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Breakup of High Solid Volume Fraction Oil-Particle Cluster in Simple Shear

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Article  in  Colloids and Surfaces A Physicochemical and Engineering Aspects · July 2015

DOI: 10.1016/j.colsurfa.2015.06.054

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 Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Breakup of high solid volume fraction oil–particle cluster in simple

shear flow
Sasan Mehrabian a , Markus Bussmann a , Edgar Acosta b,∗
a
Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada M5S 2E4
b
Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 3E5

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Breakup of clusters with high vol-

ume fractions can be characterized as
droplet breakup.
• A critical capillary number was
obtained for oil–particle clusters to
breakup.
• Systems with high viscosity ratios
require longer shearing time for
breakup.
• The liberated oil may coalesce with
secondary clusters at low interfacial
tensions.

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

Article history: Experiments were conducted of the low-Reynolds number breakup and separation of oil–particle clusters
Received 11 April 2015 characterized by a high volume fraction of relatively large solid particles, under simple shear in an aqueous
Received in revised form 20 June 2015 solution. The breakup of such oil–particle clusters, and the separation of particles from the clusters, are
Accepted 26 June 2015
evaluated as a function of viscosity ratio of the oil phase to the aqueous solution, interfacial tension, and
Available online 15 July 2015
shearing time. When the viscosity ratio is high, clusters are more difficult to breakup, a longer shear time
is needed, and few particles detach. At low viscosity ratios, clusters are easily deformed and break up
Keywords:
into smaller clusters, and more clean particles detach. Lowering the interfacial tension also facilitates the
Oil sands
Bitumen
liberation of oil droplets from particles.
Solid/liquid/liquid separation The results show that the breakup of oil–particle clusters with a high volume fraction of large particles
Capillary number can be characterized as simple droplet breakup, meaning that the viscosity of the oil governs the dynamics
Coalescence of the cluster, rather than an effective viscosity that is a function of the solid volume fraction. The degree
of cluster breakup and the separation of particles from the primary cluster is related to a cluster-based
capillary number and the viscosity ratio. There is a critical capillary number required to obtain clean
particles.
© 2015 Elsevier B.V. All rights reserved.

∗ Corresponding author.
E-mail address: edgar.acosta@utoronto.ca (E. Acosta).

