A Review of The Effects of The Grinding Environment On The Flotation of Copper Sulphides

International Journal of Mineral Processing 100 (2011) 113
Contents lists available at ScienceDirect
International Journal of Mineral Processing

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i j m i n p r o
A review of the effects of the grinding environment on the otation of

copper sulphides
W.J. Bruckard , G.J. Sparrow, J.T. Woodcock 1
CSIRO Minerals, Box 312, Clayton South, Vic, 3169, Australia
a r t i c l e
i n f o
Article history:
Received 4 August 2010
Received in revised form 20 February 2011
Accepted 3 April 2011
Available online 12 April 2011
Keywords:
Grinding environment
Copper sulphides
Flotation
a b s t r a c t
The reported effects of the grinding method and grinding medium upon the otation performance of sulphide
minerals has shown that the pulp chemical environment, the ore composition, the properties and type of the
grinding media, the size reduction method employed, pre-conditioning stages prior to otation, and reagent
interactions during grinding (and conditioning) can inuence the subsequent otation process. These factors
are reviewed and discussed in relation to the otation of copper sulphide minerals.
Galvanic interactions between sulphide minerals and steel grinding media increase iron levels, lower the
dissolved oxygen concentration in the slurry, and result in the formation of iron hydroxides. These changes
can be deleterious to copper otation. It has been shown that chrome alloy balls can have benecial effects on
otation performance in some systems by limiting the formation of hydroxides in the pulp. As well, galvanic
interactions between the sulphide minerals can occur, depending on the mineralogy of the ore, and they can
inuence the separation efciency in otation.
While reagent additions, such as collector, lime, or cyanide, during milling can alter the pulp chemistry during
grinding, there is little clear evidence in the literature that their addition during grinding has any strong
inuence on the subsequent oatability of copper sulphide particles.
Improvements in copper recovery by otation following fully autogenous milling in comparison with
conventional milling using steel rod and ball mills at the same grind size have been noted in several laboratory
and plant studies.
Crown Copyright 2011 Published by Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
4.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . .
Chemical interaction of grinding media and sulphide minerals .
2.1.
Effect of pulp potential . . . . . . . . . . . . . . . .
2.2.
Effect of galvanic interactions between sulphide minerals
2.3.
Effect of dissolved oxygen . . . . . . . . . . . . . . .
2.4.
Effect of oxyhydroxide species . . . . . . . . . . . . .
2.5.
Effect on froth characteristics . . . . . . . . . . . . .
Physical effects of media type . . . . . . . . . . . . . . . .
3.1.
Sources and nature of wear detritus . . . . . . . . . .
3.2.
Inuence of media composition . . . . . . . . . . . .
3.3.
Relevant laboratory ndings . . . . . . . . . . . . . .
3.4.
Corrosion control . . . . . . . . . . . . . . . . . . .
3.5.
Flotation of wear detritus . . . . . . . . . . . . . . .
3.6.
Methods for removing wear detritus . . . . . . . . . .
Effect of added reagents . . . . . . . . . . . . . . . . . . .
4.1.
Collector . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Lime . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Sodium sulphide . . . . . . . . . . . . . . . . . . .
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Corresponding author. Tel.: + 61 3 95458500; fax: + 61 3 9562 8919.

E-mail address: Warren.Bruckard@csiro.au (W.J. Bruckard).
1
Deceased.
0301-7516/$ see front matter. Crown Copyright 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2011.04.001
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W.J. Bruckard et al. / International Journal of Mineral Processing 100 (2011) 113
4.4.
Cyanide . . . . . . . . . . . . . . . .
4.5.
Wood extracts . . . . . . . . . . . .
5.
Effect of the gaseous atmosphere during milling
6.
Effect of grinding method . . . . . . . . . .
6.1.
Autogenous grinding . . . . . . . . .
6.2.
Semi-autogenous grinding . . . . . . .
6.3.
Re-grinding . . . . . . . . . . . . . .
6.4.
Dry grinding . . . . . . . . . . . . .
7.
Summary . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . .
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1. Introduction
Wet milling in ball mills followed by otation is the general
practice employed in the beneciation of copper sulphide ores in
which the major minerals of commercial signicance typically are
chalcopyrite (CuFeS2), bornite (Cu5FeS4), covellite (CuS) and chalcocite (Cu2S). The otation response of ground minerals can be
inuenced by the grinding conditions used, including interaction of
the minerals with the grinding media, the generation or presence of
oxyhydroxide species in the pulp, the gaseous atmosphere used in the
milling, the effects of any added reagents or chemicals, and the type of
grinding method employed. The complex interactions that occur
between sulphide minerals in the ore assemblage, and between the
sulphide minerals and the grinding media, are poorly understood. In
general these interactions are thought to occur through the aqueous
phase by dissolution and re-deposition of metal ions or their
hydrolysis products, direct electrochemical interaction (galvanic
coupling), and in situ surface reactions, for example oxidation.
The specic topic of galvanic coupling, or interaction between
sulphide minerals and grinding media, has attracted much attention
in recent years. Despite numerous studies on the effect of galvanic
interactions during grinding, there is little documented evidence of
the effects of the milling environment on the subsequent stage of
otation, particularly for plant operations. Much laboratory work has
been conducted on isolated minerals, in solutions only, in small-scale
otation cells at low pulp density, or in batch laboratory grinding mills
using media and conditions unseen and impracticable in modern
sulphide concentrators. These limitations were seen by Graham and
Heathcote (1982) who reduced the efciency of their laboratory
otation cell and added metallic iron to lower the levels of dissolved
oxygen in the pulp to better simulate plant conditions.
Evaluating changes at plant scale often is costly, due to tests
usually being run over a prolonged period of time to ensure the effects
of any changes in the circuit are clearly seenconducting on-off plant
trials will rarely produce statistically reliable information. The
development of the Magotteaux Mill (Greet et al., 2004) has allowed
better simulation of laboratory and plant conditions by enabling the
pH and pulp potential to be controlled during grinding and postgrinding conditioning (Pietrobon et al., 2004).
The key factors such as media-mineral interactions, milling
methods, media type, (copper) mineral properties, redox potential
and hydroxide effects, and the inuence of the gaseous environment
are discussed in detail in this review. It should be noted that there is
much overlap between many of these factors with respect to their
effects on otation of copper sulphides.
2. Chemical interaction of grinding media and sulphide minerals
Sulphide minerals are generally more noble electrochemically
than steel grinding media (balls, rods, and liners) and consequently
develop higher rest potentials under most conditions (Rao et al., 1976;
Yelloji Rao and Natarajan, 1989a). During the intimate contact in
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milling between media and sulphide minerals, galvanic interactions

are likely to occur. Steel grinding media, being more active (less
noble) than the sulphide minerals, act as anodes and undergo
oxidation, whilst the sulphides act as cathodes and are sites for
reduction. The net results of such interactions can be not only an
increase in the corrosive wear of the grinding media but also a change
of the surface properties and pulp chemistry of the ground minerals,
which in turn affect subsequent otation. The pulp potential normally
is affected, and the practical control of the redox conditions in the
otation slurry becomes increasingly difcult, depending on the
extent of the galvanic interactions. However, the pulp potential
during grinding can be as important as that used in conditioning
before otation in determining the efciency of otation since it
controls the oxidation of the sulphide minerals and so the potential
release of activating species (Grano and Huang, 2006). Another major
effect of the interaction between sulphide minerals and mild steel
grinding media is that the amount of dissolved oxygen present in the
pulp is reduced. The effects of the grinding media-sulphide mineral
interactions on otation are summarised below, with specic
reference to the otation of copper sulphides.
2.1. Effect of pulp potential

When metallic iron present in steel grinding media is oxidised, the
anodic reactions shown in Eqs.(1) and (2) may occur:
0
Fe 2OH
FeOH2 2e
FeOH2 OH
FeOH3 e
Oxidation of iron will be strongly favoured, under most conditions,

reducing the pulp oxygen content as a result of the cathodic reduction
shown in Eq. (3).
O2 2H2 O 4e
4OH
The measured potential of an indicator electrode such as platinum

in combination with a suitable non-polarisable reference electrode
exhibits a mixed potential (Rand and Woods, 1984) between that
developed by the anodic processes in Eqs.(1) and (2) and that
developed by the cathodic reaction, Eq. (3). The exact potential
reects the relative rates (exchange current densities) of each halfcell reaction. The measured pulp potential, referenced to the standard
hydrogen electrode (SHE), depends on this mixed potential, and the
potential resulting from any other redox reactions in the pulp, such as
reactions of added collectors.
In most sulphide systems, the electrochemical reactions described
above result in removal of dissolved oxygen from the system, shifting
the mixed potential towards more negative reducing or cathodic
values, and lowering the pulp potential. Since most sulphide milling is
conducted in iron mills, strongly reducing grinding pulp potentials are
seen whenever these measurements have been made in operating
plants (Woodcock and Jones, 1970a, b; Graham and Heathcote, 1982;

