International Journal of Mineral Processing 114–117 (2012) 51–62

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International Journal of Mineral Processing

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The effect of cations on the activity of anionic polyacrylamide flocculant solutions☆

M.I. Witham b, 1, A.F. Grabsch a, A.T. Owen a, 2, P.D. Fawell a,⁎
a
CSIRO Process Science and Engineering, PO Box 7229, Karawara, WA, 6152, Australia
b
School of Chemical Engineering, Curtin University of Technology, GPO Box U1987, Perth, WA, 6001, Australia

a r t i c l e i n f o a b s t r a c t

Article history: The conformation of acrylamide/acrylate copolymers' aqueous solutions is known to be affected by the pres-
Received 31 May 2012 ence of cations to varying degrees. Such effects are expected to be reflected in the flocculation activity of the
Received in revised form 27 September 2012 polymer solutions, but the published literature in this area is far from convincing, particularly on the influ-
Accepted 20 October 2012
ence of divalent cations. Part of the problem was believed to stem from the inevitable poor control of the ap-
Available online 30 October 2012
plied shear conditions (both intensity and duration) in conventional batch cylinder or jar tests. To address
Keywords:
this, continuous flocculation was achieved in a Couette mixing device that allowed operator-independent
Polyacrylamide settling rate measurements to be made, with much greater control over the residence time under shear
Flocculant and its intensity. A standard calcite (calcium carbonate) slurry was then used as the substrate for comparison
Flocculation between flocculants of increasing anionic character in the presence of selected cations at various concentra-
Cation tions. Rather than shifting the dosage response curve, the divalent cations Ca 2+ and Mg 2+ were found to limit
Settling rate the settling rates that could be achieved at higher dosages, but this effect could be masked under stronger applied
shear conditions that favour some degree of aggregate breakage and also limit settling rates. Such effects in-
creased with the flocculant's anionic character and the cation concentration. In contrast to the conventional an-
ionic products, a flocculant that contained an alternative functional chemistry (BASF Rheomax® 1050) was
found to be far less affected by the presence of these cations. Low levels of iron (either as Fe2+ or Fe3+) were suf-
ficient to deactivate dilute flocculant solutions, but had reduced effects when present in stock solutions. The
mechanisms by which the different cations affect flocculant solutions are discussed, together with the practical
implications for flocculant make-up and application within gravity thickening as practiced in mineral processing.
Crown Copyright © 2012 Published by Elsevier B.V. All rights reserved.

1. Introduction
1.1. Thickening and flocculation
The hydrometallurgical processing of mineral ores invariably re-
sults in slurries that have a fine particle size and require at least one
stage of solid–liquid separation. While filtration and centrifugation
are used, gravity thickening usually represents the most practical op-
tion for achieving a high throughput and the desired performance.
A schematic of a gravity thickener is shown in Fig. 1 (although it
should be noted that the ratio of height to diameter and the angle
of the cone section can vary greatly). Typically, low solid feed streams
are pumped into the feedwell, generally with a high inlet velocity.
The initial function of thickeners and their feedwells was to dissipate
the energy of this feed, with the solids then allowed to settle and con-
solidate. Globally, as ore grades deteriorate, fine particle slurries with
☆ A paper for submission to: International Journal of Mineral Processing.
⁎ Corresponding author. Fax: +61 8 9334 8001.
E-mail address: phillip.fawell@csiro.au (P.D. Fawell).
1
Current address: Orica Mining Services, 15 Greenleaf Road, Kooragang Island, NSW,
2304, Australia.
2
Current address: Technology Delivery Group, Alcoa of Australia, PO Box 161, Kwinana,
WA, 6167, Australia.
very low settling rates have become more common and thickening is only
practical if high molecular weight water-soluble polymers (flocculants)
are used to induce aggregation and thereby enhance sedimentation. Floc-
culant solutions are typically mixed with the feed slurry through addition
to the feedwell, the feedpipe or a combination of both.
Older thickeners were often over-sized and thereby quite forgiving
of sub-optimal flocculation. This has changed as throughputs increase
and grinding practices produce higher proportions of fines. Newer gen-
eration units offer much better performance, but with much reduced
margins for operational error. In particular, the settling rates required
to comfortably exceed the rate of liquor upflow (often referred to as
the nominal thickener rise velocity, ignoring hydrodynamic issues,
and is determined by dividing the volumetric flow to the overflow by
the available horizontal cross-sectional settling area) are much higher.
As a consequence, the need to optimise the flocculation process is great-
ly increased.
The factors affecting flocculation have been extensively studied and
frequently reviewed (e.g. Henderson and Wheatley, 1987a; Gregory,
1989; Hocking et al., 1999; Fellows and Doherty, 2006); while these
offer many useful insights, there is a danger in assuming that floccula-
tion behaviour and mechanisms observed on sub-micron sized particles
can be directly translated to the larger particles that are normally en-
countered in hydrometallurgical thickening. In addition, the timescales

