Journal of Colloid and Interface Science 407 (2013) 375381

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A family of alkyl sulfate gemini surfactants. 2. Wateroil interfacial

tension reduction
Bo Gao , Mukul M. Sharma
Department of Petroleum and Geosystems Engineering, The University of Texas at Austin, Austin, TX 78712, United States

a r t i c l e

i n f o

Article history:
Received 15 May 2013
Accepted 28 June 2013
Available online 12 July 2013
Keywords:
Sulfate gemini surfactants
Enhanced oil recovery (EOR)
Interfacial tension (IFT) reduction
Phase behavior

a b s t r a c t
A family of sulfate gemini surfactants that has great potential for various industrial applications was previously prepared and characterized in our lab. The unique and versatile structure of these surfactants has
endowed them with properties that are attractive for enhanced oil recovery (EOR). A detailed experimental study was carried out and is presented here on the wateroil interfacial properties of these novel molecules. This series of seven sulfate gemini surfactants of different hydrophobic tail and spacer group
lengths shows systematic trends in interfacial tension (IFT) reduction with changing solution conditions.
These molecules exhibit extraordinary aqueous stability even in high salinity and hard brines. Ultra-low
interfacial tension values were measured with low surfactant concentrations. The results from this study
showed the potential of utilizing these surfactants at low concentrations and in harsh reservoir
environments.
2013 Elsevier Inc. All rights reserved.

1. Introduction
Although low liquidliquid interfacial tension (IFT) is important
in promoting emulsication and in the removal of oily contaminants by detergents, advances in our knowledge of the factors governing the reduction at that interface stem from the intense
interest in enhanced oil recovery (EOR) by use of surfactant solutions [1]. A series of systematic studies in the 1970s marked an
important milestone in surfactant research and application in
petroleum industry and had led to the recognition that the capillary number controlled the amount of residual oil remaining after
ooding an oil-containing core [25]. These studies revealed that it
is necessary to reduce interfacial tension between the oil and the
slug of surfactant-bearing water to ultra-low (<10 3 mN m 1) values for effective displacement of oil from the pores and capillaries
of petroleum reservoir rock. Such an ultra-low interfacial tension
can be achieved with suitable surfactants by adsorbing at the
wateroil interface under pre-designed conditions. Given the low
oil prices from late 1980s to early 2000s, the number of surfactant
EOR research and eld projects saw a sharp decline. However, recent oil price developments combined with the evolution of advanced technologies and current outlook on supply/demand
forecasts have resulted in a new emphasis on improving recovery
factors through implementation of EOR processes, including various surfactant related processes [610].
Corresponding author. Present address: 3319 Mercer Street, URC-URC-SW204,
Houston, TX 77027, United States. Fax: +1 713 431 6360.
E-mail address: b.robert.gao@gmail.com (B. Gao).
0021-9797/$ - see front matter 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2013.06.066

Thanks to their unique and versatile structures, gemini surfactants have recently attracted considerable interest from the academic and industrial communities. Anionic geminis, in
particular, have signicant water solubility, form micelles,
zsubstantially lower the surface tension, and exhibit more interesting rheological behavior compared to conventional anionic
homologs [11]. They thus have great potential for application in
the petroleum industry [12]. This is the main motivation for our
research. A family of alkyl sulfate gemini surfactants was recently
prepared and characterized in our lab [13]. In this paper, we
discuss the interfacial tension reduction potential of these surfactants at wateroil interfaces.
2. Experimental
2.1. Materials
For current study, a family of alkyl sulfate gemini surfactants
of the type referred to below as m-s-m was prepared [13].
(n-CnH2nO)2(CH2)m(OCH2CH2SO4Na)2 represents the generic
chemical formula. Systematic characterization of chemical and
surface properties showed high purity of the synthesized sulfate
gemini surfactants. The oil phase used in the interfacial tension
measurements was pure n-alkanes purchased from SigmaAldrich.
Two branched alkyl benzene sulfonate (BABS) surfactants tested in
this study, including Petrostep A1 (C1518 BABS) and Petrostep M2
(C1618 BABS), were provided by Stepan Company in aqueous
form (with known active material content). The polymer sample
(Flopaam 3330S) was obtained from SNF Inc.

