Fluid Phase Equilibria 413 (2016) 41e47

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Equilibria of cyclopentane hydrates with varying HLB numbers of

sorbitan monoesters in water-in-oil emulsions
Seungjun Baek, Juwon Min, Jae W. Lee*
Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu,
Daejeon 305-701, Republic of Korea

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

Article history: This study investigated the effect of hydrophilic-lipophilic balance (HLB) numbers of sorbitan mono-
Received 1 August 2015 esters on equilibrium conditions of cyclopentane hydrates in water-in-oil emulsions with or without
Received in revised form NaCl. HLB numbers of the surfactants (Span 20, 40, 60, and 80), which have the same hydrophilic group,
5 October 2015
are determined by the length and shape of alkyl chain and the HLB number refers to hydrophobicity of
Accepted 7 October 2015
Available online 21 October 2015
surfactant. The equilibrium state of the hydrate phase can be affected by the HLB of the surfactants
whose number is the lowest in Span 80 (4.3) and the highest in Span 20 (8.6). The emulsion size is
proportional to the increasing HLB number of sorbitan monoesters. Equilibrium dissociation tempera-
Keywords:
Clathrate hydrates
tures of cyclopentane hydrate in the water-in-oil emulsion also rise as the HLB number increases, which
Cyclopentane was determined in micro differential scanning calorimetry (micro-DSC). In the presence of 3.5 wt % NaCl
Sorbitan monoesters in the aqueous phase, hydrate equilibrium temperatures were almost constant regardless of the HLB
Hydrate equilibrium number because the salt ions diminished the interaction between water and sorbitan esters as a ther-
Water-in-oil emulsion modynamic hydrate inhibitor. This HLB-dependent behavior provides basic insights into the relationship
between clathrate hydrate equilibria and hydrophobicity in the hydrate-forming emulsion system.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction thermodynamics, kinetics, colloidal science, and rheology [5e16].

Clathrate hydrates are ice-like crystalline solids constructed by
hydrogen bonded water cavities which encage small guest mole-
cules such as methane, hydrogen, carbon dioxide and light organic
molecules (e.g. cyclopentane). These guests are captured in the
suitable host cavity and provide the stability of hydrate structures
[1e3]. In the offshore pipeline, a non-trivial amount of light hydrate
carbon sources that are hydrate formers, commonly exist and they
can be converted to solid hydrates at desired conditions of low
temperature and high pressure. Because the hydrate conversion
occurs relatively faster than the formation of others causing pipe-
line blockage such as waxes, scale, corrosion, and asphaltene ag-
gregates, and thus clathrate hydrates have widely been investigated
for solving the flow assurance problem in gaseoil production and
delivery lines [1e4].
Due to the presence of hydrocarbon hydrate formers in seafloor
gaseoil pipelines that can induce hydrate formation, the hydrate
plugging mechanism has been investigated in various aspects of
* Corresponding author. Tel.: þ82 42 350 3940; fax: þ82 42 350 3910.
E-mail address: jaewlee@kaist.ac.kr (J.W. Lee).
Fig. 1 describes the hydrate plugging mechanism to explain how
free water is converted to hydrate plug in the pipeline [17,18].
Entrained water is emulsified by the turbulence of flow and the
presence of natural or petroleum surfactants, then water droplets
can be dispersed into the oil phase. The hydrate nucleation occurs
at the watereoil interface of emulsions, and then hydrate layers
continuously grow to the interior of water droplets. Hydrate par-
ticles generated through this process interact with other particles
or water droplets and this can cause continuous hydrate formation
and agglomeration between hydrate particles, leading to plugs on
the entire area of pipe that interrupts stable production of oil and
gas [11,19,20]. Therefore, it is important to understand the mech-
anism of hydrate crystallization at the interface between water and
oil hydrate former to maintain flow assurance in the offshore
gaseoil industry.