0301-7516/$ – see front matter. Crown Copyright © 2012 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.minpro.2012.10.007
52 M.I. Witham et al. / International Journal of Mineral Processing 114–117 (2012) 51–62
Fig. 1. General schematic of a gravity thickener as used in mineral processing. Hatched region represents available settling area.
for effective flocculation under applied shear are much shorter for larger
particles at typical thickener feed solid concentrations, measured in sec-
onds rather than the minutes often applied for sub-micron or low solid
slurries. Our research team has previously published on experimental
approaches for continuous flocculation to better capture aggregate
growth and breakage effects under tightly controlled conditions
(Farrow and Swift, 1996a; Swift et al., 2004; Heath et al., 2006),
and have applied such techniques to examine the operating factors
that are most critical towards optimising flocculation in gravity
thickeners, such as hydrodynamics, solid dilution, flocculant dilution
and residence time (Farrow and Swift, 1996b; Owen et al., 2009;
Fawell et al., 2009).
1.2. Optimising flocculant solution properties
Separate from the flocculation process itself, it is also important to en-
sure that the properties of the aqueous flocculant solution are optimised
prior to dosing. Coagulants, whether they be inorganic salts or lower mo-
lecular weight cationic polyelectrolytes, will under most circumstances
readily dissolve to give a fully active reagent that is only minimally
impacted upon by the physical make-up conditions. In contrast, the
acrylamide/acrylate copolymers used as flocculants in most mineral
processing/hydrometallurgical applications are high molecular weight,
long chain polyelectrolytes that are relatively slow to dissolve and
achieve a solution state optimal for flocculation.
Products in a powder form need to be wetted carefully to avoid gels
of agglomerated polymer that are unlikely to disperse (Hecker et al.,
1998); even under ideal make-up conditions, some powders can take
several days to reach maximum activity, after which they slowly
reconform to reduced solution dimensions and lose activity (Owen
et al., 2002, 2007). Products in an emulsion form (in which concentrat-
ed aqueous flocculant drops are dispersed in an organic phase with the
emulsion then inverted by shear during make-up) are easier to prepare
as concentrated solutions and reach a usable activity almost immediate-
ly, but still may not reach their maximum appreciably quicker than
powder products (Owen et al., 2007). In practice, ageing times rarely
exceed 4–8 h, often a compromise due to storage capacity; where pow-
der stock solution ageing times are less than an hour, required dosages
can be highly elevated, putting even greater pressure on ageing times.
Complicating the make-up and application of flocculant solutions is
their shear sensitivity. While applying low shear is an important part of
make-up, excessive shear can lead to a loss of activity. Numerous studies
of such effects have been published, with shear applied from a variety of
mixing devices. High speed stirring and the action of pumps tends to re-
sult in a permanent loss of molecular weight (Nagashiro and Tsunoda,
1977; Sylvester and Toure, 1978; Scott et al., 1996; Owen et al., 2009),
while there is evidence that transport through pipes can instead induce
entanglements and agglomeration of the polymer chains (Owen et al.,
2009); in practice, both outcomes can lead to higher flocculant dosages
and even the inability to achieve the desired settling rates in high
throughput units.
1.3. The impact of solution cations on flocculant activity
A further complication arises from the quality of the water used dur-
ing the make-up process. The solution dimensions of polyelectrolytes
are very much affected by the ionic strength and the valency of the
counterions; in the absence of dissolved salts the charged functionali-
ties along the polymer chain will favour a more extended conformation,
while the shielding of these charges at higher ionic strength will lead to
closer coiling, as would be displayed by the acrylamide homopolymer.
This not only affects the bridging capacity of the polymer during aggre-
gate formation, but also the flocculant solution viscosity, which in turn
influences make-up, transport through pipes and distribution through
the feed slurry after dosing. It is important to note that in most hydro-
metallurgical applications, the charged functionalities of anionic floccu-
lants only serve to provide chain extension, with adsorption primarily
achieved via hydrogen bonding of the amide functionality to neutral
surface sites (Hocking et al., 1999).
Numerous studies have shown the impact of ionic strength on the
solution dimensions and viscosity of acrylamide/acrylate copolymers
(Kay and Treloar, 1974; Rogan, 1995; Ye et al., 1996; Seright et al.,
2010), and such effects are often thought to be heightened for multiva-
lent cations, due to complexation with the carboxylate functionalities,
which in extreme cases can lead to precipitation (Mortimer, 1991;
Boisvert et al., 2002). In comparison, relatively few studies have consid-
ered in detail how water quality (and in particular multivalent cations)
in make-up and dilution liquors can impact upon flocculant activity. It is
important to differentiate studies of flocculant solutions from those in
which slurry liquor composition has been considered. For example,
the presence of calcium in slurry liquors and its potential to exchange
on clay surfaces is well known (de Kretser et al., 1997); similarly, calci-
um can be precipitated onto the surface of bauxite residue solids at high
pH (Chen et al., 2003). Both actions are thought to enhance flocculation,
but primarily through the flocculant adsorption process, rather than by
influencing the polymer's solution properties. Differentiation should
also be made for oxidizing cations such as iron (II), which are known
to lead to actual physical degradation of the polymers.
While the deleterious effects of soluble iron on flocculant activity is
undisputed, there is less agreement in terms of the effects of ions like cal-
cium and magnesium. Henderson and Wheatley (1987b) claimed the
presence of such ions in flocculant solutions did not influence subse-
quent clay flocculation, arguing the cations form 1:1 complexes with
the carboxylate functionalities, with a relatively minor effect on the floc-
culant solution conformation; in contrast, they believed that copper cat-
ions were able to chelate to two carboxylates, leading to a much more
compact conformation. Rey (1988) observed a significant loss of floccu-
lant activity with a predominantly clay tailings from make up and, in
 M.I. Witham et al. / International Journal of Mineral Processing 114–117 (2012) 51–62
particular, from flocculant dilution for increasing liquor concentrations of
calcium. Peng and Di (1994) saw a similar effect from calcium that they
attributed to polymer coiling and precipitation on the clay surface.
These studies offer important results, but suffer as a consequence of
the approaches taken to assessing flocculation performance. They all uti-
lise cylinder tests, which are quick and simple to execute, giving the po-
tential to screen a wide range of conditions. However, Henderson and
Wheatley (1987b) limited their tests to fixed flocculant dosages and
slurry concentrations, which may not maximise sensitivity to changes
in flocculant solution properties. The results from Henderson and
Wheatley (1987b) were obtained at clay tailing slurry concentrations
of 4–8% w/v, which may be considered high given that 70% of the solids
were smaller than 5 μm; that may narrow the dynamic range of settling
rates that could be obtained. Their diluted flocculant concentration
(0.02% w/v) was slightly higher than ideal and applied dosages low,
raising some concerns about the effectiveness of the flocculant distribu-
tion. Only the relative dosages required to maintain an initial settling
rate of 15 m h−1 are quoted in the work by Rey (1988); in this case
the feed was a quite coarse (50% b 19 μm, only 10% b 3 μm) coal tailing
slurry that varied from 4 to 6% w/v and contained a mixture of phases,
making it less than ideal for identifying potentially subtle variations in
flocculant performance. Peng and Di (1994) examined pure kaolin
clay, but only quantified the mass of the bed solids settled 3 min after
flocculant addition and mixing, which would be expected to provide
limited insights into flocculation behaviour.
By far the greatest limitation of conventional cylinder tests for mea-
suring flocculant activity is that the mixing applied during the floccula-
tion process (by inversions in the studies discussed above, but plungers
are also used) is often poorly controlled. Not only are such results highly
operator-dependent, but there is very limited scope to adequately con-
sider variations in mixing intensity, which is a major factor affecting
flocculation. The mixing of slurry and flocculant in the cylinder tests
may therefore lead to some degree of aggregate breakage, which may