http://dx.doi.org/10.1016/j.colsurfa.2015.06.054
0927-7757/© 2015 Elsevier B.V. All rights reserved.
26 S. Mehrabian et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35
Nomenclature
Ca capillary number
Cacrit critical capillary number
h gap between the plates (m)
i number of secondary clusters
K power law constant (Pa sn )
n power law index
p viscosity ratio
r distance of the cluster from the center of the plates
(m)
R radius of the projected area of the cluster (m)
Vo oil volume within the cluster (m3 )
Vs solid particle volume within the cluster (m3 )
˙ shear rate (1/s)
1 aqueous solution viscosity ratio (Pa s)
2 oil viscosity (Pa s)
 interfacial tension (N/m)
 volume fraction
ω angular velocity (rpm)
1. Introduction
Oil–particle clusters are encountered in many industrial pro-
cesses including the treatment of mineral slurries, the remediation
of oil-based drill cuttings, and the processing of oil sands. In oil
sands extraction [1,2], for example, the objective is to separate
bitumen (the oil phase) from solid particles by mechanical means
such as mixing and flotation in an aqueous environment. Bitumen
extraction from oil sands is often aided by high temperatures and
the addition of solvents to reduce the viscosity of bitumen, and the
addition of surfactants to reduce the interfacial tension of bitumen,
to facilitate oil–particle separation.
The oil phase between solid particles in oil–particle mixtures
forms liquid bridges that exert capillary forces binding the parti-
cles. The thermodynamic stability of such clusters of solid particles
bound by a dispersed fluid has been previously studied [3–7]. The
effects of interfacial tension, particle size, temperature, pH, sol-
vent dilution and particle wettability on oil–particle interaction in
batch conditions have also been studied extensively from chemi-
cal and thermodynamic points of view [8–16]. Bitumen recovery
improves dramatically with increasing temperature because bitu-
men viscosity decreases sharply [11,12]. Increasing pH facilitates
the separation of bitumen from solid particles [8,11]. The addition
of solvent improves the separation because it reduces the viscos-
ity of the oil and increases the volume of the oil, which increases
the area upon which external shear forces can act [11]. Finally, the
addition of surfactant decreases the interfacial tension, which is the
cohesive force holding clusters together, and aids recovery [13–15].
This study focuses on the separation process at the scale of single
oil–particle clusters, from a hydrodynamic standpoint, an aspect
not considered by the studies mentioned earlier. We examine the
low Reynolds number breakup of oil–particle clusters at very high
solid volume fraction, with relatively large particles, under shear
in an aqueous solution. The oil–particle clusters consist of bitumen
mixed with beach sand particles. The solid volume fraction is close
to that of Alberta oil sands (≈72%), and greater than any previous
study on oil–particle clusters [17–22].
The particle size relative to the cluster size, and the solid vol-
ume fraction  are two important parameters that determine the
fate of clusters. When the particle size relative to the cluster size is
small, so that the cluster can be considered as a continuum then
clusters undergoing shear behave like a liquid drop with a vis-
cosity governed by  [18–20]. Bonnoit et al. [20] investigated the
effect of both these parameters when they studied the detachment
of drops from dense granular suspensions (clusters). Their results
showed that the initial deformation of the cluster highly depends
on , i.e. higher  leads to a more viscous cluster, and hence slower
deformation. Whereas, at later times, close to the breakup time, the
deformation is independent of  and only depends on the viscos-
ity of the oil phase. Also, clusters breakup significantly faster than
pure oils matching the same viscosity, because the presence of the
particles within the cluster prevents the formation of a long, sta-
ble filament. Their results also showed that larger particles lead to
faster breakup.
Smith and Van de Ven [18] and Powell and Mason [19] studied
the behavior of clusters in simple shear flow and elongational flow,
respectively. The shear flow fields in [18] and [19] are more rele-
vant to the shear flow studied in this paper. At low , the particles
within the cluster rearrange themselves due to the internal circu-
lation. These particles tend to accumulate at the tips of the cluster
and are ejected if the shear stresses are strong enough [18]. As 
increases, the movement of particles within the cluster decreases
due to the particle–particle interaction. For simple shear flow, if
the shear stresses are strong enough the cluster breaks up into
two equally sized clusters [18], and for elongational flow, the clus-
ter deforms into a long cylindrical shape which pinches at regular
intervals along its length [19]. No cluster rupture is seen when
 > 0.5, and only some particles on the outside of the cluster are
pulled from the surface, because they are partially coated [18].
Various equations have been proposed to represent the viscos-
ity of solid–liquid suspensions (or clusters) [23–29]; however, these
equations are only valid when the ratio of the particle size to the
cluster is small, so that the cluster can then be considered as a con-
tinuum. This study, on the other hand, focuses on clusters where
the particle size relative to the cluster size is large O(0.1), so that
the cluster cannot be considered as a continuum. We will show that
for systems with high  and relatively large particles, the viscosity
of the oil alone governs the dynamics of the deformation and the
breakup of the cluster.
The addition of surfactants is commonly used to enhance the
separation of oil–particle–water systems. Surfactants absorb at
oil–water interfaces and not only change the interfacial proper-
ties of the two liquid phases, but can also modify the wettability of
solid particles. Surfactants can aid the separation of oil from solid
particles via three different mechanisms: roll-up, snap-off, and sol-
ubilization [30–33]. In the roll-up mechanism, shown in Fig. 1a, the
solid particle is preferentially water-wetting (contact angle greater
than 90), meaning that the oil does not wet the solid, and so when a
three phase contact line forms, the oil recedes until it detaches from
the surface. Snap-off, shown in Fig. 1b, occurs when the oil partially
or completely wets the surface (oil-wetting) and the hydrodynamic
forces are strong enough to remove a portion of the oil from the
Fig. 1. Illustration of the (a) roll-up and (b) snap-off mechanisms.
 S. Mehrabian et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35 27

Fig. 2. Critical capillary number for droplet breakup in simple shear [38].

