Journal of Molecular Liquids 329 (2021) 115523

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Journal of Molecular Liquids

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

Towards a general understanding of the effects of hydrophobic additives

on the viscosity of surfactant solutions
Wolfgang Fieber a,⁎, Alina Scheklaukov a,b, Werner Kunz b, Maximilian Pleines c,
Daniel Benczédi a, Thomas Zemb c
a
Firmenich S.A., Department of Materials Science, Corporate Research Division, 1242 Satigny, Switzerland
b
Institute of Physical and Theoretical Chemistry, University of Regensburg, 93040 Regensburg, Germany
c
Institute for Separative Chemistry Marcoule, 30207 Bagnols-sur-Cèze, France

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

Article history: Small amounts of nonpolar additives can have a tremendous impact on viscosity and viscoelasticity of giant mi-
Received 11 December 2020 celles and completely change macroscopic properties. The effect can be best understood with the establishment
Received in revised form 21 January 2021 of complete salt curves by screening surfactant viscosity as a function of electrolyte concentration. From previous
Accepted 27 January 2021
studies in micellar systems of sodium laureth sulfate (SLES) with fragrance molecules, two independent
Available online 30 January 2021
mechanisms could be identified, co-solvent type interactions leading to a decrease of the maximum viscosity,
Keywords:
and co-surfactant type interactions that cause the salt curve shift to the left. Our studies here reveal two new
Viscosity mechanisms with different effects on the salt curve. In particular, with long-chain hydrocarbons from n-octane
Wormlike micelles to n-tetradecane a right shift was observed, whereas with short-chain or cyclic hydrocarbons such as n-hexane
Packing parameter or cyclohexane the maximum viscosity increases. The two effects are interpreted via an extension of a recently
Fragrances developed thermodynamic model where changes in viscosity can be rationalized by a rebalance of the relative
Formulation concentration of the three co-existing microphases: endcaps, cylinders and branching points. The right shift is
Alkanes linked to a continuous transformation of giant micelles into microemulsions containing an internal fluid. On
the other hand, viscosity at maximum scales with the generalized bending constant of the molecular film forming
the three microphases of the surfactant system. The total of four proposed mechanisms of solute-surfactant inter-
actions that can impact amplitude and position of salt curves are independent and of different origin, but they are
all intimately linked to the location of the additives within the surfactant film: headgroup, micellar interface, sur-
factant tail region or micellar core. Further investigation will be necessary to understand the molecular driving
forces that position nonpolar additives within micellar aggregates, which would be the key for successful predic-
tion of their impact on macroscopic viscosity.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction micellar objects. For example, an increase in surfactant concentration

Surfactant aggregates in the form of giant, wormlike micelles can
have particular gel-like properties which makes them practical applica-
tion formats for consumer products in personal care and home care
[1,2]. As opposed to polymeric macromolecules, giant micelles are “liv-
ing polymers” representing dynamic systems that constantly break and
recombine [3,4]. As a consequence, viscosity and viscoelasticity result
from a complex interplay between different length and time scales, sig-
nificantly influenced by surfactant concentration, molecular structure
and polarity, temperature, or the presence of co-surfactants and other
additives. Generally, in order to obtain viscous gel like structures the
surfactant aggregates need to attain a critical size, above which viscosity
is governed by the overlap and subsequently by the entanglement of the
⁎ Corresponding author.
E-mail address: wolfgang.fieber@firmenich.com (W. Fieber).
can lead to sphere-to-rod transitions forming cylindrical and wormlike
micelles with a drastic increase of viscosity above a critical concentra-
tion [5–7]. More degrees of freedom for fine-tuning the macroscopic,
rheological behavior of giant micelles can be obtained with ionic surfac-
tants in combination with electrolytes. Typically, a continuous topolog-
ical transformation of micellar structure as a function of electrolyte
concentration is observed, from spherical to cylindrical, wormlike and
finally to branched micelles, leading to a non-monotonic trend of vis-
cosity that results in so-called “salt curves” [4,8–13]. Viscosity peaks
are also observed for mixtures of oppositely charged surfactants
[14,15], or for ternary surfactant solutions including medium and
long-chain fatty acids [16], resulting in the formation of peculiar types
of surfactant aggregates such as disks for example [17]. Adding charged
polymers to surfactant solutions of giant micelles can even induce a re-
versal of the effect of added salt, which was recently shown in the case
of potassium oleate [18]. Therefore, by carefully choosing appropriate