have the potential to mask some effects arising from flocculant solution
properties.
This paper describes investigations into the effect of make-up and
dilution liquor composition on the activity of flocculant solutions,
utilising a Taylor–Couette mixing device (the CSIRO Shear Vessel) to
contact standard feed slurry with the flocculants and provide continu-
ous flocculation. In this way it was possible to obtain settling rates on
slurries flocculated under much more controlled conditions, allowing
the effect of the applied mixing intensity to be isolated. Settling rates
were measured across a range of flocculant dosages, which was also
critical towards ensuring that the full impact of added liquor cations
was captured.
2. Experimental
2.1. Materials
Calcite slurries (calcium carbonate, known as Omyacarb 2, Omya
Australia) were prepared by measuring out a known volume of water
and known mass of solid into a 30 L baffled tank to give a solid concen-
tration of 58.5 kg m−3. The slurry was then mixed at approximately
350 rpm for 30 min using an IKA Labortechnik stirrer fitted with an
A310 impellor. The d50 (as measured by laser diffraction) was typically
3 μm.
Table 1 lists the flocculants used within this study. All are well
known in mineral processing applications and were all obtained
through BASF. The Magnafloc® products are all acrylamide/acrylate
copolymers and their general behaviour can be considered represen-
tative of nominally equivalent products obtained from other floccu-
lant suppliers. Rheomax® 1050 is believed to contain an unspecified
alternative functional chemistry to the other three products, although
still based on the polyacrylamide backbone. While this alternative func-
tional group is charged (i.e. the polymer is not nonionic), the charge
53
Table 1
Flocculants used in this study (all sourced from BASF).
Flocculant Nominal anionic Nominal molecular Physical
name character weight form
Magnafloc® E10 5% High Powder
Magnafloc® 336 30% Very high Powder
Magnafloc® 919 50% Very high Powder
Rheomax® 1050 Unknown Medium-high Powder
density is also not specified; such knowledge is not essential for the pur-
poses of this paper, for which Rheomax® serves to provide behaviour
distinct from that associated with the carboxylate functionality. All
products were also provided as powders, with their make-up and dilu-
tion prior to use described below.
Polymer (1.00 g) was “wet” with 2.00 g of absolute ethanol and
gently shaken by hand for 30 s, then let stand for 2 min. Deionised
water was then added to give a 0.50 wt.% (unless otherwise stated)
stock solution. This solution was shaken vigorously by hand for
2–3 min to ensure the powder was properly dispersed and then mixed
on a tabletop shaker for 24 h to ensure optimal ageing. Working solu-
tions, typically 0.0050 wt.%, were prepared by diluting the stock solution
in water or in a solution containing cations. This was at the lower end of
working solution concentrations as applied in practice, but was deliber-
ately chosen to minimise the potential impact of flocculant solution vis-
cosity on the flocculation process while also facilitating dispersion of the
polymer across slurry solids in the mixing stage. The solution was put
into the tabletop shaker in a vertical orientation such that when agitated
the solution was in a continuous swirling motion. Agitation was kept at
145 rpm for 20 min to ensure solution homogeneity.
The cations used in this study were Na +, Mg 2+, Ca 2+, Fe 2+ and
Fe 3+. Bulk liquor volumes containing these cations were prepared by
dissolving salts (NaCl, MgCl2, CaCl2, FeSO4 or Fe(NO3)3) in deionised
water to achieve a desired solution concentration. All reagents were AR
grade. When very dilute cation concentrations were required the bulk
solutions were further diluted using deionised water. Dilution in 0.1 M
NaCl was used as the baseline test; Na+ does not interact with the poly-
mer to the same degree as multivalent cations, but ensures that the im-
pact of electrolyte on the particle surface charge is maintained.
2.2. Shear Vessel flocculation assessment
The CSIRO Shear Vessel (Fig. 2) consists of an outer fixed cylinder
(I.D. 110 mm) and an inner rotating cylinder (O.D. 100 mm) driven
by a variable speed motor. The annular gap width is 5 mm. The inner
cylinder is constructed from stainless steel, the outer cylinder of clear
acrylic. The conical section at the base of the cylinders has a pitch of
45°, maintaining the gap of 5 mm (volume 45.5 mL).
The applied shear is set by controlling to a selected rotation rate, gen-
erally between 100 and 600 rpm (controlled to ±1 rpm). Attempting to
describe three-dimensional fluid flow by a single shear rate is not often
meaningful; this is certainly an issue for cylinder mixing or impellor-
stirred tanks, and still the case within the Shear Vessel. Fluid dynamic
studies by Rudman et al. (1994) have shown that wavy and modulated
wavy vortex flows within a Taylor–Couette device give rise to very effi-
cient mixing. However, some particles or aggregates will still experience
shear rates several times any mean value. Critically, the time taken to
achieve a given degree of mixing in such flow regimes is directly propor-
tional to the rotation rate of the inner cylinder, with faster rotation giving
faster mixing, and therefore the rpm is an acceptable measure for this
device.
Flocculant inlets (ports 1 to 4) are positioned on one side of the
outer cylinder, allowing the residence time within the vertical section
under an applied shear condition to be varied. The slurry inlet port is
positioned on the opposite side. Port 1 is located at a vertical section
height of 15 mm, with the higher ports each separated by 35 mm; the
54 M.I. Witham et al. / International Journal of Mineral Processing 114–117 (2012) 51–62
Fig. 2. CSIRO Shear Vessel used for assessment of flocculant performance.
vertical section annulus volume to port 1 is 24.8 mL, with each suc-
cessively higher port contributing an additional 57.7 mL. Residence
times were calculated from these volumes and the flow rates. Port 2
was used unless otherwise stated.
Slurry was pumped from the feed tank to the Shear Vessel using a
peristaltic pump (“Feed slurry pump”, Masterflex® 7550–62 L/S: Tygon
tubing size 17) at a constant delivery rate of 300 mL min−1. Dilute floc-
culant delivery was via a second pump (“Flocculant pump”, Masterflex®
7550–92 L/S: tubing size 14) through the flocculant ports at rates gener-
ally between 2 and 12 mL min−1. The dosages obtainable through such
a delivery were from 5.5 to 33 g of flocculant per tonne (g t−1) of (dry)
slurry. The shear conditions experienced by the suspension in the annu-
lar gap are controlled by the rotation of the inner cylinder, the shear in-
tensity correlating with the rotation rate.
The flocculated slurry flows through a glass analysis column fitted
to the base of the cylinders — this column may be isolated (through
the closure of two valves) for the measurement of settling rates, with
continuous flow maintained through the diversion line. The subsequent
underflow peristaltic pump ensured a controlled flow rate, set at 95% of
the total incoming flows. This allowed for ~5% of the flow to report to a
levelling outlet, thus maintaining a constant volume of slurry within the
vessel.
Hindered settling rates (in m h−1) were determined at each floccu-
lation condition by measuring the rate of fall of the mudline of a sample
isolated in the Shear Vessel's analysis column. The majority of experi-
ments involved setting a fixed rotation speed for the inner cylinder
and applying a range of flocculant dosages through a selected flocculant
port, thereby generating a dosage response curve for the flocculant so-
lution under consideration. Settling rates were not measured until at
least 10 min after setting the conditions to ensure stability. Some exper-
iments involved fixing the flocculant dosage and varying the rotation
rate (studying the effect of applied shear) or the flocculant port
(residence time under shear).
Note that the focus was on settling rate and potential thickener
throughput, with supernatant suspended solid (clarity) measurements
not performed after settling, although that option was available experi-
mentally. While overflow clarity can be an important practical consider-
ation, the correlation between small scale measurements and full-scale
performance is generally poor; suspended solids can be “dragged-down”
in mud-line settling within batch tests, whereas at full-scale the overflow
clarity can often reflect short-circuiting flow-streams more than floccu-
lation efficiency. Initial tests in this study found that clarity measure-
ments did not provide any additional sensitivity to the trends being
examined, and so were not continued.
3. Results and discussion
3.1. Conventional anionic flocculants
3.1.1. Sodium cation effects on dosage response
Under appropriate, well-controlled conditions (i.e. fixed solids con-
centration and applied mixing), curves of settling rates as a function of
 M.I. Witham et al. / International Journal of Mineral Processing 114–117 (2012) 51–62 55

