Journal of Molecular Liquids 310 (2020) 113193

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Nanoparticle-modified gemini surfactant foams as efficient displacing

fluids for enhanced oil recovery
Nilanjan Pal, Amit Verma, Keka Ojha, Ajay Mandal ⁎
Department of Petroleum Engineering, Indian Institute of Technology (ISM), Dhanbad, Dhanbad 826004, Jharkhand, India

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

Article history: Surfactant-nanoparticle stabilized foams hold significant potential in the field of enhanced oil recovery (EOR).
Received 27 January 2020 This article discusses an experimental methodology to characterize foam fluids containing {N, N′-bis
Received in revised form 28 March 2020 (dimethyltetradecyl)-1,6-hexanediammonium bromide (14-6-14 GS) + silica/boron nitride} and identify opti-
Accepted 19 April 2020
mal formulations, based on physicochemical evaluation. Stability studies revealed half-life time of ~6 h for 14-
Available online 22 April 2020
1
6-14 GS foam, which dramatically improved to 27 h and 33 h in the presence of silica (SiO2) and boron nitride
Keywords:
3
(BN) particles respectively. Enhanced stability was achieved in surfactant-nanoparticle fluids owing to strength-
Surfactant-nanoparticle foam
Half-life time ened mechanical barrier (electrostatic repulsion + steric) at gas-liquid interfaces. Structural morphologies of
IFT reduction foam lamellae were analyzed by macroscopic and microscopic (imaging). Gaussian, Cauchy-Lorentz and
Wettability alteration Pseudo-Voight probability distribution functions were applied to model bubble size data. Pendant drop analyses
Viscoelasticity showed that oil/brine IFT decreased from 27.2 mN/m to b5 mN/m in surfactant-NP fluids. Contact angle, zeta po-
Enhanced oil recovery tential and micro-imaging analyses showed that wetting nature of rock altered from intermediate-wet to
strongly water-wet state in the presence of analyzed fluids. Foam fluids exhibited pseudoplastic flow behavior.
Viscoelastic profile investigations showed that foams retain their “pull-and-drag” characteristics during oil dis-
placement. In summary, 14-6-14 GS-NP foams prove to be suitable candidates for EOR with robust stability, in-
terfacial activity and rheological properties.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction as compared to reservoir fluids, causing adverse mobility ratio and in-
jection efficiency due to early gas breakthrough [1–3]. In addition, grav-
Increasing world consumption of oil, coupled with declining re- ity override and reservoir heterogeneities contribute towards poor
serves are attracting new ideas and methodologies for crude oil produc- volumetric sweep efficiency [2–4]. Foams encompass a promising re-
tion. Even after exhaustion of natural drive and water-flooding search field with the ability to mitigate issues associated with poor
processes, about two-thirds of original oil in place (OOIP) remains un- sweep during conventional gas flooding [5,6]. As dispersive systems
produced. The remaining hydrocarbons become the primary objective with large gas-liquid interfaces, foams remain thermodynamically un-
of existing as well as developmental enhanced oil recovery (EOR) pro- stable and require stabilization by amphiphilic species like surfactant,
jects. The optimization and selective implementation of any EOR polymer, nanoparticle or a mixture of such components [6,7]. Foam-
method require proper scientific planning and risk assessment depend- assisted EOR is achieved using two simultaneous effects: increasing
ing on nature of injection fluids, mineralogical constraints and physico- the apparent gas viscosity and reducing the relative gas permeability
chemical evaluation. This may involve understanding of different [8,9]. This plugs high permeable and fractured pores existing in reser-
aspects of conventional gas injection process within subsurface voirs, and improves sweep efficiency of oil within low-permeable re-
hydrocarbon-bearing formations. Gas flooding is a feasible EOR method gions. Foams can be generated either at the surface before injection or
widely employed in heavy oil reservoirs, wherein gas stream is injected in reservoir pore spaces. Continuous generation of foam lamella under
into reservoir formations [1,2]. When gas is first contact-miscible or dynamic conditions is necessary for foam transport in reservoir forma-
multi contact-miscible with oil, virtually all of the oil swept by gas can tions [10–12]. In porous media, foams consist of a two-phase fluid
be displaced. However, the density and viscosity of injected gas is low wherein gas flow paths remain discontinuous by lamella formed by
thin liquid films [12]. These lamellar structures are typically stabilized
⁎ Corresponding author.
in the presence of surfactant molecules that adsorb at the gas-liquid in-
E-mail addresses: [email protected], [email protected] (N. Pal), terface. However, these lamellar structures typically possess long-term
[email protected] (A. Mandal). stability. Factors such as surfactant partitioning into crude oil, rock

https://doi.org/10.1016/j.molliq.2020.113193
0167-7322/© 2020 Elsevier B.V. All rights reserved.
2 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193