Grano et al., 1994).
In a closed mill, oxidation of the media by reaction with oxygen
continues until the available oxygen is consumed. The pH of the pulp
can also often be simultaneously reduced, presumably by consumption of hydroxyl ions produced to form precipitates with ferric and
ferrous ions. This is discussed further in a later section.
In an open mill system, consumption of oxygen continues during
the milling. Laboratory studies with sulphide ores (Fernandez et al.,
1991) have conrmed that prolonged milling with steel media
enhances the reducing conditions and so the longer the grind, the
lower the pulp potential drops.
The reducing inuence on the otation pulp caused by the mediasulphide mineral interaction has been reported in many studies
(Forssberg et al., 1993; Leppinen et al., 1998; Martin et al., 1991; Yuan
et al., 1996a, b). A concern with reducing the pulp potential is that it
might drop to levels below that for which thiol-type collectors, such as
xanthate, can adsorb onto the sulphide mineral surfaces and so
otation may be inhibited. Rao et al. (1976) suggested that the extent
of the drop in the pulp potential caused by mild steel grinding was
greater the larger the iron surface area, and when the grinding pulp
pH moved from neutral to highly alkaline values. The former effect
seems logical but the reasons for the latter suggestion are not clear.
The extent to which the pulp is made reducing during grinding in
iron mills is naturally related to the type of media used. Leppinen et al.
(1998) found, that depending on ore type, the potential difference
(after milling) for complex sulphide ores between grinding in normal
steel and stainless steel mills was about 100250 mV, while Kelebek
et al. (1995) have reported differences of 500600 mV for pyrrhotiterich coppernickel sulphide ores in the initial stages of grinding.
Leppinen et al. (1998) also noted that a lengthy aeration step after
milling and prior to otation could reduce this potential difference to
20 to 30 mV. The effects of different media types on copper otation
are discussed in more detail later.
The presence of oxygen accelerates the rusting of the iron since it
serves as an essential reactant for the cathodic reaction (Eq. (3)), that
is, iron dissolution from grinding media takes place to a lesser extent
in the absence of oxygen. This was conrmed (for chalcopyrite) by
Yelloji Rao and Natarajan (1988a) in single mineral otation tests.
They also found that there was a direct relationship between the
amount of iron dissolved and the oatability of the chalcopyrite, with
increasing iron dissolution resulting in poorer otation. Their surface
analysis studies conrmed the presence of oxyhydroxide species of
iron on the chalcopyrite surfaces and they concluded that the
adsorption of these species was responsible for the decreased
chalcopyrite oatability. The possibility of the iron species deriving
from the chalcopyrite was not considered and no size-recovery data
were reported.
Air is the most common gas used in otation and so the minerals in
the pulp are normally subjected to uninhibited aeration. Most
sulphide otation plants operate at air set potentials that are
usually in the range +100 to + 300 mV SHE. Operating at less positive
(or negative) potentials requires the addition of reducing agents,
which can be costly and can also lead to higher reagent consumptions
given the reductants are consumed by the oxygen in the otation gas.
An example is the application of NaSH in coppermolybdenum
otation circuits where reagent effectiveness and consumption can be
improved by using nitrogen as a otation gas (Poorkani and Banisi,
2005).
The oatability of copper sulphide minerals like chalcopyrite is
known to depend strongly on the pulp potential. Since the pulp
potential is reduced during grinding in an iron environment, it must
then be increased to a potential suitable for signicant otation of the
copper minerals to be achieved. In practice, this is usually achieved
automatically in the rst few cells of a otation bank or in a separate
aeration stage between grinding and otation (Graham and
Heathcote, 1982). Hydrocylones, which are often in place between

grinding and otation unit operations, can also function as aerators
and in many cases, depending on the electrochemical reactivity of the
ore, pre-aeration may not be required. By way of example, Heyes and
Trahar (1977) found that the surface of chalcopyrite is rendered
hydrophilic in a reducing environment, and then showed (in single
and mixed mineral laboratory otation tests) that the reducing
atmosphere caused by grinding in an iron mill was sufcient to
suppress the normal oatability of chalcopyrite. Importantly, they
showed that the oatability was re-established by raising the potential, either by aeration or the addition of oxidants. This restoration,
however, was not complete for the coarser size fractions.
The effects of pulp potential on sulphide mineral otation are
also related to the type of collector used (xanthate, thionocarbamate,
dithiophosphate, etc). Depending on the mechanism by which a
particular collector adsorbs on the sulphide mineral surface, such as
electrochemical or electrochemicalchemical means, the extent of the
inuence of pulp potential on mineral oatability will vary.
In terms of the electrochemical theory of otation (Fuerstenau
et al., 2007), sulphide otation with thiol-type collectors results from
anodic (oxidation) reaction between mineral and collector, that is, the
formation of dixanthogen (X2) or metal xanthate (MX2), with a rebalancing of charge through the cathodic reduction of dissolved
oxygen (Eqs.(4)(6)).
2X
X2 2e
MS 2X
MX2 S 2e
0:5O2 H2 O 2e
2OH
5
6
The pulp potential will control the extent of these reactions, and so
inuence the efciency of otation. These reactions will also modify
the pulp potential, but only to a limited extent.
Yuan et al. (1996b) have speculated that the effect of pulp
potential during otation dominates over other effects. All other
things being equal, once the pulp potential reaches the threshold level
necessary for otation, copper sulphide minerals generally oat well,
and as such, their oatability is independent of the previous grinding
conditions.
2.2. Effect of galvanic interactions between sulphide minerals
The effects of galvanic interactions between sulphide minerals and
grinding media need to be considered in conjunction with the
galvanic interactions that occur between sulphide minerals. This has
been discussed by Rao and Finch (1988), Cheng and Iwasaki (1992),
Cheng et al. (1993, 1999), and Li and Iwasaki (1992). Their laboratory
ndings all t a similar theoretical background. Galvanic interaction
or coupling can occur when two sulphide minerals are brought into
contact. Each metal sulphide mineral (MS) has a different electrochemical reactivity indicated by its rest potential, which can be
represented by the following redox equilibrium:
2
MS M
S 2e
E E RT=2F lnaM2
8
0
where E = Rest potential, E = Standard half-cell reduction potential,

R = Universal gas constant (8.31 J K 1 mol 1), T = Absolute temperature (Kelvin), F = Faraday constant (9.65 104 C mol 1), a = Chemical activity for the relevant species.
Rest potentials of sulphide minerals, which are generally determined
by the sulphide electrode surface species and the electrochemically
active solution species, play an important role in pulp electrochemical
reactions occurring during grinding. The electrochemical activities
determine which mineral or material acts as an anode or a cathode in

galvanic interaction among minerals and grinding media.
Amongst the four most common sulphide minerals, pyrite has the
highest rest potential followed by chalcopyrite and galena (Fuerstenau
et al., 2007). Mild steel has a much lower rest potential than the
common sulphides. From a thermodynamic viewpoint, the higher
the rest potential of the mineral, the less electrochemically active (or
more noble) it will be. When a sulphide with a higher rest potential is
brought into contact with a sulphide of a lower rest potential the
former will act as a cathode drawing electrons from the latter, giving
rise to a galvanic current. As with any redox system, there will be a
tendency for the potential to equilibrate at a common value. The
potential at the least electrochemically active mineral, or more noble
mineral, is lowered, which may retard the mineral's reaction with
xanthate (Woods, 1976) and reduce its oatability. Hydroxides may
form at the surface of the former as the electrons in the galvanic
current interact with dissolved oxygen. The second sulphide mineral
in the galvanic couple becomes electrochemically active, which may
promote interaction with xanthate or even promote the formation of
elemental sulphur, both of which may lead to increasing hydrophobicity of the second mineral. The galvanic interaction is stronger in
the presence of dissolved oxygen, because the oxygen can act as an
electron acceptor to form hydroxyl ions. The galvanic interaction is
weakened in the presence of nitrogen, probably because the nitrogen
displaces the oxygen and thus eliminates the formation of hydroxyl
ions that compete for adsorption sites with the collector. It seems
likely then that the presence of pyrite in an ore (pyrite having the
highest rest potential of the common sulphides) may accelerate or
enhance the oxidation of other less noble metal sulphides present,
thus lowering selectivity.
In plant practice the galvanic interference described above can often
be benecial, leading to pyrite depression by lowering the pulp potential. It is often observed that pyrite begins to oat after the removal of
the second or coupling sulphide, that is, after the galvanic couple is
broken. It has been speculated that if an additive to the otation system
could maintain the galvanic interference, then the pyrite may remain
depressed. This has yet to be demonstrated at plant scale.
In other laboratory studies, Yelloji Rao and Natarajan (1989b,
1990) conrmed that the galvanic interaction between a noble mineral (such as chalcopyrite) and an active mineral (such as sphalerite)
affects the oatability of the more noble mineral signicantly while
the effect on the active mineral is minimal. They suggested this was
primarily due to the tarnishing and passivation of the surfaces of the
more noble mineral. The oatability was strongly inuenced by the
duration of contact as well as the presence of oxygen.
Forssberg and Subrahmanyam (1993) have noted the importance
of the relative cathodic to anodic surface area in galvanic interactions
that might occur between sulphide minerals and between sulphide
minerals and media. This parameter will be inuenced most strongly
by the type of milling method. They suggested a smaller anodic surface in contact with a larger cathodic surface may lead to increased
anodic oxidation of the less noble mineral which may in turn affect its
oatability.
It seems clear that when more than one sulphide mineral is
present in a differential otation system, galvanic interactions among
the different minerals and the grinding media may play an important
role in the separation efciency in subsequent otation. However,
there is little reference in the literature to the galvanic effects related
to composite particles. These particles are generated in most primary
mills and have to be subsequently treated by re-grinding, to effect
liberation.
2.3. Effect of dissolved oxygen
A major effect of the interaction between sulphide minerals and
mild steel grinding media is that the amount of dissolved oxygen
present in the pulp is reduced. However, it is noted that a reduction in