flocculant dosage are highly sensitive to the activity of the flocculant so- to Na +, with Ca 2+ having a greater effect than Mg 2+. Such effects
lutions. For example, in their work on the short-term ageing of powder were most evident for the 50% anionic flocculant Magnafloc 919.
flocculant solutions immediately after make-up, Owen et al. (2002) ob- It was initially expected that the impact of the divalent cations
served a shift in the dosage response curves to the left (lower dosages as would be even more pronounced than that of Na + in Fig. 3, i.e. the
the ageing time approached the “optimal” duration of 24 to 48 h), but dosage curves would be shifted further to the right of the baseline
the shape of the curve was largely constant, reflecting the release of curve, reflecting a reduction in activity. Instead it was found that the
polymer chains from the dissolving and disentangling product. Tight onset of aggregation brought about by such flocculant solutions actually
control over the flocculation conditions through the use of the Shear still occurred at comparable dosages to the baseline Na+ case. At low
Vessel ensures shifts in these curves as small as 5% can be readily dosages (b 12–15 g t − 1) that yield low-to-moderate settling rates
quantified. (b 12 m h − 1), all three flocculants responded similarly, implying no re-
Throughout this study, dosage curves obtained from flocculant solu- duction in the availability of polymer chains or their polymer-bridging
tions diluted in 0.1 M Na+ were used as a baseline. Adding the salt of a activity for low level aggregation.
monovalent cation such as Na+ is expected to manifest in two distinct
effects on the flocculation process. Firstly, the Na+ ions will shield the
negative charges on the carboxylate (\COO −) groups, reducing charge
repulsion along the chain causing the polymer chains to coil. The Na +
ion itself will not directly interact with carboxylates nor will it physical-
ly or chemically bond with amide groups. However, its presence will
lead to higher dosages being required in comparison to a flocculant so-
lution made in water (Fig. 3). This effect is simply due to the chain
coiling (referred to as the polyelectrolyte effect) and becomes more
pronounced as the anionic character increases. Note that while the dos-
age shift with Magnafloc 919 was quite significant, high settling rates
(≥20 m h−1) were still readily attainable.
The second potential effect from Na + addition is to the actual sur-
face of the solid particles. This is most noticeable for those surfaces
that have exchangeable groups on the surface, such as clays, which
can interact with the sodium ions, reducing the available sites for
bridging/bonding with the flocculant. This should be negligible for
calcite as its surface is not expected to interact with the sodium
ions. An appreciable ionic strength will also reduce the magnitude
of the zeta potential through double layer compression, and this can
favour some degree of particle coagulation. However, such effects
are generally weak and are more likely to influence sub-micron parti-
cles. They are not expected to be significant for the calcite studies
here, and this is supported by the dosage response curves in Fig. 3.