Since hydrate particles are converted from emulsion water
droplets, the condition of hydrate formation is dependent on the
property of emulsions. Emulsions exist between two kinds of
immiscible liquids, commonly water and oils [21,22]. In the oil
delivery line, as mentioned, the free water phase is converted to
stable water-in-oil emulsions in presence of the surface active

http://dx.doi.org/10.1016/j.fluid.2015.10.018
0378-3812/© 2015 Elsevier B.V. All rights reserved.
42 S. Baek et al. / Fluid Phase Equilibria 413 (2016) 41e47
Fig. 1. Schematic diagram of hydrate plugging process in the gaseoil pipeline (modified from Refs. [16,17]).
agents such as wax, asphaltenes, and natural surfactants [22e24].
These surface active agents reduce the interfacial energy between
oil and water, which is required to maintain total area of surface on
the droplets. Then the size of water droplet is also reduced due to
the lower surface free energy for the same interfacial area. It can
increase the contact area between water and hydrate forming oil or
dissolved gas, and thus the rate of hydrate formation is much
higher in the emulsion than in the bulk water system [25].
Many studies have investigated the thermodynamic perspective
of clathrate hydrate formation. Clausse et al. [22] proposed a new
method, thermogranulometry, for studying concentrated, opaque,
and non-conductive water-in-crude oil emulsions. They formulated
the mathematical relationship between freezing temperature and
radius of emulsion droplets by considering the surface energy and
the occurrence probability of droplets frozen at a specified tem-
perature. Nguyen et al. [26] developed a thermodynamic model to
predict hydrate formation in water-in-oil emulsion with a surfac-
tant of AOT (sodium-bis (2-ethyl-hexyl) sulfosuccinate) by accom-
modating the chemical potential change from the formation of
reverse micelle. Prasad et al. [12] utilized micro differential scan-
ning calorimetry (micro-DSC) to study the formation and dissoci-
ation of cyclopentane hydrate in the water-in-oil emulsion with
sorbitan monooleate (Span 80). They compared two kinds of water-
in-oil emulsions, water-in-isooctane (non-hydrate former) and
water-in-cyclopentane (hydrate former), and determined the
change of heat flow in DSC thermograph to infer the amount of
hydrate formation.
Like these previous studies, the hydrate formation in water-in-
oil emulsions has widely been investigated, but the effect of
changes in physical and chemical properties of emulsifiers on hy-
drate equilibria, especially surfactants, are rarely explored. Surfac-
tants can be classified by cationic, anionic, and nonionic nature.
Ionic surfactants significantly change the electrical property on the
surface of emulsion droplets in electrolyte solutions, and then
emulsion droplets are dispersed by electrostatic stabilization [27].
On the other hand, nonionic surfactants act as physical barriers to
interrupt the coalescence of emulsion droplets [19]. Because they
provide the steric repulsion to stabilize emulsion phases, their
hydrophilic-lipophilic balance (HLB number), the balance of the
size and strength between hydrophilic and lipophilic molecular
groups, highly affect the properties of water-in-oil emulsions [28].
For this reason, this work reveals the relationship between HLB
number of various sorbitan esters and equilibrium dissociation
temperatures of cyclopentane hydrate.
This study utilized several types of sorbitan esters such as Span
20, Span 40, Span 60 and Span 80. They have the same head group
(hydrophilic region) and different hydrophobic chain lengths, and
thus we need to consider the effect of HLB number of these
nonionic surfactants on hydrate dissociation equilibria. Emulsion
size distributions were measured in an optical microscope.
Equilibrium temperatures of cyclopentane hydrate were investi-
gated using micro differential scanning calorimetry (micro-DSC).
The effect of different sorbitan esters on hydrate equilibria was also
studied with and without sodium chloride (NaCl), a major
component in sea water. This work can provide fundamental in-
formation on the equilibrium of clathrate hydrate formed from
emulsion droplets subject to HLB changes of the homologous
surfactants.
