Journal of Colloid and Interface Science 582 (2021) 1116–1127

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Journal of Colloid and Interface Science

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

Pure and mixed aqueous micellar solutions of Sodium Dodecyl sulfate

(SDS) and Dimethyldodecyl Amine Oxide (DDAO): Role of temperature
and composition
Sepideh Khodaparast a,b,⇑, William N. Sharratt a, Gunjan Tyagi a, Robert M. Dalgliesh c, Eric S.J. Robles d,
João T. Cabral a,⇑
a
Chemical Engineering Department, Imperial College London, SW7 2AZ London, United Kingdom
b
School of Mechanical Engineering, University of Leeds, LS2 9JT Leeds, United Kingdom
c
ISIS Neutron and Muon Source, Science and Technology Facilities Council, Rutherford Appleton Laboratory, OX11 0QX Didcot, United Kingdom
d
The Procter & Gamble Company, Newcastle Innovation Centre, NE12 9TS Newcastle-Upon-Tyne, United Kingdom

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

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

Article history: Aqueous mixtures of anionic and nonionic/cationic surfactants can form non-trivial self-assemblies in
Received 25 February 2020 solution and exhibit macroscopic responses. Here, we investigate the micellar phase of pure and mixed
Revised 22 May 2020 aqueous solutions of Sodium Dodecyl Sulfate (SDS) and Dimethyldodecyl Amine Oxide (DDAO) using a
Accepted 2 August 2020
combination of Small Angle Neutron Scattering (SANS), Fourier-Transform Infrared Spectroscopy (FTIR)
Available online 17 August 2020
and rheological measurements. We examine the effect of temperature (0–60
C), on the 20 wt% SDS
micellar solutions with varying DDAO (65 wt%), and seek to correlate micellar structure with zero-
Keywords:
shear solution viscosity. SANS establishes the formation of prolate ellipsoidal micelles in aqueous solu-
Temperature
Phase behaviour
tions of pure SDS, DDAO and SDS/DDAO mixtures, whose axial ratio is found to increase upon cooling.
Mixed surfactant Elongation of the ellipsoidal micelles of pure SDS is also induced by the introduction of the non-
Dimethyldodecyl Amine Oxide DDAO anionic DDAO, which effectively reduces the repulsive interactions between the anionic SDS head-
Sodium Dodecyl sulfate SDS groups. In FTIR measurements, the formation of elongated mixed ellipsoidal micelles is confirmed by
Viscosity the increase of ordering in the hydrocarbon chain tails and interaction between surfactant head-
ATR-FTIR groups. We find that the zero-shear viscosity of the mixed surfactant solutions increases exponentially
Anionic surfactant with decreasing temperature and increasing DDAO content. Significantly, a master curve for solution vis-
Ellipsoidal micelles
cosity can be obtained in terms of micellar aspect ratio, subsuming the effects of both temperature and
SANS
DDAO composition in the experimental range investigated. The intrinsic viscosity of mixed micellar solu-
tions is significantly larger than the analytical and numerical predictions for Brownian suspensions of

⇑ Corresponding authors at: School of Mechanical Engineering, University of Leeds, LS2 9JT Leeds, UK (S. Khodaparast).
E-mail addresses: [email protected] (S. Khodaparast), [email protected] (J.T. Cabral).

https://doi.org/10.1016/j.jcis.2020.08.002
0021-9797/Ó 2020 Elsevier Inc. All rights reserved.
 S. Khodaparast et al. / Journal of Colloid and Interface Science 582 (2021) 1116–1127 1117

ellipsoidal colloids, highlighting the need to consider interactions of soft micelles under shear, especially
at high concentrations.
Ó 2020 Elsevier Inc. All rights reserved.