3.1.2. Divalent cation effects on dosage response

The impact of adding the divalent Ca 2+ and Mg 2+ cations needs to
be contrasted against the baseline Na + dosage curves to properly dif-
ferentiate from general electrolyte effects. Fig. 4 shows the settling
rate response at an agitation rate of 300 rpm as a function of dosage
for the conventional flocculants diluted in solutions containing Na +,
Mg 2+ and Ca 2+ ions. Both divalent cations reduced activity relative

Fig. 3. Settling rate of calcite slurries (58.5 kg m−3) as a function of flocculant dosage Fig. 4. Settling rate of calcite slurries (58.5 kg m−3) as a function of flocculant dosage
for 0.005 wt.% solutions of Magnafloc E10, 336, 919 diluted in water (solid line) or for 0.005 wt.% flocculant solutions diluted in 0.1 M Na+, 0.05 M Mg2+ or 0.05 M Ca2+.
0.1 M Na+ (dashed line). Shear Vessel rotation rate 300 rpm, flocculant dosed through Shear Vessel rotation rate 300 rpm, flocculant dosed through port 2 (16.5 s residence
port 2 (16.5 s residence time). time).
56 M.I. Witham et al. / International Journal of Mineral Processing 114–117 (2012) 51–62
It is possible that the divalent cations impact upon both the floccu-
lant and the substrate surface, in the latter case with cation adsorp-
tion changing surface sites available for flocculant adsorption. While
this could significantly affect the aggregation process when high dos-
ages lead to flocculant adsorption at high fractional surface coverage,
in this case only low surface coverage is required to produce substan-
tial settling rates. The results in Fig. 4 for the weakly anionic floccu-
lant Magnafloc E10 show only a mild detrimental effect on settling
rates across the full dosage range studied, suggesting that surface
modification effects in this case may be minor.
It was not until higher dosages were applied that divergences in
flocculant activity related to the solution cation identity became evi-
dent, with Fig. 4 showing the presence of Ca 2+ resulting in a plateau
in the settling rate response to dosage for the flocculants with higher
anionic contents. While such behaviour was discernable for Magnafloc
336, it was more pronounced for Magnafloc 919, with no increase in
settling rate occurring beyond a dosage of ~15 g t−1; even doubling
the dosage to 30 g t−1 gave little benefit in terms of settling rate. The
settling rates will reflect changes in both aggregate size and structure,
the latter manifesting in the aggregate density or its fractal dimension.
At a constant flocculant dosage, a higher aggregate density will inevita-
bly also mean a smaller aggregate size. However, a higher density alone
would still be expected to impact upon the settling rate response at
lower dosages, and the response would also not display such a distinct
plateau at higher dosages. The results in Fig. 4 therefore suggest that the
Ca2+ ions were limiting the size of the aggregates that can form under
the applied agitation conditions, most likely linked to a change in aggre-
gate strength. The bridging capacity of the flocculant was reduced such
that once this limiting size was reached, any further flocculant addition
was not effectively utilised, in direct contrast to the baseline case.
As Magnafloc 919 was the conventional flocculant most affected
by the presence of Ca 2+, a separate set of tests were carried out in
which this flocculant was diluted using solutions with a range of
Ca 2+ concentrations from 0.001 to 0.05 M (Fig. 5). Even very low
concentrations of Ca 2+ had a significant detrimental effect on the
flocculant's performance, and as was the case in Fig. 4, this manifests
mainly in terms of the size/strength of the aggregates formed.
3.1.3. Effect of agitation (shear) intensity and residence time
The intensity and duration of shear applied during polymer-bridging
flocculation is a critical factor affecting the aggregation process (Farrow
and Swift, 1996b; Owen et al., 2002, 2008). Shear is initially required to
induce aggregate-forming bridges, but prolonged shear will rupture
these bridges and therefore the aggregates. In contrast to aggregation
induced by charge neutralisation, ruptured polymer bridges in the
Fig. 5. Settling rate of calcite slurries (58.5 kg m−3) as a function of flocculant dosage for
0.005 wt.% solutions of Magnafloc 919 diluted using varying concentrations of Ca2+. Shear
Vessel rotation rate 300 rpm, flocculant dosed through port 2 (16.5 s residence time).
majority of mineral processing applications are highly unlikely to retain
any useful bridging capacity, and so aggregate breakage is irreversible in
the absence of fresh flocculant.
Increasing the shear intensity increases the number of collisions
between aggregates; newly formed aggregates not only break up more
frequently, but are also limited to a smaller overall aggregate size. For a
constant flocculant dosage, the overall settling rate will therefore inevita-
bly decrease. This effect can be overcome by increasing the applied dos-
age, however, eventually a point will be reached where the shear
intensity is so high that no aggregates of appreciable size will form, no
matter how much extra flocculant is added. The appropriate duration
(residence time) within the shear zone depends upon the applied
shear conditions, with mild mixing requiring longer times. The response
to shear may also be both substrate and flocculant dependant.
The results in Figs. 4 and 5 were obtained at a relatively mild Shear
Vessel rotation rate (shear intensity) of 300 rpm, with a fixed resi-
dence time within the shear zone (the vertical Couette section) of
~ 17 s. Tests were therefore conducted to establish the cation effect
when the rotation rate was increased, with the residence time also
varied by changing the flocculant addition port.
Fig. 6 shows the settling rate response as a function of residence
time for Magnafloc 336 solutions containing Na + or Ca 2+ when oper-
ating the Shear Vessel at 300, 400 and 600 rpm. While there still was
an effect from introducing a divalent cation at the higher rotation
rates, it was much reduced in comparison to results at 300 rpm.
This was especially the case at 600 rpm, with the stronger shear con-
ditions limiting the aggregate size and therefore the settling rates
achieved, effectively masking the potential contribution from the so-
lution cation.
Similarly, longer residence times contribute to a greater degree of
aggregate breakage, even at 300 rpm, also leading to an apparent re-
duction in the impact of the divalent cation. Note that while the pres-
ence of both cations gave high settling rates for a very short residence
time of only ~ 5 s at 300 rpm, this particular result is considered mis-
leading as flocculation was highly inefficient under the mild conditions,
reflected in a high proportion of suspended solids in the supernatants
after settling.
Fig. 6 highlights an important consideration when attempting to
isolate one specific effect from other factors influencing flocculation per-
formance. If examining the effect of Ca 2+ under high shear (represented
here by the 600 rpm conditions) in complete isolation from results
obtained under lower shear, it would be concluded that the influence
of the divalent cation is small or non-existent, and that much higher con-
centrations may be needed to see any deleterious effect. Such a conclu-
sion in this case would arguably be correct for the specific conditions
Fig. 6. Settling rate of calcite slurries (58.5 kg m−3) as a function of both Shear Vessel
rotation rate and residence time for 0.005 wt.% solutions of Magnafloc 336 diluted in
0.1 M Na+ or 0.05 M Ca2+. Flocculant dosage is 21.5 g t−1.
 M.I. Witham et al. / International Journal of Mineral Processing 114–117 (2012) 51–62 57

but misleading in general, given that the contribution of higher shear far
outweighs that of the solution cation.
Fig. 7 highlights this effect in greater detail, showing flocculant
dosage response curves for Magnafloc 336 at the three different Shear
Vessel rotation rates for solutions prepared in 0.1 M Na+, 0.05 M Mg2+
or 0.05 M Ca2+. While increasing the rotation rate from 300 to
400 rpm did diminish the impact of cation selection through a reduction
in the size of aggregates that formed under the stronger shear, higher
dosages did favour flocculant solutions without Ca2+ present. However,
at 600 rpm the effect of the solution cation was minor across the full dos-
age range studied.
Fig. 8 shows the combined effect of rotation rate and residence
time for Magnafloc 919 at a constant dosage of 16 g t −1 in the pres-
ence of either Na + or Ca 2+. This flocculant had the highest degree
of anionic character (50%) of the products studied, which accentuated
the influence of the divalent cation, such that it was possible to ob-
serve a decline in performance for flocculant solutions containing
Ca 2+ relative to the baseline Na + results at the shortest residence
time studied (~5 s), even at 600 rpm. However, at the longest residence
time of ~40 s, even the performance of this flocculant displayed an ap-
parent independence of the solution cation that in reality is a conse-
quence of excessive aggregate breakage. This is analogous to batch
testing in stirred tanks, for which the search for reproducible mixing al-
most inevitably results in excessive shear and the masking or reduction
of flocculation performance trends.