2. Experimental section
2.1. Materials
Cyclopentane (purity of 98%), Sorbitan monolaurate (Span 20),
Sorbitan monostearate (Span 60), and Sorbitan monooleate (Span
80) were purchased from SigmaeAldrich. Sorbitan monopalmitate
(Span 40) was obtained from Tokyo Chemical Industry Co. Physical
properties and structures of sorbitan monoesters with physical
properties are represented in Fig. 2(A). Deionized water (DI water)
was produced by a Millipore Direct-Q unit with a resistivity of
18 MUcm1.
2.2. Experimental procedure
Cyclopentane (CP) is a liquid hydrate former which can be
enclathrated in the large cages of sII hydrate structure in the
ambient conditions and it is immiscible with aqueous solutions.
The structure of light hydrocarbon mixture hydrates is also known
as sII hydrate structure, and thus CP can be utilized to represent the
behavior of hydrate formers in the offshore crude oil pipeline. Thus,
it was a suitable substance to investigate the hydrate equilibrium in
the water-in-oil emulsion.
Before the mechanical stirring with DI water, 0.003 g of sorbitan
esters was completely dissolved in 4 mL of CP to prepare the ho-
mogeneous oil phase consisting of CP and Span surfactant in vials.
1 mL of DI water was added to the surfactant-dissolved CP, then
these two immiscible liquids were stirred at 5000 rpm with
WiseTis® HG-15 A homogenizer for 5 min. These samples were
stabilized for 3 h. After the stabilization, oil (CP) and water-in-oil
emulsion phases were separated as shown in Fig. 2(B), which fa-
cilitates to obtain the emulsion sample from the bottom of the vial.
All of CP cannot be converted to water-in-CP emulsions, because
the volume dosage of CP is four times as high as the dosage of DI
water. Thus, the oil phase was located over the emulsion phase, but
there is no pure DI water on the bottom side. The procedure of
emulsion preparation was identically repeated with 3.5 wt% NaCl
solution to investigate the salt effect on the hydrate equilibrium of
the emulsion system.
The size distribution of the water-in-CP emulsion was measured
by an optical microscope. 20 mL of the emulsion was injected into
 S. Baek et al. / Fluid Phase Equilibria 413 (2016) 41e47
Fig. 2. A) Molecular structures, physical properties, and hydrophilic-lipophilic balance (HLB) of sorbitan monoesters, and B) prepared water-in-cyclopentane emulsion with sorbitan
monoesters. Emulsion phases can be clearly distinguished with respect to oil phase, but there is no aqueous phase on the bottom.
the capillary rectangular tube (0.4  4 mm, Wale Apparatus), then
captured in three different regions with a Nikon AZ100 Multizoom
microscope equipped with a Nikon DS-Fi1 HD Color Camera Head.
Nikon Digital Sight Processor was connected to PC. Then the
emulsion size was measured using NIS-Elements Br 3.0 software.
We analyzed the emulsion size distribution of each sample with
calculations of emulsion diameters for over 750 droplets.
Micro-DSC is widely used to measure the equilibrium temper-
ature of clathrate hydrate [6e8,12,18,29e31]. To measure the
thermal properties of the emulsion system, Micro DSC VII, supplied
from Setaram Inc., was utilized in the present work. Micro-DSC
operation and data analysis were conducted with software SET-
SOFT 2000. Thermocouples in the DSC furnace recognized the
temperature difference between sample and reference cell, then
DSC calculated the required heat, represented by heat flow in the
DSC thermograph, to meet the zero temperature difference. Before
the thermal analysis, DSC was calibrated with naphthalene
(80.17  C), water (0  C), and n-decane (30  C) with a temperature
precision of 0.02  C. 40 mL of the water-in-CP emulsion was care-
fully taken from bottom of vials, then it was injected to the sample
cell. The operation procedure of the thermal analysis was the
following sequence: first, furnace temperature went down
to 40  C and moved up to 5  C at 1  C min1. Next, the cell was
stabilized for 10 min and reduced the heating rate to 0.1  C min1.
