| 2 | centumpondia | = | 141.3 | lbs. |
| 21/2 | " | = | 176.6 | " |
| 3 | " | = | 211.9 | " |
| 31/2 | " | = | 248.2 | " |
| 6 | " | = | 423.9 | " |
[Pg 535][25] This description of refining copper in an open hearth by oxidation with a blast and "poling"—the gaarmachen of the Germans—is so accurate, and the process is so little changed in some parts of Saxony, that it might have been written in the 20th century instead of the 16th. The best account of the old practice in Saxony after Agricola is to be found in Schlüter's Hütte Werken (Braunschweig, 1738, Chap. CXVIII.). The process has largely been displaced by electrolytic methods, but is still in use in most refineries as a step in electrolytic work. It may be unnecessary to repeat that the process is one of subjecting the molten mass of impure metal to a strong and continuous blast, and as a result, not only are the impurities to a considerable extent directly oxidized and taken off as a slag, but also a considerable amount of copper is turned into cuprous oxide. This cuprous oxide mostly melts and diffuses through the metallic copper, and readily parting with its oxygen to the impurities further facilitates their complete oxidation. The blast is continued until the impurities are practically eliminated, and at this stage the molten metal contains a great deal of dissolved cuprous oxide, which must be reduced. This is done by introducing a billet of green wood ("poling"), the dry distillation of which generates large quantities of gases, which reduce the oxide. The state of the metal is even to-day in some localities tested by dipping into it the point of an iron rod; if it be at the proper state the adhering copper has a net-like appearance, should be easily loosened from the rod by dipping in water, is of a reddish-copper colour and should be quite pliable; if the metal is not yet refined, the sample is thick, smooth, and detachable with difficulty; if over-refined, it is thick and brittle. By allowing water to run on to the surface of the molten metal, thin cakes are successively formed and taken off. These cakes were the article known to commerce over several centuries as "rosetta copper." The first few cakes are discarded as containing impurities or slag, and if the metal be of good quality the cakes are thin and of a red colour. Their colour and thinness, therefore, become a criterion of purity. The cover of charcoal or charcoal dust maintained upon the surface of the metal tended to retard oxidation, but prevented volatilization and helped to secure the impurities as a slag instead. Karsten (Archiv., 1st series, p. 46) gives several analyses of the [Pg 536]slag from refining "dried" copper, showing it to contain from 51.7 to 67.4% lead oxide, 6.2 to 19.2% cuprous oxide, and 21.4 to 23.9 silica (from the furnace bottoms), with minor quantities of iron, antimony, etc. The "bubbles" referred to by Agricola were apparently the shower of copper globules which takes place upon the evolution of sulphur dioxide, due to the reaction of the cuprous oxide upon any remaining sulphide of copper when the mass begins to cool.
Historical Note.—It is impossible to say how the Ancients refined copper, beyond the fact that they often re-smelted it. Such notes as we can find are set out in the note on copper smelting ([note 42, p. 402]). The first authentic reference to poling is in Theophilus (1150 to 1200 A.D., Hendrie's translation, p. 313), which shows a very good understanding of this method of refining copper:—"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 the 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 the 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. If, however, it should remain sound, you will cool it in water, and you cook other (copper) in the same manner." Biringuccio (III, 8) in 1540 describes the process briefly, but omits the poling, an essential in the production of malleable copper.
[Pg 538][26] Pompholyx and spodos were impure zinc oxides (see [note 26, p. 394]).
The copper flowers were no doubt cupric oxide. They were used by the Ancients for medicinal purposes. Dioscorides (V, 48) says: "Of flowers of copper, which some call the scrapings of old nails, the best is friable; it is gold-coloured when rubbed, is like millet in shape and size, is moderately bright, and somewhat astringent. It should not be mixed with copper filings, with which it is often adulterated. But this deception is easily detected, for when bitten in the teeth the filings are malleable. It (the flowers) is made when the copper fused in a furnace has run into the receptacle through the spout pertaining to it, for then the workmen engaged in this trade cleanse it from dirt and pour clear water over it in order to cool it; from this sudden condensation the copper spits and throws out the aforesaid flowers." Pliny (XXXIV, 24) says: "The flower, too, of copper (æris flos) is used in medicine. This is made by fusing copper, and then removing it to another furnace, where the repeated blast makes the metal separate into small scales like millet, known as flowers. These scales also fall off when the cakes of metal are cooled in water; they become red, too, like the scales of copper known as 'lepis,' by use of which the flowers of copper are adulterated, it being also sold for it. These are made when hammering the nails that are [Pg 539]made from the cakes of copper. All these methods are carried on in the works of Cyprus; the difference between these substances is that the squamae (copper scales) are detached from hammering the cakes, while the flower falls off spontaneously." Agricola (De Nat. Fos., p. 352) notes that "flowers of copper (flos æris) have the same properties as 'roasted copper.'"
[27] It seems scarcely necessary to discuss in detail the complicated "flow scheme" of the various minor bye-products. They are all re-introduced into the liquation circuit, and thereby are created other bye-products of the same kind ad infinitum. Further notes are given on:—
| Liquation thorns | Note | [28]. |
| Slags | " | [30]. |
| Ash-coloured copper | " | [29]. |
| Concentrates | " | [33]. |
| Cadmia | " | [32]. |
There are no data given, either by Agricola or the later authors, which allow satisfactory calculation of the relative quantities of these products. A rough estimate from the data given in previous notes would indicate that in one liquation only about 70% of the original copper came out as refined copper, and that about 70% of the original lead would go to the cupellation furnace, i.e., about 30% of the original metal sent to the blast furnace would go into the "thorns," "slags," and "ash-coloured copper." The ultimate losses were very great, as given before (p. [491]), they probably amounted to 25% of the silver, 9% copper, and 16% of the lead.
[28] There were the following classes of thorns:—
| 1st. | From liquation. |
| 2nd. | From drying. |
| 3rd. | From cupellation. |