adsorption and degradation of surfactant molecules require mixed sta- consequently improve the dynamic lifetime of foams, allowing better
bilizing agents in foams [13,14]. The amount of surfactant/nanoparticles sweep efficiency of in-situ hydrocarbons trapped within pore-throats.
required for effective formation and long-distance propagation of foams Knowledge of interfacial as well as rheological traits of nanoparticle-
from well bore affects petroleum recovery efficiency and economics laden surfactant aggregates provide important insights on inter-
[13–15]. molecular associations as well as aids in determining stabilization be-
In recent years, advances in nanoscience has led to use of nanoparti- havior of foam fluids [13,47]. Hence, foam stabilization and application
cles (NPs) as foam stabilizing agents under harsh sub-surface condi- holds promise in EOR processes.
tions, wherein surfactant-based foams is not beneficial [16]. In such The present article focusses on stabilization, physicochemical evalu-
cases, surfactant-nanoparticle mixtures closely adsorb onto gas-water ation and optimization of gemini surfactant-nanoparticle stabilized
contact area, thereby increasing interfacial elasticity and “structural foams for chemical EOR application. Relative foam height studies were
disjoining pressure”, while decreasing interfacial tension [7,17,18]. performed to identify half-life times (measure of foam stability). Foam
Though synergistic influences of surfactant and NPs are not fully under- morphologies were studied by studying evolution of foam bubbles
stood in current scenario, research investigations in the petroleum sec- with time via microscopic imaging. Bubble distribution data were ana-
tor has gained rapid interest in oil displacement processes. Gonzenbach lyzed using different probability density functions. IFT behavior at oil-
and colleagues [19] prepared ultra-stable particle stabilized foams in the fluid interfaces was investigated to corroborate their superiority over
presence of surfactants. Bayat and others [20] studied the effect of dif- conventional brine. Rock-wetting experiments were performed by con-
ferent nanoparticles on foam stability, and assessed their relative EOR tact angle and potentiometric measurements. Additionally, flow behav-
efficacies. Xue et al. [21] characterized surfactant-nanoparticle foam ior of foam systems were investigated under dynamic shear conditions
fluids in terms of IFT reduction and bubble generation. The adsorption to identify their pseudoplastic character and viscoelastic characteristics.
of cationic surfactant molecules onto nanoparticle surfaces owing to Experimental methodologies, discussed herein, encompass a systematic
electrostatic repulsion and foam stabilization mechanisms were approach to assess the stabilization, interfacial and rheological proper-
discussed in earlier papers [22,23]. Wang et al. [24] found that nanopar- ties of {14-6-14 GS +/NP} foams as EOR fluids.
ticles aid in stabilization of surfactant-stabilized foams owing to lower
surface tension and higher elasticity moduli at fluid bulk. Synergistic ef- 2. Experimental section
fect of surfactant-nanoparticle compositions in injected foams showed
enhanced oil stabilization and maintained foam mobility against in- 2.1. Materials
situ oil in porous media [24,25]. The interfacial, bulk rheological and dis-
placement behavior of surfactant foams exhibits drastic improvements Gemini surfactant, N,N′-bis(dimethyltetradecyl)-1,6-
in the presence of nanoparticles, as confirmed from increases oil recov- hexanediammonium bromide (abbreviated as 14-6-14 GS), was syn-
ery factors [26,27]. In fact, nanoparticle concentration in surfactant thesized and characterized in earlier articles [48,49]. Nanoparticles,
foams must be optimized in order to reach smaller size of aggregates, namely, silica (M.W. 60.08 g/mol) and boron nitride (M.W. 24.82 g/
which translates to thickening of foam lamellae and improved stability mol) were obtained from Sisco Research Laboratories Limited (India).
of injection fluid [18,28]. Nanoparticle addition improves robust nature, Crude oil (23.55° API) was procured from ONGC Asset, Ahmedabad
apparent viscosity and viscoelastic profile of surfactant-stabilized foams field, India.
[29–31]. Mixed particle-surfactant foams act as rigid, stable EOR agents
with favorable ionic strength, interfacial stability and bulk flow proper- 2.2. Nanoparticle characterization
ties [24,25,32,33]. Hence, mixed NPs mixed with “surface-active agents”
is cost-profitable alternative towards enhanced foam stability and phys- The morphology of nanoparticles was studied by Field Emission
ical properties [34]. Scanning Electron Microscopy (FE-SEM). Silica (SNP) and boron nitride
Application of mixed surfactant-NP assemblies to stabilize foams is (BNP) particles were initially desiccated in vacuum, and coated with
still in initial stages of surface engineering research. Hunter et al. [35] re- thin gold layer (5–10 nm) to prevent accumulation of static electric
ported that mechanisms responsible for foam stabilization may be com- fields (due to irradiation of electrons). Thereafter, dried nanopowders
plex, but NPs present in surfactant-stabilized foam fluids enhance were positioned on sticky carbon tape on standard aluminum mounts,
mechanical barrier {electrical repulsive + steric} around bubble/oil in- placed inside air-lock chamber in FE-SEM Supra 55 (Carl Zeiss,
terfaces, and reduce the tendency of foam film to coalesce. Germany). Fig. 1 shows different surface morphologies of hydrophilic
Esmaeilzadeh et al. [36] found that NPs reduce adsorption energy, indi- SiO2 and BN nanoparticles.
cating improved air-water interfacial activity and foam stabilization.
Kmetz and others [37] studied the propagation of surfactant- 2.3. Foam generation method
nanoparticle stabilized foams, and their superiority to single component
systems. Nanoparticles slow down the drainage rate of foam bubbles as Base fluid was initially prepared by mixing desired concentrations of
well as reduce adsorption capacity of injected chemicals onto reservoir NPs into aqueous 14-6-14 GS solution for 12 h. Uniform dispersion of
surfaces. Zhang et al. [38] and Liu et al. [39] reported that laponite nano- silica/boron nitride NPs into aqueous phase was achieved by
particles enhanced the stability of tetraethylene glycol mono-dodecyl ultrasonication in UP200Ht homogenizer for 30 min. For foam prepara-
ether surfactant based foams. Binks et al. [40] discussed surfactant- tion, formulated dispersions were stirred using waring blender at de-
dominant or nanoparticle-dominant induced stabilization effects in sired speed for specified time-period. Then, foam was poured into a
SiO2 particle-cationic surfactant foam bubbles. Interactions among graduated glass cylinder and sealed for observation at 303 K.
bare silica particles and surfactant molecules at foam boundary result Foamability was measured by initial foam volume. Stability of foams
in generation of stable, viscous foams [41]. Earlier reports confirmed was investigated by plotting foam height as a time function.
that strong foams are generated by nanoparticles' addition onto
surfactant-stabilized foams [11,42,43]. Interfacial/rheological behavior 2.4. Foamability and static foam tests
is primarily explained by the molecular orientation of cohesive interfa-
cial particle film(s), formed by the adsorption and subsequent build-up Bulk tests on prepared foam samples are conducted to confirm that
of hydrophobic nanoparticle-surfactant aggregates at the oil-water sur- surfactants as well as surfactant-NP mixtures are capable of stabilizing
face [44,45]. Furthermore, earlier studies on interfacial rheology proper- foams. In addition, these studies serve as pre-screening technique to
ties of surfactant-nanoparticle assemblies are related to wettability identify foam formulations with desired stability. Surfactant concentra-
alteration as well as oil-aqueous interfacial activity [46,47]. NPs tion was varied at/above critical micelle concentration (CMC) values to
 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193 3

Fig. 1. FE-SEM images of (a) silica NPs; (b) boron nitride NPs under 100 nm magnification.

identify good foamability and, thereafter, nanoparticle concentrations 2.9. Zeta potential measurements
were varied at 0.05%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and 0.35% sepa-
rately for SNP/BNP. Images of foam columns at different times were ob- Zeta potential values of oil/rock/aqueous suspensions were mea-
tained with digital camera to measure foam height. Evolution of foam sured using AntonPaar Litesizer 500 instrument. For analysis, samples
volume with time was characterized to determine half-life time, a mea- were loaded into Omega cuvette, and an electric field was activated
sure of foam stability. It is measured as the characteristic time required for potentiometric measurements.
attaining one-half of initial height of foam.
2.10. Rheological measurements
2.5. Microscopic analyses
The rheology of gemini surfactant-nanoparticle stabilized foams
To corroborate half-life test results, foam textures were analyzed were studied with Bohlin Gemini 2 Rheometer (Malvern Instruments,
with time using Olympus BX51 microscope, and variation in bubble UK) using concentric cylindrical geometry. Shear rate was varied be-
sizes were observed upto time-period of 60 min. Stream Basic 2.0 was tween 0.1 s−1 and 1000 s−1. In oscillation mode, amplitude sweep
used to capture the microscopic image of foam bubbles. tests were initially performed to identify linear viscoelastic (LVE) re-
gion, followed by frequency sweep within 1–250 rad/s range at con-
trolled strain (amplitude).
2.6. Adsorption studies