We focused on the temperature range from 5 to 10  C containing
ice and hydrate dissociation process.
3. Results and discussion
3.1. Change in emulsion size distribution
Fig. 3 shows optical microscopic images of the water-in-CP
emulsion with respect to various sorbitan esters. The size of
43
emulsions was widely distributed from 3 to 90 mm in diameter as
described in Fig. 4. Large emulsion droplets, over 50 mm in diam-
eter, can be observed in the case of the high HLB surfactant, espe-
cially Span 20, and the frequency of larger droplets is diverged from
the mean value in histograms. Although the number of large
droplets was almost the same in the cases of the other sorbitan
esters, the frequency of large droplets with the low HLB surfactant
was converged to a mean value of size distributions. It means the
coalescence of emulsion droplets was highly inhibited and small
emulsion droplets can be formed in the presence of the low HLB
surfactant. Thus, the mean size of emulsion droplets rises with the
increasing HLB number as shown in Fig. 5(A).
All sorbitan monoesters have the same hydrophilic group, sor-
bitan, formed by dehydration of sorbitol, and thus their property is
determined by length and degree of unsaturated bonding of fatty
acids. The interfacial tension between surfactant and water is
higher for the same type of surfactant with longer chains, indi-
cating the relationship between hydrophobicity and interfacial
tension of surfactants [32]. In addition, increasing hydrophobicity
of sorbitan monoesters can lead to smaller micelle structures due to
the decreased surface free energy in the emulsion system [33]. By
Bancroft's rule, the dispersed phase is generally defined by the
solubility of surfactant and it is satisfied for most systems and
highly hydrophobic oils require the lower oil solubility of surfac-
tants to form water-in-oil emulsion [21,34]. At this point, CP has a
high interfacial tension with water, over 47 mN m1 without using
any surface active agent [35,36], it is almost the same with the
interfacial tension of liquid paraffin, 50 mN m1. Thus, CP can be
considered as a highly lipophilic liquid and more hydrophobic
surfactants can stabilize emulsion droplets.
From surface chemistry, it can be explained with adsorption
behaviors of surfactant at interface between oil and water. The
general form of Gibbs adsorption equation [34,37] is
44 S. Baek et al. / Fluid Phase Equilibria 413 (2016) 41e47
Fig. 3. Optical microscopic images of water-in-cyclopentane emulsion for (A) Span 20, (B) Span 40, (C) Span 60, and (D) Span 80.
dg ¼  Go dmo  Gw dmw  Gs dms
where dg is the change in interfacial tension at the interface be-
tween water and oil, G is the surface excess concentration, and dm is
the change in chemical potential (subscripts o, w, and s refer to the
oil, water, and surfactant, respectively). It is assumed the all
adsorption processes concern the formation of monolayers. Due to
dmi ¼ RTdlnai , where ai is the activity of component i in the system,
R is the gas constant, and T is the absolute temperature, Equation
(1) can be rewritten
dg ¼  RTGo d ln ao  RTGw d ln aw  RTGs d ln as
¼  RTGo d ln xo fo  RTGw d ln xw fw  RTGs d ln xs fs
¼ RTGo dðln xo þ ln fo Þ  RTGw dðln xw þ ln fw Þ
 RTGs dðln xs þ ln fs Þ
where x is the mole fraction and f is the activity coefficient. We
utilized a tiny dosage of sorbitan monoesters, about 2 mM, and thus
the activity of solvents (oil and water) and the activity coefficient of
surfactants are assumed to be constant and the mole fraction of the
surfactant can be replaced by molar concentration Cs . Therefore,
dg ¼ RTGs d ln Cs
 
1 vg
Gs ¼ 
RT vln Cs T dissociation temperature is represented in Fig. 5(B). Concurrently
and the surface excess concentration of surfactant can be calculated
(1) by the change of interfacial tension with respect to the molar
concentration of surfactant in the system. Another aspect in
Equation (6) is that the surface excess concentration of surfactant
determines the variation of interfacial tension with the same con-
centration. Gs is one of parameters to obtain effectiveness of
adsorption, Gm , and the increase in the chain length of hydrophobic
alkyl group with the same hydrophilic head causes an increase in
Gm [34]. It means the effectiveness of adsorption (Gm ) is inversely
related to the HLB number of sorbitan monoesters and the low HLB
surfactant is more effective to stabilize emulsions than the high
HLB surfactants. Thus, the mean size of emulsion droplets increases
(2)
as the HLB number rises.