oxygen level can also occur by other means and may be strongly
inuenced by ore type. Martin et al. (1991) considered the importance
of the dissolved oxygen content during grinding and how it was
affected by interaction between sulphide minerals and grinding media.
Reactions of collectors added to the pulp can also consume oxygen as
discussed by Fuerstenau et al. (2007).
The corrosion of mild steel, as described in earlier sections,
consumes dissolved oxygen and when the supply of oxygen is limited
there is a competition for the oxygen between the abraded iron and
the sulphide minerals. This generally means that sulphide otation
will be adversely affected when dissolved oxygen levels are diminished as a result of grinding in a mild-steel or reducing environment.
Dissolved oxygen levels of pulps following laboratory grinding
with mild steel mill/media have been reported to be as low as 1 ppm
(Kelebek, 1993) due to corrosion of grinding media. In conventional
full-scale iron mill discharge pulps, dissolved oxygen levels less than
0.1 ppm have been measured (Grano et al., 1994). It could be expected
that these low levels may inuence the kinetics of subsequent otation, especially in the early stages, such as the primary rougher
stage. In other laboratory studies, Kelebek and Huls (1991) found that
the amount of iron smeared onto sulphide mineral surfaces following
grinding in an iron environment, and the extent of oxidation (via
aeration between grinding and otation), were rate determining
factors in the otation kinetics of collectorless chalcopyrite otation.
Berglund and Forssberg (1987) found that, in laboratory studies
on a complex copper-bearing sulphide ore, higher oxygen levels in
the ground pulp were obtained following milling in a non-ferrous
(porcelain) environment compared with milling in a steel mill. In the
subsequent otation a better copper grade-recovery response was
obtained following the non-ferrous milling. After ferrous grinding,
aerating the pulp before otation gave a somewhat better result than
not aerating it.
It was noted earlier that the pulp potential is lowered during
grinding in an iron environment and it must be raised to potentials at
which signicant otation of copper sulphide minerals can proceed
satisfactorily. Similarly, dissolved oxygen concentrations are signicantly reduced by grinding in an iron environment and it is thought
they too must be raised to threshold levels to enable otation. This is
generally achieved naturally in the rst few cells of a otation bank
but in some cases a separate aeration stage between grinding and
otation is used (Graham and Heathcote, 1982).
The oxygen content after milling is rarely measured in industrial
concentrators. The dissolved oxygen concentration depends upon the
sulphide mineral content of the pulp, the reactivity of the sulphides
present, the milling method and media used, and other physical
parameters including the pulp density, pH, temperature, and altitude
(height above sea level). With all these factors inuencing the
dissolve oxygen concentration it is likely to be difcult to control it in
practice.
2.4. Effect of oxyhydroxide species

Iron is present in nearly all sulphide otation feeds and may
originate from the iron-bearing sulphide minerals themselves, from
grinding material (see later), and from galvanic interactions occurring
during milling that have been described earlier.
At regions of higher alkaline pulp pH, the iron can dissolve from
the grinding media during milling as ferrous ions (see Eq. (1)) and
subsequently oxidise to the ferric form (see Eq. (2)). Ultimately it can
precipitate at the cathodic sulphide mineral sites as oxy-hydroxides
species such as Fe(OH)2,, FeOOH, and Fe(OH)3. These iron hydroxides,
which may be hydrophilic, can coat completely or partially the sulphide mineral surfaces, reducing collector/mineral interactions and
hence oatability (Smart, 1991).
Peng et al. (2003) used the Magotteaux Mill in which, during

grinding, slurry is pumped through a monitoring cell where pH
adjustments can be made, and the slurry purged with different gases
to change the oxidative conditions in the mill. Using a chalcopyrite
pyrite ore, they found that chalcopyrite otation and chalcopyrite
pyrite separation was strongly dependent on the type and amount of
oxidation species produced on the sulphide mineral surfaces under
different grinding conditions. Flotation of chalcopyrite particles
was depressed by iron oxidation species derived from the grinding
medium. Higher chalcopyrite otation recoveries were obtained
when grinding balls containing 30% Cr were used. However, purging
the slurry with nitrogen, air or oxygen gas had little effect on the
otation recovery.
There has been some debate as to whether the hydroxides formed
coat certain sulphide mineral surfaces more selectively than others.
Grano et al. (1990) found that the effect of grinding a Mount Isa
copper ore in a ceramic mill (compared with a cast iron mill) was to
increase the recoveries of iron sulphides more than for chalcopyrite.
They suggested this was due to the preferential adsorption of ferric
hydroxides originating from the media onto the iron-bearing minerals
(pyrite and pyrrhotite) rather than onto chalcopyrite, that is, iron
hydroxide species originating from the iron grinding media exhibit
partially selective afnity for pyrite and pyrrhotite. This is consistent
with the selective depression of pyrite by iron hydroxides. Yelloji Rao
and Natarajan (1990) suggested that when more than one sulphide
mineral is contacted with grinding media the effective surface coating
of the iron species will be distributed among the minerals present in
the combination. They speculated that such a distribution appeared to
be preferential, depending on the relative electrochemical activity of
the minerals, the iron distribution being more favoured on the more
noble minerals relative to the active minerals. They conrmed this
with X-ray photoelectron spectroscopy (XPS) studies. In later work,
Forssberg and Subrahmanyam (1993) suggest precipitated metal
hydroxides coat sulphide mineral surfaces indiscriminately. Clearly
the question of distribution or deportment of iron hydroxides onto
sulphide mineral surfaces is still not completely resolved.
It seems reasonable to suggest that if hydrophilic iron hydroxides
formed on the surfaces of copper sulphide minerals are deleterious in
otation, then removing these species may improve otation. Using
XPS, Li and Iwasaki (1992) identied Fe(OH)3 as a surface species on
chalcopyrite following wet grinding in an iron mill. They speculated
its presence was deleterious to subsequent otation but also noted
that following agitation of the pulp between grinding and otation,
this species could not be detected and that the chalcopyrite
oatability had improved as a result. They suggest that dispersion of
the porous species from the sulphide mineral surface with agitation
may have occurred. No size-by-size data were reported. The subject of
high intensity conditioning (HIC) to improve the otation of sulphides
is a topic in itself and beyond the scope of this review. However, there
may be merit in looking more closely at the inuence of HIC on the
otation of copper sulphide particles inuenced by hydroxide effects.
Senior and Trahar (1991a,b) have reported that hydroxides can be
dispersed from mineral surfaces at highly alkaline pH where both the
mineral and the hydroxy precipitates become negatively charged.
Chemical treatments have successfully been used to modify iron
hydroxide coatings on the surfaces of nickel sulphides minerals
resulting in an improvement in the oatability of ne pentlandite
particles (Senior and Ahveninen, 2001). These techniques have not
been tested in copper sulphide systems but this should be
investigated.
It should also be noted that other dissolved metal ions like Cu2+,
2+
Pb , and Zn2+ may form respective metal hydroxy complexes during
and after grinding which may impair the oatability of sulphide
minerals and interfere with collector adsorption. Precipitation of
inorganic salts from solution may also mean that plant water quality is
an issue in some operations (Grano, 2009).
2.5. Effect on froth characteristics