The adsorption of gemini surfactant molecules onto nanoparticle 3. Results and discussion
surface have been studied by UV spectroscopy tests using SHIMADZU
UV-1800 ultraviolet spectrophotometer. During this experiment, 3 g sil- 3.1. Surface behavior of 14-6-14 GS
ica/boron nitride was mixed with 30 ml 14-6-14 GS aqueous solution
with a magnetic stirrer for 12 h, and then allowed to centrifuge at Foam generation is strongly dependent on adsorption behavior of
2000 rpm for a period of 15 min. Surfactant solutions were analyzed be- surfactant molecules. The micellization and adsorption properties of
fore and after adsorption in order to estimate the amount of 14-6-14 GS 14-6-14 GS have been discussed in detail in our previous articles
adsorbed on nanoparticle surface(s). [48–50]. Du Noüy ring technique is useful for the assessment of surface
properties. Equilibrium surface tension values initially decreased with
gemini surfactant concentration in aqueous phase. This trend continued
2.7. Interfacial tension analyses until CMC of 0.2204 mM was achieved at 303 K. This is found to be much
lower as compared to respective values of conventional monomeric sur-
Pendant drop technique was employed to measure interfacial ten- factants such as cetyltrimethyl ammonium bromide (0.824 mM) and
sion (IFT) at oil/aqueous interface using Kruss DSA25 Analyzer. A quartz tetradecyltrimethyl ammonium bromide (3.423 mM). As expected, sur-
cuvette was filled with oil (n-heptane), and surfactant/nanoparticle face tension tends to remain nearly constant with further increase in
fluid(s) were suspended from NE44 (Φ 0.5 mm) needle in surrounding surfactant dosage. Furthermore, 14-6-14 GS solution has surface tension
oil phase. After maintaining desired temperature with TC11 chamber, of 28.5 mN/m and effectiveness of 43.4 mN/m at CMC. Mathematical
results were obtained with Advance 1.4 software by “profile-fitting” analysis of adsorption data reveals minimum area of 172 Å2 occupied
aqueous drop phase. per surfactant molecule at air-water interface. Hence, 14-6-14 GS mole-
cules accommodate onto vacant adsorption sites and reduce the free en-
2.8. Rock-wetting behavior ergy of liquid surface. This corroborates the gemini surfactant's ability to
form stable foams.
Sandstone/carbonate rock specimens were initially cleaned with
double distilled water and acetone, followed by vacuum drying for 3.2. Influence of controllable parameters on foam preparation
24 h to remove any adsorbed contaminants. Dried sample(s) were
dipped in crude oil for ~30 days to change wettability nature of rock Optimum surfactant productivity is achieved by controlling the agi-
to intermediate-wet or oil-wet state. Contact angle investigations tation speed and time during foam generation. Base fluids containing
were performed in sessile drop mode using Kruss DSA25 Drop Shape 14-6-14 GS surfactant in varying concentration were initially employed
Analyzer (Germany). In this study, specified base fluid volume was for the preparation of stable foaming fluids. In this experiment, agitation
dropped onto rock surface to study the variation of contact angle with speeds were varied as 1000, 2000, 3000 and 4000 rpm whereas the in-
time. fluence of increasing foam generation times in the range 100–400 s was
4 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193

investigated. As expected, increasing agitation speeds improved the ad- concentration limit, further surfactant addition does not contribute to-
sorption of surface-active 14-6-14 GS molecules. This showed the for- wards foam stabilization. This leads to generation of a surface tension
mation of smaller bubbles at the lower part of foam column, which gradient inside foam bubble and decrease in accommodation of surfac-
indicates increased lamellar (boundary) area. Similarly, increasing tant molecules [54].
foam generation times resulted in increased surfactant contact at air- Half-life of foam, defined as the time needed to decay to one-half of
water interface, leading to enhanced foams. For instance, foaming prop- its initial height (at t = 0), is identified from analysis of Fig. 4(a) plots.
erties of 50 ml {0.192% 14-6-14 GS, 12*CMC} base fluid with variation of With elapse of time, foam height decreased owing to gradual coales-
agitation speed and preparation time is depicted in Fig. 2. Initial foam- cence of bubbles. For foaming systems containing 14-6-14 gemini at
height values of 161 cm, 190 cm and 218 cm were observed with re- CMC, 2*CMC, 4*CMC, 6*CMC, 8*CMC and 10*CMC, the approximate
spective speeds of 1000, 2000 and 3000 rpm when time-period of 1 3 1
half-life times are 1 h, 1 h, 2 h, 3 h and 4 h respectively. The 14-6-
foam generation is kept constant at 300 s. Further increase in agitation 4 4 4
speed to 4000 rpm only recorded a foam height increase of only 14 GS based foam containing 12*CMC surfactant concentration shows
1.5 cm, which is not economically beneficial [51]. On the other hand, 1
half-life time of 6 h. However, as surfactant concentration is further in-
foams prepared after mechanical stirring/agitation for 100 s, 200 s, 5
300 s and 400 s yielded total height of 168 cm, 201 cm, 218 cm and 1
creased to 15*CMC, half-life time remains nearly constant at ~6 h. Foam
208 cm respectively. After 300 s, saturation of air-water interfaces 2
systems containing 12 times CMC {14-6-14 GS} is most beneficial in
with surfactant molecules occurs. For aeration times exceeding 300 s,
terms of foamability, foam stability and cost-effectiveness. Column im-
adverse effect on foam generation was observed owing to increased
ages showing influence of time elapse on height for foam containing
(bubble) rupture tendency stirring [51]. Therefore, input parameters
12*CMC is presented in Fig. 4(b). Surfactant impedes coalescence
with 3000 rpm (agitation speed) and 300 s (time) represent optimal
among foam bubbles owing to electrostatic repulsion effect, and slows
foam preparation conditions, and are employed in subsequent studies
down the rate of liquid drainage [53,55]. Stabilization mechanisms de-
on stability, interfacial behavior and rheology.
pend on the foam structure and forces acting within foam bubbles. It
is expected that NPs must play a synergistic role in enhancing foam sta-
3.3. Foaming behavior of gemini surfactant-stabilized systems bility and physicochemical attributes.