B. Gao, M.M. Sharma / Journal of Colloid and Interface Science 407 (2013) 375381

2.2. Methods
All of the gemini surfactant solutions were prepared by diluting
a stock (concentrated) solution in deionized water and stirred on a
magnetic stirrer at desired temperature for an hour.
2.2.1. Interfacial tension measurement
The interfacial tensions between pure hydrocarbon and gemini
surfactant solutions were measured by the spinning drop tensiometer of Texas Model 500 [14]. The spinning drop method is based
on a balance of centrifugal and interfacial tension forces. It has a
wide range of measurement, 10 5102 mN m 1. An outstanding
advantage of the method is that an interface can be studied which
is not in direct contact with any solid surface. The difculties in
using this method, on the other hand, include the following: (1)
the formation of artifacts, e.g., dumbbell shaped drops which
can appear when the tension is low and (2) specifying criteria characteristic of hydrodynamic equilibrium. Drop shapes other than
cylindrical can be avoided by increasing the rotation speed. A reasonable test of equilibrium is the agreement (or otherwise) between tensions from phases that have been contacted prior to
measurement and those obtained from system not originally at
equilibrium (more details in the Supplementary material). Most
interfacial tension values in this study were measured between
gemini solutions and dodecane as the hydrocarbon phase (hydrocarbon selection discussed in the Supplementary material).
2.2.2. Phase behavior tests
Phase behavior experiments were conducted to study the
behavior of mixtures of the hydrocarbon, brine and surfactant system at a desired temperature. Phase behavior tests were conducted
following the experimental protocols recently developed at the
University of Texas at Austin [69]. Phase behavior tests include
careful observations of the aqueous mixtures with the hydrocarbon phase over a sufciently long time for them to reach equilibrium. For conventional surfactant systems, a low viscosity
microemulsion will ideally form within a few days and exhibits ultra-low interfacial tension (IFT) with both the hydrocarbon and the
water phases [1517]. The best surfactant formulation can then be
evaluated in core oods or imbibition tests depending on the application. In the current study, experiments were carried out to see if
gemini surfactants exhibit similar phase behavior to conventional
single chain molecules.
3. Results and discussion
Anionic gemini surfactants have great potential of being applied
in surfactant ooding thanks to their unique properties of ultralow critical micelle concentration (cmc) and high efciency in
reducing the surface tension compared with conventional single
chain surfactants [13]. The interfacial tension of a surfactant system is greatly related to the adsorption of surfactant at the interface [18]. There are many factors that affect this adsorption
process. In current study, the effects of the different variables on
the interfacial tensions of gemini surfactant/pure hydrocarbon/
electrolyte system are systematically investigated.
3.1. Surfactant concentration
Surfactant molecules tend to accumulate at the wateroil interfaces where the hydrophilic and hydrophobic ends of the molecules can be in a minimum energy state. If the concentration of
surfactants at the interface is very low, the molecules may lie at
on the surface [19]. As their concentration increases, the surfactant
molecules begin to orient themselves at the interface, forming a

monolayer. This increases the surface pressure and decreases both

the interfacial energy and the interfacial tension. At a solution concentration close to the critical micelle concentration (cmc), surfactant monomers in solution begin to spontaneously associate into
larger aggregates (or micelles). At this point, no further adsorption
at the interface will occur, and therefore, interfacial tension
reaches the nal plateau value.
Aqueous samples of 14-4-14 and 18-4-18 geminis at different
surfactant concentrations were prepared in a 20 wt.% NaCl base
solution. The interfacial tensions between these solutions and
dodecane (n-C12H26) were measured at 55 C. The rst thing worth
noting here is that the solution had a very high salinity (20 wt.%
NaCl). Even under this extreme condition, no phase separation or
precipitation of any kind was observed for all the surfactant
solutions prepared. In contrast, conventional (monomeric) EOR
surfactants used in the petroleum industry today generally show
poor aqueous stability/solubility under such harsh conditions (high
salinity and/or hardness). As a result, complex surfactant formulations are routinely reported in which co-surfactant and/or co-solvent are added to improve overall solubility [7,2023]. This
unfortunately generates a whole new set of issues, including design complexity, elevated cost, and chromatographic separation
[22,23].
All the gemini surfactants synthesized in the current study have
shown extraordinary tolerance to salinity indicating that they are
very hydrophilic. The interfacial tensions (IFT) versus gemini surfactant concentration plots for the two molecules are shown in
Fig. 1. Obviously, even at extremely low concentration level,
gemini surfactants (at least the 18-4-18 molecule) are still
capable of reducing the interfacial tension to ultra-low levels
(<10 3 mN m 1). In all measurements that follow, a surfactant
concentration of 0.02 wt.% (200 mg L 1) will be used to make
sure the experimental concentration stays safely above cmc [13]
and in the meantime still remain much lower than concentrations
typically used in a conventional surfactant formulation (0.2 wt.%
to 2.0 wt.% total concentration).
3.2. Dynamic response
Dynamic surface tension (DST) is critical in many industrial and
biological processes [24,25]. The dynamic progression of surface
tension can be monitored by DST measurements [26]. Similarly,
on generation of a new liquidliquid interface, the equilibrium
interfacial tension (IFT) is not instantly reached. For the tension
to reach its equilibrium value, surfactant molecules must rst diffuse onto the interface, then adsorb, and reorient in the interfacial