solid particle. Solubilization can separate almost all of the oil, but tension, and shearing time are considered. Optimum oil–particle
requires a high concentration of surfactants, which is impractical separation conditions are then discussed in terms of the cluster-
in most industrial applications, and so is not considered here [32]. based capillary number Ca and the viscosity ratio p.
An analysis of oil–particle–water systems can be guided by the
considerable literature on the deformation and breakup of liquid 2. Materials and methods
droplets in an unbounded media subject to shear [34–42]. Two
dimensionless parameters, the capillary number and the viscosity 2.1. Experimental setup
ratio, are used to characterize such systems:
1 ˙ A rotating/stationary plate-plate shearing device outfitted with
Ca = (1) a microscope was used to generate a simple shear flow (Fig. 3).
/R
Both plates are polycarbonate and transparent, allowing observa-
2
p= (2) tion using the microscope attached to the bottom plate. The top
1 plate (5 cm diameter) is attached to an IKA EUROSTAR mixer that
1 and 2 are the viscosities of the aqueous solution and dis- rotates at an angular velocity of 30 rpm. The gap between the two
persed phase (oil drop), respectively, ˙ is the local shear rate, R plates is h = 1 mm. All experimental images shown in this paper are
relates to the curvature of the oil drop, and  is the interfacial of the x-y plane.
tension between the oil phase and aqueous solution. Ca expresses Coker feed bitumen donated by Syncrude was used as the oil
the ratio between shear stresses and interfacial tension: the shear phase (16.3 wt% saturates, 39.8 wt% aromatics, 28.5 wt% resins, and
stresses promote the deformation of the droplet, while the inter- 14.7 wt% ashphaltenes, according to a SARA analysis [48]). The bitu-
facial tension opposes the deformation. Fig. 2 presents a version men was diluted with toluene at different concentrations to yield
of the Grace curve [38], showing Cacrit required for drop breakup
in simple shear. Below the curve, the interfacial tension is strong
enough to prevent breakup. Above the curve, the shear stress is
strong enough to break a droplet. At Ca far above the critical value,
the drop quickly becomes unstable and stretches into a long cylin-
drical thread, which disintegrates into many drops. At viscosity
ratios above 3, no breakup occurs regardless of the shear applied.
While the majority of research has focused on Newtonian
systems [34–42], many fluids encountered in practice are shear
thinning or viscoelastic [43–47], which complicates droplet defor-
mation and breakup. De Bruijn [46] studied the breakup of
non-Newtonian systems extensively. He found that Cacrit for a vis-
coelastic droplet in a Newtonian aqueous solution is higher than
for a corresponding Newtonian droplet. Mighri et al. [47] observed
an increase in Cacrit with increasing droplet viscoelasticity, but a
decrease with increasing viscoelasticity of the aqueous solution.
The presence of solid particles within the drop will modify the
deformation and breakup behavior [17–22]. Nevertheless, we will
show that the deformation and breakup will continue to be a func-
tion of Ca and p, if R in Eq. (1) is used to represent the cluster
radius and p in Eq. (2) is the ratio of the viscosity of the oil (rather
than an effective cluster viscosity) to the viscosity of the aqueous
solution.
The results of this work concentrate on three different aspects of
the cluster shearing process: the breakage of the cluster, the sep-
aration of clean particles from the cluster, and the separation of
oil drops from the cluster. The effects of viscosity ratio, interfacial Fig. 3. Schematic of the experimental setup (not to scale).
28 S. Mehrabian et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35

Table 1
Properties of the fluids used in this work. p is averaged over the experiments.
2
Oil phase Aqueous phase p= 1
 (mN/m)