Basic foam tests were initially conducted by agitation in waring

blender in aqueous surfactant solution phase, and the macroscopic 3.4. Influence of NPs on relative foam height and half-life time
foam behavior was assessed. Foamability initially increases with surfac-
tant concentration upto critical limit. This is attributed to increased ad- Application of surfactant-stabilized foam is not favorable in complex
sorption of surfactant molecules onto gas/liquid interfaces [51,52]. This environments, such as petroleum reservoir wherein drastic changes in
increases the rate of bilayer formation near the air-water interfaces [52]. pressure and temperature are observed within small pore distances. In
Bilayers act as two-dimensional fluids within three-dimensional solvent such situations, NPs improve the mechanical barrier effect around bub-
matrix, which is essentially a foam system. These bilayers are particu- ble interfaces, thereby improving hydrophobicity [56]. Foam stabiliza-
larly responsible for stabilization of foams [52,53]. The mechanism of tion phenomena depends on the size and shape, specific area, nature,
surfactant adsorption and bubble stabilization has been illustrated in and surface/adsorption properties of nanoparticles. Nanoparticles aid
Fig. 3. For systems stabilized by CMC, 2*CMC, 4*CMC, 6*CMC, 8*CMC, in the formation of stronger three-dimensional surfactant-stabilized
10*CMC and 12*CMC dosage(s) of gemini surfactant, relative foam foam network with smaller bubbles, slower coalescence rate and en-
height after 24 h were found to be 7.1%, 8.5%, 11.8%, 16.2%, 18.5%, hanced stability. In this article, the influence of silicon dioxide NPs and
22.4% and 27.2% respectively of initial foam height (t = 0). The synergis- boron nitride NPs on foam stability and bulk-scale foamability have
tic behavior of surfactant addition on foam height is pronounced when been studied. Initially, the relative foam height increases with increas-
concentration is increased to 0.192 wt% (12 times CMC). In foams, liquid ing NP addition. Nanoparticles function by providing a mechanical (ste-
drains through the lamella due to gravity forces. Beyond optimal ric) barrier around surfactant-stabilized interfaces within foam

Fig. 2. Influence of agitation speed and time-period on behavior of surfactant-stabilized foams prepared by mechanical stirring technique.
 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193 5

Fig. 3. Schematics of proposed mechanism of adsorption behavior and foam bubble stabilization with increasing gemini surfactant (14-6-14 GS) concentration in aqueous media.

lamellae, which decreases the rate of coalescence of adjacent bubble stabilized foam system, half-life times gradually increase with SiO2
surfaces [56,57]. This results in the formation of robust, strong bilayers 1 1
nanoparticle addition, as evident from measured values of 6 h, 9 h,
(by interaction among different layers) encapsulating foam bubbles, as 2 4
illustrated in Fig. 5. 10 h, 14 h, 17 h and 27 h for 0.05%, 0.10%, 0.15%, 0.20%, 0.25% and
Fig. 6(a) and (b) shows that optimum foam life is observed in case of 0.30% concentrations. Further addition of silica at 0.35% dosage de-
0.30% silica and 0.25% boron nitride respectively. For 14-6-14 GS creases the foam half-life time to 24 h. Foam decay behavior in

(a) 1.0
15 CMC 12 CMC
0.9
10 CMC 8 CMC
0.8 6 CMC 4 CMC
R e la ve Fo a m h e ig h t

2 CMC CMC
0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0
0 4 8 12 16 20 24 28 32
Time (h)

Fig. 4. (a) Relative foam height versus time plots for prepared foams at different compositions (≥CMC) of 14-6-14 GS. (b) Vertical column images for (12*CMC) 14-6-14 GS foam at different
time-intervals.
6 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193

Fig. 5. Illustration of the stabilizing behavior of nanoparticle(s) in surfactant-based foam fluids.

BN + gemini surfactant stabilized foams, the half-lives follows a similar The foam stabilities of optimized surfactant-NP foams, measured by
3 1 their corresponding half-life times, are found to be much longer as com-
trend as 12 h, 17 h, 21 h, 24 h, 34 h, 30 h and 26 h for BNP concentra-
4 3 1
tions of 0.05%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30% and 0.35% respectively. pared to that of surfactant foams (6 h). Fig. 6(c) depicts a vertical col-
5
Beyond optimal concentration, NPs effectively aggregate and saturate umn plot of half-life times of 14-6-14 GS stabilized foams containing
gas-liquid boundaries, causing subsequent rupture of bubbles [31,57]. silica/boron nitride nanoparticles. The presence of silica and boron

1.0 1.0
GS + 0.05% SNP GS + 0.05% BNP
0.9 (a) GS + 0.10% SNP 0.9 (b) GS + 0.10% BNP
0.8 GS + 0.15% SNP 0.8 GS + 0.15% BNP
Relative Foam Height

GS + 0.20% SNP
Relative Foam Height

GS + 0.20% BNP
0.7 GS + 0.25% SNP 0.7 GS + 0.25% BNP
GS + 0.30% SNP GS + 0.30% BNP
0.6 0.6
GS + 0.35% SNP GS + 0.35% BNP
0.5 0.5

0.4 0.4

0.3 0.3

0.2 0.2

0.1 0.1

0.0 0.0
0 6 12 18 24 30 36 42 48 54 60 66 72 0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96

Time (h) Time (h)

36

33
(c) Silica NP
30
Boron Nitride NP
27
Half-life time (h)

24

21

18

15

12

0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

Nanoparticle concentration (wt. %)

Fig. 6. Relative foam height versus time graphs for 14-6-14 GS stabilized foam in the presence of (a) SiO2; and (b) BN nanoparticles. (c) Half-life times of surfactant-nanoparticle foams.
 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193 7

1 A superimposed, translucent lamellar network is observed in foam skel-

nitride NPs increase the half-life of 14-6-14 GS foams to 27 h and 34 h
3 eton of {14-6-14 GS + BNP}. Robust foam structures are produced in the
respectively. AlYousef et al. [58] investigated the stability of surfactant- presence of inter-linked BNPs, but SNP foams have a distinct lamella of
nanoparticle systems, and observed that optimized SNP within stabilizing aggregate structures.
0.25–0.75% concentration range improved the stability of alcohol
ethoxylate foams to nearly 20–29 h, depending on structural attributes 3.6. Microscopic analyses of foam morphology
of surfactant. The presence of surfactant/nanoparticle in foam fluids re-
sult in bilayer formation near air-water interface, which increases foam Micrometric experiments were performed as function of time for
stability but may reduce foamability [59,60]. Similar behavior was ob- systems containing optimized compositions of 0.192% 14-6-14 GS,
served during stability tests on silica/boron nitride nanoparticle stabi- {0.192% 14-6-14 GS + 0.30% SNP} and {0.192% 14-6-14 GS + 0.25%
lized 14-6-14 GS foams in the present article. The initial foam height BNP}. In general, it was observed that homogeneity and stability of
formed during NP addition decreased to some extent, but their half- foam samples decreased with time, as evident from increasing bubble
life times improved significantly. Our primary objective in EOR should sizes seen in Fig. 8(a), (b) and (c). This behavior is attributed to increase
be to produce stronger foams with minimal expenditure to produce a in coalescence/coarsening rate of dispersed foam films. Plateau borders
high-pressure drop, accompanied by favorable crude oil displacement get narrowed, eventually rupture and coalesce within foam layer [61].
within mature reservoir formations. Nanoparticle dosage is kept as This results in the appearance of larger bubbles with time. However, ad-
low as possible, considering the cost-profitability factor and stability at- dition of SNP or BNP imparts better stability with slower rate of defor-
tributes [58–60]. Hence, NPs were introduced into gemini surfactant mation/distortion of foam bubbles. This is because nanoparticles are
foams to produce strong foams with favorable stability. likely to bridge together, enhancing the mechanical barrier (electro-
static shielding + steric effect) influence at foam boundary
3.5. Macroscopic scale of foams [52,56,57,62]. Interestingly, BNP stabilized surfactant-foam shows bet-
ter stability in comparison to silica-based foams. This is due to stronger
The bubble structures of highly stable foams, formed with magnitude of BNP-induced steric stabilization (lamellar thickening) at
surfactant-nanoparticle combinations, were investigated. The 14-6-14 gas/liquid interfaces. In summary, surfactant-NP assemblies exhibit syn-
GS based foams containing silica (SiO2) have surprisingly different la- ergism on foam ageing properties.
mellar structure(s) as compared to foams in the presence of BN parti-
cles. Fig. 7 depicts the photographs of foam samples containing 3.7. Bubble size distribution studies
{0.192% GS + 0.30% SiO2} and {0.192% GS + 0.25% BN} after 24 h of
preparation. It is evident that foams consist of homogenous networks Statistical model investigations for bubble size distribution were
with uniform bubble sizes. Interestingly, {14-6-14 GS + SNP} stabilized performed for different foaming compositions. In this study, number
foam represents a transparent, less-dense network of bubble structures. distribution of foam bubbles after preparation (t = 5 min) was