100

Interfacial tension /mN m-1

376

10
1
0.1
0.01
0.001
0.0001
0.1

10

100

Concentration /mg L-1

Fig. 1. Variation in interfacial tension (IFT) with gemini concentration: , 14-4-14;
18-4-18. Measured in 20 wt.% NaCl base solution at 55 C; against dodecane.

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B. Gao, M.M. Sharma / Journal of Colloid and Interface Science 407 (2013) 375381

region. In the meantime, some of the adsorbed molecules will try

to get desorbed and go back to the bulk aqueous phase under the
inuence of thermal motions. This is, therefore, a dynamic and
competing process among diffusion, adsorption, and desorption.
At initial time, interface density is really low and adsorption dominates, which results in steady reduction in IFT. As time goes on,
more and more surfactant molecules accumulate at the interface,
the adsorption rate decreases and gradually reaches equilibrium
with desorption, and nally, the IFT reaches plateau value.
Fig. 2 is the plot of dynamic interfacial tension against time for
0.02 wt.% 16-4-16 and 18-4-18 solutions measured at temperature
of 55 C and 85 C. It can be see here that both surfactants are very
effective in reducing the interfacial tension between oil and water.
Furthermore, 16-4-16 is more efcient than 18-4-18 in terms of
time spent for interfacial tension to reach equilibrium. At 55 C,
for 16-4-16, it took about 10 min to reach equilibrium, in contrast
to a much longer period of 40 min for 18-4-18. Fig. 2 also shows
the effect of temperature on the dynamic interfacial tensions.
Higher temperature apparently expedites the equilibrium process.
For instance, at 85 C, it only took 15 min for IFT of 18-4-18 solution to stabilize. Elevated temperature affects the mutual solubility
of the solvents, the CMC, and the adsorption kinetics of surfactant
molecules, and the distribution of the surfactants between oil and
water. It is crucial in all experiments to give every sample ample
time to reach true IFT plateau. This can be monitored and achieved
by following the equilibration criteria that require three consecutive drop radius readings from the tensiometer to agree
within 0.001 cm.
One of the initial concerns of conducting experiments at elevated temperatures (>65 C) was the chemical stability of sulfate
surfactants under such conditions [27,28]. Experimental observations from our study seem to suggest good chemical integrity of
the studied sulfate geminis, although more rigorous analysis
should be conducted to conrm such statement. Supporting evidence includes the following: (1) clear aqueous solution throughout the experiments (no phase separation or precipitation), since
it would be expected to see large diol compound dropping out of
solution if the hydrolysis was to happen on sulfate geminis [28]
and (2) unusual reversible viscosity response of gemini solutions
to temperature [29].
3.3. Mixing with polymer
Surfactant-based formulations often contain water-soluble
polymers that improve the properties of the formulations (overall
mobility in EOR formulations). Therefore, it is important to study

the interaction of gemini surfactants with water-soluble polymers.

The study of interactions between surfactants and polymers is an
active eld of interest in colloid science. We investigated the effect
of 500 ppm Flopaam 3330S addition (hydrolyzed polyacrylamide,
average MW of 8,000,000) on the dynamic interfacial tension between oil and gemini surfactant solution.
It can be seen from Fig. 3 that polymer has a remarkable effect
on the dynamic IFT response. It takes more time to reach the equilibrium interfacial tension with the addition of polymer, but it has
little if any effect on the equilibrium IFT values [20,22]. This can be
explained by the fact that the addition of polymer will increase the
viscosity of the solution, which in turn reduces the rate of diffusion
of the surfactant molecules, thereby slowing down the adsorption
of the surfactant onto the interface.