https://doi.org/10.1016/j.molliq.2021.115523
0167-7322/© 2021 Elsevier B.V. All rights reserved.
W. Fieber, A. Scheklaukov, W. Kunz et al.
surfactants and additives the desired macroscopic properties for a given
application can be obtained. In reality this process is still time consum-
ing, though, even for experienced formulators. Moreover, in application,
surfactant solutions are rarely used alone, but on top of their primary
cleansing function for skin, hair, surfaces or laundry, they are conve-
nient delivery systems for different types of oil-soluble, active ingredi-
ents, such as fragrances, essential oils, emollients, pigments etc. In the
presence of such additives the viscoelastic structure and the macro-
scopic behavior can be significantly perturbed, leading to undesired
phenomena such as base thinning, base thickening or phase separation.
It is therefore of crucial importance to understand molecular mecha-
nisms that lead to changes in micellar topology.
In the recent past theoretical approaches based on analytical models
have been developed, which allow the prediction of surfactant aggrega-
tion and as a consequence rheological properties. For example, Danov
et al. have presented a self-consistent quantitative model for the growth
of wormlike micelles for non-ionic surfactants [19] or surfactant mix-
tures [20,21]. The model is based on an accurate description of the dif-
ferent contributors to the micelle free energy: interfacial tension,
steric repulsion of headgroups, and conformational free energy of the
surfactant hydrocarbon chains in the micellar core. An excellent agree-
ment between the expectation from theory at meso-scale and experi-
mental values has been achieved. In another approach, Choi et al.
demonstrated that based on the HLD-NAC theory (hydrophilic – lipo-
philic difference concept combined with the net-average curvature
model [22]) it is possible to quantify curvature changes of surfactant
systems and to predict the formulation conditions required to obtain
viscoelasticity [23]. Thus the sphere-to-rod transition and the formation
of wormlike micelles or liquid crystalline phases as a function of the
equivalent alkane carbon number (EACN) of added fragrance oils can
be predicted.
We recently published a thermodynamic model to predict viscosity
salt curves of sodium laureth sulfate (SLES) [24]. The method is based
on the calculation of the distribution of three co-existing microphases
in thermodynamic equilibrium, namely endcaps, cylinders, and
branching points (junctions), as a function of ionic strength. We use
here the conceptual framework as introduced by Charles Tanford
some forty years ago [25]. A microphase is an ensemble of “small” vol-
umes that have a homogenous content, but are not segregated as
when a macro-phase separation occurs. The first success of microphase
separation theory was to consider the diluted solution of surfactants in
equilibrium with a microphase made from all micelles and their hydra-
tion water. The thermodynamic “micellar” microphase is the ensemble
of all micelles, separated by a virtual interface from all bulk solution. In
the work described here, the ensemble of all the cylindrical parts of the
micelles, as well as endcaps and branching points are considered as
microphases in equilibrium. Standard reference chemical potentials
and subsequently the probability of occurrence of each microphase
can be explicitly derived at specific electrolyte concentrations. Thus, en-
tire salt curves can be calculated for surfactant mixtures of SLES in the
presence of various added salts, showing an excellent match with ex-
perimentally derived data. The model is based on well-established con-
cepts of molecular packing parameters, supramolecular curvature and
elasticity of the surfactant film, as well as polymer physics extended
to micellar systems As the very basis we used an alternative definition
of the spontaneous packing parameters by taking into account the
length of the whole surfactant molecule and not only the hydrocarbon
chain length. The underlying principles of this model have also served
as a basis for the prediction of cloud points of nonionic, ethoxylated
surfactants [26].
The impact of fragrances on viscosity and viscoelastic properties of
surfactant systems has been reported in the past. For example, the pres-
ence of primary or terpene alcohols was shown to lead to a shift of the
viscosity maximum with respect to salt content [27], or surfactant com-
position [28], respectively. From coarse-grained molecular simulations
a correlation could be established between the location of hydrophobic
2
Journal of Molecular Liquids 329 (2021) 115523
fragrance molecules along the surfactant interface and micellar length
and viscosity, respectively [29]. Mitrinova et al. [30] reported significant
effects of medium-chain additives on the viscosity of mixtures of an-
ionic and zwitterionic surfactants. In particular, C8-C10 molecules had
the largest impact, which was explained by an optimal chain packing
in the cylindrical region of the micelles which reduces the energy of
this region. Thereby the energy difference between cylinders and
endcaps that lead to micellar growth increases as a consequence. Previ-
ous studies from our group on the impact of fragrance molecules on vis-
cosity and viscoelasticity of systems of wormlike micelles revealed the
existence of two independent mechanisms that have specific effects, a
co-solvent type interactions leading to a decrease of the maximum vis-
cosity of the salt curve and co-surfactant type interactions that lead to a
left shift [31]. An appropriate extension of our predictive model was
made that takes into account these two mechanisms [24], which
allowed the prediction of the impact of fragrance molecules on ampli-
tude and position of SLES salt curves.
Here we present results obtained with different classes of additives,
notably hydrocarbons. So far unobserved effects on the salt curve of
SLES were obtained, and further extensions of the model had to be
made in order to take into account for the new mechanisms. A compre-
hensive overview over the different effects of organic additives to salt
curves of SLES is presented.
2. Material and methods
2.1. Chemicals
SLES was obtained from BASF under the trade name Texapon N70
(70%). Test substances were purchased from Merck, Germany:
n-hexane (p.a.), n-octane (p.s.), isooctane (p.a.), 1-octene (p.s.), o-
xylene (p.s.), p-xylene (p.s.); from Sigma-Aldrich: n-decane (≥95%), n-
dodecane (≥99%), n-tetradecane (≥99%), 1-dodecene (95%), cyclooctane
(99%), ethylbenzene (p.a.), n-butylbenzene (≥99%), n-hexylbenzene
(97%); from TCI: isohexane (≥98%, mixture of isomeric branched hex-
anes); from Alfa Aesar: isododecane (techn. 80%), 1-hexene (98%);
and from Fisher Scientific: cyclohexane (p.a.), toluene (p.a.). NaCl
(>99%) was purchased from Sigma-Aldrich.
2.2. Sample preparation and viscosity measurements
For sample preparation, a stock solution of 20% w/w of the surfactant
was prepared with Milli-Q water. The appropriate amount of NaCl was
dissolved in Milli-Q water and mixed with the stock solution, leading
to the same concentration of surfactant, 10% w/w (0.26 M), in all sam-
ples. Test substances were added at a concentration of 0.5% w/w and
mixed well with the surfactant solutions. Samples were allowed to
equilibrate for at least 24 h before measurement. Percentages are de-
fined in w/w throughout the article.
All experiments were carried out on a Bohlin CVO 100 or CVO 120
rheometer at 25 °C. A cone and plate geometry was used with a diame-
ter of 40 mm and a cone angle of 4°. The zero-shear viscosity was deter-
mined by measuring the viscosity, while increasing the shear rate from
0.1 to 100 s−1. Flow curves were fitted to the Carreau A model to deter-
mine the viscosity at the zero-shear rate [32]. Experimental salt curves
were fitted to a Gaussian function.
3. Theory
Previously we have presented a predictive model which allows the
calculation of entire salt curves of the anionic surfactant SLES [24]. In
that model, transient networks of giant micelles of charged surfactants
