quantities of gold in native form, and the possibility of working it cold, did not necessitate any particular metallurgical ingenuity. The earliest indications of metallurgical work are, of course, among the Egyptians, the method of washing being figured as early as the monuments of the IV Dynasty (prior to 3800B.C.). There are in the British Museum two stelae of the XII Dynasty (2400B.C.) (144 Bay 1 and 145 Bay 6) relating to officers who had to do with gold mining in Nubia, and upon one there are references to working what appears to be ore. If this be true, it is the earliest reference to this subject. The Papyrus map (1500B.C.) of a gold mine, in the Turin Museum (seenote 16, p. 129), probably refers to a quartz mine. Of literary evidences there is frequent mention of refining gold and passing it through the fire in the Books of Moses, arts no doubt learned from the Egyptians. As to working gold, ore as distinguished from alluvial, we have nothing very tangible, unless it be the stelae above, until the description of Egyptian gold mining by Agatharchides (seenote 8, p. 279). This geographer, of about the 2nd centuryB.C., describes very clearly indeed the mining, crushing, and concentration of ore and the refining of the concentrates in crucibles with lead, salt, and barley bran. We may mention in passing that Theognis (6th CenturyB.C.) is often quoted as mentioning the refining of gold with lead, but we do not believe that the passage in question (1101): "But having been put to the test and being rubbed beside (or against) lead as being refined gold, you will be fair," etc.; or much the same statement again (418) will stand much metallurgical interpretation. In any event, the myriads of metaphorical references to fining and purity of gold in the earliest shreds of literature do not carry us much further than do those of Shakespeare or Milton. Vitruvius and Pliny mention the recovery or refining of gold with mercury (seenote 12, p. 297on Amalgamation); and it appears to us that gold was parted from silver by cementation with salt prior to the Christian era. We first find mention of parting with sulphur in the 12th century, with nitric acid prior to the 14th century, by antimony sulphide prior to the 15th century, and by cementation with nitre by Agricola. (See historical note on parting gold and silver, p.458.) The first mention of parting gold from copper occurs in the early 16th century (seenote 24, p. 462). The first comprehensive description of gold metallurgy in all its branches is inDe Re Metallica.[Pg 400][34]Rudissilver comprised all fairly pure silver ores, such as silver sulphides, chlorides, arsenides, etc. This is more fully discussed innote 6, p. 108.[35]Evolent,—volatilize?[36]Lapidis plumbarii facile liquescentis. The German Translation givesglantz,i.e., Galena, and theInterpretatioalso givesglantzforlapis plumbarius. We are, however, uncertain whether this "easily melting" material is galena or some other lead ore.[37]Molybdaenais usually hearth-lead inDe Re Metallica, but the German translation in this instance usespleyertz, lead ore. From the context it would not appear to mean hearth-lead—saturated bottoms of cupellation furnaces—for such material would not contain appreciable silver. Agricola does confuse what are obviously lead carbonates with his othermolybdaena(seenote 37, p. 476).[Pg 401][38]The termcadmiais used in this paragraph without the usual definition. Whether it wascadmia fornacis(furnace accretions) orcadmia metallica(cobalt-arsenic-blende mixture) is uncertain. We believe it to be the former.[39]Ramentum si lotura ex argento rudi. This expression is generally used by the author to indicate concentrates, but it is possible that in this sentence it means the tailings after washing rich silver minerals, because the treatment of therudissilver has been already discussed above.[40]Ustum. This might be rendered "burnt." In any event, it seems that the material is sintered.[Pg 402][41]Aes purum sive proprius ei color insederit, sive chrysocolla vel caeruleo fuerit tinctum, et rude plumbei coloris, aut fusci, aut nigri.There are six copper minerals mentioned in this sentence, and from our study of Agricola'sDe Natura Fossiliumwe hazard the following:—Proprius ei color insederit,—"its own colour,"—probably cuprite or "ruby copper."Tinctum chrysocolla—partly the modern mineral of that name and partly malachite.Tinctum caeruleo, partly azurite and partly other blue copper minerals.Rude plumbei coloris,—"lead coloured,"—was certainly chalcocite (copper glance). We are uncertain offusci aut nigri, but they were probably alteration products. For further discussion see note on p.109.[42]Historical Note on Copper Smelting.—The discoverer of the reduction of copper by fusion, and his method, like the discoverer of tin and iron, will never be known, because he lived long before humanity began to make records of its discoveries and doings. Moreover, as different races passed independently and at different times through the so-called "Bronze Age," there may have been several independent discoverers. Upon the metallurgy of pre-historic man we have some evidence in the many "founders' hoards" or "smelters' hoards" of the Bronze Age which have been found, and they indicate a simple shallow pit in the ground into which the ore was placed, underlaid with charcoal. Rude round copper cakes eight to ten inches in diameter resulted from the cooling of the metal in the bottom of the pit. Analyses of such Bronze Age copper by Professor Gowland and others show a small percentage of sulphur, and this is possible only by smelting oxidized ores. Copper objects appear in the pre-historic remains in Egypt, are common throughout the first three dynasties, and bronze articles have been found as early as the IV Dynasty (from 3800 to 4700B.C., according to the authority adopted). The question of the origin of this bronze, whether from ores containing copper and tin or by alloying the two metals, is one of wide difference of opinion, and we further discuss the question innote 53, p. 411, under Tin. It is also interesting to note that the crucible is the emblem of copper in the hieroglyphics. The earliest source of Egyptian copper was probably the Sinai Peninsula, where there are reliefs as early as Seneferu (about 3700B.C.), indicating that he worked the copper mines. Various other evidences exist of active copper mining prior to 2500B.C.(Petrie, Researches in Sinai, London, 1906, p. 51, etc.). The finding of crucibles here would indicate some form of refining. Our knowledge of Egyptian copper metallurgy is limited to deductions from their products, to a few pictures of crude furnaces and bellows, and to the minor remains on the Sinai Peninsula; none of the pictures were, so far as we are aware, prior to 2300B.C., but they indicate a considerable advance over the crude hearth, for they depict small furnaces with forced draught—first a blow-pipe, and in the XVIII Dynasty (about 1500B.C.) the bellows appear. Many copper articles have been found scattered over the Eastern Mediterranean and Asia Minor of pre-Mycenaean Age, some probably as early as 3000B.C.This metal is mentioned in the "Tribute of Yü" in the Shoo King (2500B.C.?); but even less is known of early Chinese metallurgy than of the Egyptian. The remains of Mycenaean, Phoenician, Babylonian, and Assyrian civilizations, stretching over the period from 1800 to 500B.C., have yielded endless copper and bronze objects, the former of considerable purity, and the latter a fairly constant proportion of from 10% to 14% tin. The copper supply of the pre-Roman world seems to have come largely, first from Sinai, and later from Cyprus, and from the latter comes our word copper, by way of the Romans shorteningaes cyprium(Cyprian copper) tocuprum. Research in this island shows that it produced copper from 3000B.C., and largely because of its copper it passed successively under the domination of the Egyptians, Assyrians, Phoenicians, Greeks, Persians, and Romans. The bronze objects found in Cyprus show 2% to 10% of tin, although tin does not, so far as modern research goes, occur on that island. There can be no doubt that the Greeks obtained their metallurgy from the Egyptians, either direct or second-hand—possibly through Mycenae or Phoenicia. Their metallurgical gods and the tradition of Cadmus indicate this much.By way of literary evidences, the following lines from Homer (Iliad,XVIII.) have interest as being the first preserved description in any language of a metallurgical work. Hephaestus was much interrupted by Thetis, who came to secure a shield for Achilles, and whose general conversation we therefore largely omit. We adopt Pope's translation:—There the lame architect the goddess foundObscure in smoke, his forges flaming round,While bathed in sweat from fire to fire he flew;[Pg 403]And puffing loud the roaring bellows blew.* * *In moulds prepared, the glowing ore (metal?) he pours.* * *"Vouchsafe, oh Thetis! at our board to shareThe genial rites and hospitable fare;While I the labours of the forge forego,And bid the roaring bellows cease to blow."Then from his anvil the lame artist rose;Wide with distorted legs oblique he goes,And stills the bellows, and (in order laid)Locks in their chests his instruments of trade;Then with a sponge, the sooty workman dress'dHis brawny arms embrown'd and hairy breast.* * *Thus having said, the father of the firesTo the black labours of his forge retires.Soon as he bade them blow the bellows turn'dTheir iron mouths; and where the furnace burn'dResounding breathed: at once the blast expires,And twenty forges catch at once the fires;Just as the God directs, now loud, now low,They raise a tempest, or they gently blow;In hissing flames huge silver bars are roll'd,And stubborn brass (copper?) and tin, and solid gold;Before, deep fixed, the eternal anvils stand.The ponderous hammer loads his better hand;His left with tongs turns the vex'd metal round.And thick, strong strokes, the doubling vaults reboundThen first he formed the immense and solid shield;Even if we place the siege of Troy at any of the various dates from 1350 to 1100B.C., it does not follow that the epic received its final form for many centuries later, probably 900-800B.C.; and the experience of the race in metallurgy at a much later period than Troy may have been drawn upon to fill in details. It is possible to fill a volume with indirect allusion to metallurgical facts and to the origins of the art, from Greek mythology, from Greek poetry, from the works of the grammarians, and from the Bible. But they are of no more technical value than the metaphors from our own tongue. Greek literature in general is singularly lacking in metallurgical description of technical value, and it is not until Dioscorides (1st CenturyA.D.) that anything of much importance can be adduced. Aristotle, however, does make an interesting reference to what may be brass (see note on p.410), and there can be no doubt that if we had the lost work of Aristotle's successor, Theophrastus (372-288B.C.), on metals we should be in possession of the first adequate work on metallurgy. As it is, we find the green and blue copper minerals from Cyprus mentioned in his "Stones." And this is the first mention of any particular copper ore. He also mentions (XIX.) pyrites "which melt," but whether it was a copper variety cannot be determined. Theophrastus further describes the making of verdigris (seenote 4, p. 440). From Dioscorides we get a good deal of light on copper treatment, but as his objective was to describe medicinal preparations, the information is very indirect. He states (V, 100) that "pyrites is a stone from which copper is made." He mentionschalcitis(copper sulphide, see note on, p.573); while hismisy,sory,melanteria,caeruleum, andchrysocollawere all oxidation copper or iron minerals. (See notes on p.573.) In giving a method of securingpompholyx(zinc oxide), "the soot flies up when the copper refiners sprinkle powderedcadmiaover the molten metal" (seenote 26, p. 394); he indirectly gives us the first definite indication of making brass, and further gives some details as to the furnaces there employed, which embraced bellows and dust chambers. In describing the making of flowers of copper (seenote 26, p. 538) he states that in refining copper, when the "molten metal flows through its tube into a receptacle, the workmen[Pg 404]pour cold water on it, the copper spits and throws off the flowers." He gives the first description of vitriol (seenote 11, p. 572), and describes the pieces as "shaped like dice which stick together in bunches like grapes." Altogether, from Dioscorides we learn for the first time of copper made from sulphide ores, and of the recovery of zinc oxides from furnace fumes; and he gives us the first certain description of making brass, and finally the first notice of blue vitriol.The next author we have who gives any technical detail of copper work is Pliny (23-79A.D.), and while his statements carry us a little further than Dioscorides, they are not as complete as the same number of words could have afforded had he ever had practical contact with the subject, and one is driven to the conclusion that he was not himself much of a metallurgist. Pliny indicates that copper ores were obtained from veins by underground mining. He gives the same minerals as Dioscorides, but is a good deal confused overchrysocollaandchalcitis. He gives no description of the shapes of furnaces, but frequently mentions the bellows, and speaks of thecadmiaandpompholyxwhich adhered to the walls and arches of the furnaces. He has nothing to say as to whether fluxes are used or not. As to fuel, he says (XXXIII, 30) that "for smelting copper and iron pine wood is the best." The following (XXXIV, 20) is of the greatest interest on the subject:—"Cyprian copper is known ascoronariumandregulare; both are ductile.... In other mines are made that known asregulareandcaldarium. These differ, because thecaldariumis only melted, and is brittle to the hammer; whereas theregulareis malleable or ductile. All Cyprian copper is this latter kind. But in other mines with care the difference can be eliminated fromcaldarium, the impurities being carefully purged away by smelting with fire, it is made intoregulare. Among the remaining kinds of copper the best is that of Campania, which is most esteemed for vessels and utensils. This kind is made in several ways. At Capua it is melted with wood, not with charcoal, after which it is sprinkled with water and washed through an oak sieve. After it is melted a number of times Spanishplumbum argentum(probably