3.4. Alkyl chain length

As the alkyl chain gets longer, we see a gradual decrease in IFT
in Fig. 4. Indeed, as the hydrophobe gets larger, the hydrophiliclipophilic balance (HLB) is adjusted in such a way that the
surfactant molecules become more lipophilic and thus have higher
tendency to move from the bulk aqueous phase onto the wateroil
interface. Once there, they can reorient, so that the large hydrophobes point toward the oil phase to reduce the free energy of
the system. All the gemini molecules shown in Fig. 4 have demonstrated their ability in effectively reducing wateroil interfacial
tension by several orders of magnitude (from the original
50 mN m 1). Remarkably, this reduction occurs at very low surfactant concentrations (0.02 wt.%) as shown by our measurements.
Ultra-low interfacial tensions (<10 3 mN m 1) were, however, only
observed for geminis with longer alkyl chain and spacer group, i.e.,
18-4-18 and 20+-4-20+, the reason being that these two molecules
are better HLB balanced (more lipophilic) under this specic set of
salinity (20 wt.% NaCl) and temperature (55 C) conditions.
Our previous HLB calculations showed that all the gemini surfactants studied here are very hydrophilic [13]. And while this
hydrophilicity helps out in dissolving these long chain surfactant
molecules into aqueous solution even at extremely high salinity,
it hurts their performance in reducing IFT. In order to further reduce the IFT, the HLB balance of these molecules must be further
adjusted. There are a few approaches to achieve this: (1) changes
in aqueous solution condition, e.g., to increase electrolyte concentration in the solution and thus push the surfactant molecules onto
wateroil interface; or raise the solution temperature and promote
adsorption at the interface and (2) manipulations on the molecular

10

Interfacial tension /mN m-1

Interfacial tension /mN m -1

10

0.1

0.01

0.001

0.0001

1
0.1
0.01
0.001
0.0001

10

100

Time /min.
Fig. 2. Dynamic IFT response for 0.02 wt.% gemini solutions at two different
temperatures: 16-4-16 (55 C); 16-4-16 (85 C); 18-4-18 (55 C); 18-4-18
(85 C). Measured in 20 wt.% NaCl base solution, against dodecane.

10

100

1000

Time /min.
Fig. 3. Dynamic IFT response for 0.02 wt.% gemini solutions: 16-4-16; 16-4-16
w/ polymer;
18-4-18;
18-4-18 w/ polymer. Measured in 20 wt.% NaCl base
solution at 55 C, against dodecane.

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B. Gao, M.M. Sharma / Journal of Colloid and Interface Science 407 (2013) 375381

Interfacial tension /mN m-1

0.1

(10 wt.%). Therefore, one potential area where gemini surfactants

can be used and may perform better would be in high temperature,
high salinity environments, which are commonly encountered in
the oil reservoirs around the world. It should be noted that over
the wide range of salinities examined in this section, we have yet
to nd a minimum of interfacial tension with regard to salinity.

0.01

3.6. Divalent salt (CaCl2) concentration

0.001

0.0001
12

14

16

18

20

22

24

Alkyl chain length, m

Fig. 4. Impact of alkyl chain length on IFT for 0.02 wt.% geminis: m-2-m;
m. Measured in 20 wt.% NaCl solution at 55 C, against dodecane.

m-4-

structure, e.g., to make the surfactant more hydrophobic by introducing longer tail (as shown in Fig. 4) and spacer groups, or switching to more lipophilic head groups, such as carboxylates.

3.5. Monovalent salt (NaCl) concentration

The interfacial tensions were measured between hydrocarbon
and gemini solutions with various amount of NaCl added. Results
in Fig. 5 show the positive impact of higher NaCl concentration
on lowering the tension of an wateroil interface. The solubility
of gemini surfactants in highly saline solutions should be noted.
As more NaCl is added, the interfacial tension steadily goes down.
This is consistent with data for other surfactants and is to be expected. However, we did not observe any salting out of the surfactant indicating that gemini surfactants show good salt tolerance.
The increase in effectiveness of surfactant by the addition of salt
is a result that has been well explained earlier through a modication of electrical double layer at the wateroil interface and the
reduced hydrophilicity of the surfactant at high salinities due to
ion binding at the surfactant head groups.
Notice that the lower IFT values were observed toward the
higher end of the salinity range (1520 wt.%) for gemini surfactants. For conventional surfactants, on the other hand, the lowest
interfacial tension typically occurs over a narrow salinity window
below a total dissolved solid (TDS) content of 100,000 ppm