Fig. 7. Sectional images of surfactant-NP stabilized foams after 24 h of preparation.

8 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193

Fig. 8. Micrometric images showing foam bubble distribution: (a) 0.192% 14-6-14 GS foam; (b) 0.192% 14-6-14 + 0.30% SNP foam; (c) 0.192% 14-6-14 GS + 0.25% BNP foam, under 100-
μm magnification at different time intervals.

expressed as frequency (f) versus bubble diameter (db) plots; and The Pseudo-Voight distribution model is a linear combination (or
thereafter, fitted with Gaussian, Cauchy-Lorentz and Pseudo-Voight convolution) of the Gaussian and Cauchy-Lorentz functions. Its density
models. The Gaussian (or normal) density function, which describes function is shown in Eq. (3):
every variable as a cumulative sum of small and independent variables,
is expressed in Eq. (1): 2μ:A w 2ð1−μ Þ
 e−4 ln ð2Þðdb −dc Þ2 =w2
f ¼ f0 þ : þ ð3Þ
π 4ðdb −dc Þ2 þ w2 π
A 2 w√
π e−2ðdb −dc Þ =w
2
f ¼ f0 þ ð1Þ ln ð2Þ
w√
2
In the above equations, w is standard deviation, A represents area
The Cauchy-Lorentz (or Breit-Wigner) model represents an infi- under normalized distribution curve, fo is offset frequency value, R2 is
nitely divisible, “pathological” distribution profile, in which dispersed the coefficient of determination and dc is the average bubble diameter
foam bubble sizes never reach a finite range on either side, and is (or location parameter). The value of R2 is useful in determining how ac-
depicted as Eq. (2): curately the experimental data is fitted by the model. The standard de-
viation (w) is a measure of the amount of variation of foam bubble size
2A w ranges from lowest to highest value. A significant parameter is dc, which
f ¼ f0 þ : ð2Þ
π 4ðdb −dc Þ2 þ w2 depicts the average bubble diameter corresponding to peak position
(maximum frequency) as per model assumptions. Table 1 shows the
 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193 9

Table 1
Comparison of probability function parameters for frequency versus foam bubble size plots using different statistical models.

Probability distribution function Fitting parameters Composition of foam fluid

0.192% 14-6-14 GS 0.192% 14-6-14 GS + 0.30% SNP 0.192% 14-6-14 GS + 0.25% BNP

Gaussian Center (dc) ± S.E. 144.2 ± 4.7 137.8 ± 9.9 104.4 ± 4.3
Std. deviation (w) 113.36 12.77 83.19
Offset (Io) 0.718 3.11 1.24
Adjusted R2 0.960 0.371 0.892
Cauchy-Lorentz Center (dc) 144.9 ± 5.5 135.0 ± 11.7 104.1 ± 5.0
Std. deviation (w) 141.85 16.08 112.75
Offset (Io) 1.12 2.93 0.91
Adjusted R2 0.945 0.396 0.867
Pseudo-Voight Center (dc) 327.8 ± 38.3 133.1 ± 2.8 104.6 ± 4.0
Std. deviation (w) 166.84 15.94 93.80
Offset (Io) 8.36 0.92 3.29
Profile shape factor (μ) −87.16 2.07 −37.4
Adjusted R2 0.542 0.766 0.894

fitting parameters obtained by fitting experimental data of bubble sizes' (a)). For 14-6-14 GS foam, the adjusted values of coefficient of determi-
distribution. nation (R2) are 0.960 for Gaussian, 0.945 for Cauchy-Lorentz, and 0.542
Foam bubbles' size profile was analyzed by ImageJ analysis tool; and for Pseudo-Voight models. However, the significance of application of
distribution plots were fitted with different functions, as described in the Pseudo-Voight model is discerned in surfactant-nanoparticle
Fig. 9. As expected, foam fluids recorded bigger foam bubbles in the ab- foams, as evident from Fig. 9(b) and (c). Silica/boron nitride particles
sence of silica or boron nitride NPs. This shows that foam bubble size is function by adsorbing onto the foam boundary, impeding inter-bubble
inversely proportional to foam stability. It is pertinent to note that the diffusion and subsequent coalescence [31,55,56]. As a result, the me-
same distribution equation cannot be employed to fit different foaming chanical barrier effect is strengthened around the oil droplets brought
composition models. Gemini surfactant-stabilized foams were best about by NP-induced steric stabilization. The coefficient of determina-
fitted with Gaussian function or Cauchy Lorentz function (see Fig. 9 tion (R2) in case of {14-6-14 GS + SNP} system is found to be 0.766

Fig. 9. Frequency-weighted distribution of foam bubble sizes with Gaussian, Cauchy-Lorentz and Pseudo-Voight modeling of experimental data for varying compositions: (a) 0.192% 14-6-
14 GS; (b) 0.192% 14-6-14 GS + 0.30% SNP foam; and (c) 0.192% 14-6-14 GS + 0.25% BNP foam.
10 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193