pewter) is added to it in proportion of ten pounds of the lead to one hundred pounds of copper, and thereby it is made pliable and assumes that pleasing colour which in other kinds of copper is effected by oil and the sun. In many parts of the Italian provinces they make a similar kind of metal; but there they add eight pounds of lead, and it is re-melted over charcoal because of the scarcity of wood. Very different is the method carried on in Gaul, particularly where the ore is smelted between red hot stones, for this burns the metal and renders it black and brittle. Moreover, it is re-melted only a single time, whereas the oftener this operation is repeated the better the quality becomes. It is well to remark that all copper fuses best when the weather is intensely cold." The red hot stones in Gaul were probably as much figments of imagination as was the assumption of one commentator that they were a reverberatory furnace. Apart from the above, Pliny says nothing very direct on refining copper. It is obvious that more than one melting was practised, but that anything was known of the nature of oxidation by a blast and reduction by poling is uncertain. We produce the three following statements in connection with some bye-products used for medicinal purposes, which at least indicate operations subsequent to the original melting. As to whether they represent this species of refining or not, we leave it to the metallurgical profession (XXXIV, 24):—"The flowers of copper are used in medicine; they are made by fusing copper and moving it to another furnace, where the rapid blast separates it into a thousand particles, which are called flowers. These scales are also made when the copper cakes are cooled in water (XXXIV, 35).Smegais prepared in the copper works; when the metal is melted and thoroughly smelted charcoal is added to it and gradually kindled; after this, being blown upon by a powerful bellows, it spits out, as it were, copper chaff (XXXIV, 37). There is another product of these works easily distinguished fromsmega, which the Greeks calldiphrygum. This substance has three different origins.... A third way of making it is from the residues which fall to the bottom in copper furnaces. The difference between the different substances (in the furnace) is that the copper itself flows into a receiver; the slag makes its escape from the furnace; the flowers float on the top (of the copper?), and thediphrygumremains behind. Some say that in the furnace there are certain masses of stone which, being smelted, become soldered together, and that the copper fuses around it, the mass not becoming liquid unless it is transferred to another furnace. It thus forms a sort of knot, as it were, in the metal."[Pg 405]Pliny is a good deal confused over the copper alloys, failing to recogniseaurichalcumas the same product as that made by mixingcadmiaand molten copper. Further, there is always the difficulty in translation arising from the fact that the Latinaeswas indiscriminately copper, brass, and bronze. He does not, except in one instance (XXXIV., 2), directly describe the mixture ofcadmiaand copper. "Next to Livian (copper) this kind (corduban, from Spain) most readily absorbscadmia, and becomes almost as excellent asaurichalcumfor makingsesterces." As to bronze, there is no very definite statement; but theargentatiumgiven in the quotation above fromXXXIV, 20, is stated inXXXIV, 48, to be a mixture of tin and lead. The Romans carried on most extensive copper mining in various parts of their empire; these activities extended from Egypt through Cyprus, Central Europe, the Spanish Peninsula, and Britain. The activity of such works is abundantly evidenced in the mines, but very little remains upon the surface to indicate the equipment; thus, while mining methods are clear enough, the metallurgy receives little help from these sources. At Rio Tinto there still remain enormous slag heaps from the Romans, and the Phoenician miners before them. Professor W. A. Carlyle informs us that the ore worked must have been almost exclusively sulphides, as only negligible quantities of carbonates exist in the deposits; they probably mixed basic and siliceous ores. There is some evidence of roasting, and the slags run from .2 to .6%. They must have run down mattes, but as to how they ultimately arrived at metallic copper there is no evidence to show.The special processes for separating other metals from copper by liquation and matting, or of refining by poling, etc., are none of them clearly indicated in records or remains until we reach the 12th century. Here we find very adequate descriptions of copper smelting and refining by the Monk Theophilus (seeAppendix B). We reproduce two paragraphs of interest from Hendrie's excellent translation (p. 305 and 313): "Copper is engendered in the earth. When a vein of which is found, it is acquired with the greatest labour by digging and breaking. It is a stone of a green colour and most hard, and naturally mixed with lead. This stone, dug up in abundance, is placed upon a pile and burned after the manner of chalk, nor does it change colour, but yet loses its hardness, so that it can be broken up. Then, being bruised small, it is placed in the furnace; coals and the bellows being applied, it is incessantly forged by day and night. This should be done carefully and with caution; that is, at first coals are placed in, then small pieces of stone are distributed over them, and again coals, and then stone anew, and it is thus arranged until it is sufficient for the size of the furnace. And when the stone has commenced to liquefy, the lead flows out through some small cavities, and the copper remains within. (313) Of the purification of copper. Take an iron dish of the size you wish, and line it inside and out with clay strongly beaten and mixed, and it is carefully dried. Then place it before a forge upon the coals, so that when the bellows act upon it the wind may issue partly within and partly above it, and not below it. And very small coals being placed round it, place copper in it equally, and add over it a heap of coals. When, by blowing a long time, this has become melted, uncover it and cast immediately fine ashes of coals over it, and stir it with a thin and dry piece of wood as if mixing it, and you will directly see the burnt lead adhere to these ashes like a glue. Which being cast out again superpose coals, and blowing for a long time, as at first, again uncover it, and then do as you did before. You do this until at length, by cooking it, you can withdraw the lead entirely. Then pour it over the mould which you have prepared for this, and you will thus prove if it be pure. Hold it with pincers, glowing as it is, before it has become cold, and strike it with a large hammer strongly over the anvil, and if it be broken or split you must liquefy it anew as before."The next writer of importance was Biringuccio, who was contemporaneous with Agricola, but whose book precedesDe Re Metallicaby 15 years. That author (III, 2) is the first to describe particularly the furnace used in Saxony and the roasting prior to smelting, and the first to mention fluxes in detail. He, however, describes nothing of matte smelting; in copper refining he gives the whole process of poling, but omits the pole. It is not until we reachDe Re Metallicathat we find adequate descriptions of the copper minerals, roasting, matte smelting, liquation, and refining, with a wealth of detail which eliminates the necessity for a large amount of conjecture regarding technical methods of the time.[43]Cadmia metallica fossilis(see note on p.112). This was undoubtedly the complex cobalt-arsenic-zinc minerals found in Saxony. In the German translation, however, this is given asKalmey, calamine, which is unlikely from the association with pyrites.[44]The Romanmodius(modulus?) held about 550 cubic inches, the English peck holding 535 cubic inches. Then, perhaps, his sevenmoduliwould be roughly, 1 bushel 3 pecks, and 18 vessels full would be about 31 bushels—say, roughly, 5,400 lbs. of ore.[Pg 406][45]Exhausted liquation cakes (panes aerei fathiscentes). This is the copper sponge resulting from the first liquation of lead, and still contains a considerable amount of lead. The liquation process is discussed in great detail inBook XI.[Pg 407][46]The method of this paragraph involves two main objectives—first, the gradual enrichment of matte to blister copper; and, second, the creation of large cakes of copper-lead-silver alloy of suitable size and ratio of metals for liquation. This latter process is described in detail inBook XI. The following groupings show the circuit of the various products, the "lbs." being Romanlibrae:—Charge.Products.1stCrude ore5,400 lbs.Primary matte (1)600 lbs.Lead slags3 cartloadsSilver-copper alloy (A)50 "Schist1 cartloadSlags (B)Flux20 lbs.Concentrates from slags & accretionsSmall quantity2ndPrimary matte (1)1,800 lbs.Secondary matte (2)1,800 lbs.Hearth-lead & litharge1,200 "Silver-copper-lead alloy (liquation cakes) (A2)1,200 "Lead ore300 "Slags (B2)Rich hard cakes (A4)500 "Liquated cakes200 "Slags (B)Concentrates from accretions3rdSecondary matte (2)1,800 lbs.Tertiary matte (3)1,300 lbs.Hearth-lead & litharge1,200 "Silver-copper-lead alloy (liquation cakes) (A3)1,100 "Lead ore300 "Slags (B3)Rich hard cakes (A4)500 "Slags (B2)Concentrates from accretions4thTertiary matte (3)11 cartloadsQuaternary hard cakes matte (4)2,000 lbs.Poor hard cakes (A5)3 "Rich hard cakes of matte (A4)1,500 "Slags (B3)Concentrates from accretions5thRoasted quartzPoor hard cakes of matte (A5)1,500 lbs.Matte (4) (three times roasted)11 cartloadsFinal cakes of matte (5)6thFinal matte three times roasted is smelted to blister copper.The following would be a rough approximation of the value of the various products:—(1.)Primary matte=158ounces troy per short ton.(2.)Secondary matte=85" " "(3.)Tertiary matte=60" " "(4.)Quaternary matte=Indeterminate.A.Copper-silver alloy=388ounces Troy per short ton.A2Copper-silver-lead alloy=145" " "A3" " "=109" " "A4Rich hard cakes=97" " "A5Poor hard cakes=Indeterminate.Final blister copper=12ozs. Troy per short ton.[Pg 408][47]This expression is usually used for hearth-lead, but in this case the author is apparently confining himself to lead ore, and apparently refers to lead carbonates. The German Translation givespleyschweiss. The pyrites mentioned in this paragraph may mean galena, as pyrites was to Agricola a sort of genera.[48](Excoquitur) ... "si verò pyrites, primò è fornace, ut Goselariae videre licet, in catinum defluit liquor quidam candidus, argento inimicus et nocivus; id enim comburit: quo circa recrementis, quae supernatant, detractis effunditur: vel induratus conto uncinato extrahitur: eundem liquorem parietes fornacis exudant." In the Glossary the following statement appears: "Liquor candidus primo è fornace defluens cum Goselariae excoquitur pyrites,—kobelt; quem parietes fornacis exudant,—conterfei." In this latter statement Agricola apparently recognised that there were two different substances,i.e., that the substance found in the furnace walls—conterfei—was not the same substance as that which first flowed from the furnace—kobelt. We are at no difficulty in recognizingconterfeias metallic zinc; it was long known by that term, and this accidental occurrence is repeatedly mentioned by other authors after Agricola. The substance which first flowed into the forehearth presents greater difficulties; it certainly was not zinc. InDe Natura Fossilium(p. 347), Agricola says that at Goslar the lead has a certain white slag floating upon it, the "colour derived from the pyrites (pyriten argenteum) from which it was produced."Pyriten argenteumwas either marcasite or mispickel, neither of which offers much suggestion; nor are we able to hazard an explanation of value.Historical Note on Zinc.The history of zinc metallurgy falls into two distinct[Pg 409]lines—first, that of the metal, and second, that of zinc ore, for the latter was known and used to make brass by cementation with copper and to yield oxides by sublimation for medicinal purposes, nearly 2,000 years before the metal became generally known and used in Europe.There is some reason to believe that metallic zinc was known to the Ancients, for bracelets made of it, found in the ruins of Cameros (prior to 500B.C.), may have been of that age (Raoul Jagnaux,Traité de Chimie Générale, 1887,II, 385); and further, a passage in Strabo (63B.C.