1. Introduction reported a ternary phase diagram of C14AO and SDS in water, at

less than 30 wt% total surfactant concentration. Adding C14AO to
Surfactants are key components in numerous formulated mix- aqueous solutions with a fixed amount of SDS was found to pro-
tures with applications in food, enhanced oil recovery, agriculture mote the transition from roughly spherical micelles to elongated
and soil treatment, as well as household, cosmetic and pharmaceu- rods and eventually to a hexagonal liquid crystalline phase [22].
tical products [1–7]. For a given application, surfactants molecules Summerton et al. performed Small Angle X-ray Scattering (SAXS)
and their self-assembled structures may play one or several diverse measurements of a SDS/DDAO mixture at a fixed concentration
roles as detergents, foaming and wetting agents, and dispersants (20 wt% SDS and 3 wt% DDAO) and compared their findings with
[8]. Almost without exception, formulated mixtures contain sev- those obtained for pure SDS micelles (20 wt%). They found both
eral types of surfactant molecules to achieve the desired stability pure and mixed systems to form prolate ellipsoidal micelles, with
and functionality in the final product [9]. From an academic point larger axial ratios prevalent in the latter case [31,34]. Whilst most
of view, over the past decades, mixtures of surfactants have pro- studies on the micellar phase of mixed surfactants have investi-
vided both theoretical and experimental challenges in defining gated the effects of chemical additives and molar ratios of the com-
the links between interactions at the molecular scale and the ponents (mainly the surfactant mixture), the effect of temperature,
macroscopic bulk properties of the corresponding solutions [10– and especially cooling below room temperature, is yet to be inves-
14]. tigated in detail, despite its practical importance (e.g. in low tem-
Mixtures of anionic and nonionic/cationic surfactants are of perature detergency).
particular scientific interest due to the (potential) synergistic inter- The main goal of this study is to investigate the effect of tem-
actions between dissimilarly charged head-groups [15–18], that perature variation over a wide range of 0
C < T < 60
C on the
can be exploited in practical applications. Typically, upon mixing molecular structure and rheological response of the micellar phase
surfactants of differing head-group charge, (i) the Critical Micelle of SDS, DDAO and their mixtures. We first report SANS measure-
Concentration (CMC) of the solution is significantly reduced com- ments of micellar phases of pure solutions of SDS and DDAO for
pared to predictions for ideal micelles, (ii) relatively larger micelles concentrations below 30 wt%, as they are both frequently used in
with modified shapes are formed, (iii) the temperature- applications where temperature variations may occur [35–38].
concentration equilibrium phase boundaries between the micellar We then examine mixed solutions of primarily 20 wt% SDS with
and liquid crystalline and/or crystalline phases are shifted and (iv) varying DDAO content (1–5 wt%), see Fig. 1 for an illustration. This
viscosity of the mixed solution significantly increases compared to range of surfactant concentration and composition is chosen to: (1)
that of individual surfactant solutions at similar total surfactant thermally extend one of the most interesting areas of the ternary
concentrations [19–23,18,24–26]. phase diagram of SDS/DDAO/H2 O, where minimal thermal, compo-
Here, we investigate the effect of adding an amphoteric surfac- sitional and/or concentration fluctuations lead to dramatic meso-
tant Dimethyldodecyl Amine Oxide (DDAO) to a commonly used scopic and macroscopic changes of solution properties (Fig. 1)
anionic surfactant Sodium Dodecyl sulfate (SDS), a combination [22]. (2) Provide a molecular underpinning to the thermal stability
that is often found in liquid detergents [27,26]. Amphoteric surfac- of model formulated detergent mixtures and their response to
tants are a class of surface active agents that carry a net charge thermal fluctuations, particularly cooling below ambient tempera-
which is sensitive to both pH of the solution and the presence of ture, where these mixtures often do not perform or appear as
other surfactants in the mixture. In particular, for DDAO molecules, desired.
the amine oxide group exists in either a nonionic (at pH> 7) or We first use Dynamic Light Scattering (DLS) and cross-polarised
cationic (at pH< 5) form due to protonation of the oxygen atom Optical Microscopy (OM) to identify the temperature-
in the amine oxide head-group [28]. When added to anionic surfac- concentration boundaries of the micellar phase. SANS is then
tants, DDAO has been found to promote the formation of mixed employed to determine the shape, size, and net charge of micelles
micelles, significantly reduce the CMC and modify the shape, in pure and mixed aqueous solutions of SDS and DDAO. We com-
charge and aggregation number of the micelles [29–32]. In this bine these data with FTIR spectroscopy measurements to elucidate
work, we focus on the micelles formed in mixtures of DDAO and the synergistic interactions between the two surfactants in mixed
SDS in pure water, without altering the pH of the solution through micelles. Finally, we perform rheological measurements for pure
addition of acid or base. The pH of the solutions remains around 7 and mixed solutions of SDS and DDAO across the desired range
and above, for which DDAO alone would be expected to behave as of temperature to highlight the effects of micellar structural
a nonionic surfactant. changes on the viscosity of the surfactant solutions.
Previously, structural analyses of mixed DDAO and SDS micellar
systems have predominately focused on lower total surfactant con- 2. Materials and methods
centrations (< 10 wt%) [31]. In general, relatively elongated
micelles, compared to pure micelles of either SDS or DDAO, were Sodium dodecyl sulfate SDS (>99.0% purity) and an aqueous
found to form in mixed DDAO/SDS systems. Incorporation of DDAO solution of 30 wt% C12 AO were purchased from Sigma–Aldrich
into SDS micelles was found to decrease the net charge of the and used as received. Solutions for DLS, OM and FTIR measure-
micelles, reducing the area designated for each surfactant head- ments were prepared by diluting the surfactants in deionised
group, and consequently increasing the packing parameter [33]. water. For SANS measurements, DDAO and SDS (both of >99.0%
By contrast, the effect of added DDAO to concentrated SDS solu- purity) were used and all solutions were prepared in D2 O. Consid-
tions, particularly in terms of the size and shape of self- ering the density difference between H2O and D2O, a correction
assembled structures, has received considerably less attention. was made when preparing samples in D2O to keep the molar frac-
Based on rheological solution behaviour, Weers et al. (1990) tion of surfactant constant.
1118 S. Khodaparast et al. / Journal of Colloid and Interface Science 582 (2021) 1116–1127

Fig. 1. Investigated range of compositions and temperature within the ternary phase map of SDS/DDAO/water [22]. Aqueous binary solutions of SDS and DDAO, with
concentrations below 30 wt%, as well as mixtures with fixed concentration of SDS (20 wt%) and varying concentrations of DDAO (1–5 wt%), were studied within 0–60
C.
Mixed SDS/DDAO/water solutions reside in the micellar phase (L1 ) 0-60
C. Upon cooling the mixtures down to room temperature, solutions with higher DDAO content (P 5
wt%) form a liquid crystalline phase (LC), whilst others with lower DDAO content remain in the L1 phase. At lower temperatures (T ¼ 0
C), a single crystalline phase (C) or
coexisting L1 , LC and C phases may exist, which are highly dependent on the DDAO content.