3.1.4. Effect of iron

It is well known that iron species in solution can have a serious
detrimental effect on anionic flocculant solutions both in terms of their
activity (Henderson and Wheatley, 1987a, 1987b) and their viscosity
(Shupe, 1981). The effects of preparing dilute solutions of Magnafloc
E10, 336 and 919 in the presence of both Fe2+ and Fe3+ on the subse-
quent ability of the flocculants to induce aggregation were investigated.
The Fe2+or Fe3+ concentration was varied to determine if there is a
threshold at which their effect is negated or minimised for practical
usage.
Fig. 9 shows settling rate as a function of dosage for each flocculant in
the presence of different concentrations of Fe3+ ions. At 10−3 M Fe3+, all
three flocculants were observed to precipitate out of solution. For 336
and 919, this resulted in complete inactivation (i.e. aggregation could
not be induced by the solution), while some residual activity remained
for E10. A small degree of precipitation still occurred with 919 on reduc-
ing the Fe3+ concentration to 10−4 M.
Lowering the Fe3+ concentration of the flocculant diluent to 10−4 M
led to some retention of activity, although this was still much reduced in
comparison to that of the baseline 0.1 M Na+ case. The detrimental effect
was further reduced at 10−5 M Fe3+, with the dosage response of all
three flocculants shifted only slightly to right of the baseline. As was
the case for Mg2+ and Ca2+, the deactivating effect of Fe3+ increased Fig. 7. Settling rate of calcite slurries (58.5 kg m−3) as a function of flocculant dosage and
Shear Vessel rotation rate for 0.005 wt.% solutions of Magnafloc 336 diluted in 0.1 M Na+,
for flocculants of higher anionic character, consistent with the interac-
0.05 M Mg2+ or 0.05 M Ca2+. Flocculant dosed through port 2 (16.5 s residence time).
tions of the cations being through the carboxylate functionality.
The effect of diluting the flocculants in solutions containing Fe 2+
was more pronounced than with Fe 3+, especially for the more anionic
products (Fig. 10). All three flocculants were again found to precipi- prepared using water containing 0.05 M and 0.005 M Ca2+ ions. The
tate out of solution at 10 −3 M Fe 2+. For both 336 and 919, Fe 2+ con- concentrated flocculant solutions were then diluted in deionised
centrations as low as 10 −5 M were sufficient to severely diminish water to 0.005 wt.% for flocculation tests.
activity. Preparation in the presence of 0.05 M Ca 2+ resulted in the imme-
diate formation of a white precipitate for all the flocculant solutions.
3.1.5. Effect of cations on concentrated flocculant solutions After allowing the solutions to stand for 24 h there was no evidence
To provide contrast to the results described in the previous sections of the precipitates dissolving and the solution displayed none of the
for flocculant dilution into solutions containing cations immediately viscous nature expected of an active flocculant. This was an interest-
prior to use, a brief investigation was undertaken into the effect of pre- ing result, given that no precipitation was observed after dilution of
paring concentrated flocculant solutions in the presence of cations. stock solutions (0.50 wt.%) made in deionised water with 0.05 M Ca2+.
Magnafloc 919 was used, as the most anionic of the flocculants was This suggested that there could be a flocculant concentration threshold
expected to be the most affected by the make-up solution composition. above which precipitation occurs, which is discussed in more detail
Flocculant solutions at concentrations of 0.10, 0.25 and 0.50 wt.% were later (Section 3.3).
58 M.I. Witham et al. / International Journal of Mineral Processing 114–117 (2012) 51–62

Fig. 8. Settling rate of calcite slurries (58.5 kg m−3) as a function of both Shear Vessel
rotation rate and residence time for 0.005 wt.% solutions of Magnafloc 919 diluted in
0.1 M Na+ or 0.05 M Ca2+. Flocculant dosage is 16 g t−1.

When a 0.25 wt.% stock was prepared in 0.005 M Ca 2+, the pow-
der product readily went into solution, but its activity was found to
have diminished relative to an equivalent concentrated flocculant so-
lution made in deionised water (Fig. 11).
The flocculant Magnafloc 919 was also prepared at 0.25 or 0.50 wt.%
in solutions containing either Fe2+ or Fe3+ at concentrations of 10−3 and
10−4 M. These stock flocculant solutions were then diluted in deionised
water to 0.005 wt.% prior to use in flocculation tests (Fig. 12). For stock
made in 10−4 M Fe3+, flocculation performance was virtually equivalent
to that found when made in deionised water. At 10−3 M Fe3+, a small
but noticeable amount of brown precipitate formed; while there was a
decline in performance relative to the stock made in water, it
was minor in comparison to dilution of flocculant solutions with
10 − 3/10 − 4 M Fe 3+ (Fig. 9).
Similar trends in the settling rate response to dosage were seen for
919 stock solutions made in the presence of Fe 2+, although the drop
in performance at 10 −3 M was much greater for Fe 2+ than Fe 3+.

3.2. Rheomax® 1050

Rheomax® 1050 was included in this study to provide an alterna-

tive functional chemistry to the conventional acrylamide/acrylate co-
polymer flocculants. It has been shown in separate studies to offer
enhanced sediment properties (either through higher settled densi-
ties or a lower yield stress at comparable solids volume fractions)
compared to Magnafloc 336 when used to flocculate calcite under
certain conditions. There is also evidence to suggest that it is less sen-
sitive to pH and ionic strength changes.
Fig. 13 shows the settling rate response to dosage at a rotation rate
of 300 rpm for Rheomax® 1050 diluted in solutions containing Na +,
Ca 2+ and Fe 2+. The presence of Ca 2+ had a relatively minor effect rel-
ative to that seen for 336 (Fig. 4), with only a small divergence from
the baseline 0.1 M Na + curve. Doubling the Ca 2+ concentration
from 0.05 M to 0.1 M also had minimal effect.
In stark contrast to the dramatic reduction in activity observed for the
three conventional anionic products when diluted in Fe2+ solutions, the
corresponding effect on Rheomax® 1050 was only a relatively small shift
in the dosage response curve to the right. The plateau in settling rate re-
sponse, evident at as low as 10−5 M Fe2+ for 336 and 919 (Fig. 10), was
absent for Rheomax® 1050 at 10−4 M Fe2+. At 10−3 M Fe2+ there was a
small amount of curve flattening at the highest dosages studied.
Fig. 14 shows the effect of changing Shear Vessel rotation rate and
residence time on the settling rate response for flocculation with
Rheomax® 1050 (17 g t −1) diluted in 0.1 M Na + or 0.05 M Ca 2+.
Fig. 9. Settling rate of calcite slurries (58.5 kg m−3) as a function of flocculant dosage
for 0.005 wt.% solutions of Magnafloc E10, 336 and 919 diluted in 0.1 M Na+ or varying
concentrations of Fe3+. Shear Vessel rotation rate 300 rpm, flocculant dosed through
port 2 (16.5 s residence time).
At 300 rpm the results were in agreement with Fig. 12, in that the
Ca 2+ curve was slightly but consistently lower than the baseline
(Na +) curve. Only at long residence times (> 30 s) was this differen-
tial negated, indicating that at this residence time shear-induced ag-
gregate breakage was the dominant process.
At both 400 and 600 rpm the Ca2+ and baseline curves for Rheomax®
1050 were effectively indistinguishable at all residence times. The general
response to shear was very similar to that of 336 (Figure 6), indicating
comparable aggregate strengths, with the only difference being the
smaller cation effect with Rheomax® 1050, which was only evident
under the milder flocculation conditions.
 M.I. Witham et al. / International Journal of Mineral Processing 114–117 (2012) 51–62 59

Fig. 11. Settling rate of calcite slurries (58.5 kg m−3) as a function of flocculant dosage for
0.005 wt.% solutions of Magnafloc 919 (diluted in water), prepared from stock (0.25 wt.%)
solutions made-up in either water (squares) or 0.005 M Ca2+ (diamonds). Shear Vessel
rotation rate 300 rpm, flocculant dosed through port 2 (16.5 s residence time).

