See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/254329426

Experimental Investigation of Rheological and Morphological Properties of

Water in Crude Oil Emulsions Stabilized by a Lipophilic Surfactant

Article  in  Journal of Dispersion Science and Technology · January 2012

DOI: 10.1080/01932691.2012.667297

CITATIONS READS

15 383

4 authors:

Mohammad Bagher Sadeghi Ahmad Ramazani S.A.

Shiraz University Sharif University of Technology
8 PUBLICATIONS   17 CITATIONS    193 PUBLICATIONS   2,528 CITATIONS   

SEE PROFILE SEE PROFILE

Vahid Taghikhani C. Ghotbi

Sharif University of Technology Sharif University of Technology
129 PUBLICATIONS   2,597 CITATIONS    156 PUBLICATIONS   2,185 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Thesis View project

study on Rheological behavior of W/O Emulsions View project

All content following this page was uploaded by Mohammad Bagher Sadeghi on 31 October 2018.

The user has requested enhancement of the downloaded file.

This article was downloaded by: [Northeastern University]
On: 21 October 2014, At: 19:50
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Journal of Dispersion Science and Technology

Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/ldis20

Experimental Investigation of Rheological and

Morphological Properties of Water in Crude Oil
Emulsions Stabilized by a Lipophilic Surfactant
a a a a
Mohammad Bagher Sadeghi , Ahmad Ramazani S. A. , Vahid Taghikhani & Cyrus Ghotbi
a
Department of Chemical and Petroleum Engineering , Sharif University of Technology ,
Tehran , Iran
Accepted author version posted online: 01 Mar 2012.Published online: 25 Feb 2013.

To cite this article: Mohammad Bagher Sadeghi , Ahmad Ramazani S. A. , Vahid Taghikhani & Cyrus Ghotbi (2013)
Experimental Investigation of Rheological and Morphological Properties of Water in Crude Oil Emulsions Stabilized by a
Lipophilic Surfactant, Journal of Dispersion Science and Technology, 34:3, 356-368, DOI: 10.1080/01932691.2012.667297

To link to this article: http://dx.doi.org/10.1080/01932691.2012.667297

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
 Journal of Dispersion Science and Technology, 34:356–368, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932691.2012.667297

Experimental Investigation of Rheological and

Morphological Properties of Water in Crude Oil
Emulsions Stabilized by a Lipophilic Surfactant
Mohammad Bagher Sadeghi, Ahmad Ramazani S. A., Vahid Taghikhani, and
Cyrus Ghotbi
Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran, Iran

GRAPHICAL ABSTRACT
Downloaded by [Northeastern University] at 19:50 21 October 2014

Rheological behavior of two crude oils and their surfactant-stabilized emulsions with initial
droplet sizes ranging from 0.5 to 75 lm were investigated at various temperatures under steady
and dynamic shear testing conditions. In order to evaluate the morphology and Stability of
emulsions, microscopic analysis was carried out over three months and average diameter and size
distribution of dispersed droplets were determined. The water content and surfactant concen-
tration ranged from 10 to 60% vol/vol and 0.1 to 10% wt/vol, respectively. The results indicated
that the rheological properties and the physical structure and stability of emulsions were signifi-
cantly influenced by the water content and surfactant concentration. The crude oils behaved as
Newtonian fluids over a wide range of shear rates, whereas the emulsions behaved as non-
Newtonian fluids, indicating shear-thinning effects over the entire range of shear rates. The
viscosity, storage modulus and degree of elasticity were found to be significantly increased with
the increase in water content and surfactant concentration. The maximum viscosity was observed
at the point close to the phase inversion point where the emulsion system changes from water-in-
oil emulsion to oil-in-water emulsion. The results also indicated that the rheological properties of
crude oils and their emulsions are significantly temperature-dependent.

Received 7 January 2012; accepted 6 February 2012.

The authors would like to thank Mr. Peymanpou at SUT biochemistry research center for his useful helps and comments on the
performing the microscopic investigations.
Address correspondence to Ahmad Ramazani S. A., Department of Chemical and Petroleum Engineering, Sharif University of
Technology, Azadi Avenue, P.O. Box 11365-9465, Tehran, Iran. E-mail: Ramazani@sharif.edu