Van Deventer et al. (1991, 1993) conducted batch otation testwork on a South African complex sulphide ore using a ceramic mill
operated under either oxygen or nitrogen atmospheres and where
different levels of powdered metallic iron were added to the mill. They
found that the best copper recovery and grade was obtained following
grinding in an oxygen-saturated mill in the presence of metallic iron.
While the addition of metallic iron lowered the dissolved oxygen
level, more importantly a stable and well-drained froth with large
bubbles was formed. In contrast, in the absence of the metallic iron,
the froth was at and brittle with small bubbles, and the bubbles
collapsed almost as soon as they were formed. The frother used was
triethoxybutane (TEB). They concluded that, in the presence of
metallic iron, galvanic interaction with the iron media reduced the
rest potentials of minerals present, inhibiting the formation of
dixanthogen on the mineral surfaces. This in turn reduced the
oatabilities of all minerals, especially the iron-bearing gangue
minerals. The poor otation results in the absence of iron were
explained by the enhanced oatability of iron-bearing gangue
minerals, which ruptured lms and suppressed froth stability owing
to bubble overloading. No size-recovery data were presented.
The effect of the milling environment on froth stability is
important in that it seems possible that galvanic interactions that
occur during grinding may lead to enhanced mineral oatability, but
this does not necessarily translate to enhanced recovery in otation if
destabilisation of the froth also occurs as a result. The otation of a
specic mineral is dependent on not only galvanic interaction with
that mineral but also on the effect of galvanic interactions with
associated minerals and their effect on froth phase stability.
3. Physical effects of media type
From laboratory studies, it is believed that wear detritus from
comminution circuits has an important bearing on pulp potential and
on subsequent otation performance in the treatment of sulphide
copper ores. Researchers in laboratory studies have used balls or rods
made from mild steel, ceramic, stainless steel or glass to change or
control the pulp potential during milling, to reduce or eliminate the
effects of galvanic interactions and iron contamination, or both (Wang
and Xie, 1990). However, in plant practice, the choice of grinding
media often is inuenced by the economics of their use in a particular
circuit on a particular ore, with respect to abrasive and corrosive wear,
with little consideration of otation performance.
3.1. Sources and nature of wear detritus
Wear detritus from plant components can enter otation feed
from many sources. These include the following forms:
General mining wear debris (e.g. drills, shovels, and loaders);

Crushers (jaw wear plates, cone crusher mantles and liners);
SAG, rod, and ball mill liners;
Rods and balls;
Pump impellers and bodies (especially cyclone feed pumps);
Cyclones (liners, vortex nders, and spigots);
Piping in the grinding circuit;
Recycled products (e.g. scavenger concentrates) containing oated
wear debris from otation impellers, shrouds, and pumps.
Whilst the majority of wear detritus originates from media and

liners all these sources constitute wear debris of different compositions and amounts. Most of the materials used are steels and cast irons
but rubber liners are now commonly used in ball mills, cyclones, and
many otation cells.
3.2. Inuence of media composition

Compositions of the various steels and cast irons are listed in
Taggart (1945) and Weiss (1985) and are not discussed in detail here.
However, it is important to realise that the properties of steels are
governed by their carbon content, their alloying element content, and
their heat treatment. Meulendyke and Purdue (1989) have presented
data from a test program to determine the extent of wear rates for
grinding balls in different grinding environments. Mild steel (b0.1% C)
consists of ferrite (a dilute solution of carbon in iron) and is too soft to
be a useful grinding medium. Medium-carbon (0.4% C) medium-alloy
(34% Ni or Cr) steels in the chill cast or forged and normalised form
can be useful. These contain ferrite and cementite (iron carbide, Fe3C).
No studies have been conducted on the effect of cementite on pulp
potentials. Manganese, high-chromium and high-carbon (0.9% C)
steels are used in crushers and mill liners. They contain austenite or
martensite which work hardens readily to give an abrasion resistant
material. Similarly, no work has studied the effects of martensite or
austenite on pulp potential.
Cast iron (N3.5% C) and Ni-hard (3% Ni, 3% C) contain little ferrite
but substantial amounts of cementite and some graphite. Heat
treatment is very important in that chill-cast balls (cast in metal
moulds) are harder and more brittle than sand-cast balls. This is
important since brittleness can lead to fracture when the balls wear
down to a critical size. The wear debris from all these alloys is different
and requires separate study. Note that chill-cast balls are probably the
cheapest grinding media in terms of initial price.
Typical wear rates from all these materials when used for grinding
different ores are listed in Taggart (1945) and Weiss (1985). However,
these data are thought to be total consumption and therefore include
the reject portions (ball chips or scats rejected from ball mill discharge
trommels, broken rods, crusher liner remnants) and the actual
amounts entering plant otation feed are thus unknown.
Rubber mill liners also produce wear debris which can affect pulp
potential and otation of copper sulphides by the reducing action of
the rubber components present and some of the llers or curing
agents used (such as mercapto-benzothiazole compounds) which
resemble otation collectors.
Stainless steel media are expensive and soft and their use is
generally restricted to laboratory studies. Nickel-containing media are
often avoided to minimise the nickel content of copper concentrates
and thus minimise nickel removal problems in electro-rening of
copper. The more positive potentials seen in stainless steel laboratory
grinds are most likely only replicated in modern industrial milling
circuits when high-chrome cast or forged balls are used in conjunction
with rubber liners.
Ceramic and glass media are generally restricted to use in benchscale testing where iron exclusion is required or desired.
3.3. Relevant laboratory ndings

Ahn and Gebhardt (1991) found that chalcopyrite recovery in
otation was highest at more positive potentials following grinding
with high-carbon steel balls at pH 11.5. When a nitrogen atmosphere
was used in grinding, the pulp potential following grinding was lower,
as was the chalcopyrite recovery. When stainless steel balls were
substituted for the high-carbon steel balls chalcopyrite oatability
was enhanced regardless of whether the mill was purged with air or
nitrogen. This was attributed to the fact that stainless steel was more
easily passivated than high-carbon steel. Therefore, galvanic interactions between stainless steel and chalcopyrite would be less
severe than those for chalcopyrite ground with high-carbon steel.
Stainless steel grinding resulted in less reducing conditions, as the
potentials were about 100 mV higher after grinding with stainless
steel in both air-purged and nitrogen-purged mills.
Adam et al. (1984) have also noted different otation responses

when sulphides are galvanically coupled with different grades of
media. They examined pyrrhotite oatability after interaction with
mild steel, austenitic, and martensitic stainless steels, and found that
grinding in steel adversely affected the otation of pyrrhotite, but
more importantly, the more active the steel the greater the decrease
in oatability. Auger electron spectroscopy (AES) and XPS studies
indicated the galvanic coupling between the pyrrhotite and the active
metals resulted in the formation of hydroxide or oxide and sulphate
species of iron on the pyrrhotite surfaces. In this case the source of the
iron in these species may have been the pyrrhotite itself, as well as
abraded iron from the media.
It is possible that the effects of grinding media on otation systems
can be exaggerated in studies carried out at the laboratory scale. Khan
and Kelebek (2001) reported that ne grinding of quartz to 97% minus
45 m introduced about 3 kg/t iron from the grinding mill and media
into the pulp. Such a high level of electrochemically active iron in the
slurry resulted in highly reducing conditions of around 350 mV
(SCE), corresponding to about 0.1 ppm oxygen in the pulp. The low
oxygen levels could be reversed to over 7.5 ppm in an aeration step
with addition of a sufcient amount of sodium chromate as a
corrosion inhibitor. Such effects by grinding media are likely to be
much smaller in otation practice of porphyry copper sulphides due
to the relatively short contact times between the ore and grinding
media and the coarser grind sizes.
A comparison of results for otation of a copper ore (4% bornite)
ground in rubber-lined and un-lined mills with stainless and carbon
steel rods and balls indicated that the best copper recovery was
achieved when the rubber-lined mill and stainless steel media were
used. These conditions promoted oxidation of xanthate collector to
dixanthogen and the copper minerals to form a layer of metal
sulphide, decient in metal, at their surfaces that assisted adsorption
of the collector (Gonalves et al., 2003).
In a recent study (Greet et al., 2008a) with a nickel sulphide ore, a
laboratory Magotteaux Mill and a CSIRO on-line UV reagent
monitoring system were used in grinding tests with different media
types and xanthate additions to the mill. The total xanthate levels in
the grinding pulp were analysed in situ as a function of grinding time.
The results showed rapid adsorption of the collector with the xanthate
level in the ground pulp decreasing as grinding proceeded. In general
the more chromium in the media the faster and more extensive was
the xanthate adsorption. With a 100 g/t initial dose, 60% of the added
xanthate was adsorbed after 20 min grinding with forged steel media
while 95% was adsorbed with a high-chrome (30% Cr white iron)
media. The faster and more extensive collector uptake was attributed
to the higher pulp potentials afforded during grinding with the highchrome media. The mill discharge pulp potential values were 106
and +245 mV SHE, respectively. This is consistent with the understanding that sulphide minerals exhibit a lower limiting threshold
potential for a given collector, below which collector adsorption will
not occur and above which it will occur rapidly. The potential for
pentlandite, the major nickel sulphide present in the system, is
about +200 mV SHE (Senior et al., 1994). No data were given by
Greet et al. (2008a) for any subsequent otation tests. It is not unreasonable to expect that similar trends would occur with the milling of
copper sulphide ores, but the effects on otation are unclear.
It has been stated by Martin et al. (1991) that the galvanic
interactions between sulphide minerals and mild steel media are
stronger by several orders of magnitude than those between sulphide
minerals and stainless steel media. Huang and Grano (2008) showed
that 15, 21 and 31% chromium media are less electrochemically active than mild steel and their use resulted in better bornite
oatability as a result of lower oxidation of the grinding media and
consequently lower production of oxidised iron species. Also the
less electrically active grinding media (higher chromium content)
was benecial to the otation of the ne (10 m) bornite. Greet
(2009) obtained markedly increased otation rates for copper, nickel