for Pseudo-Voight function, which is significantly greater as compared interfacial tension and foamability of aqueous fluids [64–66]. Several re-
to respective R2 values of 0.371 and 0.396 for Gaussian and Cauchy func- searchers report that faster rate of surfactant adsorption improves the
tions. For {14-6-14 GS + BNP} foam fluid, the Pseudo-Voight model diffusivity of stabilizing agents to interface, and hence enhance
proves to be slightly better as compared to other probability distribution foamability [64,65]. On the contrary, other groups argue that slower
models. However, each employed model exhibited favorable results in rates of IFT reduction improve IFT gradients along air-solution interface,
fitting bubble distribution data of {14-6-14 GS + BNP} foam owing to contributing to Gibbs-Marangoni effect and improved foaming behavior
the presence of superimposed bubble (lamellar) structure (clear from [66]. However, such contradictions agree on the fundamental require-
Fig. 7). Such a system can be fitted, depending on constraints of applied ment that IFT must be reduced to achieve beneficial application in ter-
distribution function(s). R2 values obtained by Gaussian, Cauchy- tiary oil recovery. Fig. 11(a) shows the equilibrium IFT for oil-brine
Lorentz and Pseudo-Voight modeling are 0.892, 0.897 and 0.894 respec- and oil-surfactant/nanoparticle systems. The IFT value at the heptane-
tively. Average bubble diameter(s) of 14-6-14 GS foam, {14-6-14 brine interface is 27.2 mN/m. Gemini surfactant/nanoparticle assem-
GS + SNP} foam and {14-6-14 GS + BNP} foam as per the best fitting blies favorably increase interfacial activity of base fluids. The IFT values
model were evaluated as 144.2 (±4.7) μm, 133.1 (±2.8) μm and obtained from pendant drop analyses are 8.93 mN/m, 4.57 mN/m and
104.6 (±4.0) μm respectively. Furthermore, it is to be noted that data- 4.91 mN/m for aqueous fluids containing 14-6-14 GS, {14-6-14
fit obtained with each function was performed successfully, irrespective GS + SNP} and {14-6-14 GS + BNP} respectively. At optimum NP con-
of the parametric result fit-accuracy. centration, slight difference in interfacial properties of silica and boron
nitride stabilized solution is observed owing to slight variations in
3.8. Surfactant adsorption onto nanoparticle surface their steric stabilization effects. This qualitatively corroborates the fact
that displacement ability of GS/NP fluids is better than that of conven-
Static adsorption tests were conducted to determine the residual tional brine-flood.
surfactant adsorption that remain adsorbed at silica/boron nitride nano- Dynamic IFT at oil-aqueous interfaces was studied as function of
particle surface. Adsorption behavior of cationic 14-6-14 GSs expressed time to reveal the chemical fluid's ability to displace oil. Fig. 11
as the amount of surfactant adsorbed versus concentration plots is pre- (b) presents the pendant drop IFT versus time plots for different fluid
sented in Fig. 10. The polar heads of the surfactant are positively compositions. With elapse of time, the IFT values of chemical fluids de-
charged, whereas nanoparticles initially possess hydrophilic character. crease owing to gradual saturation of oil-aqueous micro-interfaces with
Therefore, this study is useful in explaining the role of electrostatic surfactant and/or {surfactant + nanoparticle} assemblies [67,68]. Sur-
forces on surfactant-nanoparticle interactions. Adsorption behavior of factant/nanoparticle molecules diffuse from the bulk to the interface
cationic 14-6-14 GS molecules endows the surface of hydrophilic sil- until saturation limit is reached. Gradually, the slope of IFT versus time
ica/boron nitride with hydrophobicity. With increasing surfactant con- plot decreases owing to eventual adsorption of “vacant” sites for ad-
centration, the adsorbed surfactant quantity increases gradually, sorption at the oil-aqueous interface [68–70]. An equilibrium condition
which is attributed to increasing strength of inter-molecular electro- is finally reached, which indicates the state of complete saturation of oil-
static repulsive forces among 14-6-14 GS polar head-groups [23,55]. water interface with stabilizer molecules such as 14-6-14 GS and silica/
This renders improved adsorption behavior of surfactant onto nanopar- boron nitride particles. This is indicative of synergistic interactions
ticle, and improves the hydrophobic nature of {14-6-14 GS + silica/ among injected fluid components and displaced oil, which is desirable
boron nitride particle} aggregates. Consequently, 14-6-14 GS molecules for effective oil displacement process in reservoir formations [67,70].
are able to gradually saturate nanoparticle dispersions, and influence
surface activity of nanoparticles to a more hydrophobic or lyophilic
3.10. Wettability alteration behavior of 14-6-14 GS/nanoparticle
character [55,63]. Hence, surfactant-nanoparticle aggregates formed in
assemblies
analyzed foam compositions enhance the oil-attracting capacity of
surfactant-nanoparticle dispersions, which is desirable for EOR
Wetting nature of reservoir rock is favorably altered in the presence
application.
of 14-6-14 GS and/or nanoparticle assemblies. In this section, wettabil-
ity alteration behavior of rock has been studied with the aid of different
3.9. Interfacial tension measurements
experimental methods.
Surface interactions between oil and aqueous phase govern foam
stabilization and oil trapping/mobilization. IFT reduction is necessary 3.10.1. Contact angle (sessile drop) investigations
to facilitate formation of stable foam films with minimal external forces.
Previous literature has only discussed conflicting relations between Dynamic contact angle obtained at different time intervals during
sessile drop analysis onto sandstone and carbonate rock systems is
shown in Fig. 12. Surfactants function by diffusing and interacting
27.5
with oleic components existing at the surface, altering the state of
25.0 Silica surface
Boron nitride surface hydrocarbon-bearing reservoirs towards water-wetness [71]. The pres-
22.5
ence of nanoparticles develops a wedge film, thereby inducing extra
Adsorbed amount (mg/g)

20.0
pressure on (adsorbed) crude oil phases. This pressure is referred to as
17.5 “structural disjoining pressure”, which represents the interacting forces
15.0 existing between water-rock and water-oil interfaces [71,72]. It com-
12.5 prises of long-range interactions i.e. Van der Waals and electrical forces;
10.0 and short-range structural forces (at distances b5 nm). For favorable oil
7.5
displacement, disjoining pressure must be positive and exceed the cap-
5.0
illary pressure responsible for oil entrapment within the forward-
moving displaced fluid [72,73]. In an earlier study, Sefiane et al. [72]
2.5
found that the change in the contact angle of oil, water, and rock surface
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 is attributed to combination of “structural disjoining pressure” and “ad-
14-6-14 GS concentration sorption” of nanoparticles on the rock's surface. Hence, an ordered
layering arrangement of {surfactant-nanoparticle} develops onto rock
Fig. 10. Adsorption density of 14-6-14 GS onto nanoparticle surface at 303 K. substrate and subsequently strips trapped oil phases from rock surface.
 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193 11

45 45
(a) (b)
1.0% NaCl brine
40 40 14-6-14 GS solution
14-6-14 GS + SiO2 solution
35 35 14-6-14 GS + BN solution

Interfacial tension (mN/m)

In terfacial ten sio n (m N /m )

30 IFT = 27.2 mN/m IFT = 8.93 mN/m IFT = 4.57 mN/m IFT = 4.91 mN/m 30

25 25

20 20

15
15

10
10

5
5

0
0 0 50 100 150 200 250
1.0% NaCl brine 14-6-14 GS 14-6-14 GS + SNP 14-6-14 GS + BNP
Time (s)

Fig. 11. (a). Interfacial tension (IFT) obtained between oil and chemical fluid by pendant drop analysis; (b) dynamic IFT at oil-aqueous interfaces for different chemical fluids, expressed as a
function of time.