356
 WATER IN CRUDE OIL EMULSIONS WITH LIPOPHILIC SURFACTANT
Keywords Droplet size, rheological behavior, surfactant, water-in-crude oil emulsion
1. INTRODUCTION
Emulsion is a disperse system consisting of at least two
immiscible liquids in which liquid droplets (dispersed
phase) of very small size spread within a second immiscible
liquid (continuous phase).[1,2] Emulsions can be found at
many practical applications such as cosmetics, pharmaceu-
ticals, petroleum industry, food products, painting, biologi-
cal liquids, etc. This wide range of uses of emulsions is a
result of their highly variable physical properties.[1,3–6] In
the case of petroleum industry, presence of emulsions is
very common;[7] in fact the emulsions can be encountered
in almost every part of the petroleum production and
recovery process and also at many stages during drilling,
producing, transporting, and processing of crude oil.[8]
Downloaded by [Northeastern University] at 19:50 21 October 2014
Different criteria can be used to classify the emulsions. In
the most known classification of emulsions, water and oil
are as the immiscible phases, which either water or oil can
be defined as the dispersed phase. Emulsions owning
completely different physical characteristics are usually
obtained depending on which one is the dispersed phase;
thus, the emulsions may be distinguished in principle as
the simple and multiple emulsions. The simple emulsions
include water-in-oil (water droplets dispersed in continuous
oil phase (W=O)) and oil-in-water (oil droplets dispersed in
continuous water phase (O=W)). Multiple or double emul-
sions are the emulsions in which the dispersed phase
droplets themselves in a continuous phase contain finely
dispersed droplets of a separate phase. Water-in-oil-in-
water (W=O=W) and oil-in-water-in-oil (O=W=O) emul-
sions are two common types of multiple emulsions.[9,10]
However, it should be noted that more complicated mul-
tiple emulsions can also exist. Contrary to many industries,
in the petroleum industry, W=O emulsions are more
common as compared to the O=W emulsions;[7] therefore,
W=O emulsions are sometimes referred to as normal
emulsions while O=W emulsions are referred to as reverse
emulsions. Another criterion to classify the emulsions is
based on the average droplet size of the emulsions. There-
fore, the emulsions can be divided into three different
groups: microemulsions (10–100 nm), miniemulsions (100–
1000 nm) and macroemulsions (0.5–100 mm). The first
group includes the emulsions that are thermodynamically
stable; this means the two immiscible phases do not separate
over time and emulsion can maintain stable whereas
miniemulsions and macroemulsions are thermodynamically
unstable and tend to break down over time.[5]
The emulsion stability is conferred by the presence of
emulsifying agents at the interfaces that may defer the tend-
ency of the liquids to separate. Such agents which are often
referred to as surfactants are the molecules with polar and
nonpolar chemical groups in their structure. Usually in the
357
presence of a surfactant, the dispersed phase in the emul-
sion tends to form the spherical droplets.[11] The surfac-
tants lower the interfacial tension and, hence, the Laplace
pressure so that the energy required for emulsification is
reduced.[12] As a general rule (Bancroft’s rule) it can be sta-
ted that the phase in which the surfactant is more soluble
constitutes the continuous phase.[13] Fingas et al.[14] studied
the stability of W=O emulsion and defined that the stable
emulsion is an emulsion in which the water persists for
more than 5 days. They found that the high viscosity of
stable W=O emulsions may be attributed to a semi-solid
or gel formed from the crude oil phase. Several studies have
been carried out to find the role of asphaltenes, resins, and
waxes on stability of water-in-crude oil emulsions. Results
revealed that asphaltenes and wax crystals adsorb at the
water-oil interface and promote the stability, whereas
resins reduce the stability by solubilizing the asphaltenes
in oil, and removing them from the interface.[13,15]
One of the most important properties of emulsions is
their flow or in other words their rheology.[16,17] Emulsions
as the colloidal systems are a very attractive subject of rheo-
logical investigations; hence, in recent years the rheology of
emulsions has attracted the attention of many fields not
only for fundamental scientific understanding but also for
practical industrial applications. Rheology is defined as
the study of the deformation and flow of materials.[16,18]
The understanding of the rheological properties, especially
viscous behavior of emulsions, is very important in the
formulation, stability, handling, processing, storage, and
pumping of such colloidal systems.[9]
In order to study on emulsion stability, an understanding
of surface forces, droplet interactions and film stability is
seen as being essential to get the right approach. The desta-
bilization mechanism of an emulsion involves two general
steps; the collisions between the droplets may cause the
transient films formation between them. If repulsive interac-
tions between the droplets are not enough strong and if
adhesion energies are large enough, adhesion can be pro-
moted; this phenomenon, flocculation, is the first step of
destabilization mechanism. Coalescence is the second step
in which formed films will gradually start to thin and rup-
ture, hence, the droplets combine into larger ones.[13]
Adsorbed surfactant layer on dispersed phase droplet inter-
faces ensures that there is a short range repulsive force
between them, which prevents coalescence of droplets and
subsequently phase separation.[1] If the attractive van der
Waals interactions become higher than the repulsive inter-
actions, flocculation process may be take place.
A vast amount of published literature exists on rheo-
logical study of emulsions under different applied
conditions;[8–10,16,18–21] however, crude oil emulsions which
 358 M. B. SADEGHI ET AL.
have great importance in the oil industry have received less
attention. Rheological properties of crude oil emulsions are
strongly influenced by several significant parameters such
as dispersed phase content, temperature, rate of defor-
mation or shear rate, surfactant concentration, average
droplet size, droplet size distribution, etc.[22] One of the
most challenging problems in the petroleum industry is
the formation of water-in-crude oil emulsion. This problem
may effetely results in the enhancement of crude oil
viscosity and consequently the reduction of oil production.
The viscoelastic properties of emulsions are an interest-
ing subject to get a better understanding of the rheological
behavior of such disperse systems. Viscoelasticity is the
property of materials that is referred to the combination
of viscous and elastic characteristics. Viscoelastic properties
can be investigated using oscillatory measurements.[2] In
general, dilute emulsions behave as Newtonian fluid. As
Downloaded by [Northeastern University] at 19:50 21 October 2014
the dispersed phase content increases, the behavior of emul-
sions approaches to the non-Newtonian flow behavior. In
more concentrated emulsions, interactions between the
droplets play an important role to control the viscoelastic
behavior of emulsions and to determine the relative contri-
butions of viscous and elastic properties. It has been shown
that the non-Newtonian flow behavior and viscoelastic
effects of colloidal systems such as emulsions can be attrib-
uted to the deformable nature of dispersed phase droplets,
even when immiscible phases behave as a Newtonian fluid
separately.
Many works have been carried out to investigate the
rheological properties of concentrated emulsions. In this
case it is essential to take into account the effect of Brownian
motion and interactions between the dispersed phase dro-
plets. Brownian motion and droplet-droplet interactions in
the emulsions strongly depend on the average size and size
distribution of droplets. As the size of dispersed phase dro-
plets decreases, the contributions of droplet-droplet interac-
tions and Brownian motion become more pronounced.
Rheological properties of emulsions, especially concen-
trated emulsions, are strongly influenced by the droplet size
and droplet size distribution.[8,21] As droplet size of dis-
persed phase decreases, the viscosity of emulsion increases.
In fact, by decreasing the droplet size of emulsion, the
number of dispersed phase droplets per unit volume of
emulsion increases; hence, average distance between dro-
plets decreases and emulsion becomes more rigid.[23]
The objective of this work was to study the rheological
behavior and morphological properties of a series of emul-
sions formed by aqueous phase containing deionized water
and oil phase represented by the crude oils in the presence of
a lipophilic surfactant. Hence, in the first part the stability
and structural properties of synthetic emulsions were inves-
tigated. In the second part the steady shear and oscillatory
shear measurements were carried out and the effects of
some important parameters such as the dispersed phase
content, temperature, surfactant concentration and rate of
deformation on rheological behavior of emulsions were
investigated.
2. EXPERIMENTAL
2.1. Materials and Emulsion Preparations
The experiments were carried out using two heavy crude
oils named Soroush and Nowruz as continuous phase.
Some physical and chemical properties of these crudes are
presented in Table 1. A commercially available oil-soluble
surfactant, Sorbitan monooleate (Span 80), obtained from
Merck-Schuchardt, Germany, with the hydrophilic–
lipophilic balance (HLB) value of 4.3, was used to stabilize
water-in-crude oil emulsions. Chemical structure of this
nonionic surfactant with polar head of hydrophilic sorbitan
group and nonpolar tail of hydrophobic oleic acid group is
shown in Figure 1. In all cases, deionized water was used for
emulsification as the aqueous phase.
In order to prepare the synthetic emulsion, the crude oil
and emulsifier (Span 80) were mixed at 60
C while stirring
using a standard four blade propeller at speed of 500 rpm
for 20 minutes to obtain homogenous solution. The concen-
tration of surfactant varied from 0.1% to 10% wt=vol. At
this stage, the stirrer was switched off and the solution
was left to reach room temperature. Then water-in-crude
oil emulsions were prepared by adding deionized water (dis-
persed phase) gradually to the solution while agitating vig-
orously at speed of 2000 rpm and room temperature for 30
minutes. The volume fraction of deionized water in the
emulsions ranged from 0.1 to 0.6.
2.2. Microscopic Observations
Emulsion types and droplet size distributions were deter-
mined by analyzing the photomicrographs. The photomi-
crographs were taken with an Olympus BH-2 polarized
light microscope equipped with a digital camera (CoolSnap
Pro, Media Cybernetics). Glass microslides and coverslips
were used to prepare microscopic samples throughout the
experiments. Photomicrographs were analyzed using
image-analysis software (Image-Pro Plus V. 4.5.1.22) to
obtain the size distribution and average diameter of dis-
persed droplets. To determine the mean diameter and the
droplet size distribution, about 40 photomicrographs were
taken for each emulsion and approximately 600–700
droplets were counted.
2.3. Rheological Measurements
Rheological properties of the crude oils and their emul-
sions were investigated using a Physica MCR 301 rheometer
(Anton Paar, GmbH Graz, Austria) operated by the
Rheoplus software. The analyses were carried out using a
parallel-plate (plate diameter ¼ 25 mm) geometry measuring
 WATER IN CRUDE OIL EMULSIONS WITH LIPOPHILIC SURFACTANT 359