This last point is in apparent conflict with our results, which show
the presence of 0.05 M Ca 2+ mildly reducing the activity of dilute 336
and severely impacting upon dilute 919 (Figures 4 and 5). Much

Fig. 10. Settling rate of calcite slurries (58.5 kg m−3) as a function of flocculant dosage
for 0.005 wt.% solutions of Magnafloc E10, 336 and 919 diluted in 0.1 M Na+ or varying
concentrations of Fe2+. Shear Vessel rotation rate 300 rpm, flocculant dosed through
port 2 (16.5 s residence time).

3.3. Mechanisms

The ability of cations and in particular multivalent cations to form

complexes, precipitates and even gels with polyelectrolytes has been
extensively investigated. Henderson and Wheatley (1987a, 1987b)
showed that while a 0.02% w/v solution of a polyacrylamide homo-
polymer was completely unaffected by the presence of up to 0.1 M
Na +, K +, Ca 2+, Mg 2+, Cu 2+, Zn 2+, Pb 2+, Al 3+ and Fe 3+, several of
these ions were extremely detrimental to the activity of a 30% anionic
copolymer. They concluded that complex formation between a cation Fig. 12. Settling rate of calcite slurries (58.5 kg m−3) as a function of flocculant dosage
for 0.005 wt.% solutions of Magnafloc 919 (diluted in water), prepared from stock
and an anionic flocculant is not in itself sufficient to reduce floccula- (0.25 or 0.5 wt.%) solutions made-up in either water,10−3 or 10−4 M Fe2+ or Fe3+.
tion performance, highlighting that Ca 2+ and Mg 2+ form such com- Shear Vessel rotation rate 300 rpm, flocculant dosed through port 2 (16.5 s residence
plexes but do not influence the flocculant's activity. time).
60 M.I. Witham et al. / International Journal of Mineral Processing 114–117 (2012) 51–62
Fig. 13. Settling rate of calcite slurries (58.5 kg m−3) as a function of flocculant dosage
for 0.005 wt.% solutions of Rheomax® 1050 diluted in Na+, Ca2+ or Fe2+. Shear Vessel
rotation rate 300 rpm, flocculant dosed through port 2 (16.5 s residence time).
higher Ca2+ concentrations also resulted in precipitation of the polymer.
Huber (1993) indicated Ca2+ ions bind to the carboxylate groups of dis-
sociated polyacrylates in aqueous solution and if the binding capacity is
exceeded, an insoluble salt forms. Others have interpreted this as gela-
tion from bond formation between the cation and polyacrylate chains
and that addition of Ca2+ to partly neutralized polyacrylates causes a
much stronger coil contraction than an equivalent amount of Na+
(Wall and Drenan, 1951; Flory and Osterheld, 1954).
Both Henderson and Wheatley (1987a, 1987b) and Sommerauer
et al. (1967) indicated that Ca2+ and Mg2+ form one-to-one complexes
with carboxylate groups and therefore only have a minor influence on
polymer conformation through the polyelectrolyte effect. In contrast,
Cu2+ has a greater ability to form a chelate by bonding to two charged
functionalities that are much more likely to be on the same chain, there-
by causing a much more compact polymer conformation.
We believe that the apparent conflict of our results with those of
Henderson and Wheatley (1987a, 1987b) may be explained in the con-
text of the results shown in Figure 7. The influence of Ca2+ and Mg2+ on
flocculant solution conformation is shown here to be sufficient to re-
duce potential flocculation performance, but it is possible that this effect
was masked in the earlier study by the application of slightly excessive
mixing during the batch cylinder tests. There can be a tendency to
over-shear in batch tests that may improve reproducibility and still
allow differentiation of major changes in activity, but with some loss
Fig. 14. Settling rate of calcite slurries (58.5 kg m−3) as a function of both Shear Vessel
rotation rate and residence time for 0.005 wt.% solutions of Rheomax® 1050 diluted in
0.1 M Na+ or 0.05 M Ca2+. Flocculant dosage 17 g t−1.
of sensitivity to more subtle effects; such issues are reduced in continu-
ous testing.
The impact of Fe 2+ and Fe 3+ on flocculant activity was much more
pronounced, and could be clearly captured with even the most poorly
optimised batch testing procedures. With Fe3+, a concentration of only
10−3 M was sufficient to form precipitates with dilute (0.005 wt.%) so-
lutions of all three conventional products, and even 10 −4 M led to some
precipitation with 919 (50% anionic). Henderson and Wheatley (1987a,
1987b) saw similar deactivation with Fe3+. In this study the effect of
Fe 2+ was even greater, with 10−5 M severely diminishing the activity
of 336 and 919. While such concentrations are low, they are of the
same order as the polymer in solution, and still exceed the levels of ac-
rylate on a molar basis.
Interestingly, 919 solutions at the much higher make-up concen-
trations (0.25 or 0.50 wt.%) gave only a very small amount of precip-
itate when exposed to the above low concentrations of Fe 2+ or Fe 3+,
and the solutions still retained much of their activity on dilution. In
contrast, concentrated solutions (0.1, 0.25 or 0.50 wt.%) made in the
presence of 0.05 M Ca 2+ developed extensive precipitation and com-
plete flocculant deactivation. Clearly both the flocculant and cation
concentrations are key factors.
Studies of polyacrylate precipitation have identified two mecha-
nisms, termed H- and L-type (Ikegame and Imai, 1962; Huber, 1993;
Sabbagh and Delsanti, 2000). In H-type, the so-called critical cation con-
centration at which precipitation occurs is high and independent of the
polyelectrolyte concentration. L-type precipitation occurs when cation
concentrations are low, with the critical value generally proportional
to the polyelectrolyte concentration. Sabbagh and Delsanti (2000)
concluded that all polyacrylates chemically react with inorganic
multivalent counter-ions by the L-type mechanism, i.e. the critical
cation concentration for precipitation would rise for flocculants
under make-up conditions.
In a study of Ba 2+ and Al3+ reactions with sodium polystyrene sul-
fonate (at pH ~3), Narh and Keller (1993, 1994) also proposed two dis-
tinct precipitation mechanisms. They concluded that sulfonate groups
on their own can form a precipitate with Ba2+ but not with higher
valency cations, such as Al 3+ and Sn4+. The precipitation of ionic groups
from the insoluble association of Ba2+ and sulfonate then drags from
solution the full polymer chain to which the sulfonate is attached. In
contrast, the trivalent Al3+ cation caused multiple intra-chain bridges
and increased interactions of the hydrophobic chain members, leading
the chain to collapse and precipitating the whole molecule (including
soluble and dispersed sulfonate groups) from solution. The threshold
Al3+ concentration for precipitation was linear with polymer concen-
tration, while with Ba 2+ the relationship was effectively reversed,
i.e. high cation levels were needed for precipitation at low polymer
concentrations.
The above mechanisms are expected to contribute to the results
observed in this study with Fe 3+. It has also been previously observed
that the presence of Fe 2+ leads to oxidation to Fe 3+ and chain scis-
sion, with the reduction in molecular weight then a major factor in
the deterioration of flocculant activity (Stocks and Parker, 2006).
4. Practical implications
The majority of mineral processing operations are located in areas in
which the streams available for flocculant make-up (e.g. process water,