Cross-polarised Optical Microscopy (OM). Cross-polarised structure factor at high micellar concentrations studied here,
optical microscopy was used to detect phase transition from the self-consistency checks controlling the volume of surfactant, Scat-
isotropic micellar phase to the birefringent liquid crystalline and tering Length Densities and ensuring continuous trends in charge,
the crystalline phases, following procedures described in a previ- dimensions and structure modifications were performed for all
ous publication [39]. Approximately 3 ll of the solution was placed analyses presented here across a wide range of temperature and
between two thin glass cover slips. Solvent evaporation during the concentrations [41,42].
experiments was minimised by sealing the area surrounding the FTIR spectroscopy. FTIR spectra were recorded in Attenuated
droplet using a gasket. Isothermal experiments were performed Total Reflectance (ATR) mode using a Bruker Tensor 27 System
by initially stabilizing the droplet at 60
C before a rapid quench with a Platinum ATR accessory. For each spectrum, 64 single beam
(at 80
C/min) to the final temperature of interest. OM images were scans were averaged with 4 cm1 resolution in the range of 4000 to
captured with an Olympus BX41M-LED microscope, using a 10X 600 cm1 . Results were examined in the absorbance unit using
objective and a CMOS camera (Basler ac2040-90) that provided OPUS 8.5 software. Standard baseline correction was performed
an overall spatial resolution of 1.5 lm per pixel. on all the spectra analysed with no further data processing.
Dynamic Light Scattering (DLS). Dynamic light scattering Viscosity measurements. Viscosity measurements were per-
(DLS) was performed using a Zetasizer Nano S (Malvern Panalyti- formed in a thermally controlled concentric cylinder setup of a
cal), which operates with a back-scattering detector (h ¼ 173
) Rheometer (AntonPaar MCR302). All tests were started by stabilis-
and a 633 nm He-Ne laser yielding a fixed value of ing the solution at T ¼ 60
C. Cooling measurements were started
q ’ 0:0026 Å1. The cuvette temperature was controlled with a by stabilising the solution at the temperature of interest for
Peltier system in the range of 60
C down to 0
C. All cooling cycles 3 min and measuring the viscosity over a range of shear rates
were started from 60
C to ensure that sample were initially in the (1 s1 < c_ < 2000 s1 ). Zero-shear viscosity of the solutions was
isotropic micellar phase. Data were acquired in triplicate. Time- extrapolated from the viscosity vs. shear-rate curves by averaging
resolved measurements, over 30 min, were performed to probe the data in the low shear rate region as they reached a plateau.
the transition from micellar to liquid crystalline and crystalline
phases. The raw correlograms could be interpreted without cumu-
3. Results and discussion
lant fitting or CONTIN analysis, in order to identify the boundaries
of the micellar phase.
We first report our findings on the micellar structures in pure
Small Angle Neutron Scattering (SANS). SANS experiments in
aqueous solutions of SDS and DDAO. Mixed SDS/DDAO systems
linear and isothermal cooling cycles were performed on the Larmor
were then prepared by increasing the concentration of DDAO in
diffractometer (ISIS, Harwell, UK), with a polychromatic k=0.9–
SDS solutions of 20 wt% until the onset of the micellar to liquid
13.3 Å unpolarised and divergent incident beam with sample-to-
crystalline phase transitions was detected, see Fig. 1. Primary
detector distance = 4.1 m, yielding a fixed momentum transfer
phase boundaries of the micellar phase in both pure and mixed
range of approximately 0.005 < Q < 0.6 Å1 with the peak flux
systems, in the range of temperature tested here (T < 60
C), were
in the intermediate Q range. Quartz cells (1 mm banjo, Starna) con-
identified by means of DLS and OM, whilst structural analyses of
taining the surfactant solutions were installed into a metallic sam-
the micelles were carried out using SANS and FTIR. Findings on
ple changer that was thermally controlled using a liquid bath.
the volumetric concentration, shape and size of the micelles are
Experiments were started at 60
C, where all solutions were in
then used to describe trends found for zero-shear viscosity of solu-
the isotropic micellar phase, and then a variety of cooling ramps
tion as a function of composition at various temperatures (ranging
were imposed to reach 0
C [39]. The resulting SANS data were
from 60
C down to 0
C).
reduced, using standard procedures, in MANTID [40]. Reduced data
from Larmor were fitted in SASView (V4.1.2) using an ellipsoidal
3.1. Sodium Dodecyl Sulfate, SDS
core–shell model for the form factor and the Hayter-Penfold
Rescaled Mean Spherical Approximation (RMSA) to model the
DLS analysis of 20 wt% SDS solutions shows a fairly mono-
structure factor. Due to the expected large contribution of the
disperse (micellar) population whose size gradually increases as
 S. Khodaparast et al. / Journal of Colloid and Interface Science 582 (2021) 1116–1127 1119

temperature decreases. Upon reaching temperatures below 14
C, a respectively [41,44]. Prolate ellipsoidal micelles are defined by
secondary population of larger fast-growing objects, characterised the major axis a and the minor axis b. Upon cooling aqueous solu-
by a slower decay of the auto correlation function, appears which tions of SDS at a fixed concentration, the minor axis of the ellipsoid
corresponds to the onset of crystallisation in the solution b remains unchanged, while the major axis a grows significantly
(Fig. 2a). Additionally, nucleation and growth of SDS crystals in (Fig. 2d) [45]. The prolate ellipsoidal micelles become more elon-
solutions of 20 wt% SDS, at temperatures below 14
C, was clearly gated upon cooling illustrated through their axial ratio (a=b)
detected in OM experiments, shown in the inset images in Fig. 2a. increasing from around 1.4 at 60
C to 2 at 14
C, before SDS crys-
These, preliminary findings from DLS and OM are used as guideli- tallisation begins and consumes the micellar phase [45]. Consider-
nes in defining the temperature range for SANS measurements of ing the SDS molecules to occupy an average volume of 410 Å3 and
the micellar structures during cooling experiments. the volume of the ellipsoidal micelles to be solely occupied by
SANS experiments upon cooling of 20 wt% SDS solutions were these molecules, the aggregation number (N agg ) of SDS micelles
performed between 60 and 0
C at the rate of ’0.1
C/min. In line can be estimated to increase from ’95 at 60
C to ’130 at 14
C.
with the findings from our DLS and OM analyses, SANS data of pure These findings, summarized in Fig. 2e, are in agreement (about
SDS aqueous solutions at temperatures above 14
C exhibit one 5% larger) with values reported by Hammouda [41]. Both axial
single broad intensity peak in the intermediate-Q region, which ratio and the aggregation number of micelles are expected to
is associated with the structure factor of charged SDS micelles decrease for lower concentrations of SDS [31]. The overall net
[43,41]. Upon cooling, the intermediate-Q peak increases in inten- charge per micelle slightly decreases at lower temperatures, thus
sity whilst moving towards lower Q values (Fig. 2b). Below 14
C, resulting in significantly lower charge per head-group of SDS mole-
formation of SDS crystals in the solution leads to the simultaneous cules at lower temperatures, where aggregation numbers are con-
appearance of a sharp Bragg peak at Q  0:2 Å1 and an upturn in siderably larger (Fig. 2e). In the range of temperatures studied here,
the low-Q region (Fig. 2b). The location of the Bragg peak corre- the average micellar volume fraction is very close to the volumetric
sponds to the average d-spacing (about 32–33 Å) between fraction of the surfactant in the solutions, considering an average
surfactant-rich and water-rich layers in hydrated crystals of SDS density of 1.01 g/cm3 for SDS. These trends are also consistent with
[41]. previous work by Hammouda [41] for aqueous solutions of 20 wt%
We next focus on the effect of cooling on micellar solutions of of SDS in the temperature range of 20
C < T < 80
C.
20 wt% SDS above the crystallisation temperature. The intermedi-
ate micellar peak is best fit by the core–shell prolate ellipsoidal 3.2. Dimethyldodecyl Amine Oxide DDAO
model, see Fig. 2c. Prolate ellipsoids were found to systematically
provide a better self-consistent fit to our data when compare to SANS analyses of aqueous solutions of DDAO were carried out
oblate ellipsoids. The scattering length densities SLD of the sodium for a large range of concentrations (1–30 wt%) and temperatures
sulfate shell and dodecyl core of the SDS micelles were calculated (4
C < T < 60
C), since their effect on DDAO micelles has not been
and set at fixed values of 4  106 Å2 and 0:37  106 Å2, previously reported. Within this parameter space, pure DDAO solu-