Bitumen (%wt) Toluene (%wt) 2 (Pa s) CMC (%wt) SDHS (ppm) 1

K (Pa sn ) n

A1 0 13
A2 800 4.5
59 41 0.015 2.0 1.3 0.76 0.032
A3 1500 0.62
A4 3000 0.02

B1 0 13
B2 800 4.5
77 23 0.10 1.5 0.44 0.79 0.51
B3 1500 0.62
B4 3000 0.02

C1 0 13
C2 800 4.5
77 23 0.10 1.0 0.051 2.5
C3 1500 0.62
C4 3000 0.02

a wide range of viscosities. Toluene (99.5% purity) was purchased
from Caledon Lab, Canada. Washed and dried beach sand (mesh
70–100) with an average radius of 160.8 ␮ m (standard deviation
of 34.3 ␮ m) was used as the solid phase. An oil/sand mixture was
prepared with a solid volume fraction of  = VsV+V s
o
= 0.72, where
Vo is the oil volume, and Vs the solid volume. The volume fraction of
solid particles used in this work is much higher than any previous
work, and similar to that of Alberta oil sands. An aqueous solution of
Carboxymethyl Cellulose (CMC, with an average molecular weight
of 250,000) was purchased from Sigma–Aldrich, Canada. The con-
centration of the CMC varied in the aqueous solution depending on
the viscosity ratio that was studied. The surfactant sodium dihexyl
sulfosuccinate (SDHS, 80% aqueous solution) was purchased from
Sigma–Aldrich. 3% NaCl was added to the aqueous solution to opti-
mize the performance of the interfacial tension [49].
A TA Instrument Carrie-Med rheometer was used to measure
the viscosities of both the oil phase and the aqueous solution. The
aqueous solutions were non-Newtonian (shear thinning) and can
be described by a power law equation  = K ˙ n . An oscillation test
was also performed at several shear stresses to verify that the fluids
were not viscoelastic. To characterize the viscosity ratio of the oil
phase to the aqueous solution, we require an apparent viscosity for
the CMC solutions. The apparent viscosity of a power law fluid is
given by the following equation:
viscosity ratios, B1–B4 intermediate viscosity ratios, and C1 to C4
high viscosity ratios. Four different interfacial tensions were also
examined: moving from systems 1–4, the interfacial tension was
decreased by increasing the concentration of SDHS in the aqueous
solution.
2.2. Experimental procedure
After preparing each batch of oil/sand mixture, a small amount
of the batch was separated and placed on the bottom plate which
was already filled with the aqueous solution. A few drops of the
aqueous solution were then poured over the cluster, to completely
engulf it. Then the bottom plate was moved toward the top plate,
which is attached to the mixer, until the height of the gap between
the two plates was 1 mm. With this procedure, we ensured that
the cluster never touched the plates. An image of the initial (“pri-
mary”) cluster was taken before shearing. Once the upper plate
began to rotate about its axis, the cluster was subjected to a shear
force generated by the aqueous solution. Upon completion of the
experiment, the broken (“secondary”) clusters and the separated
oil drops were imaged for further analysis. After collecting theses
images, the mixer was restarted at very high speed for a consid-
erable amount of time to break any remaining cluster into single
particles. Then using the microscope, the total number of single

1 = K ˙ n−1 (3)

where K is the consistency index and n the power law index. For
the experimental setup in this work:
rω
˙ = (4)
h
where r is the relative distance of the cluster from the center of
the plate, ω is the angular velocity, and h is the height of the gap
between the two plates. We kept the angular velocity and the gap
constant for all experiments, and so the shear rate varied from 42
to 64 1/s depending on the value of r.
For systems where  > 1, the interfacial tension values were
measured using the Du Nouy Ring method using a Sigma70
tensiometer (KSV Instrument), and for systems where  < 1 the
spinning drop method was employed (Temco Inc. Model #500).
In all measurements, toluene was used as the oil phase because it
is a good substitute for bitumen–toluene mixture [49]. Table 1 lists
the fluid properties of each system.
12 systems with different capillary numbers and viscosity ratios
Fig. 4. 12 different systems with different viscosity ratios and interfacial tensions
were studied and compared to the results of Grace [38], as illus-
studied in this work (red dots) and compared to Grace curve [38]. (For interpretation
trated in Fig. 4. The capillary numbers and the viscosity ratios of the references to color in this figure legend, the reader is referred to the web
were calculated using Eqs. (1)–(4). Systems A1–A4 represent low version of this article.)
 S. Mehrabian et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35 29

Fig. 5. Different combinations of oil drops, clean sand particles, and secondary clusters. The figures in the first and second column are same, but with different backgrounds.
The images in the first column are taken with a white background to show the oil drops, and a polarizer film is used as the background in the second column to show the
sand particles. The schematic figures of each system is given in the third column where the black circles represent oil drops, and the red circles represent sand particles. The
schematic figures are not to scale. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

particles were counted. To study the effect of shearing time on the
breakup, two sets of experiments were conducted; one set with
30 s of shear and one set with 90 s of shearing time. Each experi-
ment was repeated three times. Each experiment took about 2 h to
conduct.
In systems where a cluster breaks up, a combination of clean
solid particles, oil droplets, and secondary clusters is generated.
The secondary clusters can be singlets (one solid particle partially
coated by oil), doublets (two solid particles attached by an oil
droplet), and n-plets (where n is the number of solid particles bound
by an oil droplet). Fig. 5 illustrates images of oil drops, clean sand
particles, and different secondary clusters. The first and second col-
umn in Fig. 5 correspond to the same images, but with different
background. The first column has a white background to show oil

Fig. 6. Different modes of deformation and breakup of oil–particle clusters. System C1, high  and high p, do not breakup. System A1, high  and low p, and system A4, low
 and low p, do breakup. The scale corresponds to all frames.
30 S. Mehrabian et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35

Table 2
Capillary number at t = 0 (primary cluster), t = 30 and 90 s. Camin is based on the single particle diameter.