-24A.D.) is of much interest. He states: (XIII, 1, 56) "There is found at Andeira a stone which when burnt becomes iron. It is then put into a furnace, together with some kind of earth, when it distils a mock silver (pseudargyrum), or with the addition of copper it becomes the compound calledorichalcum. There is found a mock silver near Tismolu also." (Hamilton's Trans., II, p. 381). About the Christian era the termsorichalcumoraurichalcumundoubtedly refer to brass, but whether these terms as used by earlier Greek writers do not refer to bronze only, is a matter of considerable doubt. Beyond these slight references we are without information until the 16th Century. If the metal was known to the Ancients it must have been locally, for by its greater adaptability to brass-making it would probably have supplanted the crude melting of copper with zinc minerals.It appears that the metal may have been known in the Far East prior to such knowledge in Europe; metallic zinc was imported in considerable quantities from the East as early as the 16th and 17th centuries under such terms astuteneque,tuttanego,calaëm, andspiauter—the latter, of course, being the progenitor of our term spelter. The localities of Eastern production have never been adequately investigated. W. Hommel (Engineering and Mining Journal, June 15, 1912) gives a very satisfactory review of the Eastern literature upon the subject, and considers that the origin of manufacture was in India, although the most of the 16th and 17th Century product came from China. The earliest certain description seems to be some recipes for manufacture quoted by Praphulla Chandra Ray (A History of Hindu Chemistry, London, 1902, p. 39) dating from the 11th to the 14th Centuries. There does not appear to be any satisfactory description of the Chinese method until that of Sir George Staunton (Journal Asiatique Paris, 1835, p. 141.) We may add that spelter was produced in India by crude distillation of calamine in clay pots in the early part of the 19th Century (Brooke, Jour. Asiatic Soc. of Bengal, vol.XIX, 1850, p. 212), and the remains of such smelting in Rajputana are supposed to be very ancient.The discovery of zinc in Europe seems to have been quite independent of the East, but precisely where and when is clouded with much uncertainty. Themarchasita aureaof Albertus Magnus has been called upon to serve as metallic zinc, but such belief requires a hypothesis based upon a great deal of assumption. Further, the statement is frequently made that zinc is mentioned in Basil Valentine's Triumphant Chariot of Antimony (the only one of the works attributed to this author which may date prior to the 17th Century), but we have been unable to find any such reference. The first certain mention of metallic zinc is generally accredited to Paracelsus (1493-1541), who states (Liber MineraliumII.): "Moreover there is another metal generally unknown calledzinken. It is of peculiar nature and origin; many other metals adulterate it. It can be melted, for it is generated from three fluid principles; it is not malleable. Its colour is different from other metals and does not resemble others in its growth. Its ultimate matter (ultima materia) is not to me yet fully known. It admits of no mixture and does not permit of thefabricationesof other metals. It stands alone entirely to itself." We do not believe that this book was published until after Agricola's works. Agricola introduced the following statements into his revised edition ofBermannus(p. 431), published in 1558: "It (a variety of pyrites) is almost the colour of galena, but of entirely different components. From it there is made gold and silver, and a great quantity is dug in Reichenstein, which is in Silesia, as was recently reported to me. Much more is found at Raurici, which they callzincum, which species differs from pyrites, for the latter contains more silver than gold, the former only gold or hardly any silver." InDe Natura Fossilium(p. 368): "For thiscadmiais put, in the same way as quicksilver, in a suitable vessel so that the heat of the fire will cause it to sublime, and from it is made a black or brown or grey body which the Alchemists callcadmia sublimata. This possesses corrosive properties to the highest degree. Cognate with thiscadmiaand pyrites is a compound which the Noricans and Rhetians callzincum." We leave it to readers to decide how near this comes to metallic zinc; in any event, he apparently did not[Pg 410]recognise hisconterfeifrom the furnaces as the same substance as thezincumfrom Silesia. The first correlation of these substances was apparently by Lohneys, in 1617, who says (Vom Bergwerk, p. 83-4): "When the people in the smelting works are smelting, there is made under the furnace and in the cracks in the walls among the badly plastered stones, a metal which is calledzincorcounterfeht, and when the wall is scraped it falls into a vessel placed to receive it. This metal greatly resembles tin, but it is harder and less malleable.... The Alchemists have a great desire for thiszincor bismuth." That this metal originated from blende or calamine was not recognised until long after, and Libavis (Alchymia, Frankfort, 1606), in describing specimens which came from the East, did not so identify it, this office being performed by Glauber, who says (De Prosperitate Germanias, Amsterdam, 1656): "Zink is a volatile mineral or half-ripe metal when it is extracted from its ore. It is more brilliant than tin and not so fusible or malleable ... it turns (copper) into brass, as doeslapis calaminaris, for indeed this stone is nothing but infusible zinc, and this zinc might be called a fusiblelapis calaminaris, inasmuch as both of them partake of the same nature.... It sublimates itself up into the cracks of the furnace, whereupon the smelters frequently break it out." The systematic distillation of zinc from calamine was not discovered in Europe until the 18th Century. Henkel is generally accredited with the first statement to that effect. In a contribution published as an Appendix to his other works, of which we have had access only to a French translation (Pyritologie, Paris, 1760, p. 494), he concludes that zinc is a half-metal of which the best ore is calamine, but believes it is always associated with lead, and mentions that an Englishman lately arrived from Bristol had seen it being obtained from calamine in his own country. He further mentions that it can be obtained by heating calamine and lead ore mixed with coal in a thick earthen vessel. The Bristol works were apparently those of John Champion, established about 1740. The art of distillation was probably learned in the East.Definite information as to the zinc minerals goes back to but a little before the Christian Era, unless we accept nebular references toaurichalcumby the poets, or what is possibly zinc ore in the "earth" mentioned by Aristotle (De Mirabilibus, 62): "Men say that the copper of the Mossynoeci is very brilliant and white, no tin being mixed with it; but there is a kind of earth there which is melted with it." This might quite well be an arsenical mineral. But whether we can accept the poets or Aristotle or the remark of Strabo given above, as sufficient evidence or not, there is no difficulty with the description ofcadmiaandpompholyxandspodosof Dioscorides (1st Century), parts of which we reproduce innote 26, p. 394. Hiscadmiais described as rising from the copper furnaces and clinging to the iron bars, but he continues: "Cadmiais also prepared by burning the stone called pyrites, which is found near Mt. Soloi in Cyprus.... Some say thatcadmiamay also be found in stone quarries, but they are deceived by stones having a resemblance tocadmia."Pompholyxandspodosare evidently furnace calamine. From reading the quotation given on p.394, there can be no doubt that these materials, natural or artificial, were used to make brass, for he states (V, 46): "Whitepompholyxis made every time that the artificer in the working and perfecting of the copper sprinkles powderedcadmiaupon it to make it more perfect, the soot arising from this ... ispompholyx." Pliny is confused between the mineralcadmiaand furnacecalamine, and none of his statements are very direct on the subject of brass making. His most pointed statement is (XXXIV, 2): "... Next to Livian (copper) this kind best absorbscadmia, and is almost as good asaurichalcumfor making sesterces and double asses." As stated above, there can be little doubt that theaurichalcumof the Christian Era was brass, and further, we do know of brass sesterces of this period. Other Roman writers of this and later periods refer to earth used with copper for making brass. Apart from these evidences, however, there is the evidence of analyses of coins and objects, the earliest of which appears to be a large brass of the Cassia family of 20B.C., analyzed by Phillips, who found 17.3% zinc (Records of Mining and Metallurgy, London, 1857, p. 13). Numerous analyses of coins and other objects dating during the following century corroborate the general use of brass. Professor Gowland (Presidential Address, Inst. of Metals, 1912) rightly considers the Romans were the first to make brass, and at about the above period, for there appears to be no certainty of any earlier production. The first adequate technical description of brass making is in about 1200A.D.being that of Theophilus, who describes (Hendrie's Trans., p. 307) calciningcalaminaand mixing it with finely divided copper in glowing crucibles. The process was repeated by adding more calamine and copper until the pots were full of molten metal. This method is repeatedly described with minor variations by Biringuccio, Agricola (De Nat. Fos.), and others, down to the 18th Century. For discussion of the zinc minerals see note on p.112.
[30]There follow eight different methods of treating crude bullion or rich concentrates. In a general way three methods are involved,—1st, reduction with lead or antimony, and cupellation; 2nd, reduction with silver, and separation with nitric acid; 3rd, reduction with lead and silver, followed by cupellation and parting with nitric acid. The use of sulphur or antimony sulphide would tend to part out a certain amount of silver, and thus obtain fairly pure bullion upon cupellation. But the introduction of copper could only result deleteriously, except that it is usually accompanied by sulphur in some form, and would thus probably pass off harmlessly as a matte carrying silver. (Seenote 33 below.)
[30]There follow eight different methods of treating crude bullion or rich concentrates. In a general way three methods are involved,—1st, reduction with lead or antimony, and cupellation; 2nd, reduction with silver, and separation with nitric acid; 3rd, reduction with lead and silver, followed by cupellation and parting with nitric acid. The use of sulphur or antimony sulphide would tend to part out a certain amount of silver, and thus obtain fairly pure bullion upon cupellation. But the introduction of copper could only result deleteriously, except that it is usually accompanied by sulphur in some form, and would thus probably pass off harmlessly as a matte carrying silver. (Seenote 33 below.)
[31]It is not very clear where this lead comes from. Should it be antimony? The German translation gives this as "silver."
[31]It is not very clear where this lead comes from. Should it be antimony? The German translation gives this as "silver."
[Pg 398][32]These powders are described in Book VII., p.236. It is difficult to say which the second really is. There are numbers of such recipes in theProbierbüchlein(seeAppendix B), with which a portion of these are identical.
[Pg 398][32]These powders are described in Book VII., p.236. It is difficult to say which the second really is. There are numbers of such recipes in theProbierbüchlein(seeAppendix B), with which a portion of these are identical.
[33]A variety of methods are involved in this paragraph: 1st, crude gold ore is smelted direct; 2nd, gold concentrates are smelted in a lead bath with some addition of iron—which would simply matte off—the lead bullion being cupelled; 3rd, roasted and unroasted pyrites andcadmia(probably blende, cobalt, arsenic, etc.) are melted into a matte; this matte is repeatedly roasted, and then re-melted in a lead bath; 4th, if the material "flies out of the furnace" it is briquetted with iron ore and lime, and the briquettes smelted with copper matte. Three products result: (a) slag; (b) matte; (c) copper-gold-silver alloy. The matte is roasted, re-smelted with lead, and no doubt a button obtained, and further matte. The process from this point is not clear. It appears that the copper bullion is melted with lead, and normally this product would be taken to the liquation furnace, but from the text it would appear that the lead-copper bullion was melted again with iron ore and pyrites, in which case some of the copper would be turned into the matte, and the lead alloy would be richer in gold and silver.[Pg 399]Historical Note on Gold.—There is ample evidence of gold being used for ornamental purposes prior to any human record. The occurrence of large quantities of gold in native form, and the possibility of working it cold, did not necessitate any particular metallurgical ingenuity. The earliest indications of metallurgical work are, of course, among the Egyptians, the method of washing being figured as early as the monuments of the IV Dynasty (prior to 3800B.C.). There are in the British Museum two stelae of the XII Dynasty (2400B.C.) (144 Bay 1 and 145 Bay 6) relating to officers who had to do with gold mining in Nubia, and upon one there are references to working what appears to be ore. If this be true, it is the earliest reference to this subject. The Papyrus map (1500B.C.) of a gold mine, in the Turin Museum (seenote 16, p. 129), probably refers to a quartz mine. Of literary evidences there is frequent mention of refining gold and passing it through the fire in the Books of Moses, arts no doubt learned from the Egyptians. As to working gold, ore as distinguished from alluvial, we have nothing very tangible, unless it be the stelae above, until the description of Egyptian gold mining by Agatharchides (seenote 8, p. 279). This geographer, of about the 2nd centuryB.C., describes very clearly indeed the mining, crushing, and concentration of ore and the refining of the concentrates in crucibles with lead, salt, and barley bran. We may mention in passing that Theognis (6th CenturyB.C.) is often quoted as mentioning the refining of gold with lead, but we do not believe that the passage in question (1101): "But having been put to the test and being rubbed beside (or against) lead as being refined gold, you will be fair," etc.; or much the same statement again (418) will stand much metallurgical interpretation. In any event, the myriads of metaphorical references to fining and purity of gold in the earliest shreds of literature do not carry us much further than do those of Shakespeare or Milton. Vitruvius and Pliny mention the recovery or refining of gold with mercury (seenote 12, p. 297on Amalgamation); and it appears to us that gold was parted from silver by cementation with salt prior to the Christian era. We first find mention of parting with sulphur in the 12th century, with nitric acid prior to the 14th century, by antimony sulphide prior to the 15th century, and by cementation with nitre by Agricola. (See historical note on parting gold and silver, p.458.) The first mention of parting gold from copper occurs in the early 16th century (seenote 24, p. 462). The first comprehensive description of gold metallurgy in all its branches is inDe Re Metallica.
[33]A variety of methods are involved in this paragraph: 1st, crude gold ore is smelted direct; 2nd, gold concentrates are smelted in a lead bath with some addition of iron—which would simply matte off—the lead bullion being cupelled; 3rd, roasted and unroasted pyrites andcadmia(probably blende, cobalt, arsenic, etc.) are melted into a matte; this matte is repeatedly roasted, and then re-melted in a lead bath; 4th, if the material "flies out of the furnace" it is briquetted with iron ore and lime, and the briquettes smelted with copper matte. Three products result: (a) slag; (b) matte; (c) copper-gold-silver alloy. The matte is roasted, re-smelted with lead, and no doubt a button obtained, and further matte. The process from this point is not clear. It appears that the copper bullion is melted with lead, and normally this product would be taken to the liquation furnace, but from the text it would appear that the lead-copper bullion was melted again with iron ore and pyrites, in which case some of the copper would be turned into the matte, and the lead alloy would be richer in gold and silver.