Divalent ions like Ca2+ and Mg2+ are more efcient in driving
surfactant molecules onto the wateroil interface than monovalent
ions. Most conventional EOR surfactants do not work well with
divalent ions, often showing precipitation or phase separation
upon the addition of Ca2+ and Mg2+ into their aqueous solutions.
As shown earlier, gemini surfactant solutions can withstand high
concentrations of NaCl; it is thus natural to test the aqueous stability and IFT reduction potential of gemini solutions under the inuence of divalent ions.
A series of 0.02 wt.% gemini solutions (already containing
15 wt.% NaCl) were prepared with different amounts of CaCl2
added, and the IFT values were measured between these aqueous
solutions and pure dodecane. The results are shown in Fig. 6. First
and foremost, no solubility problems were encountered in these
tests, even when the CaCl2 concentration went as high as
4.0 wt.%. The addition of divalent ions helps further reduce the
IFT, and ultra-low values were observed. Formation brines with
TDS (mono- and di-valent ions together) in excess of
150,000 ppm are generally considered to be difcult targets for
industrial operations like enhanced oil recovery (EOR). Gemini surfactants are shown here to perform well (in terms of solubility and
interfacial tension reduction) in such environments, making it possible to handle these difcult situations with simpler chemical
systems.
3.7. Temperature
Temperature affects solubilities and interaction energies of
hydrophobes and head groups in aqueous solution. It is worth discussing here the effect of temperature on the solution and interfacial behaviors of gemini surfactants, since they are directly related
to micelle formation and interfacial tension reduction.
A strong driving force of the ultra-low cmc values for geminis is
the huge free energy reduction associated with the transfer of the
twin tails from water into micelle core [12]. This is fundamentally
determined by the incompatibility (or insolubility) of hydrocarbon

10

Interfacial tension /mN m-1

Interfacial tension /mN m-1

1
1

0.1

0.01

0.001

0.0001
0

10

15

20

25

NaCl concentration /wt.%

Fig. 5. Impact of NaCl concentration on IFT values for 0.02 wt.% geminis solutions:
14-2-14;
14-4-14;
16-4-16;
18-2-18;
18-4-18. Measured at 55 C
against dodecane.

0.1

0.01

0.001

0.0001

CaCl2 concentration /wt.%

Fig. 6. Impact of CaCl2 concentration on IFT for 0.02 wt.% gemini solutions: 14-414;
18-4-18;
20+-4-20+. Measured in 15 wt.% NaCl base solution at 55 C,
against dodecane.

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B. Gao, M.M. Sharma / Journal of Colloid and Interface Science 407 (2013) 375381

0.1

Interfacial tension /mN m-1

tails with (or in) water. When the solution temperature increases,
the solubility of hydrocarbon tails in water is enhanced. And this in
turn delays the micellization and renders higher cmc values. It is,
however, very important to note that this temperature effect (on
cmc values) is very minor, as compared to other factors such as
hydrocarbon chain length or spacer group size [12]. On the other
hand, the IFT measurements are conducted at concentrations much
higher than cmc. The IFT reduction is monitored in our opinion by
the adsorption of surfactant molecules at wateroil interface.
While higher temperature increases the solubility (only slightly),
it seems to have a stronger impact, as illustrated in Fig. 7, in accelerating and promoting adsorption of gemini molecules onto
wateroil interface and hence reduce the interfacial free energy
or interfacial tension.