that lead to a viscosity peak when increasing the amount of added salt
are built from three coexisting microphases in dynamic equilibrium
with each other, cylinders, endcaps, and junctions. Standard reference
chemical potentials and subsequently the occurrence of each
W. Fieber, A. Scheklaukov, W. Kunz et al.
microphase can be explicitly derived at specific salt concentrations. The
distribution of microphases depends on the evolution of the spontane-
ous packing parameter that continuously increases with the amount
of added salt due to charge screening. To calculate the spontaneous
packing parameter at a given salt concentration we extrapolate the
evolution of the area per headgroup according to an association-
dissociation process by assuming an empirical dissociation constant de-
scribing the local binding of positively charged counterions to the neg-
atively charged sulfate headgroup of SLES. By regarding the micellar
topology at nanoscale as connected cylinders decorated by endcaps,
the position and intensity of the viscosity maximum of the so-called
salt curve can be calculated from physical quantities with a minimum
of adjustable parameters. A summary of the entire model is given in
the Supplementary Material.
According to observations on the impact of hydrocarbons on micel-
lar shape and surfactant viscosity, a separation of a fraction of the solu-
bilized hydrocarbons in the form of small oil droplets in the micellar
core was hypothesized in previous works reported in literature
[33–37]. We postulate that the observed effects on experimental salt
curves in this study are based on similar mechanisms. In order to simu-
late the demixing process of solubilized hydrocarbons we need an ex-
tension of our original model. The volume of the separated
hydrocarbon droplet for each microphase can be defined as:
sep , μ−phase μ−phase
vHC ¼ xHC ∙ χ sep
HC ∙ β ∙ vHC ∙ N agg
where xHC is the molar ratio of the hydrocarbon solute over surfactant in
the mixture, β is a function of logPO/W, which is the octanol-water par-
tition coefficient of organic solutes, and takes into account micellar
partitioning of the solute between surfactant micelles and the water
phase. It represents the number of hydrocarbon molecules which are
solubilized in the micellar phase over the total number of hydrocarbon
molecules in the mixture [24]. vHC is the molecular volume of the hydro-
carbon, and N μphase
agg is the aggregation number in each of the three
microphases, endcaps, cylinders, and junctions. Note that the cmc of
SLES is 0.027% (0.7 mM). The fraction of monomers is therefore negligi-
ble in solutions of 10% of SLES (260 mM) and it is considered that the
surfactant molecules are almost entirely within one of the microphases.
χ sep
HC represents the number of hydrocarbon molecules that demix as
separate oil droplets into the micellar core over the total number of hy-
drocarbon molecules in the micellar phase. χ sep sep
HC is related to Δμ 0 , which
is the apparent Gibbs free energy of a solute that has demixed into hy-
drocarbon droplet minus the Gibbs free energy of the solute mixed with
the micelle alkyl chains:
sep
−Δμ sep =kB T
χ sep
HC = 1−χ HC ¼ e
0 ð2Þ
Upon demixing of the hydrocarbon into the micellar core, the
μphase
microphases swell, and the radius of each microphase, lswollen , increases
sep; μphase
with the size of the hydrocarbon droplet, r HC , that forms inside
the micelles,
μ−phase sep,μ−phase
lswollen ¼ lCþI þ r HC
where lC+I is the mean surfactant length, composed of the interface
sep;μphase
thickness dI and the length of the hydrocarbon chain [24]. r HC
sep;μphase sep;μphase
can be derived from vHC defined in Eq. (1), where r HC is
the radius of a sphere for endcaps, and the radius of a cylinder in the cyl-
inder microphase. Note that the latter is defined as a cylindrical segment
with a length equal to the cylinder diameter. Junctions are more com-
plex geometrical objects, and for the development of our predictive
model we approximated junctions by a bilayer part represented by a
prism and three short cylinders [24]. A spontaneous packing parameter
μphase
for each microphase, ρ0 , is then calculated by considering the addi-
tional volume of solubilized hydrocarbon molecules
Journal of Molecular Liquids 329 (2021) 115523
μ−phase vSLES þ xHC ∙β∙vHC
P0 ¼ ð4Þ
μ−phase
aI ∙lswollen
with vSLES representing the effective molecular volume of SLES, includ-
ing hydrophobic tail and polar headgroup, as well as hydration water
[24]. aI is the respective area per surfactant at the water-micelle inter-
face. Eq. (4) yields two different spontaneous packing parameters, one
for endcaps and the other for cylinders and junctions. Note that the total
volume of the solubilized hydrocarbon is added to the volume of the
surfactant molecule, whether the solutes are mixed with the surfactant
tails or whether the oil partially phase separates, and therefore the var-
μphase μphase
iation in ρ0 is entirely driven by lswollen .
Another extension of our original model is needed with regard to the
observation in the present work of an apparent increase of the ampli-
tude of the salt curve in the presence of some hydrocarbon molecules.
We consider this effect being a consequence of increased interface stiff-
ness induced by solubilized molecules near the surfactant chain end.
The bending contribution of the micellar interface to the free energy
of the surfactant can be expressed by a harmonic approximation, as
the deviation of the actual surfactant geometry from the preferred one
multiplied by the bending modulus κ⁎, which is of the order of 2–3 kBT
per molecule, i.e. 5 kJ/mol [24]. In order to account for the observed ef-
fects, a scaling factor σ is introduced that increases the effective bending
ð1Þ modulus:
σ∙κ ⁎  μ−phase μ−phase
2
F bending ¼ P −P 0 ð5Þ
2
where Pμ-phase is the effective packing parameter of the respective mi-
crophase and ρ0
μphase
the spontaneous packing parameter, defined in
Eq. (4). Pμ-phase is well defined for endcaps considered as half-spheres
(1/3) and long cylinders, flexible or not (1/2). For junctions, the value
is intermediate between that of cylinders and of bilayers, since they
can be regarded as a central bilayer-like region surrounded by three
semi-toroidal sections. Therefore, the approximate value for junctions
formed by SLES molecules was set to 0.8, assuming a slightly higher in-
fluence of the bilayer part.
4. Results and discussion
4.1. Hydrocarbon additives
Similar to previous studies on the impact of perfumery ingredients
on viscosity and viscoelasticity of surfactants systems [24,31], solutions
of 10% of SLES were mixed with 0.5% of the hydrocarbon solutes, and
salt curves were obtained by increasing the concentration of NaCl up
to about 9%. Higher ion strengths mostly lead to phase separation in
the samples. A series of linear n-alkanes is shown in Fig. 1. The impact
of the individual n-alkanes on amplitude and position of the salt curve
is highly dependent on the chain length. n-Hexane increases the maxi-
mum viscosity of the salt curve, and shifts it slightly to lower NaCl con-
centrations, whereas with increasing chain-length of the hydrocarbon
ð3Þ additive, the salt curve is shifted to higher NaCl concentrations, while
the maximum viscosity decreases. These results are surprising, because
from previous studies using perfumery ingredients, we only have ob-
served shifts to the left and decreasing viscosity, respectively [31].
Those effects are linked to the presence of polar functional groups in
the molecules, such as alcohols or aldehydes, which are absent in
n-alkanes. We therefore postulate that the observed effects in the pres-
ence of n-alkanes are linked to the highly nonpolar nature and the ab-
sence of polar functional groups in the molecules.
General trends can be observed with different isomers in the form of
branching (isoform), unsaturation (1-ene isomers), and cyclic forms
with the same number of carbon atoms, see Fig. 2. A striking feature is
observed with cyclohexane and cyclooctane, which have the most
3
W. Fieber, A. Scheklaukov, W. Kunz et al. Journal of Molecular Liquids 329 (2021) 115523