[Pg 399]Historical Note on Gold.—There is ample evidence of gold being used for ornamental purposes prior to any human record. The occurrence of large quantities of gold in native form, and the possibility of working it cold, did not necessitate any particular metallurgical ingenuity. The earliest indications of metallurgical work are, of course, among the Egyptians, the method of washing being figured as early as the monuments of the IV Dynasty (prior to 3800B.C.). There are in the British Museum two stelae of the XII Dynasty (2400B.C.) (144 Bay 1 and 145 Bay 6) relating to officers who had to do with gold mining in Nubia, and upon one there are references to working what appears to be ore. If this be true, it is the earliest reference to this subject. The Papyrus map (1500B.C.) of a gold mine, in the Turin Museum (seenote 16, p. 129), probably refers to a quartz mine. Of literary evidences there is frequent mention of refining gold and passing it through the fire in the Books of Moses, arts no doubt learned from the Egyptians. As to working gold, ore as distinguished from alluvial, we have nothing very tangible, unless it be the stelae above, until the description of Egyptian gold mining by Agatharchides (seenote 8, p. 279). This geographer, of about the 2nd centuryB.C., describes very clearly indeed the mining, crushing, and concentration of ore and the refining of the concentrates in crucibles with lead, salt, and barley bran. We may mention in passing that Theognis (6th CenturyB.C.) is often quoted as mentioning the refining of gold with lead, but we do not believe that the passage in question (1101): "But having been put to the test and being rubbed beside (or against) lead as being refined gold, you will be fair," etc.; or much the same statement again (418) will stand much metallurgical interpretation. In any event, the myriads of metaphorical references to fining and purity of gold in the earliest shreds of literature do not carry us much further than do those of Shakespeare or Milton. Vitruvius and Pliny mention the recovery or refining of gold with mercury (seenote 12, p. 297on Amalgamation); and it appears to us that gold was parted from silver by cementation with salt prior to the Christian era. We first find mention of parting with sulphur in the 12th century, with nitric acid prior to the 14th century, by antimony sulphide prior to the 15th century, and by cementation with nitre by Agricola. (See historical note on parting gold and silver, p.458.) The first mention of parting gold from copper occurs in the early 16th century (seenote 24, p. 462). The first comprehensive description of gold metallurgy in all its branches is inDe Re Metallica.
[Pg 400][34]Rudissilver comprised all fairly pure silver ores, such as silver sulphides, chlorides, arsenides, etc. This is more fully discussed innote 6, p. 108.
[Pg 400][34]Rudissilver comprised all fairly pure silver ores, such as silver sulphides, chlorides, arsenides, etc. This is more fully discussed innote 6, p. 108.
[35]Evolent,—volatilize?
[35]Evolent,—volatilize?
[36]Lapidis plumbarii facile liquescentis. The German Translation givesglantz,i.e., Galena, and theInterpretatioalso givesglantzforlapis plumbarius. We are, however, uncertain whether this "easily melting" material is galena or some other lead ore.
[36]Lapidis plumbarii facile liquescentis. The German Translation givesglantz,i.e., Galena, and theInterpretatioalso givesglantzforlapis plumbarius. We are, however, uncertain whether this "easily melting" material is galena or some other lead ore.
[37]Molybdaenais usually hearth-lead inDe Re Metallica, but the German translation in this instance usespleyertz, lead ore. From the context it would not appear to mean hearth-lead—saturated bottoms of cupellation furnaces—for such material would not contain appreciable silver. Agricola does confuse what are obviously lead carbonates with his othermolybdaena(seenote 37, p. 476).
[37]Molybdaenais usually hearth-lead inDe Re Metallica, but the German translation in this instance usespleyertz, lead ore. From the context it would not appear to mean hearth-lead—saturated bottoms of cupellation furnaces—for such material would not contain appreciable silver. Agricola does confuse what are obviously lead carbonates with his othermolybdaena(seenote 37, p. 476).
[Pg 401][38]The termcadmiais used in this paragraph without the usual definition. Whether it wascadmia fornacis(furnace accretions) orcadmia metallica(cobalt-arsenic-blende mixture) is uncertain. We believe it to be the former.
[Pg 401][38]The termcadmiais used in this paragraph without the usual definition. Whether it wascadmia fornacis(furnace accretions) orcadmia metallica(cobalt-arsenic-blende mixture) is uncertain. We believe it to be the former.
[39]Ramentum si lotura ex argento rudi. This expression is generally used by the author to indicate concentrates, but it is possible that in this sentence it means the tailings after washing rich silver minerals, because the treatment of therudissilver has been already discussed above.
[39]Ramentum si lotura ex argento rudi. This expression is generally used by the author to indicate concentrates, but it is possible that in this sentence it means the tailings after washing rich silver minerals, because the treatment of therudissilver has been already discussed above.
[40]Ustum. This might be rendered "burnt." In any event, it seems that the material is sintered.
[40]Ustum. This might be rendered "burnt." In any event, it seems that the material is sintered.
[Pg 402][41]Aes purum sive proprius ei color insederit, sive chrysocolla vel caeruleo fuerit tinctum, et rude plumbei coloris, aut fusci, aut nigri.There are six copper minerals mentioned in this sentence, and from our study of Agricola'sDe Natura Fossiliumwe hazard the following:—Proprius ei color insederit,—"its own colour,"—probably cuprite or "ruby copper."Tinctum chrysocolla—partly the modern mineral of that name and partly malachite.Tinctum caeruleo, partly azurite and partly other blue copper minerals.Rude plumbei coloris,—"lead coloured,"—was certainly chalcocite (copper glance). We are uncertain offusci aut nigri, but they were probably alteration products. For further discussion see note on p.109.
[Pg 402][41]Aes purum sive proprius ei color insederit, sive chrysocolla vel caeruleo fuerit tinctum, et rude plumbei coloris, aut fusci, aut nigri.There are six copper minerals mentioned in this sentence, and from our study of Agricola'sDe Natura Fossiliumwe hazard the following:—Proprius ei color insederit,—"its own colour,"—probably cuprite or "ruby copper."Tinctum chrysocolla—partly the modern mineral of that name and partly malachite.Tinctum caeruleo, partly azurite and partly other blue copper minerals.Rude plumbei coloris,—"lead coloured,"—was certainly chalcocite (copper glance). We are uncertain offusci aut nigri, but they were probably alteration products. For further discussion see note on p.109.
[42]Historical Note on Copper Smelting.—The discoverer of the reduction of copper by fusion, and his method, like the discoverer of tin and iron, will never be known, because he lived long before humanity began to make records of its discoveries and doings. Moreover, as different races passed independently and at different times through the so-called "Bronze Age," there may have been several independent discoverers. Upon the metallurgy of pre-historic man we have some evidence in the many "founders' hoards" or "smelters' hoards" of the Bronze Age which have been found, and they indicate a simple shallow pit in the ground into which the ore was placed, underlaid with charcoal. Rude round copper cakes eight to ten inches in diameter resulted from the cooling of the metal in the bottom of the pit. Analyses of such Bronze Age copper by Professor Gowland and others show a small percentage of sulphur, and this is possible only by smelting oxidized ores. Copper objects appear in the pre-historic remains in Egypt, are common throughout the first three dynasties, and bronze articles have been found as early as the IV Dynasty (from 3800 to 4700B.C., according to the authority adopted). The question of the origin of this bronze, whether from ores containing copper and tin or by alloying the two metals, is one of wide difference of opinion, and we further discuss the question innote 53, p. 411, under Tin. It is also interesting to note that the crucible is the emblem of copper in the hieroglyphics. The earliest source of Egyptian copper was probably the Sinai Peninsula, where there are reliefs as early as Seneferu (about 3700B.C.), indicating that he worked the copper mines. Various other evidences exist of active copper mining prior to 2500B.C.(Petrie, Researches in Sinai, London, 1906, p. 51, etc.). The finding of crucibles here would indicate some form of refining. Our knowledge of Egyptian copper metallurgy is limited to deductions from their products, to a few pictures of crude furnaces and bellows, and to the minor remains on the Sinai Peninsula; none of the pictures were, so far as we are aware, prior to 2300B.C., but they indicate a considerable advance over the crude hearth, for they depict small furnaces with forced draught—first a blow-pipe, and in the XVIII Dynasty (about 1500B.C.) the bellows appear. Many copper articles have been found scattered over the Eastern Mediterranean and Asia Minor of pre-Mycenaean Age, some probably as early as 3000B.C.This metal is mentioned in the "Tribute of Yü" in the Shoo King (2500B.C.?); but even less is known of early Chinese metallurgy than of the Egyptian. The remains of Mycenaean, Phoenician, Babylonian, and Assyrian civilizations, stretching over the period from 1800 to 500B.C., have yielded endless copper and bronze objects, the former of considerable purity, and the latter a fairly constant proportion of from 10% to 14% tin. The copper supply of the pre-Roman world seems to have come largely, first from Sinai, and later from Cyprus, and from the latter comes our word copper, by way of the Romans shorteningaes cyprium(Cyprian copper) tocuprum. Research in this island shows that it produced copper from 3000B.C., and largely because of its copper it passed successively under the domination of the Egyptians, Assyrians, Phoenicians, Greeks, Persians, and Romans. The bronze objects found in Cyprus show 2% to 10% of tin, although tin does not, so far as modern research goes, occur on that island. There can be no doubt that the Greeks obtained their metallurgy from the Egyptians, either direct or second-hand—possibly through Mycenae or Phoenicia. Their metallurgical gods and the tradition of Cadmus indicate this much.By way of literary evidences, the following lines from Homer (Iliad,XVIII.) have interest as being the first preserved description in any language of a metallurgical work. Hephaestus was much interrupted by Thetis, who came to secure a shield for Achilles, and whose general conversation we therefore largely omit. We adopt Pope's translation:—There the lame architect the goddess foundObscure in smoke, his forges flaming round,While bathed in sweat from fire to fire he flew;[Pg 403]And puffing loud the roaring bellows blew.* * *In moulds prepared, the glowing ore (metal?) he pours.* * *"Vouchsafe, oh Thetis! at our board to shareThe genial rites and hospitable fare;While I the labours of the forge forego,And bid the roaring bellows cease to blow."Then from his anvil the lame artist rose;Wide with distorted legs oblique he goes,And stills the bellows, and (in order laid)Locks in their chests his instruments of trade;Then with a sponge, the sooty workman dress'dHis brawny arms embrown'd and hairy breast.* * *Thus having said, the father of the firesTo the black labours of his forge retires.Soon as he bade them blow the bellows turn'dTheir iron mouths; and where the furnace burn'dResounding breathed: at once the blast expires,And twenty forges catch at once the fires;Just as the God directs, now loud, now low,They raise a tempest, or they gently blow;In hissing flames huge silver bars are roll'd,And stubborn brass (copper?) and tin, and solid gold;Before, deep fixed, the eternal anvils stand.The ponderous hammer loads his better hand;His left with tongs turns the vex'd metal round.And thick, strong strokes, the doubling vaults reboundThen first he formed the immense and solid shield;Even if we place the siege of Troy at any of the various dates from 1350 to 1100B.C., it does not follow that the epic received its final form for many centuries later, probably 900-800B.C.; and the experience of the race in metallurgy at a much later period than Troy may have been drawn upon to fill in details. It is possible to fill a volume with indirect allusion to metallurgical facts and to the origins of the art, from Greek mythology, from Greek poetry, from the works of the grammarians, and from the Bible. But they are of no more technical value than the metaphors from our own tongue. Greek literature in general is singularly lacking in metallurgical description of technical value, and it is not until Dioscorides (1st CenturyA.D.) that anything of much importance can be adduced. Aristotle, however, does make an interesting reference to what may be brass (see note on p.410), and there can be no doubt that if we had the lost work of Aristotle's successor, Theophrastus (372-288B.C.), on metals we should be in possession of the first adequate work on metallurgy. As it is, we find the green and blue copper minerals from Cyprus mentioned in his "Stones." And this is the first mention of any particular copper ore. He also mentions (XIX.) pyrites "which melt," but whether it was a copper variety cannot be determined. Theophrastus further describes the making of verdigris (seenote 4, p. 440). From Dioscorides we get a good deal of light on copper treatment, but as his objective was to describe medicinal preparations, the information is very indirect. He states (V, 100) that "pyrites is a stone from which copper is made." He mentionschalcitis(copper sulphide, see note on, p.573); while hismisy,sory,melanteria,caeruleum, andchrysocollawere