Cat=0 (standard deviation) Cat=30 s (standard deviation) Cat=90 s (standard deviation) Camin

A1 1.2 (0.13) 0.37 (0.011) 0.31 (0.016) 0.27

A2 2.9 (0.65) 1.1 (0.21) 0.98 (0.018) 0.86
A3 28 (1.9) 6.9 (1.2) 6.9 (0.77) 6.8
A4 866 (120) 230 (24) 226 (19) 212
B1 0.67 (0.73) No breakup
B2 1.9 (0.19) 0.73 (0.11) 0.46 (0.031) 0.41
B3 12 (1.2) 4.4 (0.43) 3.2 (0.73) 2.4
B4 365 (128) 94 (15) 78 (3.3) 75
C1 0.015 (0.035) No breakup
C2 0.21 (0.034) No breakup
C3 1.7 (0.12) No breakup 0.72 (0.073) 0.47
C4 69 (11) 26 (4.8) 18 (0.83) 12

using a global threshold (gray-level) [50]. Smaller primary clusters

are closer to have a spherical shape, but large clusters tend to have
cylindrical shape since they are closer to the plates. The primary
and secondary clusters, and the oil drops formed after shearing
were assumed to have circular projected areas. By converting the
projected areas of the clusters and of the oil droplets to equivalent
circles, radii were calculated using the MATLAB code. The radii of
primary clusters ranged from 345 to 782 ␮ m.

3. Results and discussion

3.1. Cluster breakup

Experimental results of cluster breakup are presented as a func-

Fig. 7. Histogram of secondary clusters for system B2 after 90 s of shear. The solid
blue line results from fitting the data using the Weibull distribution function. (For
interpretation of the references to color in this figure legend and in text, the reader
is referred to the web version of this article.)
droplets, which are black. The second column has a polarizer film
in the background to show sand particles that appear as clear areas
(light gray).
We quantify our results using the cluster-based capillary num-
ber defined in Eq. (1) and the viscosity ratio defined in Eq. (2), where
R refers to the radius of the cluster and 2 refers to the viscos-
ity of the oil, not the effective viscosity of the cluster. Cluster sizes
were determined using MATLAB image processing toolbox. The res-
olution of the RGB images taken was about 13 ␮ m per pixel. The
RGB images were converted to grayscale format and then to binary
tion of viscosity ratio p and interfacial tension , for clusters
characterized by a high volume fraction  of relatively large solid
particles. Fig. 6 depicts different modes of deformation and breakup
observed in the experiments. Fig. 6, system C1 (high , and high p),
shows the case where no breakup takes place. In this case the clus-
ter rotates about its own center and about the center of the plate at
a velocity of about rω2
. The cluster initially deforms, but eventually
acquires a stable shape. In Fig. 6, system A1 (high , low p), the shear
stresses are strong enough to overcome the forces that hold the pri-
mary cluster together. The oil that binds the particles elongates into
a thread that grows in length until it breaks. If an oil droplet was
sheared at similar conditions, its deformation and breakup would
be predictable. Cluster breakup, on the other hand, is stochastic and
cannot be predicted because of the random distribution of particles.
The rupture leads to the generation of a few secondary clusters (last
sequence of Fig. 6, system A1), which may then lead to a few clean
solid particles, and a few oil droplets (not shown in Fig. 6). Due to the
high solid volume fraction, there are some solid particles that are

Fig. 8. Weibull distribution for system B2 ( = 4.5 mN/m, p = 0.5). Each curve represents an individual experiment. The number of secondary clusters increases and the size
of the secondary clusters decreases as the shearing time increases from 30 s to 90 s.
 S. Mehrabian et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35 31

Fig. 9. Weibull distribution for system A3( = 0.62 mN/m, p = 0.03). Each curve represents an individual experiment. The number and size of secondary clusters are almost
similar for shearing times of 30 and 90 s.