Fig. 1. Experimental NaCl salt curves of 10% SLES with 0.5% of n-alkanes: n-hexane (white
circles), n-octane (light grey), n-decane (medium grey), n-dodecane (dark grey), and n-
tetradecane (black). The salt curve of pure SLES is schematically depicted (dashed line).

pronounced effect on the maximum viscosity of the salt curve, while

shifting the salt curve slightly to the left. On the other hand, within
the same group in terms of number of carbon atoms, the right-hand
shift of the salt curve is in the order isoalkanes > n-alkanes > alkenes.
So, not only the hydrocarbon chain length determines the effect on
the viscosity profile of the salt curve, but also volume and shape, differ-
ent degrees of free chain rotation, or the presence of slightly polar
groups (double bonds).
Interestingly, in our previous studies, limonene was considered as an
outlier of the four fragrance molecules tested, by slightly increasing the
viscosity maximum [31], and showing large deviations of the calculated
salt curves based on a model using logPO/W as input parameter (the
lower the logPO/W the higher the co-solvent effect) [24]. Based on our
observations here, since limonene does not contain any polar functional
groups, it would rather have to be considered as a hydrocarbon, com-
prising a cyclic structure, branching and unsaturation, with an effect
that is similar to the one of C6 analogues shown above (slight left-
hand shift and increased viscosity).
In another series, we studied the concentration effect of the different
hydrocarbon additives. In Fig. 3, the impact of cyclohexane and of n-
dodecane was studied in the range between 0.1% and 1%. Viscosity in-
creases slightly with the increase of cyclohexane concentration,
whereas the decrease in the presence of n-dodecane levels off at higher
concentrations. On the other hand, the right-hand shift of the salt curve
with increasing n-dodecane concentrations seems to be linear, while
with cyclohexane the left-hand shift levels off at 1% of additive. This dif-
ferent concentration dependence suggests different mechanisms that
either lead to left- or right-hand shifts, or to viscosity increase or de-
crease, respectively. On the other hand, the continuous nature of the
salt curve shift with concentration is an indicator for one single molec- Fig. 2. Experimental NaCl salt curves of 10% SLES with 0.5% of n-alkanes (white circles),
ular mechanism for each of the two effects. isoalkanes (grey squares), 1-alkenes (stars), and cycloalkanes (black triangles). The salt
curve of pure SLES is schematically depicted (dashed line). Top panel: C6 isomers,
middle panel: C8 isomers, bottom panel: C12 isomers.