Fig. 2. Effect of cooling on 20 wt% SDS aqueous solutions. During a cooling cycle, SDS solutions remain in the micellar phase until reaching temperatures below T ’ 14
C. (a)
DLS measurements show the appearance of fast-growing larger objects with long decay times, in addition to the primary micelles, as the solution is cooled down to T ¼ 13
C.
OM images confirm the isotropic micellar phase at higher temperature T P 14
C and the mixed micellar and crystalline phase at T ’ 13 °C (inset). (b) SANS measurements of
micellar SDS solutions show a shift in the mid-Q micellar peak towards lower Q values upon cooling. For T < 14
C, the micellar peak gradually disappears as a Bragg peak at
high-Q and upturn at low-Q, both associated with the crystallisation of SDS, are detected. T ¼ 8
C (1) and T ¼ 8
C (2) correspond to the data acquired at early time (first
3 min) and late time (3–6 min) from the start of experiment at T ¼ 8
C, respectively. (c) Illustrative SANS data of SDS micellar phase at 20 °C fitted to a core–shell ellipsoidal
model. (d) Prolate micelles of major axis a and minor axis b were found to elongate as the solution is cooled from 60 °C to 14 °C. a increases monotonically upon cooling, while
b remains unchanged. Error bars correspond to the uncertainties in data fitting procedure. (e) Comparatively larger micelles with larger aggregation numbers are obtained
upon cooling. The net charge per head-group of SDS molecules (calculated by dividing the fitted total net charge over the aggregation number) also decreases with decreasing
temperature.
1120 S. Khodaparast et al. / Journal of Colloid and Interface Science 582 (2021) 1116–1127

tions always remained in the micellar phase during the cooling parison between calculated values of 1=S0 from the present SANS
cycles. Examples of SANS data obtained at various concentrations data and those estimated considering the Percus–Yevick closure
of DDAO are presented in Fig. 3a. At higher concentrations (above for hard spheres, SPY :
5 wt%) a clear peak appears in the intermediate-Q range, character-
ð1  /Þ4
istic of the structure factor of charged micelles. This feature is, SPY ¼ : ð2Þ
however, not present in SANS measurements acquired at lower ð1 þ 2/Þ2
concentrations of DDAO (Fig. 3a). The relatively larger deviation for higher concentration of DDAO
The SANS intensity IðQ Þ of the micellar solutions is the product (> 5 wt%), indicates that other sources of interaction between the
of the volumetric concentration of the micelles /, contrast factor micelles must be considered when modelling micellar solutions of
Dq and form PðQ Þ and structure factor SðQ Þ of the system: higher concentrations of DDAO. Here, the Rescaled Mean Spherical
Approximation RMSA is used to model the structure factor for all
IðQ Þ ¼ /V m ðDqÞ2 PðQ ÞSðQ Þ þ BG; ð1Þ
solutions of DDAO and considering the intra-micellar interaction
where Dq is scattering length density difference between the as Coulombic repulsion [42,47].
micelle and the surrounding solvent, V m is the volume of the micelle The best fits to SANS data of aqueous solutions of C12AO across
and BG is the background intensity. In order to eliminate the effect the entire range of temperatures and concentrations were obtained
of the (mostly incoherent) background BG and volumetric concen- using a prolate ellipsoidal core–shell model (Fig. 4a) [36,48]. The
tration of the micelles /, it is customary to rescale the scattering scattering length densities SLD for the dimethyl amine oxide shell
intensity of SANS measurements with concentration / of DDAO to and the dodecyl core of DDAO micelles were taken as 0:76  106
obtain the ðI  BGÞ=/, as presented in Fig. 3b. The form factor Å2 and 0:37  106 Å2, respectively [36]. Increasing concentra-
PðQ Þ for DDAO micelles was estimated for the most dilute solution tion of DDAO induced minor elongation in the prolate ellipsoidal
(at 1 wt%), where SðQ Þ is not prevalent. The corresponding micelles (Fig. 4b). The axial ratio of the micelles increased from
V m ðDqÞ2 PðQ Þ term is depicted by a red dashed curve in Fig. 3b. around a=b ¼ 1:7 to a=b ¼ 1:9. DDAO micelles were also found to
We then calculate the structure factor SðQ Þ for the micellar solu- carry small amount of net charge, especially at higher concentra-
tions of DDAO at various concentrations by simply dividing the cor- tions of surfactant, resulting in a repulsive interaction between
responding SANS intensities by V m ðDqÞ2 PðQ Þ, see Fig. 3c. This the micelles [36]. The increase in the net charge of micelles is
procedure allows for quantification of the structure factor at zero believed to correspond to the protonation of the head group of
scattering angle S0 and consequently estimation of the osmotic DDAO molecules which leads to a slight increase in the pH of the
compressibility of the system (e.g. [44,46]). Fig. 3d shows the com- solution at higher DDAO concentrations (Fig. 4c) [49,28]. This fitted
net charge per DDAO micelles becomes significant only at concen-
trations above 5 wt% of DDAO, in agreement with conclusions
based on estimation of compressibility of the micellar solutions
reported in Fig. 3d. The net charge per head-group of DDAO is esti-
mated to be around 0.1 for 20 wt% DDAO, using the fitted values
obtained for the aggregation number of micelles. This value is in
good agreement with previous reports in the literature [36]. Over-
all, unlike in SDS solutions, the size and shape of DDAO micelles
remain relatively invariant upon cooling, as shown in the SANS
data in Fig. 4d,e for solutions of 3 and 30 wt% of DDAO as a function
of temperature. This likely reflects the difference in inter- and
intra-micellar interactions in anionic and non-ionic surfactant
solutions. In anionic surfactant solutions, the size, shape and
inter-micellar interactions are dominated by electrostatic interac-
tions between charged head groups and counterions. At lower tem-
peratures, much like for cationic surfactants [50], counterion
binding increases and screens head-group repulsion and allows
micelles to swell (predominantly in the axial direction). For the
non-ionic (or minimally charged) DDAO micelles, no such ionic
effect is prevalent and changes in temperature appear to have min-
imal effect on the hydration of head-group and packing of the tails
and therefore do not affect the micelle size or shape.
In order to examine the packing and interaction of the amine
oxide head-groups and its relation to the shape of the DDAO
micelles, we perform FTIR measurements (Fig. 5). To monitor the
protonation of the head-group and the elongation of the micelles
Fig. 3. Analyses of SANS data for increasing concentration of DDAO at fixed T ¼ 40
of DDAO, we focus on the frequency bands at 1180–1280 cm1