and PGM + Au from UG2 ore by using 1230% chrome grinding media
in a Magotteaux Mill.
3.4. Corrosion control
Media wear can occur by abrasion and corrosion. The relative
economic importance of corrosive wear in wet grinding has not been
quantied and is beyond the scope of this review. However, it is worth
noting that it has been speculated (Bond, 1964) that well over half of
the media wear results from corrosion or dissolution from the active
nascent metal surfaces continuously being exposed in wet grinding.
Clearly corrosion control is a potential method of reducing wear as is
moving to dry grinding (see later). Hoey et al. (1975, 1977) demonstrated the role played by corrosive wear in wet ball milling through
the use of corrosion inhibitors. They reported a reduction in steel
ball wear of up to 49% in grinding of nickelcopper sulphide ores in
laboratory mills. Effective rust inhibitors used were sodium nitrite,
sodium chromate, and sodium metasilicate. A critical inhibitor
concentration was observed (typically 0.5%), below which effectiveness was reduced and above which relatively little change occurred.
For some reagents a critical pH was also observed. Similar results
were obtained by Forssberg and Subrahmanyam (1993) in laboratory
studies using a Pb/Zn ore.
For such reagents to be suitable for plant use, not only would the
cost of the reagent need to be covered by the savings in media
consumption but any effect, adverse or otherwise, of such reagents in
downstream otation would also need to be taken into account.
concentration but the wear detritus particles are of unknown size

and may consist of magnetic or non-magnetic alloys. However, it is
well known that in gold gravity plants, in which relatively coarse
native gold is recovered, a substantial amount of wear detritus
reports in the gold concentrate. This must be removed during processing
and this is often done by a combination of tabling and magnetic
separation.
Similarly, much wear detritus is known to be sufciently magnetic
to be readily recovered by wet magnetic separation. In fact, this was
practiced by Mount Morgan Ltd, Queensland, at one time (Staff of.
Mount Morgan Limited, 1965). The metallics recovered were added to
the slime otation section where they precipitated dissolved copper
and the precipitate was recovered during subsequent otation of
chalcopyrite.
4. Effect of added reagents

While there is extensive literature on the effects of reagents added
during otation on the otation of copper sulphides, there is little
documented evidence for the any effects on the subsequent otation
of otation reagents added during grinding. Greet et al. (2008a)
monitored xanthate levels in the pulp during grinding but otation
data for the system was not obtained. Typically, the reagents added to
grinding mills in copper sulphide concentrators are collectors, lime,
cyanide and sometimes sodium sulphide.
4.1. Collector
3.5. Flotation of wear detritus
Flotation of wear detritus, either inadvertently or deliberately, in
the treatment of copper ores is rarely considered. However, this can
be an important factor when using nickel-containing grinding balls
because the contained nickel can contaminate the nal copper concentrate leading to increased electro-rening problems in the nal
stages of the production of pure copper.
Woodcock (unpublished data) studied some aspects of this
problem using Ni-hard balls and ceramic pebbles for comparison
during grinding, and typical laboratory otation procedures on 500 g
ore charges. It was found that the amount of Ni-hard abraded from the
balls was comparable with that obtained on similar ores to those used
in the tests. It was also found that the amount of Ni-hard reporting in a
copper rougher concentrate, based on nickel assays, was about 5% of
that abraded. The increase of the nickel content of the concentrate
ranged from about 13 ppm to 33 ppm, depending on the quantity of
concentrate produced. That is, low grade ores showed the larger
increases because less concentrate was produced.
The effect of pH was uncertain, but more Ni-hard seemed to oat in
slightly acid solution, but there was not much difference between
soda ash and lime circuits. Collectors such as ethyl xanthate, secondary butyl xanthate, or Aerooat 208 seemed to oat about the
same amount of Ni-hard. There was some evidence that Reagent 404
oated more Ni-hard than the other collectors.
3.6. Methods for removing wear detritus
If it is shown that wear detritus is detrimental to otation of
copper sulphides in a particular operating plant, then consideration
could be given to changing the grinding media or to removing the
detritus from the otation feed. Changing the media to something less
detrimental could be a cost-effective approach, provided a material is
available.
It may be possible to remove the detritus, at least partly, by
gravity separation, magnetic separation, or both. All ferrous media
have a high density (about 11 g/cm3), which is useful for gravity
Most commercial otation operations use at least one collector to

adequately recover valuable minerals. In many sulphide concentrators the collector, or more usually, some portion of the total collector
addition, is added directly to the mill. This is a particularly useful
strategy when oily collectors are used, as they require more intense
agitation or mixing to adequately disperse in the pulp. Adding
collector at the point where freshly broken mineral surfaces are
produced, and before they are oxidised, is also thought to be
benecial. In electrochemical studies using chalcopyrite and highcarbon chromium steel media, Yelloji Rao and Natarajan (1988b)
found that the deleterious effects of the galvanic interaction between
the media and sulphide tended to disappear with increasing collector
addition (sodium isopropyl xanthate). Adding collector to the mill
minimized or often eliminated the effects of the galvanic interaction.
It was speculated that the electron transfer during galvanic coupling is
impeded by surface active agents such as thiol collectors. However,
while the addition of collector can change the pulp chemistry, there is
no detailed evidence in the literature to show that collector addition
during comminution signicantly improves the subsequent otation
of copper sulphides.
As indicated above, whilst it is common practice to add some, or
all, of the collector to the mill, this does not necessarily mean that
collector will be readily adsorbed onto the (copper) sulphide mineral
surfaces as they are exposed during grinding. As has been shown by
Greet et al. (2008a), for a nickel ore in laboratory tests, and by Greet
et al. (2008b), for a lead ore in full-scale plant trials, collector
(xanthate) adsorption during grinding was faster and more extensive
when high-chrome media was used compared with forged steel
media. In laboratory tests using nickel ore, higher pulp potentials
were observed when using high-chrome media compared with forged
steel media, and this was proposed as the reason for the improved
collector adsorption when the high-chrome media were used. In the
plant trial, improved lead otation metallurgy was observed with the
high-chrome media relative to the forged steel media. Whether or not
similar trends would be achieved with a copper ore is yet to be
determined.
4.2. Lime
Lime (as CaO or Ca(OH)2) is added to many copper sulphide
otation plants, partly as a pH modier to depress iron sulphides, and
partly to improve, in general, the oatability of copper sulphide
minerals.
Kalapudas et al. (2000) and Leppinen et al. (1998) conducted
laboratory and pilot plant grinding and otation studies on a porphyry
copper ore. They found that the reducing effect of iron, caused by
grinding in a mild steel environment, could be largely eliminated by
adding lime to the mill. They conrmed that the copper sulphides
present (chalcocite and chalcopyrite) oated more strongly after noniron or autogenous grinding, but also conrmed that the lime addition
to the grind could compensate for the differences between the
grinding methods, in most cases obtaining similar otation results
from the two different grinding environments. They found that
dissolved oxygen concentrations were much lower with mild steel
grinding than with autogenous grinding but levels were the same
when the lime was added. They attributed the effects of the lime to its
role in eliminating dissolved iron ions in the ground slurry by the
precipitation of iron hydroxide species favoured at the alkaline pH
levels generated by the lime addition. However, the deleterious effects
on otation caused by the precipitation of iron hydroxides were
largely ignored. This would seem to indicate that hydroxide effects
were not important in otation for the ore tested. The amount of lime
added to milling was unfortunately not quoted and no size-by-size
data were presented.
Grano (2010) showed that, with addition of lime to a laboratory
grinding mill to obtain pH values above ten, pyrite recovery was
markedly decreased while chalcopyrite recovery and its otation rate
were increased. In practice these results indicate that addition of lime
in grinding to passivate, or oxidise, the pyrite would allow collector
added after grinding to be directed towards chalcopyrite, and not
pyrite, resulting in improved otation performance.
the ne sizes. It was speculated that the ne particles may have been
more oxidised than the coarse particles in the ores and hence the
greater improvement in copper oatability was for the minus 10 m
size fractions. Unfortunately, no account of the effects of NaHS on
frothing and hence entrainment was considered. Of note is that in the
paper by Orwe et al. (1998) there is reference to other unpublished
work by the same authors of improved copper recoveries from an
unspecied monzodiorite ore by NaHS additions to the laboratory
grinding mill (rather than after grinding). It should also be noted that
oxidation of minerals like chalcocite and digenite can occur not only
during milling but also in re-grinding and otation.
4.4. Cyanide
Cyanide is a reagent commonly added in copper sulphide otation
circuits to help depress pyrite otation. Often all, or a portion, of the
cyanide addition is made to the mill ahead of otation. Its presence
can also affect the otation of copper minerals. Grano et al. (1994)
found in plant and laboratory studies at Mount Isa that chalcopyrite
otation was retarded by excess cyanide addition to the milling
circuit. Data obtained from plant studies where a conventional
grinding circuit (crusher/rod mill/two stage ball milling) and a
modern circuit (fully autogenous grinding/one stage ball milling)
were compared showed that the onset of chalcopyrite depression
occurred at lower cyanide additions for the autogenous line. The
authors proposed mechanisms for cyanide depression of chalcopyrite
and for the differences observed between the results from the two
different milling circuits are not discussed here. However, of
importance here are the size-by-size data presented for the study
which show that, for both the conventional and autogenous circuits
the recovery of chalcopyrite from the ne (10 m) size fractions
remains unchanged when sodium cyanide additions of up to 80 g/t
are made to the grinding circuit.
4.5. Wood extracts
4.3. Sodium sulphide