all oxidation copper or iron minerals. (See notes on p.573.) In giving a method of securingpompholyx(zinc oxide), "the soot flies up when the copper refiners sprinkle powderedcadmiaover the molten metal" (seenote 26, p. 394); he indirectly gives us the first definite indication of making brass, and further gives some details as to the furnaces there employed, which embraced bellows and dust chambers. In describing the making of flowers of copper (seenote 26, p. 538) he states that in refining copper, when the "molten metal flows through its tube into a receptacle, the workmen[Pg 404]pour cold water on it, the copper spits and throws off the flowers." He gives the first description of vitriol (seenote 11, p. 572), and describes the pieces as "shaped like dice which stick together in bunches like grapes." Altogether, from Dioscorides we learn for the first time of copper made from sulphide ores, and of the recovery of zinc oxides from furnace fumes; and he gives us the first certain description of making brass, and finally the first notice of blue vitriol.The next author we have who gives any technical detail of copper work is Pliny (23-79A.D.), and while his statements carry us a little further than Dioscorides, they are not as complete as the same number of words could have afforded had he ever had practical contact with the subject, and one is driven to the conclusion that he was not himself much of a metallurgist. Pliny indicates that copper ores were obtained from veins by underground mining. He gives the same minerals as Dioscorides, but is a good deal confused overchrysocollaandchalcitis. He gives no description of the shapes of furnaces, but frequently mentions the bellows, and speaks of thecadmiaandpompholyxwhich adhered to the walls and arches of the furnaces. He has nothing to say as to whether fluxes are used or not. As to fuel, he says (XXXIII, 30) that "for smelting copper and iron pine wood is the best." The following (XXXIV, 20) is of the greatest interest on the subject:—"Cyprian copper is known ascoronariumandregulare; both are ductile.... In other mines are made that known asregulareandcaldarium. These differ, because thecaldariumis only melted, and is brittle to the hammer; whereas theregulareis malleable or ductile. All Cyprian copper is this latter kind. But in other mines with care the difference can be eliminated fromcaldarium, the impurities being carefully purged away by smelting with fire, it is made intoregulare. Among the remaining kinds of copper the best is that of Campania, which is most esteemed for vessels and utensils. This kind is made in several ways. At Capua it is melted with wood, not with charcoal, after which it is sprinkled with water and washed through an oak sieve. After it is melted a number of times Spanishplumbum argentum(probably pewter) is added to it in proportion of ten pounds of the lead to one hundred pounds of copper, and thereby it is made pliable and assumes that pleasing colour which in other kinds of copper is effected by oil and the sun. In many parts of the Italian provinces they make a similar kind of metal; but there they add eight pounds of lead, and it is re-melted over charcoal because of the scarcity of wood. Very different is the method carried on in Gaul, particularly where the ore is smelted between red hot stones, for this burns the metal and renders it black and brittle. Moreover, it is re-melted only a single time, whereas the oftener this operation is repeated the better the quality becomes. It is well to remark that all copper fuses best when the weather is intensely cold." The red hot stones in Gaul were probably as much figments of imagination as was the assumption of one commentator that they were a reverberatory furnace. Apart from the above, Pliny says nothing very direct on refining copper. It is obvious that more than one melting was practised, but that anything was known of the nature of oxidation by a blast and reduction by poling is uncertain. We produce the three following statements in connection with some bye-products used for medicinal purposes, which at least indicate operations subsequent to the original melting. As to whether they represent this species of refining or not, we leave it to the metallurgical profession (XXXIV, 24):—"The flowers of copper are used in medicine; they are made by fusing copper and moving it to another furnace, where the rapid blast separates it into a thousand particles, which are called flowers. These scales are also made when the copper cakes are cooled in water (XXXIV, 35).Smegais prepared in the copper works; when the metal is melted and thoroughly smelted charcoal is added to it and gradually kindled; after this, being blown upon by a powerful bellows, it spits out, as it were, copper chaff (XXXIV, 37). There is another product of these works easily distinguished fromsmega, which the Greeks calldiphrygum. This substance has three different origins.... A third way of making it is from the residues which fall to the bottom in copper furnaces. The difference between the different substances (in the furnace) is that the copper itself flows into a receiver; the slag makes its escape from the furnace; the flowers float on the top (of the copper?), and thediphrygumremains behind. Some say that in the furnace there are certain masses of stone which, being smelted, become soldered together, and that the copper fuses around it, the mass not becoming liquid unless it is transferred to another furnace. It thus forms a sort of knot, as it were, in the metal."[Pg 405]Pliny is a good deal confused over the copper alloys, failing to recogniseaurichalcumas the same product as that made by mixingcadmiaand molten copper. Further, there is always the difficulty in translation arising from the fact that the Latinaeswas indiscriminately copper, brass, and bronze. He does not, except in one instance (XXXIV., 2), directly describe the mixture ofcadmiaand copper. "Next to Livian (copper) this kind (corduban, from Spain) most readily absorbscadmia, and becomes almost as excellent asaurichalcumfor makingsesterces." As to bronze, there is no very definite statement; but theargentatiumgiven in the quotation above fromXXXIV, 20, is stated inXXXIV, 48, to be a mixture of tin and lead. The Romans carried on most extensive copper mining in various parts of their empire; these activities extended from Egypt through Cyprus, Central Europe, the Spanish Peninsula, and Britain. The activity of such works is abundantly evidenced in the mines, but very little remains upon the surface to indicate the equipment; thus, while mining methods are clear enough, the metallurgy receives little help from these sources. At Rio Tinto there still remain enormous slag heaps from the Romans, and the Phoenician miners before them. Professor W. A. Carlyle informs us that the ore worked must have been almost exclusively sulphides, as only negligible quantities of carbonates exist in the deposits; they probably mixed basic and siliceous ores. There is some evidence of roasting, and the slags run from .2 to .6%. They must have run down mattes, but as to how they ultimately arrived at metallic copper there is no evidence to show.The special processes for separating other metals from copper by liquation and matting, or of refining by poling, etc., are none of them clearly indicated in records or remains until we reach the 12th century. Here we find very adequate descriptions of copper smelting and refining by the Monk Theophilus (seeAppendix B). We reproduce two paragraphs of interest from Hendrie's excellent translation (p. 305 and 313): "Copper is engendered in the earth. When a vein of which is found, it is acquired with the greatest labour by digging and breaking. It is a stone of a green colour and most hard, and naturally mixed with lead. This stone, dug up in abundance, is placed upon a pile and burned after the manner of chalk, nor does it change colour, but yet loses its hardness, so that it can be broken up. Then, being bruised small, it is placed in the furnace; coals and the bellows being applied, it is incessantly forged by day and night. This should be done carefully and with caution; that is, at first coals are placed in, then small pieces of stone are distributed over them, and again coals, and then stone anew, and it is thus arranged until it is sufficient for the size of the furnace. And when the stone has commenced to liquefy, the lead flows out through some small cavities, and the copper remains within. (313) Of the purification of copper. Take an iron dish of the size you wish, and line it inside and out with clay strongly beaten and mixed, and it is carefully dried. Then place it before a forge upon the coals, so that when the bellows act upon it the wind may issue partly within and partly above it, and not below it. And very small coals being placed round it, place copper in it equally, and add over it a heap of coals. When, by blowing a long time, this has become melted, uncover it and cast immediately fine ashes of coals over it, and stir it with a thin and dry piece of wood as if mixing it, and you will directly see the burnt lead adhere to these ashes like a glue. Which being cast out again superpose coals, and blowing for a long time, as at first, again uncover it, and then do as you did before. You do this until at length, by cooking it, you can withdraw the lead entirely. Then pour it over the mould which you have prepared for this, and you will thus prove if it be pure. Hold it with pincers, glowing as it is, before it has become cold, and strike it with a large hammer strongly over the anvil, and if it be broken or split you must liquefy it anew as before."The next writer of importance was Biringuccio, who was contemporaneous with Agricola, but whose book precedesDe Re Metallicaby 15 years. That author (III, 2) is the first to describe particularly the furnace used in Saxony and the roasting prior to smelting, and the first to mention fluxes in detail. He, however, describes nothing of matte smelting; in copper refining he gives the whole process of poling, but omits the pole. It is not until we reachDe Re Metallicathat we find adequate descriptions of the copper minerals, roasting, matte smelting, liquation, and refining, with a wealth of detail which eliminates the necessity for a large amount of conjecture regarding technical methods of the time.
[42]Historical Note on Copper Smelting.—The discoverer of the reduction of copper by fusion, and his method, like the discoverer of tin and iron, will never be known, because he lived long before humanity began to make records of its discoveries and doings. Moreover, as different races passed independently and at different times through the so-called "Bronze Age," there may have been several independent discoverers. Upon the metallurgy of pre-historic man we have some evidence in the many "founders' hoards" or "smelters' hoards" of the Bronze Age which have been found, and they indicate a simple shallow pit in the ground into which the ore was placed, underlaid with charcoal. Rude round copper cakes eight to ten inches in diameter resulted from the cooling of the metal in the bottom of the pit. Analyses of such Bronze Age copper by Professor Gowland and others show a small percentage of sulphur, and this is possible only by smelting oxidized ores. Copper objects appear in the pre-historic remains in Egypt, are common throughout the first three dynasties, and bronze articles have been found as early as the IV Dynasty (from 3800 to 4700B.C., according to the authority adopted). The question of the origin of this bronze, whether from ores containing copper and tin or by alloying the two metals, is one of wide difference of opinion, and we further discuss the question innote 53, p. 411, under Tin. It is also interesting to note that the crucible is the emblem of copper in the hieroglyphics. The earliest source of Egyptian copper was probably the Sinai Peninsula, where there are reliefs as early as Seneferu (about 3700B.C.), indicating that he worked the copper mines. Various other evidences exist of active copper mining prior to 2500B.C.(Petrie, Researches in Sinai, London, 1906, p. 51, etc.). The finding of crucibles here would indicate some form of refining. Our knowledge of Egyptian copper metallurgy is limited to deductions from their products, to a few pictures of crude furnaces and bellows, and to the minor remains on the Sinai Peninsula; none of the pictures were, so far as we are aware, prior to 2300B.C., but they indicate a considerable advance over the crude hearth, for they depict small furnaces with forced draught—first a blow-pipe, and in the XVIII Dynasty (about 1500B.C.) the bellows appear. Many copper articles have been found scattered over the Eastern Mediterranean and Asia Minor of pre-Mycenaean Age, some probably as early as 3000B.C.This metal is mentioned in the "Tribute of Yü" in the Shoo King (2500B.C.?); but even less is known of early Chinese metallurgy than of the Egyptian. The remains of Mycenaean, Phoenician, Babylonian, and Assyrian civilizations, stretching over the period from 1800 to 500B.C., have yielded endless copper and bronze objects, the former of considerable purity, and the latter a fairly constant proportion of from 10% to 14% tin. The copper supply of the pre-Roman world seems to have come largely, first from Sinai, and later from Cyprus, and from the latter comes our word copper, by way of the Romans shorteningaes cyprium(Cyprian copper) tocuprum. Research in this island shows that it produced copper from 3000B.C., and largely because of its copper it passed successively under the domination of the Egyptians, Assyrians, Phoenicians, Greeks, Persians, and Romans. The bronze objects found in Cyprus show 2% to 10% of tin, although tin does not, so far as modern research goes, occur on that island. There can be no doubt that the Greeks obtained their metallurgy from the Egyptians, either direct or second-hand—possibly through Mycenae or Phoenicia. Their metallurgical gods and the tradition of Cadmus indicate this much.