TABLE 1
Physical and chemical properties of crude oils
Crude API Density Viscosity @ Asphaltene Wax content Total sulphur
oil gravity (g=cm3) 30
C(Pa.s) content (wt%) (wt%) (wt%)

Soroush 19.8 0.9349 0.82 9.8 1.1 3.4

Nowruz 16.2 0.9579 1.39 12.6 1.4 3.7

denotes the emulsion which 1 hour is passed from its

preparation time and u is the water volume fraction. Micro-
scopic analysis indicated that as long as the distances
between the dispersed phase droplets are large enough,
droplets can be assumed to be spherical. This assumption
was more accurate for dilute emulsion. Therefore, in the
case of fresh and dilute emulsions, most of water droplets
had a spherical shape. The surfactant layer adsorbed at
Downloaded by [Northeastern University] at 19:50 21 October 2014

the interface of dispersed phase droplets and continuous

oil phase can be observed in the photomicrographs. Stab-
FIG. 1. Chemical structure of Span 80.
ility of an emulsion can be strongly affected by the thickness
of surfactant layer adsorbed at the interface. As the film
system. In all measurements, the gap width between the two thickness increases, the emulsion stability enhances. In fact,
plates was set to 0.5 mm to ensure multiple planes of the presence of this surfactant layer around droplets of the
droplets would be present in the sample. Before performing
measurements, the rheometer was checked with a cali-
bration fluid. All data were collected after sample thermal
equilibrium was achieved. It should also be pointed out that
in order to check the repeatability of the experimental data,
each rheological measurement was replicated three times
and average of the results was considered as final data.
The repeatability of the experiments was confirmed by com-
puting the standard deviations for the experimental data. A
solvent trap was used in order to avoid the evaporation of
the continuous phase from the samples during the measure-
ments at high temperatures. To ensure the equilibration of
the emulsions, each measurement was performed 10 hours
after emulsion preparation. For each emulsion, the steady
shear, strain sweep and frequency sweep data were collected.