Fig. 10. Weibull distribution for systems B2 and A2 ( = 4.5mN/m) after 30 s of shear are presented to illustrate the effect of viscosity ratio p. The number of secondary clusters
increase and the size of the secondary clusters decrease when p is lowered.

on the surface of the primary cluster and can be in contact with the
aqueous solution, so contact lines exist and hence, these particles
are partially coated, which presumably makes them more likely to
separate. Fig. 6, system A4, illustrates an experimental observation
where  and p are both very low. In this case the cluster quickly
deforms and disintegrates into a large number of oil drops, clean
particles, and singlets.
The 12 systems of Fig. 4 were sheared for two different lengths
of time: 30 and 90 s, to study the effect of time on the breakup
process. Table 2 shows (from left to right) the capillary number
of the primary cluster at t = 0, the average capillary number of the
secondary clusters at t = 30 and 90 s, and the minimum possible
capillary number for each system based on the average radius of a
clean particle. The data in Table 2 is an average of three experiments
for each system.
Primary clusters with Ca(t=0) < 1 (systems B1, C1, and C2) do
not breakup. System C3 requires a long shear time to breakup
because of the high viscosity of the oil, and does not breakup in

Fig. 11. Weibull distribution for systems B2 and B4 (p = 0.5) after 30 s of shear are presented to illustrate the effect of interfacial tension . The number of secondary clusters
increase and the size of the secondary clusters decrease when  is lowered.
32 S. Mehrabian et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35
Fig. 12. Fraction of clean particles for different Ca and p.
the first 30 s. In general, if Ca(t=0) > 1, the average Ca of the sec-
ondary clusters decreases with time, as smaller and smaller clusters
are formed until they reach Camin . As the average Ca approaches
Camin , more and more of the secondary clusters are singlets or clean
particles.
For systems with a low viscosity ratio (systems A1–A4), Ca
decreases rapidly, meaning that most of the breakup takes place in
the first 30 s. This behavior is also illustrated in Fig. 6. Even system
A1, which has a relatively high interfacial tension, the primary clus-
ter broke up into three secondary clusters in less than 10 s. Breakup
occurs even sooner at lower interfacial tensions (e.g. system A4). For
systems A1–A4, Cat=90 s are very close to Camin (less than 15% devi-
ation), meaning that 90 s of shear is sufficient to produce mostly
singlets and clean particles.
The breakup rate is slow for systems B2–B4, and even slower for
systems C3 and C4. There is a big difference between Cat=90 s and
Camin for systems C3 and C4 (more than 50% deviation), implying
that more than 90 s are required to break every secondary clus-
ter into singlets or clean particles. It was also observed that some
of the secondary clusters reached a steady state condition and did
not breakup anymore. The high viscosity ratio of systems C1–C4
slows the rate of deformation and breakup of the cluster. In conclu-
sion, systems with high viscosity ratios (e.g. C1–C4) will breakup
only when the interfacial tension is very low, and when sheared
for a long enough time to allow for the deformation of the viscous
oil.
The secondary cluster size distributions are presented here to
better understand the data in Table 2. The Weibull distribution
function is used to model the cluster size distribution since it has
been widely used to represent particle size distribution in the lit-
erature [51,52]. Fig. 7 illustrates the histogram of experimentally
obtained secondary clusters radii (red and green bars), being fitted
by a Weibull distribution function (black smooth line) for system
B2 after 90 s of shear. i = 48 represents the number of secondary
clusters in that experiment. The red bars on the right side of Fig. 7
represent n-plets, whereas the green bars on the far left side rep-
resent singlets or clean solid particles. All experimental data were
fitted within 90% of confident level.
Fig. 8 shows the Weibull distribution fitted for system B2 at 30
and 90 s of shear time. Each curve represents a single experiment.
The red curves are for 30 s, and the blue curves are for 90 s of shear,
respectively. It can be seen the red curves have a broader distri-
bution, but with a lower frequency compared to the blue curves,
meaning that as time increases the number of secondary clusters
increase but their size decrease. The number of secondary clusters
after 30 s of shear range from 5 < i < 11, and the number of secondary
clusters after 90 s of shear range from 22 < i < 55. Systems C4, B1, B3,
and B4 have similar trends over time.
As mentioned earlier in systems A1, A2, A3, and A4 (low p) most
of the breakup takes place in the very early stages of the shear, and
the results observed after 30 and 90 s are very similar. This behavior
can also be seen in Fig. 9, which shows the Weibull distribution for
system A4 at 30 and 90 s of shearing time. The number and size of