4.2. Model extension for the prediction of right shift of salt curves
In our recently published model for the prediction of SLES salt
curves, expressions were developed that describe the impact of small,
hydrophobic additives on viscosity, focusing in particular on the case
of fragrances [31]. They are based on two experimental parameters,
logPO/W and λ, where the latter is the excess solubilization defined as
the as the ratio between the additive molecules present at the surfactant
interface and the surfactant molecules [38]. However, with these algo-
rithms, neither a shift to higher salt concentrations nor an increase of
the maximum viscosity can be achieved. We therefore need to extend
the model in order to take into consideration the observed effects of
hydrocarbons.
In previous studies on the interaction of hydrocarbon solubilization
in viscoelastic surfactant systems, a drastic drop of viscosity has been
observed that was generally associated with a transformation of rods
into spherical micelles, resulting in the disruption of the transient net-
work of giant micelles [28,34–37,39–41]. In fact, from measurements
with various scattering techniques to determine size and shape of mi-
cellar objects, the addition of hydrocarbons induced the formation of
smaller micellar aggregates, typically oil-swollen micelles [33,40,42].

4
W. Fieber, A. Scheklaukov, W. Kunz et al.
Fig. 3. Impact of the concentration of hydrocarbon additives on experimental salt curves of
SLES: cyclohexane (filled circles) and n-dodecane (open circles). Upper panel: maximum
viscosity, lower panel: peak position. Solid lines are drawn to guide the eye.
Based on simple geometric considerations, it was generally assumed
that the nonpolar additives demix from the surfactant palisade layer
and form oil droplets in the micellar core, thereby favoring the forma-
tion of endcaps and in consequence spherical micelles [33,35,42]. How-
ever, there is still a debate, whether the hydrocarbon fraction is
uniformly distributed over the micellar structure, or whether it can be
accumulated in specific microphases such as endcaps or branching
points [37,41,43]. So, one of the important general lessons here is to dis-
tinguish between fragrance molecules mixing with the hydrocarbon
chains of the surfactant and molecules acting like an « oil », i.e. “internal
liquid » of a microemulsion [44]. We therefore start by implementing
the described effect of demixing of the hydrocarbons from the surfac-
tant palisade layer into our model. For this, we simply assume that the
hydrocarbon (or a fraction of the hydrocarbon), demixes from the mi-
celles and forms a separated oil droplet in the micellar core. This will
lead to a swelling of the microphase with an increase of the effective di-
ameter (twice the length of the extended surfactant molecule plus the
diameter of the oil droplet). As a consequence, the aggregation number
of each microphase will increase, because we assume that the area per
surfactant at the water – micelle interface, governed by the ionic
strength of the surfactant solution, remains unaffected. We do not attri-
bute the demixing process exclusively to endcaps or other specific
microphases, but apply the same χ sep HC of demixed oil for all three
microphases.
μphase
The spontaneous curvature ρ0 is calculated based on this new,
effective micellar radius. Due to the different geometries in endcaps and
5
Journal of Molecular Liquids 329 (2021) 115523
Fig. 4. Calculated aggregation number in each microphase as a function of the fraction of
demixed hydrocarbon oil χsep HC . Endcaps (continuous line), cylinders (dashed line), and
junctions (dotted line).
cylinders, the radii of the separated oil droplet are not the same, leading
to two different spontaneous packing parameters, one for endcaps, and
one for cylinders and junctions. In Fig. 4, the evolution of the aggrega-
tion number of the three microphases is depicted. As the fraction of
demixed oil χ sepHC increases, the number of surfactant molecules in
each microphase increases, too. Subsequently, the evolution of the
spontaneous packing parameter P0 as well as entire salt curves as a func-
tion of the excess salt content x (concentration of added NaCl divided by
the surfactant concentration) have been calculated (Fig. 5). When com-
paring surfactant solutions in the absence of additives to mixtures with
hydrocarbons, but where no demixing has occurred, the spontaneous
packing parameter of endcap increases, which leads to a left-hand
shift of the salt curve. When partial demixing of the solubilized oil is
taken into consideration, P0 generally decreases over the entire salt con-
centration range, which results in the shift of the calculated salt curves
to the right. The initial position in pure SLES micelles is reached with a
χ sep
HC of about 0.08 of hydrocarbon additive.
Fig. 5 shows that the model for oil demixing described above suc-
cessfully predicts a right-hand shift of the salt curve. As mentioned
above, no assumptions have been made on oil accumulation specifically
in endcaps. Nevertheless, the hypothesis of a rod-to-sphere transition
[33–37] seems to be confirmed. In Fig. 6, the distribution of endcaps as
a function of salt concentration shows that with increasing fractions of
separated oil, the total amount of surfactant molecules in endcaps in-
creases, in line with a rod-to-sphere transition at lower salt concentra-
tions. At higher salt concentrations, the effect is somewhat different
showing very low concentrations of junctions, especially when the frac-
tion of separated oil is high. This is probably an artefact due to the fact
that the calculated P0 curves become increasingly flat towards higher
salt concentrations, which results in very broad calculated salt curves.
For the same weight fractions of additive, one can infer from the ex-
perimental data that the extent of demixing changes along the homolo-
gous series of n-alkanes in Fig. 1. It seems as if not the entire amount of
oil demixes, but rather that the fraction of separated oil increases with
alkane chain-length. The fraction of separated oil for different hydrocar-
bons has been determined by manually matching the position of the
maximum of the calculated salt curve to the experimental data by
varying χ sep
HC until a best match was achieved. From this procedure we
obtained an χ sep
HC of 0.13 to match the salt curve in the presence of n-
octane, 0.2 in the presence of n-decane, 0.3 in the presence of
n-dodecane and 0.37 in the presence of n-tetradecane. The shift only oc-
curs for n-octane and higher alkanes. The right-hand shift could be dem-
onstrated to be based on purely geometric considerations, with a
modified spontaneous packing parameter, due to partial demixing of
W. Fieber, A. Scheklaukov, W. Kunz et al. Journal of Molecular Liquids 329 (2021) 115523