(3)
3.1.1. Equilibrium of CP hydrate with various sorbitan monoesters
If the hydrate and water-in-oil emulsion phases are in equilib-
rium, the chemical potentials of water in hydrate phase and
(4) emulsion phase are identical. Because surfactant molecules form a
reverse micelle structure in the water-in-oil emulsion, the chemical
potential of water in the emulsion phase is equal to the chemical
potential of water in the reverse micelle. The chemical potential of
water in the reverse micelle can be obtained from Gibbs free energy
of microemulsion aggregates. The Gibbs free energy per aggregate
is described by a combination of electrostatic energy, entropic
contribution, surface free energy, hydration force, and dissolution
(5) of guest molecules [26]. At this point, the surface free energy can be
directly affected by the type of surfactants and determines the size
of emulsion droplets.
(6) The relationship between the type of sorbitan monoesters and
 S. Baek et al. / Fluid Phase Equilibria 413 (2016) 41e47
Fig. 4. Size distributions of emulsion droplets is plotted by frequency versus emulsion diameter with (A) Span 20, (B) Span 40, (C) Span 60, and (D) Span 80.
with the mean size of emulsion droplets, equilibrium temperatures
of CP hydrate rise with the increasing HLB number. Thus, the sta-
bility of emulsion is highly related to hydrate equilibrium in
emulsion systems. Nguyen et al. [26] revealed the change of the
equilibrium pressure for various concentrations of surfactant AOT
on methane hydrate formation in the water-in-oil emulsion. The
equilibrium pressure of methane hydrate increases with the
increasing surfactant amount regardless of the consideration of
hydration force. Although the same dosage of Span surfactants was
used in our present work, the effect of the increasing HLB number is
similar to the effect of the increasing AOT surfactant concentration.
It can be seen in Fig. 5(A) and (B) that both emulsion droplet size
and equilibrium temperature decreases as the HLB number of
sorbitan monoesters increases.
3.1.2. Effect of NaCl for the equilibrium of CP hydrate in water-in-oil
emulsion
Fig. 6 shows the difference in the emulsion shape and size be-
tween absence (A) and presence (B) of NaCl in the aqueous phase.
The size of emulsion droplets was significantly reduced by the
addition of NaCl and the mean size of emulsion droplets is about
45
13 mm in diameter with Span 20. The reduction of the emulsion size
refers to higher stability in the emulsion system. The addition of
salt causes the direct interaction between salt ions and ionic sur-
factant and the nonionic surfactant is also influenced by the
interaction between its polar head and aqueous phase. The addition
of NaCl can reduce the size of emulsion droplets from the interfacial
film formation through the reduction of interfacial elasticity [38].
Due to the reduction of the emulsion size, some emulsion droplets
cannot be clearly observed using an optical microscope as shown in
Fig. 6(B). Therefore, it was hard to determine the size distribution of
water-in-CP emulsion with NaCl, but the size reduction of emulsion
droplets was obvious in the presence of salt.