C. (a) As the concentration of DDAO increases above 5 wt%, an intermediate-Q peak and 2800–2950 cm1 , respectively [22,51]. The significant increase
appears in the SANS data. (b) Contributions from the background intensity (BG) and in the relative intensity of peak located at about 1195 cm1 for
the volumetric concentration (/) are eliminated by rescaling the scattered intensity, higher concentrations of DDAO in Fig. 5a, which is associated with
thus yielding, for sufficiently dilute systems, the form factor PðQ Þ of the micelles as
a function of Q. The dashed red curve represents the term V m ðDqÞ2 PðQ Þ calculated
the ionic character of the N-O link, has been previously reported to
based on the form factor estimated for the lowest concentration of DDAO (at 1 wt%). be linked to the protonation of the head-group in the DDAO mole-
(c) Dividing the SANS intensities by V m ðDqÞ2 PðQ Þ provides an estimation of the cules [15]. This observation confirms the increase in net charge of
structure factor for the micellar solutions. The structure factor at Q ! 0, denoted as the DDAO and corresponding increase in the pH of the solution
S0 , is used to estimate the osmotic compressibility of the colloidal system. (d)
found from fitting SANS data, see Fig. 4c. Both symmetric (at
Measurements of 1=S0 , obtained from the SANS data for increasing concentration of
DDAO (open circles), are compared with those calculated using the Percus–Yevick around 2850 cm1 ) and antisymmetric (at around 2920 cm1 ) IR
closure (solid line) for hard spheres. absorption bands of CH2 can be used as indicators for tracking
 S. Khodaparast et al. / Journal of Colloid and Interface Science 582 (2021) 1116–1127 1121

the tail-group ordering. However, since the antisymmetric band ellipsoidal models (Fig. 6b). The major axis of the micelles was
also contains contributions from the CH3 group, here we mainly found to considerably grow in length, upon decreasing tempera-
focus on the symmetric CH2 band to monitor elongation of micelles ture. The length of the minor axis remains fairly unchanged at
[52]. Upon increasing the concentration of DDAO, a continuous all temperatures and compositions, attributed to the fact that
shift towards lower frequencies (from 2855 cm1 to 2854 cm1 ) this is predominantly fixed by the tail length of the surfactants
is observed in the location of the symmetric CH2 peak, suggesting which are nominally the same for SDS and DDAO here
an increase in the ordering of the tail groups within the micelles (Fig. 6c). Consequently, the ellipsoidal micelles elongate and
(Fig. 5b) [22]. We associate this effect to the formation of more their axial ratio a=b increases from around 1.5 to 3 as the solu-
elongated objects that is in agreement with observation of slightly tions are brought to lower temperatures. The elongation of the
more stretched ellipsoidal micelles at higher concentrations of ellipsoidal micelles is amplified with higher DDAO content due
DDAO, see Fig. 4b. to molecular interactions that will be rationalised by FTIR anal-
yses (Fig. 8). As pure and mixed micelles of SDS and DDAO
3.3. Mixed SDS/DDAO systems become more ellipsoidal upon cooling, the net charge on the
micelles decreases, thus resulting in less electrostatic repulsion
Our main goal here is to investigate the effect of cooling and between the aggregates (Fig. 6d). The aggregation number of
increasing concentration of DDAO on SDS micelles. We focus on the mixed micelles increases monotonically with increasing total
mixed SDS/DDAO systems comprising a fixed concentration of 20 surfactant concentration and decreasing temperature, similar to
wt% SDS and varying concentration of DDAO. Since no pure micel- the trends reported for aqueous solutions of SDS [53,54,41].
lar phase was found for solutions with more than 5 wt% DDAO, in At a fixed temperature, in the region where all solutions are in
the range 0–60
C (Fig. 1), our SANS and FTIR measurements were the micellar phase (T ¼ 60
C), increasing the concentration of
bounded to this limit. In general, the regions to the right and below DDAO shifts the intermediate-Q micellar peak towards lower Q val-
the phase boundaries in Fig. 1 (right side) were composed of coex- ues, indicative of a reduced spatial extent of repulsive interaction
isting L1 +LC and L1 +C and LC + C phases, which will be examined in between charged objects (Fig. 7a). These trends translate into the
a separate publication. elongation of prolate ellipsoidal micelles upon addition of DDAO
Fig. 6a exhibits an example of SANS data obtained in a cool- (Fig. 7b). As more DDAO molecules are incorporated within the
ing experiment for a mixed SDS/DDAO solution, initially in the micelles, the net charge per head-group of surfactants is signifi-
micellar region. Similar to the pure SDS solutions, a transition cantly reduced (Fig. 7c), thus allowing surfactant molecules to pack
from the pure micellar (L1 ) to the mixed micellar/crystalline more efficiently and adopt more elongated structures.
phase (L1 +C) is detected for the solution of 20 wt% SDS +3 wt Furthermore, increasing the concentration of DDAO in mixed
% DDAO, although at relatively lower temperature. In the micel- micelles causes the overall fitted scattering length density of the
lar phase, lowering the temperature shifts the L1 peak at micelles to drop to lower values (Fig. 7c). Scattering length densi-
intermediate-Q towards lower-Q values, similar to the trend ties of head-groups in SDS and DDAO are taken to be ’4 and 0.76,
observed for pure SDS micelles. Best fits to the SANS data of respectively, and therefore, a reduction in SLD values upon DDAO
mixed SDS/DDAO micelles were found using prolate core–shell addition further corroborates the formation of mixed micelles.