3. RESULTS AND DISCUSSION

3.1. Microscopic and Droplet Size Analysis
As mentioned before, determination of emulsion types
and droplet size distribution was carried out by analyzing
the photomicrographs of the emulsions obtained by optical
microscopy. This technique is a useful direct method with
much higher confidence in the analyzing the photomicro-
graphs than the other indirect techniques. The stability of
the emulsions was also monitored over a period of 3
months. Figure 2 shows the photomicrographs of water-in- FIG. 2. Photomicrographs of water-in-Soroush crude oil emulsions in
the presence of 5% wt=vol Span 80: a) u ¼ 0.10, fresh emulsion; b) u ¼ 0.10,
Soroush crude oil (SCO) emulsions containing 10 and 30% 30 days after preparation; c) u ¼ 0.10, 90 days after preparation; d)
water cuts in the presence of 5% wt=vol Span 80 at three u ¼ 0.30, fresh emulsion; e) u ¼ 0.30, 30 days after preparation; f)
different times after emulsion preparation. Fresh emulsion u ¼ 0.30, 90 days after preparation. (Figure available in color online.).
 360 M. B. SADEGHI ET AL.
dispersed phase can induce the strong disjoining pressure,
and then control the stability and the rheological properties
of emulsion systems. As another reason, this film leads to an
enhancement of the emulsion stability by increasing the
interfacial viscosity. The structure conferred by surfactant
molecules on the thin films between the dispersed droplets
and continuous phase plays an important role in emulsion
stability. As mentioned before, Span 80 molecule includes
two groups including the sorbitan ring as the hydrophilic
head group and the hydrocarbon chain as the hydrophobic
tail group. Hydrocarbon chains have an affinity for oil and
thus, they lie on the continuous oil side of the interface;
whereas the sorbitan rings have an affinity for water and
thus, they lie on the aqueous phase side. This orientation
leads to an increase in the interactions between the hydro-
carbon chains and the continuous phase. Finally, the
adsorbed surfactant film at the interface can effetely cause
Downloaded by [Northeastern University] at 19:50 21 October 2014
the reduction in the interfacial tension between the continu-
ous phase and the dispersed phase droplets; hence, the rate
of coalescence of the dispersed phase droplets reduces and
the emulsion stability enhances. It should be noted that
the instability increases with the increase in the interfacial
area between the two phases.
Microscopic analysis revealed that the average droplet
size increases by enhancing the water cut. Average droplet
size for each emulsion was determined. The average size
of dispersed droplets were 6.7 and 12.4 mm for 10 and 30%
water in SCO emulsions, respectively when 5% wt=vol Span
80 was used as the emulsifier agent. The emulsion contain-
ing 10% water cut exhibited a good stability without phase
separation during weeks. However this emulsion showed
slight increase in the droplet size with time. Whereas in
the case of emulsion containing 30% water cut enhancement
of droplet size and flocculation effect, becomes more pro-
nounced. In all emulsions prepared in this study, it was
obviously observed that the longer the emulsion storage
time, the more pronounced is the flocculation effect. As a
result it can be said that the enhancement of droplet size
by increasing the water cut or time may cause the reduction
of interfacial film thickness and, hence, emulsion stability.
It was observed that the phase inversion, where the emul-
sion system changes from W=O emulsion to O=W emulsion,
takes place between 40% and 45% of water cut for SCO and
between 45% and 50% of water cut for Nowruz crude oil
(NCO). It is too important to predict this water cut; because
in order to reduce the pumping pressure and, hence, the
costs in the petroleum pipeline transportation, crude oil
emulsions containing water cut that are far from the phase
inversion point should be pumped to the pipelines. This is
due to the direct dependency of costs and pumping pressure
on the viscosity of crude oil emulsion.
One of the primary parameters used to describe the state
of an emulsion is droplet size distribution. The droplet size
distribution in an emulsion depends on several factors
including the properties of continuous and dispersed
phases, nature and concentration of surfactant and shear
and interfacial tension. Size distribution of droplets strongly
affects the rate of coalescence of the dispersed phase dro-
plets. In general, emulsions with the smaller size droplets
and narrower droplet size distribution are more stable. It
was observed that all the emulsions, especially concentrated
emulsions, are quite polydisperse; that is, droplets are of the
different size. This can be seen from Figures 3 and 4 which
show the droplet size distributions of 10% and 30% of water
cuts, respectively, for SCO emulsions. Results indicated
that degree of polydispersity of emulsions increased with
increase in dispersed volume fraction. In fact an increase
in degree of polydispersity is expected to cause the enhance-
ment of emulsion viscosity and shear-thinning effect. The
effect of surfactant concentration on degree of polydesper-
sity was investigated for 20% water in SCO emulsion and
it was observed the degree of polydispersity decreased by
increasing the surfactant concentration (Table 2).
The droplet sizes of the emulsions prepared in this work
was found to vary from 0.5 to 75 mm. As stated previously,
emulsion droplet sizes can range from less than 10 nm to
more than 100 mm and the droplet size of macroemulsions
range from 0.5 to 100 mm; therefore, the emulsions prepared
in this work are macroemulsions. In the most emulsions, the
droplets with the size of 52 mm and more were less than 1%,
especially when the surfactant concentration was greater
than 5% wt=vol. As depicted in Figures 3 and 4, approxi-
mately 95 and 70% of droplets in the emulsions containing
10 and 30% water cuts, respectively are the droplets with the
size of 0.5 to 15 mm. Comparison between Figures 3 and 4
reveals that the emulsion with 30% water cut having droplet
size range of 0.8-64 mm has a wider size distribution than the
emulsion with 10% water cut having droplet size range of
0.5–27 mm. Therefore, it can be stated that the emulsion
with 10% water cut is more stable than the emulsion with
10% water cut. In fact, the smaller droplets in the emulsions
have a greater Interfacial surface per unit volume as com-
pared to the larger droplets in the emulsions; therefore,
the smaller droplets are thermodynamically less stable than
FIG. 3. Droplet size distribution of 10–90% W=SCO emulsion in the
presence of 5% wt=vol Span 80.
 WATER IN CRUDE OIL EMULSIONS WITH LIPOPHILIC SURFACTANT 361

SCO, especially at high temperatures, may be attributed to

FIG. 4. Droplet size distribution of 30–70% W=SCO emulsion in the
presence of 5% wt=vol Span 80.
larger droplets. As a result, flocculation takes place and
smaller droplets stick to the larger ones. If this process pro-
ceeds, the emulsion finally breaks to separate phases. Thus,
it can be concluded that an emulsion with a narrow size dis-
Downloaded by [Northeastern University] at 19:50 21 October 2014
the disintegration of wax and asphaltene structures during
shear, while at higher shear rates viscosity becomes constant
due to the stabilization of the wax and asphaltene struc-
tures.[13,15] As depicted in Figure 5, the viscosity ranged
between 0.13 and 29 Pa.s for the NCO and between 0.12
and 38 Pa.s for the SCO over a temperature range of 2 to 80
C.
All the emulsions showed shear-thinning behavior over
the entire range of shear rates investigated as demonstrated
by the flow curves of apparent viscosity versus shear rate for
emulsions containing 10, 30 and 50% water cuts in Figure 6.
That is, the apparent viscosity decreased with increase in
shear rate. This pseudoplastic behavior becomes more pro-
nounced as water cut increases. This non-Newtonian flow
behavior of emulsions may be attributed to the deformable
nature of dispersed phase droplets, even when both immis-
cible phases are Newtonian liquids.[24] As the water cut

