Modern Copper Smelting: being lectures delivered at Birmingham University, greatly extended and adapted and with and introduction on the history, uses and properties of copper. — John Shaqi
Modern Copper Smelting: being lectures delivered at Birmingham University, greatly extended and adapted and with and introduction on the history, uses and properties of copper.Levy, Donald M.
Science
Modern Copper Smelting: being lectures delivered at Birmingham University, greatly extended and adapted and with and introduction on the history, uses and properties of copper.
Levy, Donald M.
Copper -- Metallurgy
_Arsenic in Copper._—When arsenic and copper are melted together
chemical combination occurs, and a series of arsenides is produced;
the system, which has been investigated by Friedrich (from whose work
the following diagram has been constructed), Hiorns, Bengough & Hill,
and others, being one of considerable complexity. With proportions of
arsenic such as are usually present in commercial coppers, the compound
produced is probably Cu_{3}As (28·3 per cent. of arsenic), which
passes into solution in the excess of metal, and on solidification the
copper retains this arsenide in solid solution. As in the case of all
such solid solutions, the solidification takes place over a range of
temperature represented between the liquidus and solidus curves; the
purer metal crystallising out first, followed gradually by crystals
of copper which become progressively richer and richer in arsenic
(still in solid solution). In the case in question, diffusion of the
arsenic throughout the crystalline mass proceeds but slowly, and as
a result, the metal, as usually obtained in the cast state, shows
fringes of such arsenic-rich copper. By annealing, diffusion is greatly
assisted, and the material gradually becomes homogeneous, as is seen
on microscopic examination. There appears further to be some decrease
of this solubility with fall of temperature when the arsenic is high,
leading sometimes to a separation of the arsenide itself at the crystal
boundaries.
_Antimony_ appears to form an analogous compound, Cu_{3}Sb, also
capable of passing into solid solution in the copper, but to a
rather smaller extent than the corresponding arsenide. The fringes
are therefore more pronounced, and the decrease of the solubility on
further cooling is also more marked.
_Bismuth._—The influence of even minute quantities of bismuth on
copper is notorious. Bismuth appears to be soluble in liquid copper,
but not in the solid metal. In consequence, when copper containing
bismuth solidifies, the copper crystals separate first, whilst the
liquid bismuth still remains between them, until the metal reaches a
temperature of about 268° C.—the melting point of bismuth—when it too
solidifies _in situ_. The presence of such envelopes of very brittle,
fusible, and limpid bismuth material explains much of the harmful
effect of this impurity. These envelopes are found to consist almost
entirely of practically pure bismuth. Oxygen converts the bismuth into
a more compactly crystalline oxide, much less fusible and harmful.
Arsenical copper tends to the scattering of the bismuth globules
among the fringes which are formed during the gradual process of
solidification over the range of temperature already indicated, and
thus renders this impurity to some extent less dangerous.
_Lead_ behaves in apparently much the same way as bismuth, and the
effects produced upon it by the presence of oxygen and arsenic are
probably similar.
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