By way of literary evidences, the following lines from Homer (Iliad,XVIII.) have interest as being the first preserved description in any language of a metallurgical work. Hephaestus was much interrupted by Thetis, who came to secure a shield for Achilles, and whose general conversation we therefore largely omit. We adopt Pope's translation:—
There the lame architect the goddess foundObscure in smoke, his forges flaming round,While bathed in sweat from fire to fire he flew;[Pg 403]And puffing loud the roaring bellows blew.* * *In moulds prepared, the glowing ore (metal?) he pours.* * *"Vouchsafe, oh Thetis! at our board to shareThe genial rites and hospitable fare;While I the labours of the forge forego,And bid the roaring bellows cease to blow."Then from his anvil the lame artist rose;Wide with distorted legs oblique he goes,And stills the bellows, and (in order laid)Locks in their chests his instruments of trade;Then with a sponge, the sooty workman dress'dHis brawny arms embrown'd and hairy breast.* * *Thus having said, the father of the firesTo the black labours of his forge retires.Soon as he bade them blow the bellows turn'dTheir iron mouths; and where the furnace burn'dResounding breathed: at once the blast expires,And twenty forges catch at once the fires;Just as the God directs, now loud, now low,They raise a tempest, or they gently blow;In hissing flames huge silver bars are roll'd,And stubborn brass (copper?) and tin, and solid gold;Before, deep fixed, the eternal anvils stand.The ponderous hammer loads his better hand;His left with tongs turns the vex'd metal round.And thick, strong strokes, the doubling vaults reboundThen first he formed the immense and solid shield;
There the lame architect the goddess foundObscure in smoke, his forges flaming round,While bathed in sweat from fire to fire he flew;[Pg 403]And puffing loud the roaring bellows blew.* * *In moulds prepared, the glowing ore (metal?) he pours.* * *"Vouchsafe, oh Thetis! at our board to shareThe genial rites and hospitable fare;While I the labours of the forge forego,And bid the roaring bellows cease to blow."Then from his anvil the lame artist rose;Wide with distorted legs oblique he goes,And stills the bellows, and (in order laid)Locks in their chests his instruments of trade;Then with a sponge, the sooty workman dress'dHis brawny arms embrown'd and hairy breast.* * *Thus having said, the father of the firesTo the black labours of his forge retires.Soon as he bade them blow the bellows turn'dTheir iron mouths; and where the furnace burn'dResounding breathed: at once the blast expires,And twenty forges catch at once the fires;Just as the God directs, now loud, now low,They raise a tempest, or they gently blow;In hissing flames huge silver bars are roll'd,And stubborn brass (copper?) and tin, and solid gold;Before, deep fixed, the eternal anvils stand.The ponderous hammer loads his better hand;His left with tongs turns the vex'd metal round.And thick, strong strokes, the doubling vaults reboundThen first he formed the immense and solid shield;
Even if we place the siege of Troy at any of the various dates from 1350 to 1100B.C., it does not follow that the epic received its final form for many centuries later, probably 900-800B.C.; and the experience of the race in metallurgy at a much later period than Troy may have been drawn upon to fill in details. It is possible to fill a volume with indirect allusion to metallurgical facts and to the origins of the art, from Greek mythology, from Greek poetry, from the works of the grammarians, and from the Bible. But they are of no more technical value than the metaphors from our own tongue. Greek literature in general is singularly lacking in metallurgical description of technical value, and it is not until Dioscorides (1st CenturyA.D.) that anything of much importance can be adduced. Aristotle, however, does make an interesting reference to what may be brass (see note on p.410), and there can be no doubt that if we had the lost work of Aristotle's successor, Theophrastus (372-288B.C.), on metals we should be in possession of the first adequate work on metallurgy. As it is, we find the green and blue copper minerals from Cyprus mentioned in his "Stones." And this is the first mention of any particular copper ore. He also mentions (XIX.) pyrites "which melt," but whether it was a copper variety cannot be determined. Theophrastus further describes the making of verdigris (seenote 4, p. 440). From Dioscorides we get a good deal of light on copper treatment, but as his objective was to describe medicinal preparations, the information is very indirect. He states (V, 100) that "pyrites is a stone from which copper is made." He mentionschalcitis(copper sulphide, see note on, p.573); while hismisy,sory,melanteria,caeruleum, andchrysocollawere all oxidation copper or iron minerals. (See notes on p.573.) In giving a method of securingpompholyx(zinc oxide), "the soot flies up when the copper refiners sprinkle powderedcadmiaover the molten metal" (seenote 26, p. 394); he indirectly gives us the first definite indication of making brass, and further gives some details as to the furnaces there employed, which embraced bellows and dust chambers. In describing the making of flowers of copper (seenote 26, p. 538) he states that in refining copper, when the "molten metal flows through its tube into a receptacle, the workmen[Pg 404]pour cold water on it, the copper spits and throws off the flowers." He gives the first description of vitriol (seenote 11, p. 572), and describes the pieces as "shaped like dice which stick together in bunches like grapes." Altogether, from Dioscorides we learn for the first time of copper made from sulphide ores, and of the recovery of zinc oxides from furnace fumes; and he gives us the first certain description of making brass, and finally the first notice of blue vitriol.
The next author we have who gives any technical detail of copper work is Pliny (23-79A.D.), and while his statements carry us a little further than Dioscorides, they are not as complete as the same number of words could have afforded had he ever had practical contact with the subject, and one is driven to the conclusion that he was not himself much of a metallurgist. Pliny indicates that copper ores were obtained from veins by underground mining. He gives the same minerals as Dioscorides, but is a good deal confused overchrysocollaandchalcitis. He gives no description of the shapes of furnaces, but frequently mentions the bellows, and speaks of thecadmiaandpompholyxwhich adhered to the walls and arches of the furnaces. He has nothing to say as to whether fluxes are used or not. As to fuel, he says (XXXIII, 30) that "for smelting copper and iron pine wood is the best." The following (XXXIV, 20) is of the greatest interest on the subject:—"Cyprian copper is known ascoronariumandregulare; both are ductile.... In other mines are made that known asregulareandcaldarium. These differ, because thecaldariumis only melted, and is brittle to the hammer; whereas theregulareis malleable or ductile. All Cyprian copper is this latter kind. But in other mines with care the difference can be eliminated fromcaldarium, the impurities being carefully purged away by smelting with fire, it is made intoregulare. Among the remaining kinds of copper the best is that of Campania, which is most esteemed for vessels and utensils. This kind is made in several ways. At Capua it is melted with wood, not with charcoal, after which it is sprinkled with water and washed through an oak sieve. After it is melted a number of times Spanishplumbum argentum(probably pewter) is added to it in proportion of ten pounds of the lead to one hundred pounds of copper, and thereby it is made pliable and assumes that pleasing colour which in other kinds of copper is effected by oil and the sun. In many parts of the Italian provinces they make a similar kind of metal; but there they add eight pounds of lead, and it is re-melted over charcoal because of the scarcity of wood. Very different is the method carried on in Gaul, particularly where the ore is smelted between red hot stones, for this burns the metal and renders it black and brittle. Moreover, it is re-melted only a single time, whereas the oftener this operation is repeated the better the quality becomes. It is well to remark that all copper fuses best when the weather is intensely cold." The red hot stones in Gaul were probably as much figments of imagination as was the assumption of one commentator that they were a reverberatory furnace. Apart from the above, Pliny says nothing very direct on refining copper. It is obvious that more than one melting was practised, but that anything was known of the nature of oxidation by a blast and reduction by poling is uncertain. We produce the three following statements in connection with some bye-products used for medicinal purposes, which at least indicate operations subsequent to the original melting. As to whether they represent this species of refining or not, we leave it to the metallurgical profession (XXXIV, 24):—"The flowers of copper are used in medicine; they are made by fusing copper and moving it to another furnace, where the rapid blast separates it into a thousand particles, which are called flowers. These scales are also made when the copper cakes are cooled in water (XXXIV, 35).Smegais prepared in the copper works; when the metal is melted and thoroughly smelted charcoal is added to it and gradually kindled; after this, being blown upon by a powerful bellows, it spits out, as it were, copper chaff (XXXIV, 37). There is another product of these works easily distinguished fromsmega, which the Greeks calldiphrygum. This substance has three different origins.... A third way of making it is from the residues which fall to the bottom in copper furnaces. The difference between the different substances (in the furnace) is that the copper itself flows into a receiver; the slag makes its escape from the furnace; the flowers float on the top (of the copper?), and thediphrygumremains behind. Some say that in the furnace there are certain masses of stone which, being smelted, become soldered together, and that the copper fuses around it, the mass not becoming liquid unless it is transferred to another furnace. It thus forms a sort of knot, as it were, in the metal."
[Pg 405]Pliny is a good deal confused over the copper alloys, failing to recogniseaurichalcumas the same product as that made by mixingcadmiaand molten copper. Further, there is always the difficulty in translation arising from the fact that the Latinaeswas indiscriminately copper, brass, and bronze. He does not, except in one instance (XXXIV., 2), directly describe the mixture ofcadmiaand copper. "Next to Livian (copper) this kind (corduban, from Spain) most readily absorbscadmia, and becomes almost as excellent asaurichalcumfor makingsesterces." As to bronze, there is no very definite statement; but theargentatiumgiven in the quotation above fromXXXIV, 20, is stated inXXXIV, 48, to be a mixture of tin and lead. The Romans carried on most extensive copper mining in various parts of their empire; these activities extended from Egypt through Cyprus, Central Europe, the Spanish Peninsula, and Britain. The activity of such works is abundantly evidenced in the mines, but very little remains upon the surface to indicate the equipment; thus, while mining methods are clear enough, the metallurgy receives little help from these sources. At Rio Tinto there still remain enormous slag heaps from the Romans, and the Phoenician miners before them. Professor W. A. Carlyle informs us that the ore worked must have been almost exclusively sulphides, as only negligible quantities of carbonates exist in the deposits; they probably mixed basic and siliceous ores. There is some evidence of roasting, and the slags run from .2 to .6%. They must have run down mattes, but as to how they ultimately arrived at metallic copper there is no evidence to show.
The special processes for separating other metals from copper by liquation and matting, or of refining by poling, etc., are none of them clearly indicated in records or remains until we reach the 12th century. Here we find very adequate descriptions of copper smelting and refining by the Monk Theophilus (seeAppendix B). We reproduce two paragraphs of interest from Hendrie's excellent translation (p. 305 and 313): "Copper is engendered in the earth. When a vein of which is found, it is acquired with the greatest labour by digging and breaking. It is a stone of a green colour and most hard, and naturally mixed with lead. This stone, dug up in abundance, is placed upon a pile and burned after the manner of chalk, nor does it change colour, but yet loses its hardness, so that it can be broken up. Then, being bruised small, it is placed in the furnace; coals and the bellows being applied, it is incessantly forged by day and night. This should be done carefully and with caution; that is, at first coals are placed in, then small pieces of stone are distributed over them, and again coals, and then stone anew, and it is thus arranged until it is sufficient for the size of the furnace. And when the stone has commenced to liquefy, the lead flows out through some small cavities, and the copper remains within. (313) Of the purification of copper. Take an iron dish of the size you wish, and line it inside and out with clay strongly beaten and mixed, and it is carefully dried. Then place it before a forge upon the coals, so that when the bellows act upon it the wind may issue partly within and partly above it, and not below it. And very small coals being placed round it, place copper in it equally, and add over it a heap of coals. When, by blowing a long time, this has become melted, uncover it and cast immediately fine ashes of coals over it, and stir it with a thin and dry piece of wood as if mixing it, and you will directly see the burnt lead adhere to these ashes like a glue. Which being cast out again superpose coals, and blowing for a long time, as at first, again uncover it, and then do as you did before. You do this until at length, by cooking it, you can withdraw the lead entirely. Then pour it over the mould which you have prepared for this, and you will thus prove if it be pure. Hold it with pincers, glowing as it is, before it has become cold, and strike it with a large hammer strongly over the anvil, and if it be broken or split you must liquefy it anew as before."
The next writer of importance was Biringuccio, who was contemporaneous with Agricola, but whose book precedesDe Re Metallicaby 15 years. That author (III, 2) is the first to describe particularly the furnace used in Saxony and the roasting prior to smelting, and the first to mention fluxes in detail. He, however, describes nothing of matte smelting; in copper refining he gives the whole process of poling, but omits the pole. It is not until we reachDe Re Metallicathat we find adequate descriptions of the copper minerals, roasting, matte smelting, liquation, and refining, with a wealth of detail which eliminates the necessity for a large amount of conjecture regarding technical methods of the time.
[43]Cadmia metallica fossilis(see note on p.112). This was undoubtedly the complex cobalt-arsenic-zinc minerals found in Saxony. In the German translation, however, this is given asKalmey, calamine, which is unlikely from the association with pyrites.
[43]Cadmia metallica fossilis(see note on p.112). This was undoubtedly the complex cobalt-arsenic-zinc minerals found in Saxony. In the German translation, however, this is given asKalmey, calamine, which is unlikely from the association with pyrites.
[44]The Romanmodius(modulus?) held about 550 cubic inches, the English peck holding 535 cubic inches. Then, perhaps, his sevenmoduliwould be roughly, 1 bushel 3 pecks, and 18 vessels full would be about 31 bushels—say, roughly, 5,400 lbs. of ore.
[44]The Romanmodius(modulus?) held about 550 cubic inches, the English peck holding 535 cubic inches. Then, perhaps, his sevenmoduliwould be roughly, 1 bushel 3 pecks, and 18 vessels full would be about 31 bushels—say, roughly, 5,400 lbs. of ore.
[Pg 406][45]Exhausted liquation cakes (panes aerei fathiscentes). This is the copper sponge resulting from the first liquation of lead, and still contains a considerable amount of lead. The liquation process is discussed in great detail inBook XI.
