Fig. 5.—Relations of Copper and Oxygen.
It will be observed that when molten oxygenated metal containing less than about 0·38 per cent. of oxygen solidifies, copper crystallises out first, whilst later, in between the copper crystals, there solidifies a eutectic of copper and cuprous oxide. This eutectic contains about 3·45 per cent. of cuprous oxide, equivalent to 0·38 per cent. of oxygen; it melts at a temperature about 18° C. below that of the pure metal. The presence of this material, which is of a blue colour when viewed under the microscope, constituting slightly more fusible, tough, non-conducting areas between the copper crystals, accounts for many of the well-known effects of oxygen in metallic copper.
When oxygen is present in quantities above the eutectic proportion, the first constituent to solidify from the molten over-oxygenated copper is brittle copper oxide, and the presence of such brittle material disseminated through the metal explains why “dry copper” cannot be worked.
The effects of comparatively small quantities of oxygen are greatly increased on account of the fact that one part of oxygen, when present as cuprous oxide, yields a constituent in almost nine times as great a proportion by weight alone, since Cu2O : O :: 142 : 16 or 9 : 1; whilst oxygen existing as oxide-eutectic is represented in the ratio of nearly 30 : 1. The presence of excess of copper oxide in the metal is particularly dangerous when copper is to undergo annealing in a reducing atmosphere, since the reducing gases acting upon the oxides at the crystal boundaries destroy them, thus tending to produce that rottenness in the material which is so often encountered under such circumstances.
The great value and importance of oxygen in copper lies in its property of bringing the metal up to pitch as indicated above.
The effect of carbon on oxygenated copper was the subject of much enquiry in early years. It was thought at one time that the influence of carbon per se in the copper was responsible for the beneficial effects resulting from the melting of brittle “dry” copper with carbon, but the work of Percy, since confirmed, showed that its sole action is in the reduction of the injurious excess of oxide.
In addition to the specific influences of oxygen as just recorded, and to its important physical effects with regard to the solubility of gases, etc., oxygen in copper performs other valuable functions, by forming with reduced impurities which are exceedingly dangerous, oxygenated compounds more infusible and more insoluble; and this has the effect of segregating or distributing such injurious impurities into forms and positions much less harmful.