Fig. 4. SANS measurements for aqueous solutions of DDAO at different concentrations and temperatures. (a) The best fits to aqueous micellar solutions of DDAO are obtained
using the prolate core–shell ellipsoidal model as the form factor and the RMSA for the structure factor. Examples of typical fits for DDAO solutions at 3 and 30 wt% at T ¼ 40
C.
(b) The major axis of the ellipsoidal micelles a decreases with increasing DDAO concentration, while the minor axis b remains broadly unchanged. Error bars correspond to the
uncertainties in data fitting procedure. (c) The fitted net charge per surfactant head-group increases as the concentration of DDAO increases. Additionally, the pH of the
solution slightly increases to reach values about 7.5 for solutions of highest concentration of DDAO. SANS data at 3 wt% (d) and 30 wt% (e) of DDAO acquired in cooling
experiments. (d) The SANS profiles remain fairly unchanged at lower concentrations of DDAO. (e) At higher concentrations of DDAO, the intensity of the mid-Q micellar peak
increases in intensity at lower temperatures, however, its position remains constant.
1122 S. Khodaparast et al. / Journal of Colloid and Interface Science 582 (2021) 1116–1127

Fig. 5. ATR-FTIR spectra of aqueous solutions of pure DDAO for various concentrations (1–30 wt%) at T ¼ 20
C: (a) antisymmetric C-N-O stretching region (around
mas CANAO). The relative intensity of the peak at 1195 cm1 increases significantly as DDAO concentration is increased. (b) CAH stretching region. The symmetric stretching
band is often used to monitor the ordering of the hydrocarbons in tail-group of the surfactant molecules. (c) The symmetric CH2 peak shifts subtly towards lower
wavenumbers indicating a higher level ordering in the tail groups.

Infrared spectroscopy analysis of mixed SDS/DDAO systems is DDAO mixed micellar solutions in the frequency range which
used to examine the head-group interactions between the two sur- depicts the anti-symmetric SAO stretching bands of the SDS
factants and ordering of the tail-groups (Fig. 8). Comparison head-groups. In general, three bands are assigned to the sulfate
between the spectra of neat SDS solutions and those of mixed head-group vibrations of SDS molecule. Two are considered to be
micelles in the fingerprint region can elucidate the interactions generated due to SAO anti-symmetric stretching vibrations (mas
between SDS and DDAO head-groups. Fig. 8a shows a reference SAO at 1215 and 1210 cm1 ) and the third due to symmetric vibra-
SDS micellar spectrum and series of difference spectra of SDS/ tions (ms SAO at 1060 cm1 ). Interpretation of the spectral changes
of SDS head-group, in terms of mixed micelle structure, requires
understanding of how these bands respond to changes in their
local environment. The transition dipole moment of mas SAO is
located along the micelle surface and that of ms SAO is located in
the direction normal to micelle surface. Several detailed solution
studies of mixed SDS micelles attributed the shift and splitting of
mas SAO band to the lateral interactions of SAO bond [22]. Consis-
tent with those results, a constant ms SAO band in our study shows
that the interaction may not involve any component normal to the
surface. Furthermore, the observation of the splitting and shifting
of mas SAO band, which might result from a reduction in the sym-
metry of sulfate head-group, suggests lateral electrostatic interac-
tions between SDS and DDAO molecules. Since the lateral
interaction between SDS and DDAO affects the overall micellar
structure, the surfactant tail-groups must spatially rearrange to
accommodate the reduction in head-group area. The regions asso-
ciated with the symmetric and antisymmetric vibrations of CH2 in
the tail-groups are presented in Fig. 8b. In the spectra of the mix-
tures, the two major bands near 2925 cm1 (anti-symmetric CH2
stretch) and 2854 cm1 (symmetric CH2 stretch) are composites,
due to the extensive overlap of these bands in the spectra of the
individual surfactants. The CH2 stretching band frequency exhibits
a concentration dependent decrease as the DDAO content increases
in the system, Fig. 8c. The frequency decrease suggests a decrease
in the gauche/trans conformer ratio of the surfactant tails, i.e., an
increase in the ordering of the tails in the mixed micelles [52]. This
observation is in line with formation of more elongated prolate
Fig. 6. Effect of cooling on mixed SDS/DDAO micelles. (a) Example of SANS ellipsoid found from our SANS measurements.
measurements in the intermediate-Q region for an aqueous solution of 20 wt% SDS
and 3 wt% DDAO in a cooling cycle. Upon cooling the solution below 8
C, the
micellar phase coexists with the crystalline phase, marked by the simultaneous
appearance of a sharp Bragg peak and an upturn in the low-Q region. (b) An 3.4. Viscosity of mixed micellar solutions
example of a core–shell prolate ellipsoidal model fit to the SANS data acquired for
aqueous solution of 20 wt% SDS and 3 wt% DDAO at T ¼ 30
C. (c) For all solutions, The effect of micelle shape and volumetric concentration on the
the major axis of the ellipsoids a elongates upon cooling, while the minor axis b rheological behaviour of mixed surfactant solutions has been pre-
remains unchanged. Consequently, the axial ratio a=b increases from 1.5 for pure
SDS solutions at the highest temperature to about 3 for mixed solutions at the
viously studied in detail in the context of dramatic transformations
lowest temperatures of interest. (d) The net charge carried by mixed micelles from spherical to cylindrical and worm-like structures [22,55–
decreases at lower temperatures and higher DDAO concentrations. 57,14,24]. Comparatively fewer investigations have considered
 S. Khodaparast et al. / Journal of Colloid and Interface Science 582 (2021) 1116–1127 1123

Fig. 7. Effect of increasing concentration of DDAO on the structure of mixed SDS/DDAO micelles at a fixed temperature (T ¼ 60
C). (a) SANS data show a clear shift in
intensity and position of the (intermediate-Q) micellar peak. (b) Mixed micelles are well described by a core–shell prolate ellipsoidal model, and DDAO addition is found to
elongates the major axis (a) of the ellipsoidal micelles, while the minor axis (b) remains nearly unchanged. (c) The fitted net charge of the mixed micelles decreases upon
increasing DDAO content. Incorporation of DDAO into SDS micelles reduces the fitted the SLD of the shell associated to the formation of mixed micelles. The x-axes in (b) and
(c) represent the concentration of DDAO added to solutions with a fixed concentration of SDS (20 wt% in the final mixture).