0.08

0.06

0.04

0.02

0.02

0.04

0.06

0.08

0.1

Petrostep A1 (C15-18 BABS) /wt.%

3.8. Synergy with conventional surfactants
In many practical applications, different types of surfactants are
deliberately mixed together to improve the properties of the nal
product. In such cases, what is sought is synergism between the
surfactants. The goal is to obtain properties of the mixture that
are better than those attainable by the individual components. It
is evident to us that, in the future, the more hydrophilic gemini
surfactants will most likely be used in mixtures with conventional
surfactants for both cost and performance considerations. The
properties of such mixtures must thus be investigated in order to
better understand mixture behavior and properties.
In current study, we investigate the synergy between geminis
and conventional surfactants in terms of IFT reduction. The conventional surfactants studied here are branched alkyl benzene sulfonates (BABS). These surfactants are chosen because of their
hydrophobic nature. Our expectation is that the strong hydrophilicity of gemini surfactants at the wateroil interface might compensate for the relative lipophilicity of the other surfactant
molecules. Fig. 8 shows a concentration scan of C1518 BABS, conducted at 55 C and in aqueous solutions containing 0.02 wt.%
gemini and 15 wt.% NaCl. With only about 0.01 wt.% of Petrostep
A1 (C1518 BABS) added, the interfacial tensions between aqueous
solutions and dodecane were reduced to ultra-low level (<10 3
mN m 1). The authors venture to postulate that the minimum in
interfacial tension might be caused by tighter molecular packing
at the wateroil interface when small amount of BABS is added
into gemini surfactant solution. As more ABS molecules are introduced, however, the structure of the interfacial layer could change

Interfacial tension /mN m-1

0.1

0.01

0.001

0.0001

10

15

20

25

NaCl concentration /wt.%

Fig. 7. Comparison of IFT values at 55 C (lled symbols) and 85 C (open symbols)
for 0.02 wt.% gemini solutions: 16-4-16; 18-2-18; 18-4-18. Measured against
dodecane.

Fig. 8. Synergy between gemini (0.02 wt.%) and Petrostep A1 (C1518 BABS) in IFT
reduction: 14-4-14; 16-4-16. Measured in 15 wt.% NaCl base solution at 55 C,
against dodecane.

to a different conguration which does not favor interfacial activity

(further IFT reduction).
Two points worth emphasizing here are as follows: (1) the
hydrophobic surfactant, C1518 BABS, is stable and remains dissolved in an aqueous solution that contains 15 wt.% NaCl, due to
the existence of hydrophilic geminis in solution; (2) the interfacial
tension from the surfactant mixture reaches ultra-low levels,
which is not achievable by either individual surfactant. The molecular interaction between the gemini and conventional surfactants
provides mutual benets that contribute to aqueous stability and
interfacial activity. This leads to a new possibility of making use
of gemini surfactants. They can be used as co-solvents that help
the solubility of the main surfactants, or as co-surfactants that help
bring out the best performance of the surfactant mixture. More
measurement results showing a similar trend are provided in the
Supplementary material.
3.9. Phase behavior tests
Surfactant formulations for EOR applications are commonly selected on the basis of phase behavior experiments (by evaluating
the microemulsion formed with hydrocarbon, water, and surfactant mixtures). In the current study, experiments were carried
out to see if gemini surfactants exhibit similar phase behavior to
conventional single chain molecules. Table 1 below summarizes
the experimental conditions examined in the phase behavior tests.
Fig. 9 shows the phase behavior pipettes prepared for 0.2 wt.%
16-4-16 gemini surfactant. The picture was taken after the pipettes
were kept in a 55 C oven for two weeks. These pipettes represent
very well what we would observe in phase behavior tests at other
gemini surfactant concentrations listed in Table 1 (namely,
0.01 wt.%, 0.02 wt.% and 0.1 wt.%). A rst common observation
made is that even with salinity as high as 20 wt.%, no phase separation or precipitation take place, showing the superb salinity
(and/or hardness) tolerance of this molecule. Another common
observation across different tests is the absence of signicant Type
III middle phase [30]. In fact, all test pipettes showed a Type I
appearance even after an extended period of equilibration. No
obvious transition in microemulsion appearance (volume and color) was observed from low to high surfactant concentrations, since
no visually discernible middle phase can be identied across the
board. It is worth reiterating that ultra-low interfacial tensions
were indeed measured in some conditions corresponding to the
phase behavior tests, as shown in previous section. At rst, this appears to be contradictory to the common notion that ultra-low

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B. Gao, M.M. Sharma / Journal of Colloid and Interface Science 407 (2013) 375381

Table 1
Experimental conditions examined in phase behavior test.