increase, the separation distance between dispersed droplets

tribution is more stable than an emulsion with a wider size decreases and therefore, the droplets tend to flocculate due
distribution. The droplet size distribution can also affect the to an increase in hydrodynamic and colloidal interactions.
viscosity of the emulsion significantly. For a given emulsion The increase in the applied shear rate results in the defor-
the narrower droplet size range was obtained by decreasing mation and disruption of the flocs. As a result it causes a
the stirring speed and enhancing the surfactant concen- reduction in the viscosity.[21,24] Results reveal that the emul-
tration. It was observed that the narrower the droplet size sion viscosity increases as water cut increases. However,
distribution the higher the emulsion viscosity is (Table 2). after the inversion point, the continuous phase becomes
water and the viscosity of the emulsion gradually decreases
3.2. Rheological Investigations to the viscosity of water as water cut increases. Therefore, in
3.2.1. Steady Shear order to the crude oil pipeline transportation, it is essential
Steady shear experiments determine the ability of a sample to avoid the water cuts close to the water cut at which the
to resist structural breakdown while applying the shear phase inversion takes place. Because as previously stated,
energy. In the steady-state measurements, the viscosity (g)
of the crude oils and their emulsions was measured at various
temperatures within the shear rate (c) range 0.01–100 s1.
Figures 5a and 5b represent the flow curve of NCO and
SCO at different temperatures. As Figures 5 shows, it is evi-
dent that NCO behaves as a Newtonian fluid over the whole
range of shear rates, whereas SCO behavior is different. Its
behavior is like a Newtonian fluid at high applied shear rates
and like a non-Newtonian fluid at low applied shear rates.
Such viscosity reduction or shear-thinning behavior of

TABLE 2
Effects of surfactant concentration and stirring speed
on droplet size range and viscosity for 20% water in
Soroush crude oil
Surfactant Stirring Droplet Viscosity
concentration speed size range @ 30
C and
(% wt=vol) (rpm) (mm) c ¼ 0.1 s1 (Pa.s)

3 2000 0.6–64 31.9

5 2000 0.6–49 46.3
10 2000 0.5–34 82
FIG. 5. Flow curves of the crude oils at different temperatures
10 1500 0.6–47 67.6 (a) NCO, (b) SCO.
 362 M. B. SADEGHI ET AL.
Downloaded by [Northeastern University] at 19:50 21 October 2014

FIG. 6. Flow curves of emulsions in the presence of 5% wt=vol Span 80 at different temperatures: a) 10–90% W=SCO emulsion, b) 10–90% W=NCO,
c) 30–70% W=SCO emulsion, d) 30–70% W=NCO emulsion, e) 50–50% SCO=W emulsion, f) 50–50% NCO=W emulsion.