Fig. 5. Simulation of the evolution of the spontaneous packing parameter P0 for endcaps
(upper panel), and of salt curves (lower panels) as a function of the excess salt content x
at different fractions χsep
HC of separated oil, present in a total amount of 0.5%: no demixing
(dotted line), χsep
HC of 0.01 (short dashed line), 0.2 (long dashed line), and 0.3 of the oil
(continuous line). For comparison, curves are shown in the absence of oil (thick line).
The viscosity maximum of the different salt curves was normalized.

the solubilized oil in the micellar core. In Fig. 7 an overlay of an experi-

mental salt curve with 0.5% of n-dodecane and the predicted curve with
a fraction of separated hydrocarbon oil χ sep
HC of 0.3 is shown. The width of
the predicted salt curve has not been adjusted since it is a direct out-
come of the model. It is significantly broader than the experimental
one, which is due to the flat curve of calculated P0 mentioned above.
Our results are consistent with observations from other studies in
the past. For example, Hoffmann and Ulbricht reported on the transition
of rod-like to spherical micelles by the addition of hydrocarbon addi-
tives [33]. In particular, they observed a drastic drop of light scattering
intensity, when n-alkanes were added to cationic surfactant systems.
This drop shifts to lower concentrations of added alkanes with increas-
ing chain length of the additives. Based on a model calculation, the rod-
Fig. 6. Predicted concentration of surfactant molecules (cS) located in either of the three
to-sphere transition was supposed to occur at a specific hydrocarbon to microphases with respect to the entire micellar solution, as a function of the excess salt
surfactant chain volume ratio, and therefore, it was assumed that longer content x at different fractions χsep
HC of separated oil, present in a total amount of 0.5%: no
chains get only partially solubilized between the surfactant chain, demixing (dotted line), χsepHC of 0.01 (short dashed line), 0.2 (long dashed line), and 0.3

thereby increasing the volume fraction of the separated oil. Conse-
quently, the hydrocarbon concentration needed for a transition shifts
to lower values. This is consistent with our results that show that the
right shift of the salt curve, associated with an effective increase of sur-
factant molecules in endcaps, scales with the fraction of demixed oil.
Similarly, a rod-to-sphere-to-swollen micelles transition was hypothe-
sized in mixtures of CTABr with n-dodecane, observed with 2H NMR
spectroscopy [42], suggesting that a fraction of the hydrocarbon has
of the oil (continuous line). For comparison, curves are shown in the absence of oil
(thick line).
demixed from the surfactant chains. A completely different behavior
could be observed for cyclohexane, which did not induce any demixing,
but rather led to an increase of the rod-like micelles [33,42]. A different
mechanism of interaction can therefore be assumed.