Sodium sulphide (as Na2S or NaHS) is a modier that is sometimes
used in copper circuits but is rarely added during grinding.
In recent laboratory work on a North Parkes coppergold ore,
Freeman et al. (2000) found that copper otation kinetics were better
following grinding in a stainless steel environment compared with a
mild steel environment, although an aeration stage prior to otation
could improve the latter. Moreover, they found that the addition of
NaHS to the mild steel mill led to increased froth stability and hence
improved copper otation kinetics. The size-recovery data presented
are patchy but show that combined rougherscavenger copper
recovery generally increases with increasing NaHS levels (up to
100 g/t) for particle sizes between 10 m and 100 m, although the
copper concentrate grades decrease signicantly. The minus 10 m
results indicate equivalent or poorer copper recoveries with increasing NaHS additions and much poorer grades. Although not stated by
the authors, this would seem to mean that while the NaHS has
improved the oatability of all minerals above 10 m, leading to poor
selectivity, it has not improved the otation of ne copper sulphides.
It has, rather, increased the entrainment of gangue due to increased
froth stability.
Orwe et al. (1998) investigated the use of NaHS in the otation of
two Ok Tedi ores. In this case the NaHS was added after grinding
(prior to otation). Improved recovery of ne copper particles
(10 m) was obtained for both ore types. The main inuence of
the NaHS on the more oxidised chalcocite-digenitebornite ore was to
re-sulphidize the oxidised surfaces. However, improved copper
otation was also obtained with monzodiorite ore, in which the
copper mineral was predominantly chalcopyrite, a mineral not readily
oxidised. In both instances the improvement was most apparent for
In many underground copper mines, fragments of wood, derived

from mine timber, can be present in mill feed. During grinding and
otation, alkaline pH levels can extract organic compounds such as
tannin and carbohydrates from the wood. The resultant high organic
content of the pulp can be deleterious to copper mineral otation,
depending on the otation conditions used and the type of timber
present.
Selby and Woodcock (1977) reported the results of a otation
study on chalcopyrite ores from three Australian copper mines where
the effects on otation of the addition of several Australian timbers
were assessed. They found that adding up to 2 kg/t of wood had a
slight depressant effect on chalcopyrite otation at pH 7, but had a
marked effect above pH 9. The addition of wood also had some
adverse effects on frothing. They concluded that the extracted
organics were adsorbed on ore particles, competing with collector
for sulphide mineral surfaces, and adsorbed on gangue surfaces, thus
imparting a hydrophobic character to such particles under some
conditions. The deleterious effects of the added wood were only partly
overcome by adding more collector.
5. Effect of the gaseous atmosphere during milling
There has been some interest in the effects on otation of grinding
in a nitrogen atmosphere. This has stemmed chiey from laboratory
grinding and otation work where an inert gas (such as nitrogen) has
been used to exclude oxygen from the grinding environment. The
benets of this are primarily that the corrosion reactions associated
with the steel media are reduced and the formation of deleterious iron
hydroxides is diminished. On the other hand the need for oxygen in
the adsorption of xanthate collectors onto sulphide mineral surfaces is
now fairly well established. Further, it has to be remembered that

during grinding in any gaseous environment, abrasion, as opposed to
corrosion, generates ne steel debris particles (Iwasaki, 1988) which
apart from removing dissolved oxygen may also attach to sulphide
surfaces, lowering rest potentials and potentially inhibiting otation.
Ahn and Gebhardt (1991) found that chalcopyrite recovery in
otation was enhanced as the grinding solution pH was increased (up
to pH 11) when grinding was conducted under nitrogen using highcarbon steel media. This was attributed to reduced galvanic interactions caused by passivation of the high-carbon steel at high pH. The
chalcopyrite recovery was unaffected by the grinding solution pH
when the milling was conducted under air. No size-recovery data
were presented.
Yuan et al. (1996a) found that for chalcopyrite otation following
mild steel grinding, the amount of oxygen in the otation step (and preconditioning) was more important than any aeration during grinding.
Following stainless steel grinding the inuence of the pre-conditioning
and otation gas type on copper otation was found to be insignicant
(Yuan et al., 1996b). It was also noted that air-sparged mild steel
grinding gave no advantage in chalcopyrite-pyrite selectivity compared
with ordinary mild steel grinding. They attributed this result to the high
pulp densities and viscosities and low mixing action in mills relative
to otation cells which they claimed led to low gas dissolution and
diffusion rates in the ground pulps.
The concept of modifying the gaseous environment in mills by the
introduction of external gases such as nitrogen or oxygen seems
largely to be restricted to laboratory scale studies. This is most likely
because of the difculties in making such systems practical at fullscale. However, Simmons et al. (1999), overcoming the technical and
engineering challenges involved at the Lone Tree mine in Nevada,
applied their N2TEC technology in which grinding and otation
and other unit operations were all conducted under nitrogen. They
reported that treatment of a very reactive refractory auriferous sulphide ore was enhanced by this procedure.
6. Effect of grinding method
There is a variety of mill types and milling circuits currently in use
in copper concentrators. The inuence of the major milling methods
with respect to the otation of copper sulphides is now considered.
6.1. Autogenous grinding
Autogenous grinding has become popular in recent years for
processing sulphide ores, including those of copper. The claimed
advantages of autogenous milling include lower capital costs, lower
operating costs, reduced circulating loads, and improved metallurgy
as a result of either better liberation or the production of a more
desirable product size distribution for otation. Thornton (1973)
reported that in pilot plant studies with a copperleadzinc ore,
copper oatability was improved by switching from mild steel
grinding to fully autogenous grinding. His research indicated that
aeration of pulps after grinding in a mild steel mill followed by
otation gave close to the same metallurgical results as grinding in a
ceramic mill followed by otation. He suggested simply on this basis
that the abraded iron from the steel mill lowers the oxygen levels to
values that are not optimum for subsequent otation.
Bruce (1976) found that, in pilot plant studies with a CuZn ore,
autogenous grinding yielded improved copper (and zinc) recoveries
compared with grinding in a mild steel environment albeit that the
copper and zinc grades were slightly lower.
Fahlstrom (1974) and Fahlstrom et al. (1975) reported on a plant
study at Boliden's Aitik copper mill in Sweden. The results showed
that a 2% improvement in copper rougher recovery was possible if
fully autogenous grinding was used instead of steel grinding. The sizeby-size data reported show a ner otation feed size distribution
results from autogenous milling (less coarse particles and more