Group I
Salinity
Group II
Hardness

Surf. Conc.
(wt.%)

Temp.
(C)

Scan range

Oil type

0.01, 0.02,
0.1, 0.2
0.01, 0.02,
0.1, 0.2

45, 55,
85
45, 55,
85

up to 20 wt.% NaCl

C8, C10,
C12, C14
C8, C10,
C12, C14

15 wt.% NaCl + up to
4 wt.% CaCl2

interfacial tension, and Type III microemulsion phase always go together [1517,31]. Fundamentally, however, IFT reduction and oil
solubilization (Type III middle phase formation) are two separate
phenomena, controlled by different processes.
The interfacial tension of a surfactant system is greatly related
to the adsorption of surfactant molecules at the interface. The fact
that gemini surfactants can pack more closely at the interface helps
the system to reach ultra-low IFT despite a low solubilization ratio.
On the other hand, conventional surfactants cannot form an interfacial packing as compact as geminis [13]. The closer packing by
gemini molecules can be ascribed to at least two facts: (1) intramolecular level: the existence of the short spacer group chemically
constrains the distance between the two tails; (2) intermolecular
level: the extremely high salinity condition gemini surfactants
can withstand helps screen out the electrostatic repulsion between
head groups and thus facilitate even closer packing.
The oil solubilization capability of a surfactant is controlled by
the overall free energy of the hydrocarbon/surfactant (co-surfactant)/electrolyte system [32,33]. For conventional surfactants at
sufciently concentration level, the minimization of free energy requires the oil molecules be incorporated with surfactant molecules
to form swollen micelles or even bicontinuous (middle phase)
structures. Whereas for gemini surfactants, due to their high tendency to self-aggregate, especially at higher concentration and
with salt addition, it is possible that the free energy can be minimized by the gemini molecules self-assemble, without solubilizing
signicant amount of oil molecules.
Although Type III systems are not generally observed in phase
behavior experiments for current family of gemini surfactants,
the success of applying these geminis in chemical enhanced oil
recovery (CEOR) is still promising. Firstly, salinity and/or hardness
tolerance is very important for applications in harsh reservoir conditions. Moreover, for conventional surfactant systems, low IFT can

only be obtained in the Type III microemulsion window, in which

case oil can be solubilized into a microemulsion phase. However,
for gemini surfactants, the ultra-low IFT may be achieved at under-optimum conditions. Surfactant ooding under Type I phase
behavior conditions (where the surfactant remains primarily in
the aqueous phase) but with ultra-low IFT may have a huge advantage over a conventional (Type III) process since complicated phase
behavior in the reservoir can be avoided and microemulsion trapping will no longer be an issue [34].
4. Conclusions
In this article, we conducted systematical laboratory testing on
the wateroil interfacial properties for a family of alkyl sulfate
gemini surfactants [13]. These surfactants show extraordinary tolerance to salinity and/or hardness. No phase separation or precipitation of any kind was observed for all the surfactant solutions
prepared, even with the presence of extremely concentrated NaCl
(up to 20 wt.%) and/or CaCl2 (up to 5 wt.%). More importantly, ultra-low interfacial tension (IFT) values were consistently observed
toward the higher end of the salinity and/or hardness range, making the application of simple surfactant formulation in more hostile environments possible and favorable [1,9]. The synergy
between gemini and conventional surfactants provide mutual benets that contribute to aqueous stability and interfacial activity.
Geminis can therefore be used as co-solvents that help the solubility of the main surfactants, or as co-surfactants that help bring out
the best interfacial performance of the mixture.
Encouraged by their superior interfacial performance, core ood
experiments have been planned using current family of gemini
surfactants to examine the enhanced oil recovery potential. The
aforementioned two-phase (Type I microemulsion) surfactant
ooding would be a key step toward more practical applications
for these novel surfactants [34]. Further work is underway to see
if the use of carboxylate head groups will result in gemini surfactants that will be less hydrophilic and, therefore, show better phase
behavior. While the efforts are still on-going, we believe our attempt to present a systematic and application-focused study of
these sulfate geminis will benet the engineering and scientic
communities. In the next planned article in this paper series, rheological properties of these anionic geminis in aqueous solution
will be discussed.
Acknowledgments
Insightful inputs from Dr. Gary A. Pope and Dr. Upali P. Weerassoriya at The University of Texas at Austin are gratefully
acknowledged.

Oil Phase

Appendix A. Supplementary material

Interfacial region

Supplementary data associated with this article can be found, in

the online version, at http://dx.doi.org/10.1016/j.jcis.2013.06.066.
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Aqueous Phase

10

12

14

16

18

20

[wt.% NaCl]

Fig. 9. Test pipettes prepared for 0.2 wt.% 16-4-16 gemini surfactant phase
behavior. Measured at 55 C with varying aqueous solution salinity (wt.% NaCl).

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