the effect of gradual and modest shape changes in micelles, from ture, given here as absolute temperature (in K). Cooling from 60


spherical to prolate/oblate ellipsoids, on solution viscosity. For col- C to 20
C, causes the viscosity of pure SDS solutions to increase
loidal solutions of solid particles, the aspect ratio of anisometric by approximately 3-fold. This trend is similar to that obtained
particles is a critical variable defining the complex rheological when cooling the pure solvent (water), even though SDS solutions
behaviour of particle-bearing liquids, especially at higher concen- are typically more viscous than water. However, a similar reduc-
trations. In general, increasing particle anisometry significantly tion of temperature causes more than 10-fold increase in viscosity
decreases the critical jamming concentration of the solution, at a of the mixed SDS/DDAO solutions (Fig. 9a). The significant differ-
given volumetric colloidal concentration, and increases the appar- ence between the viscosity of micellar solutions of mixed SDS/
ent fluid viscosity for solutions with mild shear-thinning behaviour DDAO and pure SDS, with identical total surfactant concentrations,
[58–60]. Such effects are attributed to the enhanced orientability shows that even moderate modification of micelle composition
and particle–particle interactions in solutions of anisometric parti- and shape leads to considerable changes in the bulk properties of
cles. Here, we explore the effect of temperature and composition of the solutions. Similarly, the viscosity of mixed SDS/DDAO micellar
the SDS/DDAO solutions, where gradual spherical-prolate ellipsoid solutions increases exponentially with increasing the DDAO con-
transitions are observed in our SANS and FTIR measurements, on centration in a solution with a fixed concentration of 20 wt%
their rheological behaviour. Significantly, this transformation occur SDS. At a fixed temperature, increasing total concentration of sur-
at nearly-constant micellar volume fraction (or number density) factant by less than 20%, leads to more than a 10-fold increase in
thereby providing a suitable model system for this study. viscosity of the mixed systems, likely owing to the strong synergis-
Generally, the mixed SDS/DDAO solutions of interest are con- tic interaction between the two surfactant and elongation of the
siderably more viscous than pure SDS solutions, at similar total micelles (Fig. 9b). Since the viscosity data presented here follow
surfactant concentration. Fig. 9 presents zero-shear viscosity mea- exponential trends with both volume fraction of the surfactant
surements at different temperatures and surfactant concentra- and reciprocal of absolute temperature, a single exponential func-
tions. All solutions with 20 wt% SDS and 0–3 wt% of added DDAO tion based on a new variable, /=T, can be used to collapse all solu-
exhibited Newtonian behaviour in the parameter space studied tion viscosity data, shown in Fig. 9c, and thus provides a simple,
here. Solutions with 4 wt% DDAO showed mild shear thinning albeit empirical, predictive tool.
behaviour at higher shear rates (> 100 s1 ) and lower tempera- Based on our SANS measurements, solution composition and
tures. For both pure SDS and mixed SDS/DDAO systems, zero- temperature largely define the structure and properties of mixed
shear viscosity increases exponentially with decreasing tempera- SDS/DDAO micelles. Whilst the combined effect of added DDAO

Fig. 8. ATR-FTIR spectra of mixed SDS/DDAO micellar solutions at T ¼ 20
C. (a) SAO stretching region of sulfate head-group in SDS/DDAO mixed micelles. In each case, the
spectrum of pure SDS at 20 wt% (in light blue) is subtracted from the spectrum of mixed SDS/DDAO solutions. (b) The CAH stretching region of pure SDS solutions (20 wt%)
and mixtures of 20 wt% SDS with varying amounts of DDAO, ranging from 1 to 5 wt%. (c) The frequency of the symmetric CAH stretching is used to monitor the ordering of the
tail-groups in the mixed micelles.
1124 S. Khodaparast et al. / Journal of Colloid and Interface Science 582 (2021) 1116–1127

Fig. 9. Effect of cooling and DDAO composition on the viscosity of mixed SDS/DDAO micellar solutions: (a) Zero-shear viscosity g0 of aqueous micellar solutions of pure SDS
and mixed SDS/DDAO as a function of temperature, showing an exponential increase (by more than one order of magnitude) with decreasing temperature, which is magnified
at higher concentrations of DDAO. Viscosity measurements for pure SDS solutions at 20 wt% and 25 wt% (red dashed line) are provided for comparison. (b) Viscosity of
micellar solutions increases exponentially with increasing concentration of DDAO and total concentration of the surfactant in the solution, and this trend holds at different
temperatures within the micellar region of the phase map. The x-axis represents the volumetric concentration of micelles (/) obtained from model fits to the SANS data. (c) A
single reduced variable /=T is found to collapse all the zero-shear viscosity data of the solutions investigated, within measurement uncertainty. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)

concentration and temperature variations on the intra-micellar of ellipsoidal micelles is close to one (top-left corner of the contour
interactions is rather complex, we find a simple monotonic trend map in Fig. 10a), while axial ratios around a=b ¼ 3 are obtained at
between these two variables and the geometrical shape of the lower temperature and higher content of DDAO. Based on the find-
micelles. In particular, for our system of prolate ellipsoidal ings presented in Fig. 9c that the viscosity of our solutions of inter-
micelles, temperature and concentration of DDAO determine the est can be well described by a single variable, namely /=T, we
axial ratio of the mixed micelles a=b, see Fig. 10a for a map with investigate the relationship between this variable and the axial
contours at constant axial ratios. At high temperature and small ratio the micelles. Fig. 10b shows that a simple linear function
amount of DDAO (added to solutions of 20 wt% SDS), the axial ratio can correlate /=T to values of a=b. Consequently, it is expected that

Fig. 10. Effect of micelle shape on the viscosity of mixed micellar solutions. (a) Temperature-concentration map of contours with constant axial ratios (a=b) of mixed SDS/
DDAO ellipsoidal micelles. Values of a=b were extracted from fits to the corresponding SANS data. The x-axis represents the concentration of DDAO added to solutions of 20
wt% SDS. (b) The combined variable /=T presented in Fig. 10c is found to depend linearly on the micellar aspect ratio a=b. (c) Viscosity of mixed SDS/DDAO solutions can be
predicted by an exponential function (/ e2:8x ) of a single variable, namely the axial ratio of ellipsoidal micelles (a=b). The axial ratio of micelles is a dependent variable that is
defined by independent variables T and DDAO concentration. (d) Intrinsic viscosity of the present micellar solutions vs. the aspect ratio of the micelles. The prediction model
from Brenner [61] for Brownian colloidal suspensions is illustrated by a solid black line for comparison.
 S. Khodaparast et al. / Journal of Colloid and Interface Science 582 (2021) 1116–1127 1125