[Pg 406][45]Exhausted liquation cakes (panes aerei fathiscentes). This is the copper sponge resulting from the first liquation of lead, and still contains a considerable amount of lead. The liquation process is discussed in great detail inBook XI.
[Pg 407][46]The method of this paragraph involves two main objectives—first, the gradual enrichment of matte to blister copper; and, second, the creation of large cakes of copper-lead-silver alloy of suitable size and ratio of metals for liquation. This latter process is described in detail inBook XI. The following groupings show the circuit of the various products, the "lbs." being Romanlibrae:—Charge.Products.1stCrude ore5,400 lbs.Primary matte (1)600 lbs.Lead slags3 cartloadsSilver-copper alloy (A)50 "Schist1 cartloadSlags (B)Flux20 lbs.Concentrates from slags & accretionsSmall quantity2ndPrimary matte (1)1,800 lbs.Secondary matte (2)1,800 lbs.Hearth-lead & litharge1,200 "Silver-copper-lead alloy (liquation cakes) (A2)1,200 "Lead ore300 "Slags (B2)Rich hard cakes (A4)500 "Liquated cakes200 "Slags (B)Concentrates from accretions3rdSecondary matte (2)1,800 lbs.Tertiary matte (3)1,300 lbs.Hearth-lead & litharge1,200 "Silver-copper-lead alloy (liquation cakes) (A3)1,100 "Lead ore300 "Slags (B3)Rich hard cakes (A4)500 "Slags (B2)Concentrates from accretions4thTertiary matte (3)11 cartloadsQuaternary hard cakes matte (4)2,000 lbs.Poor hard cakes (A5)3 "Rich hard cakes of matte (A4)1,500 "Slags (B3)Concentrates from accretions5thRoasted quartzPoor hard cakes of matte (A5)1,500 lbs.Matte (4) (three times roasted)11 cartloadsFinal cakes of matte (5)6thFinal matte three times roasted is smelted to blister copper.The following would be a rough approximation of the value of the various products:—(1.)Primary matte=158ounces troy per short ton.(2.)Secondary matte=85" " "(3.)Tertiary matte=60" " "(4.)Quaternary matte=Indeterminate.A.Copper-silver alloy=388ounces Troy per short ton.A2Copper-silver-lead alloy=145" " "A3" " "=109" " "A4Rich hard cakes=97" " "A5Poor hard cakes=Indeterminate.Final blister copper=12ozs. Troy per short ton.
[Pg 407][46]The method of this paragraph involves two main objectives—first, the gradual enrichment of matte to blister copper; and, second, the creation of large cakes of copper-lead-silver alloy of suitable size and ratio of metals for liquation. This latter process is described in detail inBook XI. The following groupings show the circuit of the various products, the "lbs." being Romanlibrae:—
Charge.Products.1stCrude ore5,400 lbs.Primary matte (1)600 lbs.Lead slags3 cartloadsSilver-copper alloy (A)50 "Schist1 cartloadSlags (B)Flux20 lbs.Concentrates from slags & accretionsSmall quantity2ndPrimary matte (1)1,800 lbs.Secondary matte (2)1,800 lbs.Hearth-lead & litharge1,200 "Silver-copper-lead alloy (liquation cakes) (A2)1,200 "Lead ore300 "Slags (B2)Rich hard cakes (A4)500 "Liquated cakes200 "Slags (B)Concentrates from accretions3rdSecondary matte (2)1,800 lbs.Tertiary matte (3)1,300 lbs.Hearth-lead & litharge1,200 "Silver-copper-lead alloy (liquation cakes) (A3)1,100 "Lead ore300 "Slags (B3)Rich hard cakes (A4)500 "Slags (B2)Concentrates from accretions4thTertiary matte (3)11 cartloadsQuaternary hard cakes matte (4)2,000 lbs.Poor hard cakes (A5)3 "Rich hard cakes of matte (A4)1,500 "Slags (B3)Concentrates from accretions5thRoasted quartzPoor hard cakes of matte (A5)1,500 lbs.Matte (4) (three times roasted)11 cartloadsFinal cakes of matte (5)6thFinal matte three times roasted is smelted to blister copper.
The following would be a rough approximation of the value of the various products:—
(1.)Primary matte=158ounces troy per short ton.(2.)Secondary matte=85" " "(3.)Tertiary matte=60" " "(4.)Quaternary matte=Indeterminate.A.Copper-silver alloy=388ounces Troy per short ton.A2Copper-silver-lead alloy=145" " "A3" " "=109" " "A4Rich hard cakes=97" " "A5Poor hard cakes=Indeterminate.Final blister copper=12ozs. Troy per short ton.
[Pg 408][47]This expression is usually used for hearth-lead, but in this case the author is apparently confining himself to lead ore, and apparently refers to lead carbonates. The German Translation givespleyschweiss. The pyrites mentioned in this paragraph may mean galena, as pyrites was to Agricola a sort of genera.
[Pg 408][47]This expression is usually used for hearth-lead, but in this case the author is apparently confining himself to lead ore, and apparently refers to lead carbonates. The German Translation givespleyschweiss. The pyrites mentioned in this paragraph may mean galena, as pyrites was to Agricola a sort of genera.
[48](Excoquitur) ... "si verò pyrites, primò è fornace, ut Goselariae videre licet, in catinum defluit liquor quidam candidus, argento inimicus et nocivus; id enim comburit: quo circa recrementis, quae supernatant, detractis effunditur: vel induratus conto uncinato extrahitur: eundem liquorem parietes fornacis exudant." In the Glossary the following statement appears: "Liquor candidus primo è fornace defluens cum Goselariae excoquitur pyrites,—kobelt; quem parietes fornacis exudant,—conterfei." In this latter statement Agricola apparently recognised that there were two different substances,i.e., that the substance found in the furnace walls—conterfei—was not the same substance as that which first flowed from the furnace—kobelt. We are at no difficulty in recognizingconterfeias metallic zinc; it was long known by that term, and this accidental occurrence is repeatedly mentioned by other authors after Agricola. The substance which first flowed into the forehearth presents greater difficulties; it certainly was not zinc. InDe Natura Fossilium(p. 347), Agricola says that at Goslar the lead has a certain white slag floating upon it, the "colour derived from the pyrites (pyriten argenteum) from which it was produced."Pyriten argenteumwas either marcasite or mispickel, neither of which offers much suggestion; nor are we able to hazard an explanation of value.Historical Note on Zinc.The history of zinc metallurgy falls into two distinct[Pg 409]lines—first, that of the metal, and second, that of zinc ore, for the latter was known and used to make brass by cementation with copper and to yield oxides by sublimation for medicinal purposes, nearly 2,000 years before the metal became generally known and used in Europe.There is some reason to believe that metallic zinc was known to the Ancients, for bracelets made of it, found in the ruins of Cameros (prior to 500B.C.), may have been of that age (Raoul Jagnaux,Traité de Chimie Générale, 1887,II, 385); and further, a passage in Strabo (63B.C.-24A.D.) is of much interest. He states: (XIII, 1, 56) "There is found at Andeira a stone which when burnt becomes iron. It is then put into a furnace, together with some kind of earth, when it distils a mock silver (pseudargyrum), or with the addition of copper it becomes the compound calledorichalcum. There is found a mock silver near Tismolu also." (Hamilton's Trans., II, p. 381). About the Christian era the termsorichalcumoraurichalcumundoubtedly refer to brass, but whether these terms as used by earlier Greek writers do not refer to bronze only, is a matter of considerable doubt. Beyond these slight references we are without information until the 16th Century. If the metal was known to the Ancients it must have been locally, for by its greater adaptability to brass-making it would probably have supplanted the crude melting of copper with zinc minerals.It appears that the metal may have been known in the Far East prior to such knowledge in Europe; metallic zinc was imported in considerable quantities from the East as early as the 16th and 17th centuries under such terms astuteneque,tuttanego,calaëm, andspiauter—the latter, of course, being the progenitor of our term spelter. The localities of Eastern production have never been adequately investigated. W. Hommel (Engineering and Mining Journal, June 15, 1912) gives a very satisfactory review of the Eastern literature upon the subject, and considers that the origin of manufacture was in India, although the most of the 16th and 17th Century product came from China. The earliest certain description seems to be some recipes for manufacture quoted by Praphulla Chandra Ray (A History of Hindu Chemistry, London, 1902, p. 39) dating from the 11th to the 14th Centuries. There does not appear to be any satisfactory description of the Chinese method until that of Sir George Staunton (Journal Asiatique Paris, 1835, p. 141.) We may add that spelter was produced in India by crude distillation of calamine in clay pots in the early part of the 19th Century (Brooke, Jour. Asiatic Soc. of Bengal, vol.XIX, 1850, p. 212), and the remains of such smelting in Rajputana are supposed to be very ancient.The discovery of zinc in Europe seems to have been quite independent of the East, but precisely where and when is clouded with much uncertainty. Themarchasita aureaof Albertus Magnus has been called upon to serve as metallic zinc, but such belief requires a hypothesis based upon a great deal of assumption. Further, the statement is frequently made that zinc is mentioned in Basil Valentine's Triumphant Chariot of Antimony (the only one of the works attributed to this author which may date prior to the 17th Century), but we have been unable to find any such reference. The first certain mention of metallic zinc is generally accredited to Paracelsus (1493-1541), who states (Liber MineraliumII.): "Moreover there is another metal generally unknown calledzinken. It is of peculiar nature and origin; many other metals adulterate it. It can be melted, for it is generated from three fluid principles; it is not malleable. Its colour is different from other metals and does not resemble others in its growth. Its ultimate matter (ultima materia) is not to me yet fully known. It admits of no mixture and does not permit of thefabricationesof other metals. It stands alone entirely to itself." We do not believe that this book was published until after Agricola's works. Agricola introduced the following statements into his revised edition ofBermannus(p. 431), published in 1558: "It (a variety of pyrites) is almost the colour of galena, but of entirely different components. From it there is made gold and silver, and a great quantity is dug in Reichenstein, which is in Silesia, as was recently reported to me. Much more is found at Raurici, which they callzincum, which species differs from pyrites, for the latter contains more silver than gold, the former only gold or hardly any silver." InDe Natura Fossilium(p. 368): "For thiscadmiais put, in the same way as quicksilver, in a suitable vessel so that the heat of the fire will cause it to sublime, and from it is made a black or brown or grey body which the Alchemists callcadmia sublimata. This possesses corrosive properties to the highest degree. Cognate with thiscadmiaand pyrites is a compound which the Noricans and Rhetians callzincum." We leave it to readers to decide how near this comes to metallic zinc; in any event, he apparently did not[Pg 410]recognise hisconterfeifrom the furnaces as the same substance as thezincumfrom Silesia. The first correlation of these substances was apparently by Lohneys, in 1617, who says (Vom Bergwerk, p. 83-4): "When the people in the smelting works are smelting, there is made under the furnace and in the cracks in the walls among the badly plastered stones, a metal which is calledzincorcounterfeht, and when the wall is scraped it falls into a vessel placed to receive it. This metal greatly resembles tin, but it is harder and less malleable.... The Alchemists have a great desire for thiszincor bismuth." That this metal originated from blende or calamine was not recognised until long after, and Libavis (Alchymia, Frankfort, 1606), in describing specimens which came from the East, did not so identify it, this office being performed by Glauber, who says (De Prosperitate Germanias, Amsterdam, 1656): "Zink is a volatile mineral or half-ripe metal when it is extracted from its ore. It is more brilliant than tin and not so fusible or malleable ... it turns (copper) into brass, as doeslapis calaminaris, for indeed this stone is nothing but infusible zinc, and this zinc might be called a fusiblelapis calaminaris, inasmuch as both of them partake of the same nature.... It sublimates itself up into the cracks of the furnace, whereupon the smelters frequently break it out." The systematic distillation of zinc from calamine was not discovered in Europe until the 18th Century. Henkel is generally accredited with the first statement to that effect. In a contribution published as an Appendix to his other works, of which we have had access only to a French translation (Pyritologie, Paris, 1760, p. 494), he concludes that zinc is a half-metal of which the best ore is calamine, but believes it is always associated with lead, and mentions that an Englishman lately arrived from Bristol had seen it being obtained from calamine in his own country. He further mentions that it can be obtained by heating calamine and lead ore mixed with coal in a thick earthen vessel. The Bristol works were apparently those of John Champion, established about 1740. The art of distillation was probably learned in the East.Definite information as to the zinc minerals goes back to but a little before the Christian Era, unless we accept nebular references toaurichalcumby the poets, or what is possibly zinc ore in the "earth" mentioned by Aristotle (De Mirabilibus, 62): "Men say that the copper of the Mossynoeci is very brilliant and white, no tin being mixed with it; but there is a kind of earth there which is melted with it." This might quite well be an arsenical mineral. But whether we can accept the poets or Aristotle or the remark of Strabo given above, as sufficient evidence or not, there is no difficulty with the description ofcadmiaandpompholyxandspodosof Dioscorides (1st Century), parts of which we reproduce innote 26, p. 394. Hiscadmiais described as rising from the copper furnaces and clinging to the iron bars, but he continues: "Cadmiais also prepared by burning the stone called pyrites, which is found near Mt. Soloi in Cyprus.... Some say thatcadmiamay also be found in stone quarries, but they are deceived by stones having a resemblance tocadmia."Pompholyxandspodosare evidently furnace calamine. From reading the quotation given on p.394, there can be no doubt that these materials, natural or artificial, were used to make brass, for he states (V, 46): "Whitepompholyxis made every time that the artificer in the working and perfecting of the copper sprinkles powderedcadmiaupon it to make it more perfect, the soot arising from this ... ispompholyx." Pliny is confused between the mineralcadmiaand furnacecalamine, and none of his statements are very direct on the subject of brass making. His most pointed statement is (XXXIV, 2): "... Next to Livian (copper) this kind best absorbscadmia, and is almost as good asaurichalcumfor making sesterces and double asses." As stated above, there can be little doubt that theaurichalcumof the Christian Era was brass, and further, we do know of brass sesterces of this period. Other Roman writers of this and later periods refer to earth used with copper for making brass. Apart from these evidences, however, there is the evidence of analyses of coins and objects, the earliest of which appears to be a large brass of the Cassia family of 20B.C., analyzed by Phillips, who found 17.3% zinc (Records of Mining and Metallurgy, London, 1857, p. 13). Numerous analyses of coins and other objects dating during the following century corroborate the general use of brass. Professor Gowland (Presidential Address, Inst. of Metals, 1912) rightly considers the Romans were the first to make brass, and at about the above period, for there appears to be no certainty of any earlier production. The first adequate technical description of brass making is in about 1200A.D.being that of Theophilus, who describes (Hendrie's Trans., p. 307) calciningcalaminaand mixing it with finely divided copper in glowing crucibles. The process was repeated by adding more calamine and copper until the pots were full of molten metal. This method is repeatedly described with minor variations by Biringuccio, Agricola (De Nat. Fos.), and others, down to the 18th Century. For discussion of the zinc minerals see note on p.112.