intermediate particles) and further, the increase in copper recovery is
consistent for coarse and intermediate particles but not evident for
particles less than 15 m in size.
It has been speculated that the metallurgical benets of autogenous
grinding result from the different breakage characteristics obtained in
autogenous milling, in particular, the intergranular breakage that can
occur. It seems fair to say that in autogenous grinding, liberation and
product size distribution depend on mineralogical properties; a rock
with stable grains and weak grain boundaries may obtain a steeper size
distribution and better liberation in an autogenous mill than in a ball
mill. It has also been suggested that autogenous grinding promotes
more selective comminution along grain boundaries, due to lower
impact of falling pebbles.
Iwasaki et al. (1983) conducted pilot plant trials using a coppernickel sulphide ore (containing principally chalcopyrite and cubanite
as the copper sulphide minerals), comparing the effects of autogenous
and conventional grinding on subsequent copper and nickel otation.
They found that copper recoveries were higher (by a few percent)
following autogenous grinding for the same otation feed grind size.
More importantly, mineralogical examination of otation concentrate
and tailing samples showed little difference between the autogenously milled and conventionally milled products. They concluded
that the electrochemical interaction between the grinding media and
sulphide minerals (in conventional milling) had a greater effect on
the sulphide otation behaviour than the breakage characteristics of
the ore samples in the two mill types. No size-recovery data were
included.
Petruk and Hughson (1977) used image analysis techniques to
look at mill products from laboratory and pilot plant trials with a Zn
PbCu ore from Lake Mines Ltd., Canada. They also compared autogenous and conventional grinding using otation feeds of the same
neness and found improved chalcopyrite recoveries following
autogenous milling. They claimed that increased chalcopyrite recovery was in part due to improved liberation caused by the selective
grinding of exposed soft minerals from hard ones by the irregularlyshaped low-density grinding media (pebbles and fragments). Again
no particle size effects were considered.
The inuence of conventional and autogenous grinding on the
otation of sulphide minerals has also been investigated by Forssberg
et al. (1988) using copper sulphide samples from batch tests, pilot
plant runs, and commercial operations. They used analytical methods
to determine the degree of liberation, to describe quantitatively
particle shape, and to characterise the smoothness of particle surfaces.
It was found that autogenous grinding yielded better grades and
higher recoveries and produced rounder and smoother particles but
the link between these two ndings was not clearly established. The
impact on the contact angle as the particle surface becomes rougher
needs to be more fully understood.
In another plant-based study using products from a complex
sulphide ore concentrator, Forssberg and Hongxin (1985) used
automatic image analysis to compare primary and ball mill grinding
to fully autogenous grinding. Again they found that autogenous
grinding delivered better liberation (at otation feed size ranges) and
created smoother particles.
In further pilot plant studies comparing autogenous grinding with
conventional grinding, Forssberg et al. (1993) found autogenous
grinding produced higher copper recoveries but this was achieved at
the expense of copper grade. Sizing and liberation data showed better
liberation of minerals in coarse sizes after autogenous milling and
better liberation in ner sizes after conventional grinding. The sizerecovery plots presented show copper recoveries for the minus 10 m
size fractions are about 8% higher after autogenous milling.
A study was made by Grifn et al. (1993) comparing the
performance of a conventional grinding circuit (rod milling followed
by ball milling) and FAG (fully autogenous grinding) followed by ball
10
milling, using measurements of liberation before and after the change

from crushing and rod and ball milling to autogenous grinding and
ball milling at Mount Isa. When allowance was made for the effects of
variations in copper grade on recovery it was shown that although
higher copper recoveries were obtained with the FAG plus ball mill
circuit this was primarily due to the ner grind size (P80 of 100 m
compared with 125 m). Size-by-size modelling of the data showed
that the total recovery with the FAG plus ball mill circuit would have
in fact been lower than expected from the conventional rod mill plus
ball mill circuit if the grind size had been the same. The liberation data
suggested the FAG plus ball mill circuit resulted in an increase in the
proportion of copper in the most highly liberated fraction. However,
of the chalcopyrite occurring in all locked particles, an increased
proportion was in the least liberated fraction. In this study it was also
noted that the pulp potential of the otation feed after autogenous
grinding was some 150220 mV higher than that obtained after
conventional milling. This was shown to be more favourable for fast
chalcopyrite otation kinetics, particularly in the early stages of
otation. As otation progressed, the air introduced raised the pulp
potential to the value at which the chalcopyrite otation rate coefcient was fully developed. Of note was the observation that the
pulp potential of the autogenous mill discharge was already at this
potential.
Grano et al. (1994) also conducted metallurgical test work at
Mount Isa and obtained data from plant studies where a conventional
grinding circuit (crusher/rod mill/two stage ball milling) and a
modern circuit (fully autogenous grinding/one stage ball milling)
were compared. They showed that chalcopyrite produced in the nonreducing, low iron grinding environment of the autogenous mill
exhibited enhanced otation properties and there was 30% less iron
oxyhydroxide species present compared with conventional grinding.
The size-recovery curves presented show differences in both pyrite
and chalcopyrite otation behaviour for both milling systems, with
higher chalcopyrite recoveries for the size fractions less than 10 m
following autogenous milling.
In a pilot plant study using Mount Lyell copper ore (Clarke et al.,
2002) where single stage FAG was compared with conventional
grinding, it was found that copper recoveries were lower following
FAG by 13%. Analyses showed that autogenous milling produced
more chalcopyrite/pyrite composites and that recovery of these
composites was lower than with ball milling. In size fractions below
53 m, where chalcopyrite is well liberated, copper recovery was less
affected by the milling method. Ball milling, following the FAG milling,
appeared to completely compensate for the effects of autogenous
milling. The data presented for the ner fractions (12 m) are
difcult to interpret. Pilot scale autogenous grinding produced more
minus 12 m material than plant-scale ball milling although the
amount of copper in respective ne fractions was similar. Recovery of
copper from the ne fractions was 10% higher for plant ball milling
than for pilot autogenous milling. The comparison (pilot autogenous
versus plant ball milling) is not ideal and the authors offer no valid
explanation for the difference. The signicant difference between
laboratory, pilot plant, and full-scale data remains largely unaccounted for.
steel charge, are more commonly used. In spite of this, much of the
research reported in the literature focuses on either fully autogenous
or conventional grinding (and otation) studies and little pilot or fullscale studies involving semi-autogenous milling are found.
Plant data from the Majdanpek copper mine in Yugoslavia (Gruji
et al., 1983) indicated improved copper metallurgy (higher copper
recovery) was possible with the use of semi-autogenous milling
(compared with conventional ball milling)they too attributed the
effects to an improved degree of liberation brought on by preferential
fracture of the copper ore along grain boundaries. No size-by-size data
were presented.
6.3. Re-grinding
In many sulphide otation concentrators, rougher concentrates,
rougher-scavenger concentrates, or other products are re-ground and
re-oated to obtain acceptable nal concentrate grades. In recent
years, tower mills (or Vertimills) and other stirred mills have been
used for this application, particularly when very ne re-ground
products are required. These mills can be charged with ne steel balls,
or pebbles, or other non-steel-based media. When non-steel-based
media or steel with modied properties (e.g. elevated chromium
levels) are used, it has been suggested (Johnson, 2002) that improved
metallurgical performances as well reduced media consumption can
be achieved. The former relates not only to a cleaner otation
system (e.g. lower iron hydroxide levels), but also to reduced reagent
consumptions and improved otation kinetics.
Improved grade-recovery responses for copper sulphide systems
have been reported by Davey (2004) when using a Metso stirred
media detritor (SMD) in copper sulphide otation plants. In one
operation, copper concentrate grades were increased by about 12%
(from 27.5% Cu to 29.8% Cu) and copper recoveries by about 1% (from
91.7% to 93.2%). However, no data were presented to substantiate or
otherwise the size or size range of the particles whose oatability was
improved as a result of the use of the detritor.
The recovery of liberated nes (up to 10 m) has been suggested to
be more affected than coarser particles by the presence of iron
hydroxides in the pulp due to the higher surface area of the nes
resulting in greater adsorption of the iron hydroxides on the surface
inhibiting collector adsorption (Johnson, 2006). Peng and Grano
(2010) reported that minus 10 m particles were more easily oxidised
than the coarser 53 + 10 m particles, resulting in a higher concentration of metal oxidation species on their surfaces. Grano (2009) has
shown that the use of a stirred mill with fully electrochemically inert
grinding media (large diameter ceramic media) can signicantly
increase recovery of a chalcopyrite ore by preventing the formation of
iron hydroxides. In practice, grinding with inert ceramic media has
been claimed to include increased recovery of ne valuable minerals,
improved selectivity between sulphide and gangue minerals and
lower collector consumption (Pease et al., 2006).
6.4. Dry grinding
In the processing of sulphide minerals, wet milling is generally
preferred to dry grinding because of the following reasons:
6.2. Semi-autogenous grinding

Evidence presented earlier conrms that the grinding media affect
the otation response of copper sulphide minerals, in part, via
electrochemical interaction. As outlined above, grinding in fully
autogenous mills could conceivably be used to circumvent the
problems associated with the interaction of grinding media and
sulphide minerals, given that the particular ore responds favourably
to autogenous grinding. Unfortunately, very few ores grind with high
power efciency in fully autogenous mills and so semi-autogenous
mills, where the power efciency is maximised by the addition of a
Downstream (wet) processing requirements;