viscosity of crude oil emulsion reaches a maximum at the
point close to the inversion point and, hence, the high
pumping pressure and high costs are required to pumping
process. For each crude oil, flow curve results indicated that
the degree of shear-thinning effect increase by increasing the
water cut. From this observation, it can be said that drop-
let–droplet interactions become stronger as the water cut
increases; therefore, shear-thinning behavior is more pro-
nounced at high dispersed phase contents due to floccu-
lation of droplets and low level of structural flexibility. In
the emulsions with higher dispersed phase contents, dro-
plets are close to each other and attractive forces between
them can cause the flocculation process. It is interesting to
note that the viscosity reduction with increase in applied
shear rate becomes more prominent at low temperatures
as compared to the high temperatures. In other words,
degree of shear-thinning effect of emulsions increases with
increase in temperature. This can be ascribed to the increase
in shear rupturing and deformation of dispersed phase
droplets at high temperatures, especially at high dispersed
phase contents. In the most of emulsions prepared in this
study, it was also observed that the shear sensitivity
decreases as the shear rate increases.
3.2.2. Strain Sweep Measurements
Although steady shear measurements are used to charac-
terize the flow behavior of a wide range of systems such as
suspensions and emulsions, they do not present perfect
 WATER IN CRUDE OIL EMULSIONS WITH LIPOPHILIC SURFACTANT
understanding of the viscous and elastic properties of
the emulsions. Therefore, it is essential to investigate the vis-
coelastic properties of emulsions using oscillatory measure-
ments including strain and frequency sweep measurements.
Strain sweep were performed in order to determine the lin-
ear viscoelastic region (LVR) of the samples. The oscillation
amplitude was selected as a variable and the frequency kept
constant in the amplitude sweep test. The frequency was
1 Hz and the strain was controlled between 0.01 and
1000%. The corresponding storage modulus (G0 ), which
reflects the elasticity of the emulsion, and the loss modulus
(G00 ), which reflects the dissipation, were measured as a
function of strain. In general, the dynamic oscillatory mea-
surements are based on the application of a sinusoidal
strain or shear deformation to the viscoelastic system and
recording its response in terms of storage and loss moduli.
Shear deformation or strain (c), stress (s), G0 and G00 are
Downloaded by [Northeastern University] at 19:50 21 October 2014
described by the following equations:
c ¼ c0 sinðxtÞ ½1
s ¼ s0 sinðxt þ dÞ ½2
s0
G0 ¼ cos d ½3
c0
s0
G 00 ¼ sin d; ½4
c0
where x is the angular frequency and dis the phase angle
shift between the amplitude of oscillating stress (s0) and
the strain amplitude (c0). Loss tangent is defined by the
following equation:
G 00
tan d ¼ ½5
G0
Loss tangent or tan d is a measure of the relative magni-
tudes and balance between the viscous and elastic proper-
ties of emulsions. The higher the value of tan d, the more
viscous and liquid-like the emulsion is and vice versa.
Figure 7 displays variations of G0 , G00 and tan d versus
applied deformation strain. As can be seen, each G0 -strain
diagram is divided into two regions. In the first region or
linear viscoelastic region, G0 is independent of applied
deformation up to a critical strain value. At higher strains
than critical strain, G0 decreases as the strain increases. This
region is referred to the nonlinear viscoelastic region. Criti-
cal strain value represents the lowest strain above which the
structure of emulsion starts to break down. The higher
values of critical strain and G0 the more flocculated the
emulsion structure is. These parameters are strongly depen-
dent on the energy of attraction between the droplets. As
Figure 7 shows, as water volume fraction increases, value
of critical strain increases; therefore, the plateau region or
363
linear viscoelastic region becomes wider. Additional droplet
surface area obtained by shear deformation can control the
elasticity of emulsions. In fact, the elasticity of emulsions
may be due to the work done against interfacial tension dur-
ing droplets deformation. As the Figure 7 shows, tan d of
emulsions decreases strongly with increasing water volume
fraction, implying that the degree of elasticity of emulsions
enhances and improved with increasing water volume frac-
tion. The decrease in the loss tangent may be due to the
decrease in droplet size that leads to an enhancement of
interactions among dispersed phase droplets. Same result
was observed when surfactant concentration increased
and hence average size of droplets decreased. tan d results
showed that in the emulsions with water volume fraction
greater than 0.5 having values of tan d < 1, solid-like or elas-
tic behavior is dominant over a wide range of strains;
whereas the emulsions with lower water volume fractions
exhibit tan d > 1, indicating liquid-like or viscous behavior.
It should be noted according to equation (4), values of
tan d < 1 indicate that G0 is greater than G00 .
3.2.3. Frequency Sweep Measurements
Frequency sweep is a significant technique to investigate
the tolerance performance of emulsions under external
forces.[25] In the frequency sweep procedure, the strain ampli-
tude was kept constant (0.5%) in the linear viscoelastic region
and measurements were performed as a function of angular
frequency. The angular frequency was changed from 500 to
0.05 s1. The values of the storage modulus (G0 ), loss modu-
lus (G00 ) and loss tangent or damping factor (tan d) were used
for emulsion characterization. As mentioned before, these
rheological parameters provide quantitative characterization
of the balance between the viscous (liquid-like) and elastic
(solid-like) properties of colloidal systems such as emulsions.
G0 , G00 and tan d as a function of angular frequency at three
different temperatures for 30–70% W=SCO emulsion and
30–70% W=NCO emulsion are shown in Figure 8. It was
observed that the loss modulus is higher than the corre-
sponding storage modulus over a wide range of angular
frequencies, indicating that the emulsion displays viscous
behavior rather than elastic behavior. As Figure 8 shows,
the moduli and loss tangent decrease nonlinearly with
decrease in angular frequency, which denotes that the emul-
sions are more rigid at high frequencies. This can be ascribed
to the formation of strong droplets flocculation. In fact, a
great quantity of continuous phase will be captured by floc
structures that may lead to the enhancement of the volume
fraction of the emulsion and the net attraction between the
droplets.[26] It is worth to note that the required shear stress
to flow the emulsion increases by increasing the storage
modulus, and an emulsion can be more stable at lower shear
stresses as compared to the high shear stresses.
Figure 9 depicts a comparison between frequency sweep
responses for two different water cuts at T ¼ 30
C. It is
 364 M. B. SADEGHI ET AL.
Downloaded by [Northeastern University] at 19:50 21 October 2014
FIG. 7. G0 , G00 and tan d obtained at fixed frequency (1 Hz) as a function of strain amplitude: a) SCO emulsions, b) NCO emulsions, in the presence
of 5% wt=vol Span 80.
interesting to note that the enhancement of dispersed phase
volume fraction caused an increase in G0 and G00 values.