The dissociation temperature of CP hydrates with various sor-
bitan monoesters and 3.5 wt% NaCl solution is presented in Fig. 7
and Table S3. Even though the deviation of temperature values
was bigger than the case without NaCl, the hydrate equilibrium
temperature is almost the same regardless of HLB numbers except
for Span 60. The equilibrium temperature of CP hydrate was about
4.75  C with sorbitan monoesters and NaCl. It is quite different with
reference data of CP hydrate in bulk water, 7.0  C [39] and bulk NaCl
solution with Span 80, 5.3e5.5  C [14,40]. Because the salt ions
46 S. Baek et al. / Fluid Phase Equilibria 413 (2016) 41e47

Fig. 5. Variation of A) mean sizes of emulsion droplets and B) equilibrium temperatures of cyclopentane hydrate in water-in-oil emulsion versus HLB numbers.

strongly interact with water molecules and interrupt the hydrogen
bonding, they are commonly considered as a thermodynamic hy-
drate inhibitor inducing the shift of equilibrium to low temperature
and high pressure. In the emulsion system with both NaCl and
surfactant, the size of emulsion droplets was further reduced by
weakening the interaction of hydrophilic head group with the
aqueous phase and the equilibrium temperature dropped down to
smaller values than the equilibrium condition in the bulk aqueous
system.
The equilibrium temperature of CP hydrate with Span 60 was
higher than the cases of the other sorbitan monoesters. A possible
explanation about this exception is due to the unbalanced activity
between aqueous and oil phases. Since the NaCl concentration was
the same in all of the emulsions, the effect of NaCl on the equilib-
rium state can be almost identical. The strong interaction between
water molecules and salt ions induces the concentrated layer of
surfactant on the interfacial region, but they may also decrease the
surfactantewater interaction. The activity of the sorbitan mono-
esters in the aqueous phase is depressed due to the weaker inter-
action, and then the activity is biased to the oil phase. Also, the
degree of biased activity can rise with the increasing number of
alkyl chains [41], and thus the cases of Span 60 and Span 80 showed
a relatively high equilibrium temperatures. However, a cis double
bond in the fatty acid of Span 80 can reduce the size of emulsion
droplets [42] and this effect can compensate the increasing equi-
librium temperature of CP hydrate. However, further investigations
are needed to experimentally confirm this explanation for Span 60
as a future work.
4. Conclusion
This work introduced the effect of HLB of the sorbitan mono-
ester surfactant on the equilibrium condition of CP hydrate in the
water-in-oil emulsion. The HLB number is determined by the alkyl
chain length of the surfactants because they have the same hy-
drophilic group. It was found that the mean size of emulsion
droplets and the equilibrium temperature of cyclopentane hydrates
were proportional to the HLB number. However, the variations of
hydrate equilibrium temperature and emulsion size with the HLB
number was practically eliminated with the addition of NaCl except
for the case of Span 60. The presence of salt ions seems to drasti-
cally reduce the interfacial energy and the emulsion size. Thus, the
equilibrium temperature of cyclopentane hydrate decreases. In case
of Span 60, unbalanced activity of the surfactant can be induced by
a strong interaction between water and salt ions. Therefore, the
different HLB of Span series affect equilibria of hydrate formation in

Fig. 6. Optical microscopic images of water-in-cyclopentane emulsions with Span 20 in the A) absence and B) presence of 3.5 wt% NaCl.
 S. Baek et al. / Fluid Phase Equilibria 413 (2016) 41e47
Fig. 7. Equilibrium temperatures for cyclopentane hydrate in water-in-cyclopentane
emulsion with various sorbitan monoesters in the presence of 3.5 wt% NaCl.
the gaseoil pipeline through altered interfacial properties of the
hydrate-forming emulsion.
Acknowledgment
The authors are grateful for the financial support from both Mid-
career Researcher Program and UK-Korea Joint Research Program
through NRF grants (NRF-2014R1A2A2A01007076 and NRF-
2015M2A7A1000219) funded by the Ministry of Science, ICT, and
Future Planning.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.fluid.2015.10.018.
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