Copper electrodeposition

Introduction

In copper electrorefining a pure copper cathode is produced from an impure consumable anode which at the end of
the process is covered with a slime containing precious metals. Anodes containing at least 99.5 percent copper are cast
from fire refined blister copper which is produced from the oxidation of matte, prepared either by reverberatory
technology or oxygen/flash smelting, in a converter where most of the oxygen and other impurities are removed.
Copper is dissolved at the anode, enters the electrolyte and then selectively deposits onto the cathode under the force of
an applied direct current. Current density is limited to about 30 mA/cm2 to avoid the anode passivation effect i.e. a
sharp increase in anode potential while the current applied is kept unchanged. On the cathode side the problem of
cathode nodulation may occur.

Objectives

The purpose of this research is to investigate the effect of the presence of impurities in the electrolyte and in the anode
on the passivation of unrefined copper anodes containing known amounts of oxygen in an environment simulating the
important constituents of an industrial operation. The research is conducted in two scales:

1. A three-electrode arrangement to determine the effect of nickel on the electrochemical behaviour using Tafel
Extrapolation (TE), Cyclic Polarization (CP), Cyclic Voltammetry (CV) and Linear Polarization (LP) while the
characterization and modeling of the oxide layer is achieved using Electrochemical Impedance Spectroscopy (EIS).

2. Chronopotentiometry using a piece of unrefined copper anode in a two-electrode system to study the passivation
process.The significance of this kind of work is that it helps understand the electrodeposition process so that anode
passivation may be avoided, the current density may be increased and the copper electrorefining process may become
more effective.
PROCESS

Aluminum Production by Electrowinning

Aluminum compounds, primarily the oxide in forms of various purity and hydration, are fairly widely
distributed in nature. The feldspars, the most common rock-forming silicates, make up nearly 54% of the
earth's crust; in these, aluminum has replaced up to half the silicon atoms in SiO2. The major ore of
aluminum is bauxite, a hydrated aluminum (III) oxide (Al2O3.xH2O).

In the industrial Bayer process, bauxite is concentrated to produce aluminum hydroxide. When this
concentrate is calcined at temperatures in excess of 1000oC, anhydrous aluminum oxide, Al2O3, is formed.
Anhydrous aluminum oxide melts at over 2000°C. This is too high to permit its use as a molten medium for
electrolytic formation of free aluminum. The electrolytic process commercially used to produce aluminum
is known as the Hall process, named after its inventor, Charles M. Hall. The purified Al2O3 is dissolved in
molten cryolite, Na3AlF6, which has a melting point of 1012oC and is an effective conductor of electric
current. In the following schematic diagram of the electrolysis cell graphite rods are employed as anodes
and are consumed in the electrolysis process. The cell electrolytic reaction is:

2Al2O3 + 3C --> 4Al(l) + 3CO2(g)

Process

Most metals occur in nature in oxidized form in their ores and thus must be reduced to their metallic
forms. The ore is dissolved following some preprocessing in an aqueous electrolyte or in a molten salt and
the resulting solution is electrolyzed. The metal is deposited on the cathode (either in solid or in liquid
form), while the anodic reaction is usually oxygen evolution. Several metals are naturally present as metal
sulfides; these include copper, lead, molybdenum, cadmium, nickel, silver, cobalt and zinc. In addition, gold
and platinum group metals are associated with sulfidic base metal ores. Most metal sulfides or their salts,
are electrically conductive and this allows electrochemical redox reactions to efficiently occur in the molten
state or in aqueous solutions.
Some metals, including arsenic and nickel do not electrolyze out but remain in the electrolyte solution,
these are then reduced by chemical reactions to refine the metal. Also after the process for the original
target metal is complete, other metals which are reduced but not deposited at the cathode sink to the
bottom of the electrolytic cell, where they form a substance referred to as anode sludge or anode slime. The
metals in this sludge can be removed by standard pryrorefining methods.
Because metal deposition rates are related to available surface area, maintaining properly working
cathodes is important. Two cathode types exist, flat-plate and reticulated cathodes, each with its own
advantages. Flat-plate cathodes can be cleaned and reused, and plated metals recovered. Reticulated
cathodes have a much higher deposition rate, compared to flat-plate cathodes. However, they are not
reusable and must be sent off for recycling.

Electrowinning

Electrowinning, also called electrorefining or electroextraction, is the electrodeposition of metals from their
ores that have been put in solution or liquefied. Electrowinning is electroplating on a large scale and is an
important technique that allows purification of non-ferrous metals in an economical and straightforward
step.