the secondary clusters seen after 30 s is very similar to the number
and size of the secondary clusters seen after 90 s of shear.
Fig. 10 shows a typical example of the effect of p on the sec-
ondary cluster size distribution. This comparison is done between
systems B2 (p = 0.51) and A2 (p = 0.032) at 30 s of shearing time and
 = 4.5mN/m. The number of secondary clusters increase and the
size of the secondary clusters decrease when p decreases. Fig. 11
shows a typical example of the effect of  on the secondary clus-
ter size distribution. In here, systems B2 ( = 4.5mN/m) and B4
( = 0.02mN/m) are compared at 30 s of shearing and p = 0.5. The
number of secondary clusters increases and the size of the sec-
ondary clusters decreases when  is decreased.
Powell and Mason [19] concluded that clusters behave like
droplets, with an effective viscosity that is a function of the solid
volume fraction  as long as the cluster is considered a continuum,
i.e. when the particle size relative to the cluster size is very small.
Our results show that this approach is not valid at high , with
large particles. Our experiments show that some of the large parti-
cles cover the outer surface of the cluster and are not fully coated by
the oil (suggesting that contact lines exist), and that the oil is mostly
 S. Mehrabian et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35
Fig. 13. Coalescences and redeposition of an oil drop on a n-plet during shear for system A3 (p = 0.03 and  = 0.62mN/m).
centered in the core of the clusters. When a cluster is sheared, the
oil in the center deforms and breaks up, which results in secondary
clusters. Hence, the dynamics of clusters at high , with large par-
ticles, depends on the viscosity of the oil alone, and not an effective
viscosity of the cluster. If we were to assume that the breakup of the
cluster depends on an effective viscosity of the cluster, greater than
the viscosity of the oil, then all 12 systems shown in Fig. 4 would
shift to the right. Then systems C1, C2, C3, and C4 would definitely
be in the no breakup zone, yet our results indicate that even systems
C3 and C4 do breakup. In conclusion, one can characterize highly
concentrated clusters according to the results presented by Grace
[38] in Fig. 2, and obtain critical conditions for breakup.
3.2. Separation of particles from clusters
Next, we present results on conditions when solid particles are
separated from the clusters and contain no oil on them (clean parti-
cles). As mentioned before, we quantify separation by the number of
clean particles after shear. Fig. 12 plots the number of clean or sep-
arated particles normalized by the total number of particles within
the primary cluster after shear, for different Cat=0 and p. As indi-
cated before, Cat=0 has to be greater than 1 in order for the primary
cluster to breakup, so no clean particles was observed after shear
for systems where Cat=0 < 1 regardless of p and shearing time.
Fig. 12a corresponds to the low viscosity ratio systems (A1–A4),
where the separation process is highly stochastic: the oil that holds
the cluster together quickly stretches and breaks up into very small
oil droplets, that are dispersed throughout the circular path of the
shearing device, some of which collide and re-deposit on particles
and secondary clusters. This explains why the results obtained at
30 and 90 s of shear are not much different. Also, there is only a
slight improvement in the separation process as Ca increases from
Fig. 14. The formation of an oil droplet after the breakup of the liquid/liquid interface via the snap-off mechanism (a, b, and c are not to scale).
33
O(1) to O(103 ). Fig. 13 shows a typical observation of how an oil
re-deposits on a n-plet. The red arrow in the first frame shows the
direction of the flow. Since the oil drop is relatively smaller than
the n-plet, it will experiences a smaller drag. Consequently, the oil
drop will have a higher velocity and approaches the n-plet (frame
2). Finally in the third frame the oil drop completely sits on the
n-plet and remains attached to it.
Fig. 12b corresponds to systems B1–B4, where the separation
process is less stochastic and takes place in a more predictable
manner. At Ca ∼ O(1), a few clean particles appear after 30 s, and
many clean particles are observed after 90 s. The same behavior
takes place at Ca  1, with more clean particles. At very high capil-
lary numbers Ca ∼ O(102 ), the oil approaches complete separation
from the particles. The maximum number of clean particles is seen
for system B4.
Fig. 12c corresponds to systems C1–C4 with high viscosity ratios.
No clean particles are observed in the first 30 s of shear, regardless
of Ca, because more time is required for the oil to deform and allow
sand particles to liberate. After 90 s clean particles are observed
only for Ca > 1.
3.3. Breakup and detachment of oil droplets from clusters
Finally, we present results on the breakup and detachment of
the oil droplets from the primary and secondary clusters and their