Surfactant-NP assemblies accumulate at the confinement of oil- (15 min), 11.3° (30 min) for {14-6-14 GS + BNP} fluid. Therefore,
water-rock contact region and impose a mechanical barrier (electro- surfactant-NP fluids favorably detach oil trapped within reservoir for-
static repulsion + steric interaction) at water-rock and oil-water inter- mations, and achieve tertiary oil recovery via wettability alteration
faces. It is clear from sessile drop analyses that brine/chemical fluid mechanism. Fig. 13 shows the sessile drop images of different chemical
gradually spreads with time onto oil-saturated rock. However, the rate fluid/oil/rock systems, captured with high-resolution microscope.
of contact angle reduction varies, depending on nature of the fluid.
The aqueous layer advances and the crude oil layer retreats across the 3.10.2. Zeta potential and micro-imaging studies
surface with shifting liquid-to-liquid coverage. Initially, intermediate-
wet state of rock was confirmed, with contact angles in the range 90°- An experimental methodology was employed to evaluate the sur-
120° (at t = 0). For brine solution containing 1.0% NaCl, contact angle face potential (or charge) existing within oil/rock/brine samples. In
decreases to 51.9° after 15 min and 30.3° after 50 min for sandstone this study, rock samples were finely crushed to powdered form and,
rock; 56.8° after 15 min and 33.9° after 50 min. However, wetting prop- thereafter, saturated with crude oil. Thereafter, suspensions containing
erty of aqueous fluids improve significantly with the introduction of 14- oil-wetted rock samples in brine/chemical fluid media were prepared
6-14 GS and SNPs/BNPs. For gemini surfactant fluids, contact angles by ultrasonication; and then evaluated for potentiometric measure-
were recorded as 55.5° (5 min), 35.5° (15 min), 14.4° (45 min) for sand- ments. Dry sandstone and carbonate particles in water were character-
stone; and as 64.1° (5 min), 25.7° (15 min), 17.0° (45 min) for carbon- ized to obtain respective zeta potentials of −9.64 mV and −6.61 mV.
ate. In the presence of nanoparticles, analysis of aqueous fluid drop However, in the presence of 1.0% NaCl brine, zeta values increased (in
exhibit significantly enhanced wetting properties. In sandstone rock magnitude) to −41.17 mV and −23.54 mV for sandstone and carbonate
systems, respective contact angle values of 43.7°, 18.2°, 8.9° for {14-6- respectively, prior to simulating the rock to oil-saturated condition.
14 GS + SNP} and 46.8°, 22.3°, 9.9° for {14-6-14 GS + BNP} were ob- Crude oil samples in contact with different rock substrates were ex-
tained after 5 min, 15 min, 25 min. Similarly, carbonate rock investiga- posed to 1.0% NaCl brine and surface potential at oil-brine interfaces
tions revealed contact angles of 52.9° (5 min), 30.7° (15 min), 12.5° were measured. Zeta potential at oil-brine interfaces showed values of
(30 min) for {14-6-14 GS + SNP} fluid; and 49.8° (5 min), 25.5° −18.44 (±0.53) mV for sandstone-aged sample; and −15.51 (±0.60)

Fig. 12. Investigation of dynamic contact angle versus time plots showing rock-wetting behavior of chemical fluids in: (a) sandstone and (b) carbonate rock systems.
12 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193

Fig. 13. Time evolution of sessile drop(s) of brine/surfactant/surfactant-NP fluids onto crude oil-saturated rock specimen: (a) sandstone; (b) carbonate.

mV after carbonate wetting. Oil-brine and brine-mineral zeta potentials contributes positively to the disjoining pressure effect, and a stable
have similar polarities for both rock substrates, showing that electro- water-wet film is formed. Thus, 1.0% NaCl brine is able to favorably
static force is repulsive and brine solution favorably detaches oil phase alter the state of rock (during secondary flooding). It was observed
from mineral surface [74]. It implies that the electrostatic forces that zeta potential of brine/rock/oil samples decreased (in magnitude)
 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193 13

as compared to those obtained without crude oil addition. This is due to BNP) were obtained for oil/sandstone/surfactant based compositions.
the adsorption of crude oil components onto rock particles, which al- For carbonate rock, aqueous systems of {14-6-14 GS + SNP} and {14-
tered the mean surface charge. Potential values of −11.02 mV (for sand- 6-14 GS + BNP} showed potentials of +30.95 mV and +37.26 mV re-
stone) and −6.02 mV (for carbonate) were obtained within ±4% spectively. Sandstone particles are more uniformly dispersed/wetted
standard error limit. Zeta potential of oil/rock/surfactant systems in- by GS + SNP assemblies, whereas carbonate rock particles are more fa-
creased significantly to +49.09 mV and +51.76 mV for sandstone and vorably wetted in GS + BNP systems. It can be summarized that gemini
carbonate rock surfaces, showing favorable oil detachment from rock surfactant-NP fluids tend to establish water-wetting layers and recover
surfaces. This is attributed to strengthened electrostatic repulsive inter- incremental oil trapped in reservoir pores.
actions among oil-water-rock interfaces. Table 2 shows the zeta poten-
tial values of oil/rock/aqueous suspension(s) with varying 3.12. Rheological investigations
compositions.
The steric stabilization phenomenon cannot be definitely measured 3.12.1. Viscosity of gemini surfactant/nanoparticle stabilized foams
during potentiometric investigation, which measures degree of electro- The dynamic viscosity and shear stress profiles of surfactant-
static repulsions among interacting surfaces [75]. In fact, the steric stabi- stabilized foam fluids under the influence of nanoparticle addition are
lization barrier might contribute adversely (negatively) to zeta presented in Fig. 15(a) and (b) respectively. 14-6-14 GS addition at fa-
potential values. Therefore, micro-imaging analysis of oil/rock/surfac- vorable concentration (0.192 wt%) results in the formation of stable la-
tant/aqueous systems in the presence of silica and boron nitride parti- mellar structures with bulk foam. The viscosity of foams initially
cles was performed to explain wetting properties, as shown in Fig. 14. decreases with increasing shear rates and then reaches a plateau, be-
Zeta potential values of +30.95 mV (for SNP) and +37.26 mV (for yond which viscosity remains nearly constant or increases very slightly.
Shear thinning or pseudoplasticity of foams is due to decreased interac-
tions between liquid-gas interfaces and faster liquid drainage rates oc-
curring at higher shear rates. This behavior is particularly beneficial to
Table 2 attain mobilization of (displaced) oil. Relatively stronger supramolecu-
Surface potential of suspensions, depending on mineral and chemical fluid composition.
lar self-assembly structures are generated in the presence of nanoparti-
Composition of mineral rock - crude oil - aqueous Sandstone Carbonate cles via bridging mechanism around the foam boundary [76,77].
suspension(s) Additionally, smaller bubbles are formed in the presence of SNP/BNP,
Zeta potential ± S.D. (mV)
which translates to greater number of bubbles per specified volume
Rock + deionized water −9.64 −6.61
± 0.35 ± 0.33
[76,77]. It has been established in previous sections that boron nitride
Rock + 1.0% NaCl brine −41.17 −23.54 possesses enhanced steric stabilizing influence over silica particles.
± 1.30 ± 1.09 This leads to relatively thicker lamellar boundary and increased foam
Oil-saturated rock + 1.0% NaCl brine −11.72 −6.02 viscosity. In conventional EOR processes, polymer and/or polymeric ma-
± 0.45 ± 0.20
terials are employed as displacing agents for oil mobility control within
Oil-saturated rock + 1.0% NaCl brine + 14-6-14 GS +49.09 +51.76
± 0.84 ± 0.32 rock pore-spaces owing to their high viscosities [78,79]. However, this
Oil-saturated rock + 1.0% NaCl brine + 14-6-14 +30.95 +37.58 may still not produce sufficient drive in heavy oil reservoirs [80]. It is ev-
GS + SNP ± 0.77 ± 1.00 ident from the study that surfactant-nanoparticle based foam fluids ex-
Oil-saturated rock + 1.0% NaCl brine + 14-6-14 +37.26 +27.99 hibit much higher viscosity as compared to conventional polymer fluids,
GS + BNP ± 0.35 ± 0.61
which is subsequently responsible for improved oil mobility control
[81,82]. In summary, foam fluids stabilized by {14-6-14 GS + NP}