Higher energy efciencies associated with wet grinding;
The general requirement for a low moisture content feed (nominally
less than 2% moisture) for dry milling is difcult to produce;
The tendency of ne sulphides to oxidise in air;
The fact that dry grinding often produces strong agglomerates and
incrustation build-ups (depending on the neness of the grind)
which are difcult to subsequently disperse;
The surface properties of dry ground minerals are different to those
of the same minerals wet ground.
However, there is evidence in the literature that some of these

impediments can be overcome and that a metallurgical advantage in
otation can be achieved following dry milling. Some of the more
relevant studies to this effect are detailed below.
Hoberg et al. (1985) conducted comparative grinding and otation
tests on single sulphide minerals and sulphide ores using a laboratory
air-swept dry roller mill. They claimed that this type of mill produced
energy savings of 2030% in comparison to wet grinding mills, that
capital costs of a grinding circuit incorporating this mill type were in
fact comparable to those of a conventional wet ball milling circuit, and
that issues to do with maintaining a low moisture feed could in most
cases be accommodated if low-cost waste heat was available for
preliminary drying purposes. More importantly, their metallurgical
results showed that in some instances, higher copper sulphide
recoveries and grades were obtained by otation after dry grinding
relative to otation after wet grinding. In particular, they noted
that the collectorless otation (frother only) of some sulphides was
enhanced following dry milling. They attributed this to the effects of
oxygen adsorption during dry milling where the adsorption retarded
the wetting of mineral surfaces, especially for those minerals that
were naturally hydrophobic. They suggested that oxygen was initially
chemisorbed in ionic form, and as adsorption advanced, the form of
the oxygen bond became more covalent in nature and at the same
time sulphides were reduced to elemental sulphur, making the mineral surface more hydrophobic in nature. Longer conditioning times
were needed prior to otation, presumably to aid the dispersion of
agglomerates. The authors claimed that the dry grinding method
employed is particularly suitable for ne-grained materials, but there
were few real data presented to support this claim.
Lepetic (1974) conducted some pilot and laboratory studies on the
effects of dry autogenous milling using a Peruvian Andes chalcopyrite
ore. Using collectorless otation following dry autogenous grinding,
he reported increased chalcopyrite grades and recoveries relative to
wet grinding. When collector was added, selectivity was lost because
the other sulphides present (pyrite and pyrrhotite) then exhibited
strong oatability.
More recent laboratory work by Feng and Aldrich (2000) using a
complex sulphide from the Merensky Reef in South Africa highlighted
the inuence of topographical effects caused by dry grinding. SEM
(scanning electron microscopy) and AFM (atomic force microscopy)
studies revealed that dry ground samples had relatively rough particle
surfaces with a high concentration of microstructural defects, while wet
ground samples had smoother and cleaner surfaces. Consequently the
activated particle surfaces of the dry ground particles exhibited faster
adsorption kinetics with a SiBX collector. The effects in otation were
faster otation kinetics but poorer metallurgy, that is, lower grades and
recoveries. This was explained by the premise that some very ne
gangue particles also adsorbed onto the activated surfaces resulting in
lower otation selectivity. In contrast the wet ground particle surfaces
were cleaner and this resulted in improved selectivity. The proposition
that the ne gangue particles had also been activated by dry grinding
and oated genuinely was not considered by the authors. They looked
at whether a combination of both wet and dry milling could be used to
improve both the otation kinetics and metallurgy. They found that, by
using (wet) high intensity conditioning (HIC) after dry grinding,
improved selectivity was obtained because the high shear force elds
generated by high intensity conditioning removed the non-selectively
adsorbed nes from the activated particle surfaces.
Other workers (Martin et al., 1991) have also found that dry
grinding leads to adsorption of oxygen and enhances the collectorless
otation of sulphides, including copper, but given that there is little
practical full-scale use made of the collectorless copper sulphide
otation, the importance of this aspect of dry grinding is probably
relatively insignicant.
It should also be noted that the use of (dry) high pressure grinding
rolls (HPGR) as an alternative to conventional wet ball milling (at the
11
same otation feed size) has been observed at CSIRO Minerals (K.R.
Weller, personal communication, 1999) to produce improved selectivity of chalcopyrite over pyrite in subsequent otation. Whether the
improved copper metallurgy is due to morphology/textural effects or
pulp potential effects is not clear. Particle size effects have also not
been established.
One side issue with dry milling relates to media wear. Media wear
rates in wet grinding have been estimated to be several times greater
than in dry grinding (Bond, 1964) and this effect is enhanced when
the grinding pulp is acidic, especially below pH 5.5.
7. Summary
This review into the effects of grinding and the grinding medium
(usually iron-based) upon the otation performance of copper
sulphide minerals has identied and discussed the key factors
important in the otation of copper sulphide minerals.
Most evaluations of the effects of grinding on otation have been
made at the laboratory scale where operating conditions are closely
controlled. While there often is debate as to whether laboratory scale
results apply at the plant scale, the key issues in evaluating media
meaningfully at plant scale relate to the high cost of the trials and the
need for prolonged testing periods to ensure a full charge of the new
media is obtained and that statistically reliable information results.
Galvanic interactions between sulphide minerals and steel media
can affect the pulp potential, dissolved oxygen level, or the extent of
iron hydroxide formation and this is often deleterious to copper
otation. The use of more inert chromium alloy balls can limit the
formation of hydroxides in the pulp with resulting improvements in
otation performance. Further research is required to understand
more fully the factors affecting the formation of hydroxides during
grinding and their effects on subsequent otation, especially that of
ne particles. There is some evidence that galvanic interactions
between sulphide minerals and media during grinding can also affect
froth stability and hence selectivity.
In addition to the interactions between the grinding media and the
sulphide minerals, there are also galvanic interactions between the
sulphide minerals themselves, and these galvanic interactions play an
important role in the separation efciency in subsequent otation.
Grinding under an inert gas (such as nitrogen) has been employed
(chiey in the laboratory) to exclude oxygen from the grinding
environment. The benets of this include minimising sulphide
oxidation, minimising corrosion effects, and minimising the formation
of iron hydroxides.
The common reagents added to milling circuits in copper sulphide
concentrators are collector, lime, cyanide, and rarely, sulphide. There
is little hard evidence in the literature that collector, lime, or cyanide
addition during grinding has any signicant effects on the oatability
of copper particles.
Numerous laboratory and plant studies demonstrate an improvement in copper recovery by otation following fully autogenous
milling when compared to conventional (steel) milling at the same
grind size. A few selected studies indicate that improved otation of
copper minerals can be achieved after dry grinding (relative to wet
milling) although in many of these studies collectorless otation has
been used.
Acknowledgements
The authors wish to acknowledge comments from CSIRO colleagues Mr Graeme Heyes and Mr Steve Suthers, the journal referees
for their critical comments and suggested changes that have improved
this review, and the assistance of CSIRO library staff in obtaining
references. Permission from Rio Tinto Australia to publish this paper is
gratefully acknowledged.
12
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International Journal of Mineral Processing

A review of the effects of the grinding environment on the otation of

Corresponding author. Tel.: + 61 3 95458500; fax: + 61 3 9562 8919.

milling between media and sulphide minerals, galvanic interactions

2.1. Effect of pulp potential

Oxidation of iron will be strongly favoured, under most conditions,

The measured potential of an indicator electrode such as platinum

plants (Woodcock and Jones, 1970a, b; Graham and Heathcote, 1982;

Heathcote, 1982). Hydrocylones, which are often in place between

where E = Rest potential, E = Standard half-cell reduction potential,

determine which mineral or material acts as an anode or a cathode in

present in the pulp is reduced. However, it is noted that a reduction in

2.4. Effect of oxyhydroxide species

Peng et al. (2003) used the Magotteaux Mill in which, during

2.5. Effect on froth characteristics

General mining wear debris (e.g. drills, shovels, and loaders);

Whilst the majority of wear detritus originates from media and

3.2. Inuence of media composition

3.3. Relevant laboratory ndings

Adam et al. (1984) have also noted different otation responses

(2009) obtained markedly increased otation rates for copper, nickel

concentration but the wear detritus particles are of unknown size

4. Effect of added reagents

Most commercial otation operations use at least one collector to

4.3. Sodium sulphide

In many underground copper mines, fragments of wood, derived

now fairly well established. Further, it has to be remembered that

results from autogenous milling (less coarse particles and more

milling, using measurements of liberation before and after the change

6.2. Semi-autogenous grinding

Downstream (wet) processing requirements;

However, there is evidence in the literature that some of these

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