This enhancement in the storage and loss moduli is indica-
tive of an increase in droplet–droplet interactions between
the dispersed phase droplets. As Figure 9 shows, both mod-
uli decrease with the decrease in the frequency for both
water cuts. But in the case of higher water volume fraction
(u ¼ 0.5), the moduli decline smoothly. For the emulsion
with 30% water cut, at angular frequencies lower than
0.1 s1, G0 falls above G00 , but at angular frequencies greater
than 0.1 s1, G00 is higher than G0 . This indicates that the
emulsion is predominantly viscous over most of the angu-
lar frequency range investigated. For the emulsion with
50% water cut, cross-over frequency where the G0 overtakes
the G00 , takes place at angular frequency about 150 s1;
beyond this point, G00 falls above G0 and at angular fre-
quencies lower than cross-over frequency, G0 falls above
G00 , indicating that the emulsion behavior is predominantly
elastic. Therefore, it can be concluded that as the dispersed
phase volume fraction increases, the cross-over frequency
increases. In other words, the solid-like or elastic behavior
of emulsions becomes more pronounced with the enhance-
ment of dispersed phase volume fraction.
3.3. Effect of Temperature
Temperature is considered as a significant parameter in
order to better understanding of the structural and rheolo-
gical properties of emulsions. Temperature variation causes
changes in the interfacial tension between dispersed and
continuous phases and in the relative solubility of surfac-
tant in the two immiscible phases. Thus, temperature can
significantly affect the emulsion stability. The effect of tem-
perature on the flow behavior of crude oils and their emul-
sions was studied at temperature range of 2 to 80
C as
shown in Figures 5 and 6. Results revealed that tempera-
ture is one of the most important controlling parameters
 WATER IN CRUDE OIL EMULSIONS WITH LIPOPHILIC SURFACTANT
Downloaded by [Northeastern University] at 19:50 21 October 2014
FIG. 8. Change in frequency sweep response with temperature: a) 30–70% W=SCO emulsion, b) 30–70% W=NCO emulsion in the presence of 5%
wt=vol Span 80 at c ¼ 0.5%.
for processing and characterizing the crude oils and their
emulsions. When the temperature rises, the strong intermo-
lecular forces between the molecules will break up and,
therefore, the viscosity will decrease. In fact, the tempera-
ture controls the rheological properties of emulsion via
FIG. 9. Variation of G0 , G00 with angular frequency for SCO emulsions
containing 30 and 50% water cuts in the presence of 5% wt=vol Span 80 at
c ¼ 0.5% and T ¼ 30
C.
365
significant effects on the continuous phase. For example in
the case of flow behavior of emulsions, as temperature
increases, viscosity of continuous phase decreases. Finally
the overall viscosity of emulsion system reduces by decreas-
ing the viscosity of continuous phase. As Figure 5 shows, as
temperature varies from 2 to 80
C, viscosity of crude oils
decreases by at least two orders of magnitude. This trend
can also be observed for the emulsions as depicted in
Figure 6, but in the case of NCO emulsion containing 50%
water cut viscosity decreases by almost one order of magni-
tude. This can be simply explained by the smaller influence
of temperature on the viscosity of water, which exists as con-
tinuous phase. However, temperature variation affects the
viscosity of 50–50% SCO=W emulsion as well as W=SCO
emulsions. Almost in all samples the effect of temperature
on viscosity was more significant at high shear rates.
An increase in temperature induces a decrease in moduli
and loss tangent of emulsions as shown in Figure 8. This
reduction may be related to the effect of the temperature
rise over the viscosity of the continuous phase. However
in the case of loss tangent, this trend is not observed at
low angular frequencies. Enhancement of temperature
leads to slope reduction of loss tangent versus angular fre-
quency diagram. Therefore, it may be concluded the loss
tangent is approximately frequency independent at very
low temperatures. Finally it can be said that the rheological
 366 M. B. SADEGHI ET AL.
properties of crude oil emulsions investigated in this work
are very temperature-dependent.
3.4. Effect of Surfactant Concentration
Figure 10 displays the effect of the surfactant concen-
tration on average droplet size of SCO emulsion at two dif-
ferent water cuts. It is clearly seen that the emulsion with
higher water cut (with the same surfactant concentration)
shows bigger average droplet size as compared to the emul-
sion with lower water cut; and for each emulsion, droplet
size decreases with increasing the surfactant concentration.
This effect may be attributed to the fact that the surface
area between dispersed phase droplets and the continuous
phase increases as the surfactant concentration increases.[22]
The effect of surfactant concentration on stability of emul-
sions was investigated over 90 days. Results indicated when
the surfactant concentration was greater than 5% wt=vol,
Downloaded by [Northeastern University] at 19:50 21 October 2014
there was no significant increase in droplet size with time,
indicating stability of emulsions against coalescence. At
surfactant concentrations lower than 5% wt=vol, the dro-
plets started to flocculate and coalescence; hence, droplets
showed a small enhancement in size over 90 days. When
surfactant concentration was greater than 1% wt=vol, no
phase separation was observed over 90 days, whereas in
the case of 0.1% surfactant, flocculation and coalescence
of dispersed droplets was increased during storage with time
and eventually the emulsion was partially separated. The
magnitude of the interactions between the hydrocarbon
chains of the nonionic surfactant, Span 80, seems to be
the responsible for controlling the stability and dispersed
droplet size of emulsion.[27] In fact, the addition of a surfac-
tant to an emulsion leads to a reduction in interfacial
tension and hence prevents the dispersed droplets from
FIG. 10. Variation of average droplet size with surfactant concen-
tration for 10–90% and 40–60% W=SCO emulsions.
flocculating and coalescing by increasing the repulsion
interactions.[28] A decrease of the dispersed droplet size
can lead to a significant reduction in creaming or sedimen-
tation over the storage time. This is due to the decrease in
the Brownian motion and the gravity force as the droplet
size decreases. When the surfactant concentration increases,
the film thickness of adsorbed surfactant relative to droplet
size increases and, hence, leads to reduction in disruption
of the film around the droplets. As a result it can be said
that the stability of emulsion against flocculation and
coalescence enhances by increasing the surfactant
concentration.
Rheological behavior of colloidal systems, especially
emulsions, can be significantly influenced by adsorbed sur-
factant layers at the interface between the continuous phase
and dispersed droplets. Figure 11 shows the variation of
the apparent viscosity for 20% W=SCO emulsion with the
surfactant concentration at two different shear rates and
T ¼ 30
C. The viscosity increased with an increase in the
surfactant concentration. As stated before, as the surfac-
tant concentration increases the average droplet size of
the emulsion decreases. Therefore, such reduction in drop-
let size results in increase in apparent viscosity of emulsion;