6
W. Fieber, A. Scheklaukov, W. Kunz et al.
Fig. 7. Experimental NaCl salt curve of pure SLES (filled circles), and in the presence of 0.5%
of n-dodecane (open circles). Calculated salt curve (thick line) calculated with a fraction of
separated hydrocarbon oil χsep HC of 0.3. The amplitude of the calculated curve was
normalized manually to the one of the experimental data in the presence of n-dodecane
by application of a vertical scaling factor (see [24]).
We can regard the demixing process as the partitioning of hydrocar-
bon molecules between two states, pure liquid (separated oil) and
mixed within the micelles. The extent of the demixing results from
the difference of free energy between the two states (Eq. (2)). As long
as the molar ratio χ sep sep sep
HC /(1 − χ HC ) does not exceed unity, Δμ 0 for the
demixing process is positive and therefore mixing with the micelles is
more favorable. Nevertheless, compatibility of the hydrocarbons with
the alkyl chains of the micelles seems to play an important role. χ sep
HC in-
creases with the chain length of the hydrocarbon molecules, which
means that the energy difference between the two states becomes
smaller. However, as opposed to uniform distribution of solutes in
bulk solvents, an equilibrium gradient of solute concentration in the mi-
cellar core can be expected. For example, neutron scattering techniques
have shown that alkanes are primarily located in the center of surfactant
bilayers [45], which was corroborated by computer simulations on hex-
ane, revealing that only the very center of the bilayers has properties of
a bulk liquid [46]. The lipid chain ordering becomes a dominant factor,
when approaching the surfactant headgroup, and the partition coeffi-
cients of hexane into the membranes significantly decreases, when
the surface density of the surfactant bilayers increases, resulting in in-
creased chain ordering [47]. This suggests that for alkanes with different
chain-lengths, entropy as well as excluded volume effects play an essen-
tial role for the partitioning process. In another study, the solubility of
methane in alkanes was investigated [48]. Although intuitively one
wouldn't expect considerable differences based on the chemical compo-
sition of solute and solvent, it has been observed that molecular solubil-
ity of methane significantly decreases in alkane solvents with increasing
chain length. This effect was later attributed to the increase in the seg-
mental densities of the alkane solvents [49]. It can therefore be assumed
that the demixing process of long-chain hydrocarbon oils, which is re-
sponsible for the right shift of the salt curve, is complex and driven by
both, entropy and enthalpy contributions. A more thorough investiga-
tion will be necessary to dissect the different contributions, neverthe-
less this would be beyond the scope of this article.
4.3. Model extension for the prediction of viscosity increase of the salt curve
In the next step, we want to elucidate the origin of the viscosity in-
crease of the salt curve. From the salt concentration scans shown
above (c.f., Fig. 3), we postulated different mechanisms that are respon-
sible for the right shift and for the increase of the salt curve, respectively,
7
Journal of Molecular Liquids 329 (2021) 115523
in the presence of hydrocarbons. In the original model a vertical scaling
factor is needed to adjust the predicted curve to the experimental data.
This factor corresponds to the proportionality constant in the Cates
model, linking micellar length to viscosity (η ~ L3) [50]. For the analysis
of the horizontal shift above we neglected the variation of the amplitude
of the calculated salt curves by applying a manual normalization process
based on the curve maxima (cf. Fig. 5). Now, for the analysis of the ver-
tical shift we first did a manual adjustment of the calculated curve to the
experimental data of pure SLES. As we noted earlier, the salt curve shifts
to the right with increasing χ sep
HC , and this shift can be fitted to the right-
ward shift of experimental data with increasing alkane chain length by
taking χ sep
HC to be an increasing function of alkane chain length from
around 0 to 0.4. However, the experimental data also show a decrease
in amplitude of the viscosity curve with increasing alkane chain length.
On the contrary, our model with 0.5% solubilized hydrocarbon, by keep-
ing the same vertical scaling parameter, shows that as the solubilized
fraction χ sep
HC increases from 0 to 0.4, the amplitude of the viscosity
curve increases by a factor of about three rather than decreasing (data
not shown). We therefore conclude that changing χ sep HC to model in-
creasing alkane chain length cannot simultaneously predict both the
right shift of the salt curve and its decreasing amplitude. As a conse-
quence horizontal and vertical shift will be modelled separately with
an additional extension of the model to account for the an increasing
amplitude.
In our previous work we observed a decrease of the salt curve in the
presence of certain molecules, which we attributed to a “softening” of
the micellar interface. In fact, these additives were supposed to act as
co-solvents, where the penetration of the molecules into the hydro-
philic part of the surfactant interface is in direct relationship with the
hydrophilicity of the molecules, mainly related to the HLB of the mole-
cule irrespective of the chemical functional groups. The experimental
data are consistent with a shortening of the micellar length and a reduc-
tion of the micellar persistence length [31]. In our predictive model, we
implemented an empirical expression based on the logPO/W of the mol-
ecules that decreases the bending modulus k*, which leads as a conse-
quence to lower overall viscosity [24]. However, this equation does
not permit an increase of k*, and therefore we have to define a new ex-
pression in order to simulate the observed effects. A SANS study on the
viscoelastic nature of wormlike micelles of oleyl amidopropyl betaine in
the presence of various organic additives gave interesting insights into
the potential location of these molecules at the surfactant interface
[40]. In particular, when adding nonpolar molecules such as n-
heptane, and even more methylcyclohexane, a significant increase of
the Kuhn length of the micelle was observed. It was suggested that
the hydrocarbon additives intercalate between the surfactant tail
groups, therefore rendering the micelles more rigid. On the other
hand, more polar additives such as phenol led to a drastic decrease of
the Kuhn length, due to a supposed partitioning into the surfactant
headgroup region and acting as co-solvent, and the micellar interface
becomes softer, consistent with our previous findings [31]. We there-
fore hypothesize that the solubilization of short nonpolar hydrocarbon
chains takes place more at the end of the aliphatic chains of the surfac-
tant rather than close to the micellar interface, where typically amphi-
philic molecules are located. This is corroborated by neutron
scattering as well as computational studies, which show that hexane
is located in the very center of surfactant bilayers, i.e. close to the ends
of the alkyl chain lengths [45,46]. As a consequence, the packing density
in the micellar interior is supposed to increase, which would affect the
bending modulus and make the micelles stiffer [40]. Therefore, in an
empirical approach, we adjust the bending modulus k* in our model
by a simple scaling factor σ (see Eq. (5)). k* is proportional to the free
energy needed to deform the micellar curvature, determined by the mi-
cellar persistence length (~ Kuhn length) [51]. In Fig. 8, a comparison of
the experimental data of a salt curve of SLES and a calculated salt curve,
both in the presence of 0.5% of cyclohexane, is shown. The calculated
W. Fieber, A. Scheklaukov, W. Kunz et al. Journal of Molecular Liquids 329 (2021) 115523

Fig. 8. Experimental NaCl salt curve of pure SLES (filled circles), and in the presence of 0.5%
of cyclohexane (open circles). Calculated salt curve with 0.5% of cyclohexane (thick line)
calculated with a k*-scaling factor σ of 1.28.

salt curve for pure SLES was fitted to the experimental data by adjusting
the vertical scaling factor. Subsequently, by keeping the same vertical
scaling factor, an additional k* scaling factor σ of 1.28 was used in
Eq. (5) for the calculated salt curve in the presence of 0.5% of cyclohex-
ane in order to match the viscosity of the experimental data. Note that
the simulation has been made assuming no separated oil, leading to
an almost perfect overlap of the horizontal position of the salt curves.
This indicates that the left-hand shift of the salt curve is almost entirely
due to solubilization in the surfactant palisade layer.