the viscosity of the solutions can be simply related to the axial ratio to be more elongated than neat solutions of either surfactant [31].
of the micelles by a single exponential function (g0 / e2:8ða=bÞ ), see This finding is in general agreement with observations reported for
Fig. 10c. other mixed SDS/DDAO solutions of different composition and con-
A convenient and commonly used approach to characterise the centrations. In parallel to the findings from SANS measurements,
effect of shape of non-spherical particles on rheological behaviour elongation of the ellipsoidal micelles is clearly accompanied by
of colloidal suspensions is through determination of the intrinsic the decreasing frequency of the symmetric C-H bond with FTIR,
viscosity, defined as: analogous to those observed during spherical-to-rodlike transi-
tions [52,22]. Moreover, head-group interactions between SDS
g0  gs
½g0  ¼ ; ð3Þ and DDAO were captured by monitoring the FTIR spectral bands
gs / of the sulfate groups in mixed micellar solutions.
where / is volume fraction of the colloids and gs is the viscosity of Detailed zero-shear viscosity measurements for mixed SDS/
the solvent, see the inset in Fig. 10c. The impact of colloidal shape, DDAO solutions at various compositions and temperatures charac-
especially aspect ratio of elongated colloids on the intrinsic viscos- terised bulk solution properties which we sought to link to molec-
ity of Brownian suspensions, has been extensively investigated ular structure. Mixed solutions were found to be significantly more
through analytical and numerical methods. Classic predictions of viscous than pure SDS solutions at identical surfactant concentra-
intrinsic viscosity for prolate Brownian rigid colloidal suspensions tion. We found exponential trends between viscosity of the solu-
are compared to those obtained for our current surfactant micellar tion and both temperature and volume fraction of the micellar
solutions in Fig. 10d as a function of aspect ratio of the particles phase, and empirically found that a single combined variable,
[61,62]. Interestingly, current measurements of intrinsic viscosity namely /=T, can be used to estimate the viscosity of the solutions
of mixed micellar solutions are up to two orders of magnitude lar- in the experimental range studied. Based on our SANS measure-
ger than theoretical predictions for Brownian suspensions. Consid- ments, we obtained a contour map of micellar shape, and specifi-
ering that solution viscosity is enhanced at higher content of cally aspect ratio of the micelles, as a function of the
DDAO and lower temperature at which the intra-micellar electro- temperature and DDAO content in the solution. We found the vari-
static repulsive interaction is significantly reduced compared to able /=T to be a linear function of the micellar aspect ratio, thus
pure SDS solutions of similar concentrations, we speculate the effect allowing for the viscosity of the solutions to be predicted by a sin-
to be caused by the appearance of local anisotropic domains within gle exponential function of aspect ratio. We suggest that this
the micellar solution under shear. Increased surfactant concentra- approach may be more widely applicable to other soft, anisometric
tion and alignment of ellipsoidal micelles within these domains particulate systems. We highlighted the effect of micellar size and
may promote local phase transformation to liquid crystals that is shape on the viscosity of the solution by considering the intrinsic
expected for higher concentration of DDAO at lower temperature. viscosity. Compared to classic models for intrinsic viscosity predic-
Note that the increase in the absolute viscosity values (103 to tion in suspensions of prolate ellipsoidal colloids, mixed SDS/DDAO
micelles are significantly more viscous [61].
101 Pa.s) for our concentrated solutions of elongated micelles
Complementary to common expectation in the surfactant liter-
reported in Fig. 10c, although significant, is much lower than that
ature that significant viscosity increases (up to 5–6 orders of mag-
expected for transformations from globular to worm-like micelles
nitude) in the micellar solutions are often linked to dramatic
in similar systems which is typically on the order (103 to 105 Pa. spherical-to-wormlike or rodlike shape transitions, here we report
s) [63–65], therefore, it cannot be attributed to such dramatic trans- changes in micellar solution viscosity of up to 2–3 orders of mag-
formation. Rational interpretation of the relatively significant vis- nitude that are associated with comparatively modest micellar
cosity increase observed here requires further under-shear elongation (a=b < 10). The small elongation regime investigated
scattering and/or (electron) microscopy measurements. here covers the initial stages of the growth before worm-like
micelles are formed. The enhanced viscosity of micellar solutions
4. Conclusion observed in this regime might be attributed to appearance of ani-
sotropic domains where local fluctuation in concentration and
We have systematically investigated the effect of cooling in the other degrees of freedom may cause phase transformations. Precise
wide range of 60
C down to 0
C on pure and mixed micellar solu- validation of this speculation requires further real-time multiscale
tions of SDS and DDAO using complementary experimental tools. investigation of these systems under shear.
In order to relate the molecular scale understanding of our systems
to their bulk properties, we combined inter- and intra-micellar CRediT authorship contribution statement
structural analyses through SANS and FTIR measurements, along-
side zero-shear viscosity measurements. Sepideh Khodaparast: Conceptualization, Methodology, Inves-
In pure SDS solutions, decreasing the temperature causes micel- tigation, Validation, Formal analysis. William N. Sharratt: Concep-
lar elongation, in agreement with previously reported trends at tualization, Methodology, Investigation, Validation, Formal
higher temperatures [41]. Both SANS and FTIR measurements sug- analysis. Gunjan Tyagi: Methodology, Investigation, Validation,
gest that pure DDAO micelles carry a net charge due to the proto- Formal analysis. Robert M. Dalgliesh: Methodology. João T. Cab-
nation of the head-group especially at higher concentrations ral: Conceptualization, Supervision.
(above 5 wt%). We then analysed mixed solutions of 20 wt% SDS
and varying DDAO content. No pure micellar phase existed within Declaration of Competing Interest
our current range of temperatures for DDAO concentrations above
5 wt%, therefore, SANS and FTIR measurements were focused on The authors declare that they have no known competing finan-
this composition range [22]. We confirmed the formation of mixed cial interests or personal relationships that could have appeared
micelles by monitoring the interactions between the SDS and to influence the work reported in this paper.
DDAO head-groups using SANS and FTIR measurements. Incorpo-
ration of DDAO into SDS micelles was found to decrease the net Acknowledgements
charge of the micelles, reducing the area designated to the surfac-
tant head-group and consequently increasing the packing parame- We thank the National Formulation Centre (NFC) of the Centre
ter. In turn, mixed SDS/DDAO prolate ellipsoidal micelles are found for Process Innovation (CPI, UK), Procter & Gamble and BP-Castrol
1126 S. Khodaparast et al. / Journal of Colloid and Interface Science 582 (2021) 1116–1127

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