this is becomes more significant in the case of concentrated
emulsions. This may be attributed to the enhancement of
hydrodynamic interactions between the droplets when the
distance of separation between the dispersed droplets
reduces by decreasing the droplet sizes. Aggregation and
flocculation of dispersed droplets due to the Brownian
motion and van der Waals attractive interactions between
droplets may be another reasons that are the responsible
for such viscosity enhancement.[21,24] In fact the possibility
FIG. 11. Variation of apparent viscosity with surfactant concentration
for 20% W=SCO emulsion at two different shear rates and T ¼ 30
C.
 WATER IN CRUDE OIL EMULSIONS WITH LIPOPHILIC SURFACTANT
of aggregation of droplets increases with the distance
reduction between them. It can be seen that up to 3%
wt=vol surfactant concentration, there is a rapid increment
in viscosity with increase of surfactant concentration.
Such increment becomes less significant between 3 and
8% wt=vol surfactant concentration. Above 8% wt=vol sur-
factant concentration, viscosity shows the increase with a
sharper slope as the surfactant concentration increases.
This trend is more pronounced in the case of higher rate
of deformation (c_ ¼ 10 s1 ), where the effect of deformatio-
n on dispersed droplets and their interactions becomes
more significant.
Figure 12 depicts the effect of the surfactant concen-
tration on G0 , G00 and tan d for 20% W=SCO emulsion at
x ¼ 1 s1 and T ¼ 30
C. G00 is higher than G0 and, hence,
tan d > 1 over the entire range of surfactant concentrations,
indicating dominant liquid-like or viscous character of the
Downloaded by [Northeastern University] at 19:50 21 October 2014
emulsion. As Figure 12 shows, as the surfactant concen-
tration increases, G00 increases and reaches a maximum at
8% wt=vol surfactant concentration and then shows a
reduction with further increase in surfactant concentration.
In the case of G0 no optimum point was observed and it
increased with the increase in the surfactant concentration
in the entire surfactant concentration range. As can be seen
from Figure 12, tan d approximately shows a plateau up to
8% wt=vol surfactant concentration, indicating a balance
between the viscous and elastic properties of emulsion.
Above 8% wt=vol surfactant concentration, tan d starts to
decrease that means the elastic or solid-like behavior of
emulsion increases with the increase in surfactant concen-
tration. This transition from fluid to solid behavior may
be ascribed to the increasing the interactions and, hence,
net attraction among dispersed droplets.[24]
FIG. 12. Variation of G0 , G00 and tan d with surfactant concentration
for 20% W=SCO emulsion at x ¼ 1 s1 and T ¼ 30
C.
367
4. CONCLUSION
Experimental morphological and rheological results for
the emulsions of two heavy crude oils in the presence of a
lipophilic nonionic surfactant were presented. Results
showed that low volume fractions of dispersed phase and
high surfactant concentrations led to the emulsions with
small droplets, low degree of polydispersity and high stab-
ility. Shear steady rheological measurements revealed that
NCO exhibit typically as a Newtonian fluid over the entire
range of shear rates, while SCO exhibit non-Newtonian
behavior at low shear rates and Newtonian behavior at
high shear rates. All the emulsions investigated in this
study exhibited as non-Newtonian fluids, indicating
shear-thinning behavior. The degree of shear-thinning
effect increased as the volume fraction of dispersed phase
increased. In fact droplet deformability plays an important
role in controlling the shear-thinning behavior. The emul-
sion viscosity was found to be increased with the increase
in water content and surfactant concentration. An emulsion
with liquid-like characteristics could be made to have
solid-like characteristics with the increase in the dispersed
phase content, surfactant concentration and or with the
decrease in the temperature. In the case of dilute emulsions
there was no cross-over between G0 and G0 , and G00 was
greater than G0 over the entire range of angular frequencies,
indicating a predominant viscous behavior. As a result, it
can be said that the increase in the rheological parameters
such as viscosity, shear-thinning effect, G0 and G00 with the
increase in water volume fraction and with the decrease in
the droplet size can be ascribed to the enhancement of floc-
culation of droplets. By increasing water content and sur-
factant concentration, it was observed that the elastic
behavior of emulsions and value of cross-over increase.
The water content at which phase inversion takes place
was predicted to be about 45% (3%) where the variation
of apparent viscosity with water content shows a maximum.
From this result, it can be concluded that in order to reduce
the pumping pressure, energy consumption and the costs,
crude oil emulsions containing water contents that are far
from the phase inversion point should be pumped to the
pipelines.
REFERENCES
[1] Datta, S.S., Gerrard, D.D., Rhodes, T.S., Mason, T.G., and
Weitz, D.A. (2011) Phys. Rev. E, 84: 041404-1–6.
[2] Derkach, S.R. (2009) Adv. Colloid Interface Sci., 151: 1–23.
[3] Capron, I., Costeux, S., and Djaburov, M. (2001) Rheol.
Acta, 40: 441–456.
[4] Dimitrova, T.D. and Leal-Calderonb, F. (2004) Adv. Colloid
Interface Sci., 108–109: 49–61.
[5] Windhab, E.J., Dressler, M., Feigl, K., Fischer, P., and
Megias-Alguacil, D. (2005) Chem. Eng. Sci., 60: 2101–2113.
[6] Weiss, J. and McClements, D.J. (2000) Langmuir, 16:
5879–5883.
 368 M. B. SADEGHI ET AL.
[7] Kang, W., Xu, B., Wang, Y., Li, Y., Shan, X., An, F., and
Liu, J. (2011) Colloids Surf. A, 384: 555–560.
[8] Pal, R. (2000) J. Colloid Interface Sci., 225: 359–366.
[9] Pal, R. (2008) Food Hydrocoll., 22: 428–438.
[10] Pal, R. (2011) Curr. Opin. Colloid Interface Sci., 16: 41–60.
[11] Otsubo, Y. and Prud’homme, R.K. (1994) Rheol. Acta, 33:
303–306.
[12] Tadros, T.F., Izquierdo, P., Esquena, J., and Solans, C.
(2004) Adv. Colloid Interface Sci., 108–109: 303–318.
[13] Langevin, D., Poteau, S., Hénaut, I., and Argillier, J.F.
(2004) Oil Gas Sci. Technol., 59: 511–521.
[14] Fingas, M., Fieldhouse, B., and Mullin, J. (1994) Proceedings
of the Arctic Marine Oilspill Program Technical Seminar,
Canada, Ottawa, Ontario, 213–244.
[15] Lee, R.F. (1999) Spill Sci. Technol. Bull., 5: 117–126.
[16] Barnes, H.A. (1994) Colloids Surf. A, 91: 89–95.
[17] Weiss, J. and McClements, D.J. (2000) Langmuir, 16: 2145–2150.
[18] Tadros, T.F. (1994) Colloids Surf. A, 91: 39–55.
Downloaded by [Northeastern University] at 19:50 21 October 2014
View publication stats
[19] Masmoudi, H., Piccerelle, P., Le Dréau, Y., and Kister, J.
(2006) Pharm. Res., 23: 1937–1947.
[20] Mason, T.G. (1999) Curr. Opin. Colloid Interface Sci., 4:
231–238.
[21] Pal, R. (1996) AIChE J., 42: 3181–3190.
[22] Watson, D.J. and Mackley, M.R. (2002) Colloids Surf. A,
196: 121–134.
[23] Hayati, I.N., Che Man, Y.B., Tan, C.P., and Idris, N.A.
(2007) Food Res. Int., 40: 1051–1061.
[24] Pal, R. (1997) Chem. Eng. J., 67: 37–44.
[25] Peng, J., Xia, H., Liu, K., Gao, D., Yang, M., Yan, N., and
Fang, Y. (2009) J. Colloid Interface Sci., 336: 780–785.
[26] Tadros, T.F. (2004) Adv. Colloid Interface Sci., 108–109:
227–258.
[27] Márquez, A.L., Palazolo, G.G., and Wagner, J.R. (2007)
Colloid. Polym. Sci., 285: 1119–1128.
[28] Noor El-Din, M.R. and Al-Sabagh, A.M. (2012) J. Disper-
sion Sci. Technol., 33: 68–74.