Fig. 14. Micro-images of rock/liquid suspensions: (a) sandstone-oil-aqueous-GS-SNP; (b) sandstone-oil-aqueous-GS-BNP; (c) carbonate-oil-aqueous-GS-SNP; (d) carbonate-oil-aqueous-
GS/BNP.
14 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193

14-6-14 GS 100 14-6-14 GS

1000 14-6-14 GS + 0.20% SNP 14-6-14 GS + 0.20% SNP
14-6-14 GS + 0.25% SNP 14-6-14 GS + 0.25% SNP
14-6-14 GS + 0.30% SNP 14-6-14 GS + 0.30% SNP
14-6-14 GS + 0.20% BNP 10 14-6-14 GS + 0.20% BNP

S hear stress (P a)
V iscosity (m P a.s)

14-6-14 GS + 0.25% BNP 14-6-14 GS + 0.25% BNP

14-6-14 GS + 0.30% BNP 14-6-14 GS + 0.30% BNP
1
100

0.1

(a) (b)
10 0.01
0.1 1 10 100 1000 0.1 1 10 100 1000

Shear rate (s-1) Shear rate (s-1)

Fig. 15. Flow behavior profiles showing the influence of addition of silica/boron nitride NPs on (a) viscosity, and (b) shear stress of 14-6-14 GS stabilized foams with varying shear rates.

assemblies show favorable flow characteristics for oil displacement nature of foams. This behavior ceases till moderately low specific fre-
application. quency range (b10 rad/s). Beyond specific frequency, G′ exceeds G″
Shear stress versus strain plots depicted in Fig. 15(b) were initially which confirms that the analyzed foams possess dominant elasticity at
fitted using Herschel-Bulkley model. However, result analyses revealed high shear rates. The deforming/rupturing force applied during dynamic
negative values of yield stress, which is not physically possible. Hence, oscillatory motion does not exceed inter-bubble repulsions and interfa-
surfactant-NP foams undergo plastic deformation under shear and can- cial stresses [6,75,83–85]. Therefore, {14-6-14 GS +/nanoparticle}
not be investigated using this model. Hence, Power law (or Ostwald–de foams retain their “pull-and-drag” characteristics while producing re-
Waele) fluid model is employed to generalize and interpret rheological sidual oil during EOR process.
datasets. Viscosity profile of foam fluids (in pseudoplastic region, upto
critical shear rate) was modeled with the help of Power law Eq. (4) as: 4. Conclusions

μ ¼ k:γ̇n−1 ð4Þ The manuscript discusses an experimental methodology to investi-

gate the suitability of gemini surfactant-nanoparticle stabilized foam
In the above equation, k is consistency index, n is flow behavior fluids in EOR. Stable foams were prepared by mechanical agitation tech-
index, μ is dynamic viscosity, and γ̇ is shear rate. The value of ‘n’ is less nique under controlled input parameters. Relative foam volume studies
than one, implying pseudoplastic or shear-thinning character of studied revealed half-life time of ~6 h for 14-6-14 GS foams (at 12*CMC), which
foam systems. The coefficient of determination (R2) values were found significantly improved to 27 h and 33 h 20 min at optimal concentra-
to close to one (N0.9), showing good fitting of experimental data with tions of SNP and BNP respectively. Enhanced stability in the presence
employed model constraints. Table 3 shows the Power law fitting pa- of NPs was attributed to strengthening of mechanical barrier effect at
rameters obtained for different foams. gas-liquid interfaces. Macroscopic studies identified different structural
morphologies of foam lamellae, depending on the type of NPs
3.12.2. Viscoelastic profile investigations employed. Bubble size distribution data were analyzed and modeled
with the help of probability density functions. Average bubble diame-
Petroleum reservoirs typically consist of numerous pore-throat sec- ter(s) of 14-6-14 GS foam, {14-6-14 GS + SNP} foam and {14-6-14
tions with varying permeability, and the introduced foam fluid must be GS + BNP} foam were respectively determined as 144.2 (±4.7) μm
sufficiently viscoelastic in order to its stability/structure during porous
media flow. Fig. 16 shows the dynamic viscoelastic profile of elastic
modulus (G′) and viscous modulus (G″) for different foaming composi- G', 14-6-14 GS
1000
tions. Gemini surfactant foam as well as gemini surfactant-nanoparticle G'', 14-6-14 GS
G', 14-6-14 GS + 0.25% SNP
Dynamic moduli, G' and G'' (Pa)

foam exhibit significant viscoelastic traits, as evidenced from increasing

G'', 14-6-14 GS + 0.25% SNP
moduli values with increasing angular frequencies. At low angular fre- 100
G', 14-6-14 GS + 0.25% BNP
quencies, G″ is found to be greater than G′, showing the viscous, flowing G'', 14-6-14 GS + 0.25% BNP
10
Table 3
Model parameters for viscosity behavior of foam fluids with varying gemini surfactant/
nanoparticle compositions in the pseudoplastic region. 1

Foam composition Power law model parameters

k (Pa.sn) n R2 0.1

14-6-14 GS 0.204 0.567 0.975

14-6-14 GS + 0.20% SNP 0.214 0.373 0.935 0.01
14-6-14 GS + 0.25% SNP 0.268 0.408 0.927 1 10 100
14-6-14 GS + 0.30% SNP 0.278 0.385 0.941 Angular frequency (rad/s)
14-6-14 GS + 0.20% BNP 0.253 0.545 0.976
14-6-14 GS + 0.25% BNP 0.288 0.548 0.966
Fig. 16. Viscoelasticity versus frequency plots showing dynamic variation of elastic and
14-6-14 GS + 0.30% BNP 0.293 0.506 0.955
viscous moduli for 14-6-14 based foam fluids in the presence of silica/boron nitride NPs.
 N. Pal et al. / Journal of Molecular Liquids 310 (2020) 113193 15

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