raw water, recycle water, and thickener/clarifier overflow) are less than
ideal. Some are hypersaline or contain high amounts of “hard” cations
such as calcium and magnesium. Boiler water applications may contain
residual iron contaminants in solution, while recycled streams from
CCD washing circuits can contain significant concentrations of accumu-
lated cations from leaching processes.
Operations are therefore forced to deal with a number of factors that
will influence the effectiveness of flocculants used in gravity thickening.
Techniques are available to remove ions from water (ultra-filtration,
 M.I. Witham et al. / International Journal of Mineral Processing 114–117 (2012) 51–62
reverse osmosis, chemical precipitation, desalination), but are often ex-
pensive and are rarely viable for anything more than small volume
streams. Desalination is one of the few techniques to have gained any
traction for use on large scale plants.
This work highlights the potential sensitivity of a flocculant to its
make-up and dilution environment. The best available water should
be used for the concentrated stock solution make-up. However, even
if that is strictly adhered to, it still leaves concerns over the liquor to
be used for secondary flocculant dilution. The same high quality water
used for make-up would often also be ideal for dilution, but is rarely
available in the required volumes. It should be noted that in some appli-
cations the use of such water for dilution is not favoured, as it may im-
pact upon pregnant liquor composition in downstream processing.
The secondary dilution of a stock flocculant solution using liquors
containing low divalent cation concentrations should be possible without
excessive activity loss, provided the contact time between the flocculant
and dilution liquor is minimised. Dilution should always be performed as
close to the point of application as possible, i.e. close to the flocculant dos-
ing point within a feedwell, feedpipe or launder. Only a few seconds
should be required for a stock solution to homogenously mix into
what is invariably a highly turbulent dilution stream (in-line dilution
is assumed here). Short mixing times are known to greatly reduce the
problems associated with shear-induced activity losses from flocculant
transport through pipes and valves (Owen et al., 2009); given that cat-
ion effects on flocculant properties may not be immediate, minimising
contact prior to application can also be expected to limit such effects.
The exception to this may be if the cations are at very high concentra-
tions (several g L−1 and higher) or are particularly aggressive towards
flocculants (e.g. iron); in such cases the impact upon the flocculant
may still be significant and a re-evaluation of the flocculant dilution
strategy would be required. The stock concentrated flocculant could be
dosed directly into the feedwell (or feedpipe/launder). While the results
obtained here suggest this may reduce cation effects on the flocculant so-
lution, adding such a high flocculant concentration to the slurry of fine
particles introduces a range of complications to do with flocculant/slurry
contact, the mixing of a viscous flocculant stream and inevitable ineffi-
cient flocculation. Reducing the stock solution concentration (e.g. from
0.4 to 0.1 wt.%) would be a potential better alternative for direct dosing,
but in practice may suffer from (i) limited stock flocculant holding tank
volumes, thereby affecting ageing times prior to use and (ii) the need
to pump the reduced concentration stock at a higher velocity over longer
distances, which can lead to transport related activity losses.
Another key outcome from this work is an appreciation of under
which operational circumstances the described cation effects on floccu-
lant activity may or may not be expected to be a significant factor to-
wards feedwell and thickener performance. For conventional thickeners
in which the nominal rise velocity is low (say less than 5 m h −1), it is
likely with many substrates that settling rates comfortably in excess of
the rise velocity may still be achieved even with flocculants affected by
the presence of cations. Rise velocities will increase at higher through-
puts, with high values also a feature of more modern high rate or paste
thickeners; the ability to achieve high settling rates then becomes critical,
and under these conditions the quality of the liquor used to dilute floccu-
lants may become a major issue. The advantages of using a flocculant that
is less sensitive to the presence of cations (such as BASF Rheomax®
1050) may be more fully realised under such conditions.
Similarly, the shear environment under which flocculation is
achieved will also play a role in whether or not the influence of divalent
cations manifests in the observed flocculation performance. If the shear
within the feedwell is high and prolonged (i.e. flocculant is dosed high
in the feedwell, close to the entry point into the feedwell when there
is visible evidence of turbulence across the entire feedwell volume),
then there is a reasonable prospect that the aggregates formed may re-
ceive excessive shear, limiting the size of aggregates formed and there-
by masking potential cation effects. The same may almost invariably be
expected when flocculant is dosed exclusively to a feedpipe or launder
61
that then discharges into a feedwell, given that the residence time
under shear will be long.
5. Conclusion
It has long been known that multivalent cations have the potential
to lower the activity of acrylamide/acrylate copolymer flocculants,
but this study has provided new insights into how such effects man-
ifest under different flocculation conditions. While solution iron is
highly detrimental to the performance of dilute flocculant solutions,
the impact of divalent calcium and magnesium cations is more subtle,
with settling rates at low flocculant dosages largely unaffected, but
becoming limited at higher dosages; in the case of calcium, a plateau
in the settling rate response is observed. This can be interpreted as a
reduction in the aggregate size that can be achieved at these higher
dosages. As a consequence, high shear or prolonged residence times
under shear during the flocculation process that lead to aggregate
breakage can mask the influence of these divalent cations on the
flocculant's apparent activity. Results obtained under tightly con-
trolled continuous flocculation conditions serve to explain why detri-
mental effects on flocculant activity from such cations may not be
observed from conventional batch cylinder or jar tests. They also pro-
vide useful guidelines as to when their presence in dilution streams
may represent a problem in achieving the desired performance out-
comes from a full-scale thickener feedwell.
Acknowledgements
This research has been supported under the Australian Government's
Cooperative Research Centre (CRC) Program, through the Parker Centre
for Integrated Hydrometallurgy Solutions. Sponsorship from BHP Billiton
for M. Witham under the Parker Centre Summer Student Program is
gratefully acknowledged. BASF are thanked for the provision of the floc-
culants studied; Stephen Adkins (BASF) is also thanked for his comments
on the manuscript.
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