size distribution as a function of viscosity ratio and interfacial ten-
sion. By carefully examining the images of the breakup process, it
is evident that the formation of oil droplets during shearing is the
result of either the rupture of liquid/liquid interfaces via snap-off
(Fig. 14), or the detachment of oil from sand particles via roll-up
(Fig. 15). Fig. 14 illustrates different ways that droplets form due to
the breakup of a liquid/liquid interface. The right column in Fig. 14
34 S. Mehrabian et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35
Fig. 15. Separation of an oil drop from a singlet via the roll-up mechanism.
Fig. 16. Droplet size distribution using the Weibull distribution for different (a) interfacial tensions and (b) viscosity ratios.
depicts some experimental observations. In the snap-off mecha-
nism, the liquid bridge that binds particles together stretches into
a thread and eventually breaks due to capillary wave instabilities,
leaving a clean droplet behind. Breaking up the liquid/liquid inter-
face requires overcoming the work of cohesion. The amount of
stretching depends on the viscosity of the oil. The stability of the
oil thread has been studied elsewhere [53,54]. This mechanism is
frequently seen in systems A1–A4, where the viscosity of the oil
is low, so that the energy required to deform the oil is low. Fig. 15
demonstrates a typical experiment where an oil drop partially coats
a particle (singlet), and due to low interfacial tension and the mag-
nitude of the shear, the contact angle of the drop on the particle
increases and eventually separates. This separation overcomes the
work of adhesion. The size of the oil drop relative to the size of
the particle is an important factor. Larger oil drops increase the
area subjected to shear, and hence separate more easily; very small
drops are more difficult to remove from particles.
The presence of surfactants strongly affects the droplet size dis-
tribution. Their primary role is to reduce , which increases Ca,
hence, facilitating the breakup of the liquid–liquid interface. This
causes the droplets to breakup into a greater amount of smaller
droplets compared to a system with no surfactants. Fig. 16a shows
how the droplet size changes with respect to interfacial tension
after 90 s of shear, for viscosity ratio p=0.03. As the interfacial ten-
sion becomes lower, the number of oil droplets increase but their
size decrease. Fig. 16b shows how droplet size changes with respect
to viscosity ratio at a constant interfacial tension of 0.02 mN/m. As
the viscosity ratio decreases, the number of oil droplets increase but
their size decrease. The dashed lines in Fig. 16a and b show the pixel
resolution of the captured images. Droplets that have radii smaller
than 13 ␮ m could not be detected. However, smaller droplets
than 13 ␮ m can be expected when p = 0.03 and  = 0.02 mN/m
(system A4).
4. Conclusions
We studied the shear-induced breakup of oil–particle clusters,
and the separation of particles from clusters at very high volume
fractions of solids in oil, at low Reynolds numbers. It is shown that
the breakup of oil–particle clusters at high solid volume fractions
depends on the viscosity of the oil phase and not on the effective
viscosity of the cluster. The oil phase in clusters with high solid
volume fractions is mostly located in the center of the cluster and
the particles are attached to the cluster by liquid bridges. When
the primary cluster is sheared, the oil in the center of the cluster
deforms and ruptures; hence, the cluster breaks up into secondary
clusters. Different modes of breakup were observed depending on
the viscosities of the oil and the aqueous solution, and the interfacial
tension between them. The results of the cluster breakup experi-
ments are very similar to the results of droplet breakup presented
by Grace [38], meaning that if Ca > Cacrit , the primary cluster will
breakup into smaller secondary clusters. Interestingly, no cluster
breakup and no clean particles were observed after shear if Cat=0 < 1,
regardless of viscosity ratio, and shearing time.
Systems with high drop/continuous phase viscosity ratios resist
deformation and eventual break up. Cluster disintegration is facil-
itated by lower interfacial tensions and longer shearing time. The
use of surfactants to reduce the interfacial tension accelerated the
disintegration of the cluster, and the eventual separation of oil from
the particles. The liberated oil droplets will further breakup into
smaller droplets and may coalescence and re-deposit on the sec-
ondary clusters, particularly at near ultra-low interfacial tensions.
Acknowledgments
The financial assistance received from the Institute for Oil Sands
Innovation (IOSI) at the University of Alberta is highly appreciated.
 S. Mehrabian et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 483 (2015) 25–35
The authors also thank Professor A. Ramchandran for his comments
and advice on earlier versions of the manuscript.
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