[48](Excoquitur) ... "si verò pyrites, primò è fornace, ut Goselariae videre licet, in catinum defluit liquor quidam candidus, argento inimicus et nocivus; id enim comburit: quo circa recrementis, quae supernatant, detractis effunditur: vel induratus conto uncinato extrahitur: eundem liquorem parietes fornacis exudant." In the Glossary the following statement appears: "Liquor candidus primo è fornace defluens cum Goselariae excoquitur pyrites,—kobelt; quem parietes fornacis exudant,—conterfei." In this latter statement Agricola apparently recognised that there were two different substances,i.e., that the substance found in the furnace walls—conterfei—was not the same substance as that which first flowed from the furnace—kobelt. We are at no difficulty in recognizingconterfeias metallic zinc; it was long known by that term, and this accidental occurrence is repeatedly mentioned by other authors after Agricola. The substance which first flowed into the forehearth presents greater difficulties; it certainly was not zinc. InDe Natura Fossilium(p. 347), Agricola says that at Goslar the lead has a certain white slag floating upon it, the "colour derived from the pyrites (pyriten argenteum) from which it was produced."Pyriten argenteumwas either marcasite or mispickel, neither of which offers much suggestion; nor are we able to hazard an explanation of value.
Historical Note on Zinc.The history of zinc metallurgy falls into two distinct[Pg 409]lines—first, that of the metal, and second, that of zinc ore, for the latter was known and used to make brass by cementation with copper and to yield oxides by sublimation for medicinal purposes, nearly 2,000 years before the metal became generally known and used in Europe.
There is some reason to believe that metallic zinc was known to the Ancients, for bracelets made of it, found in the ruins of Cameros (prior to 500B.C.), may have been of that age (Raoul Jagnaux,Traité de Chimie Générale, 1887,II, 385); and further, a passage in Strabo (63B.C.-24A.D.) is of much interest. He states: (XIII, 1, 56) "There is found at Andeira a stone which when burnt becomes iron. It is then put into a furnace, together with some kind of earth, when it distils a mock silver (pseudargyrum), or with the addition of copper it becomes the compound calledorichalcum. There is found a mock silver near Tismolu also." (Hamilton's Trans., II, p. 381). About the Christian era the termsorichalcumoraurichalcumundoubtedly refer to brass, but whether these terms as used by earlier Greek writers do not refer to bronze only, is a matter of considerable doubt. Beyond these slight references we are without information until the 16th Century. If the metal was known to the Ancients it must have been locally, for by its greater adaptability to brass-making it would probably have supplanted the crude melting of copper with zinc minerals.
It appears that the metal may have been known in the Far East prior to such knowledge in Europe; metallic zinc was imported in considerable quantities from the East as early as the 16th and 17th centuries under such terms astuteneque,tuttanego,calaëm, andspiauter—the latter, of course, being the progenitor of our term spelter. The localities of Eastern production have never been adequately investigated. W. Hommel (Engineering and Mining Journal, June 15, 1912) gives a very satisfactory review of the Eastern literature upon the subject, and considers that the origin of manufacture was in India, although the most of the 16th and 17th Century product came from China. The earliest certain description seems to be some recipes for manufacture quoted by Praphulla Chandra Ray (A History of Hindu Chemistry, London, 1902, p. 39) dating from the 11th to the 14th Centuries. There does not appear to be any satisfactory description of the Chinese method until that of Sir George Staunton (Journal Asiatique Paris, 1835, p. 141.) We may add that spelter was produced in India by crude distillation of calamine in clay pots in the early part of the 19th Century (Brooke, Jour. Asiatic Soc. of Bengal, vol.XIX, 1850, p. 212), and the remains of such smelting in Rajputana are supposed to be very ancient.
The discovery of zinc in Europe seems to have been quite independent of the East, but precisely where and when is clouded with much uncertainty. Themarchasita aureaof Albertus Magnus has been called upon to serve as metallic zinc, but such belief requires a hypothesis based upon a great deal of assumption. Further, the statement is frequently made that zinc is mentioned in Basil Valentine's Triumphant Chariot of Antimony (the only one of the works attributed to this author which may date prior to the 17th Century), but we have been unable to find any such reference. The first certain mention of metallic zinc is generally accredited to Paracelsus (1493-1541), who states (Liber MineraliumII.): "Moreover there is another metal generally unknown calledzinken. It is of peculiar nature and origin; many other metals adulterate it. It can be melted, for it is generated from three fluid principles; it is not malleable. Its colour is different from other metals and does not resemble others in its growth. Its ultimate matter (ultima materia) is not to me yet fully known. It admits of no mixture and does not permit of thefabricationesof other metals. It stands alone entirely to itself." We do not believe that this book was published until after Agricola's works. Agricola introduced the following statements into his revised edition ofBermannus(p. 431), published in 1558: "It (a variety of pyrites) is almost the colour of galena, but of entirely different components. From it there is made gold and silver, and a great quantity is dug in Reichenstein, which is in Silesia, as was recently reported to me. Much more is found at Raurici, which they callzincum, which species differs from pyrites, for the latter contains more silver than gold, the former only gold or hardly any silver." InDe Natura Fossilium(p. 368): "For thiscadmiais put, in the same way as quicksilver, in a suitable vessel so that the heat of the fire will cause it to sublime, and from it is made a black or brown or grey body which the Alchemists callcadmia sublimata. This possesses corrosive properties to the highest degree. Cognate with thiscadmiaand pyrites is a compound which the Noricans and Rhetians callzincum." We leave it to readers to decide how near this comes to metallic zinc; in any event, he apparently did not[Pg 410]recognise hisconterfeifrom the furnaces as the same substance as thezincumfrom Silesia. The first correlation of these substances was apparently by Lohneys, in 1617, who says (Vom Bergwerk, p. 83-4): "When the people in the smelting works are smelting, there is made under the furnace and in the cracks in the walls among the badly plastered stones, a metal which is calledzincorcounterfeht, and when the wall is scraped it falls into a vessel placed to receive it. This metal greatly resembles tin, but it is harder and less malleable.... The Alchemists have a great desire for thiszincor bismuth." That this metal originated from blende or calamine was not recognised until long after, and Libavis (Alchymia, Frankfort, 1606), in describing specimens which came from the East, did not so identify it, this office being performed by Glauber, who says (De Prosperitate Germanias, Amsterdam, 1656): "Zink is a volatile mineral or half-ripe metal when it is extracted from its ore. It is more brilliant than tin and not so fusible or malleable ... it turns (copper) into brass, as doeslapis calaminaris, for indeed this stone is nothing but infusible zinc, and this zinc might be called a fusiblelapis calaminaris, inasmuch as both of them partake of the same nature.... It sublimates itself up into the cracks of the furnace, whereupon the smelters frequently break it out." The systematic distillation of zinc from calamine was not discovered in Europe until the 18th Century. Henkel is generally accredited with the first statement to that effect. In a contribution published as an Appendix to his other works, of which we have had access only to a French translation (Pyritologie, Paris, 1760, p. 494), he concludes that zinc is a half-metal of which the best ore is calamine, but believes it is always associated with lead, and mentions that an Englishman lately arrived from Bristol had seen it being obtained from calamine in his own country. He further mentions that it can be obtained by heating calamine and lead ore mixed with coal in a thick earthen vessel. The Bristol works were apparently those of John Champion, established about 1740. The art of distillation was probably learned in the East.
Definite information as to the zinc minerals goes back to but a little before the Christian Era, unless we accept nebular references toaurichalcumby the poets, or what is possibly zinc ore in the "earth" mentioned by Aristotle (De Mirabilibus, 62): "Men say that the copper of the Mossynoeci is very brilliant and white, no tin being mixed with it; but there is a kind of earth there which is melted with it." This might quite well be an arsenical mineral. But whether we can accept the poets or Aristotle or the remark of Strabo given above, as sufficient evidence or not, there is no difficulty with the description ofcadmiaandpompholyxandspodosof Dioscorides (1st Century), parts of which we reproduce innote 26, p. 394. Hiscadmiais described as rising from the copper furnaces and clinging to the iron bars, but he continues: "Cadmiais also prepared by burning the stone called pyrites, which is found near Mt. Soloi in Cyprus.... Some say thatcadmiamay also be found in stone quarries, but they are deceived by stones having a resemblance tocadmia."Pompholyxandspodosare evidently furnace calamine. From reading the quotation given on p.394, there can be no doubt that these materials, natural or artificial, were used to make brass, for he states (V, 46): "Whitepompholyxis made every time that the artificer in the working and perfecting of the copper sprinkles powderedcadmiaupon it to make it more perfect, the soot arising from this ... ispompholyx." Pliny is confused between the mineralcadmiaand furnacecalamine, and none of his statements are very direct on the subject of brass making. His most pointed statement is (XXXIV, 2): "... Next to Livian (copper) this kind best absorbscadmia, and is almost as good asaurichalcumfor making sesterces and double asses." As stated above, there can be little doubt that theaurichalcumof the Christian Era was brass, and further, we do know of brass sesterces of this period. Other Roman writers of this and later periods refer to earth used with copper for making brass. Apart from these evidences, however, there is the evidence of analyses of coins and objects, the earliest of which appears to be a large brass of the Cassia family of 20B.C., analyzed by Phillips, who found 17.3% zinc (Records of Mining and Metallurgy, London, 1857, p. 13). Numerous analyses of coins and other objects dating during the following century corroborate the general use of brass. Professor Gowland (Presidential Address, Inst. of Metals, 1912) rightly considers the Romans were the first to make brass, and at about the above period, for there appears to be no certainty of any earlier production. The first adequate technical description of brass making is in about 1200A.D.being that of Theophilus, who describes (Hendrie's Trans., p. 307) calciningcalaminaand mixing it with finely divided copper in glowing crucibles. The process was repeated by adding more calamine and copper until the pots were full of molten metal. This method is repeatedly described with minor variations by Biringuccio, Agricola (De Nat. Fos.), and others, down to the 18th Century. For discussion of the zinc minerals see note on p.112.