4.4. Mixtures of additives

Based on previous results and from the data presented here, we can Fig. 9. Experimental NaCl salt curves of 10% SLES with 0.5% of mixtures of two additives.
identify at least four different mechanisms from the addition of small, Upper panel: n-hexane and hexanal in the w/w ratios 100:0 (black circles), 75:25 (dark
grey), 50:50 (medium grey), 25:75 (light grey), and 0:100 (white). Lower panel: n-
hydrophobic molecules, which lead to four different effects on the salt
dodecane and 1-dodecanol in the same ratios as above.
curve: horizontal shifts to the left and to the right, and vertical shifts
by increase and decrease of the amplitude, respectively. We now want
to explore the impact of mixtures of two additives that shift in opposite
dodecane within the micellar environment, leading to a reduction of
directions: will the two effects compensate for each other, or will one
the fraction of demixed oil.
dominate?
For the vertical shifts, pure n-hexane increases the maximum viscos-
For the study of the horizontal shifts, we used mixtures of n-
ity by 7.9 Pa s, whereas pure hexanal decreases it by 20.7 Pa s, and a cal-
dodecane (right shift) and 1-dodecanol (left shift), which both show
culated average of 72:28 of n-hexane would be necessary to
around the same amplitude of the salt curve. On the other hand, for
compensate the two effects, again assuming that the additives have no
the vertical shifts, we studied mixtures of n-hexane (increase) and he-
mutual influence on each other within the micelle. As it has been the
xanal (decrease), which both show around the same horizontal shift
case above, the opposing effects do not seem to have the same weight
of the salt curve. In Fig. 9, experimental salt curves at different mixing
in binary mixtures, because from the experimental salt curves, one
ratios of the two pairs are depicted. In both cases, the mixtures combin-
can see that a total compensation occurs only at a ratio of at least
ing molecules with opposite effects on the salt curves compensate each
85:15 of n-hexane. In this case, our observation would be compatible
other proportionally. No additional, orthogonal shift of the salt curves of
with a solubilization of n-hexane further up the alkyl chain in the surfac-
the mixtures can be observed, i.e. no horizontal shift for vertical shifting
tant interface, induced by hexanal, which is situated close to the surfac-
mixtures and vice versa, proving the independent nature of the various
tant headgroups. As a consequence, the stiffening effect from the
mechanisms. In both cases, the mechanisms that lead to a left shift of the
solubilization of the alkanes close to the alkyl chain ends would be
salt curve and to a viscosity decrease, respectively, seem to be stronger
attenuated.
than the opposing mechanisms for the same mass fraction of total addi-
tives. For the horizontal shift, pure n-dodecane shifts the salt curve by
+1.8% of NaCl, whereas pure dodecanol shifts it by −2.2% NaCl in the 5. Conclusion and outlook
opposite direction, and a calculated weighted average of 55:45 would
be necessary to compensate the two effects, assuming that the additives Small amounts of hydrophobic additives can have tremendous ef-
have no mutual influence on each other within the micelle. However, it fects on viscosity and viscoelasticity of surfactant systems and can
seems as if the opposing shifts do not have the same weight in binary completely change the macroscopic properties. Salt curves are a conve-
mixtures, though, because a ratio of 75:25 of n-dodecane is needed to nient tool to discern different effects of surfactant-solute interactions.
bring the salt curve back to its original position (Fig. 10). One possible From previous work, we could identify two independent mechanisms
explanation would be a synergistic effect of the first additive on the sec- of fragrance molecules on SLES, which is commonly used as surfactant
ond, in such a way that dodecanol favors the solubilization of n- in personal care consumer products [24,31]. Co-solvent type

8
W. Fieber, A. Scheklaukov, W. Kunz et al.
Fig. 10. Effect of mixtures of additives on the peak position and maximum viscosity of
experimental salt curves of 10% of SLES. Upper panel: mixtures of n-hexane and
hexanal. Lower panel: mixtures of n-dodecane and dodecanol. The total additive
concentration is 0.5%. The dotted lines indicate the respective values of the salt curve of
SLES in the absence of additives. Solid lines are drawn to guide the eye.
interactions close to the surfactant headgroups, typically observed for
more polar organic additives, lead to an interface softening and as a con-
sequence to a decrease of the maximum viscosity of the surfactant sys-
tem. On the other hand, a co-surfactant type interaction, typically
observed for amphiphilic organic additives such as terpene alcohols,
lead to a left shift of the salt curve. These two mechanisms are supposed
to be independent, and the impact of organic, fragrance molecules are
linear combinations of both with different weighting. In the present
work, we have identified two additional mechanisms for the impact of
organic additives on the salt curve, which are responsible for a right
shift and for a viscosity increase, respectively. These effects are only ob-
servable in the presence of highly nonpolar hydrocarbons. We can dis-
tinguish between long-chain alkane molecules, which partially demix
from the surfactant film and form separate oil droplets in the micellar
core, leading to a right shift of the salt curve as a consequence of an in-
crease of the spontaneous curvature, and short or cyclic hydrocarbons,
which lead to an increase of the amplitude of the salt curve as a conse-
quence of their location at the alkyl-chain ends and a resulting stiffening
of the interface.
The impact of hydrocarbons and their disruptive effect on the viscos-
ity of surfactant based systems has previously been described in the lit-
erature and was generally attributed to a demixing process of a fraction
of the hydrocarbon additive that demixes from the surfactant chain en-
vironment [35–37,43]. As a consequence, a rod-to-sphere transition
takes place, which was shown to be a consequence of the increased for-
mation of energetically favored micellar endcaps. In some cases, a
9
Journal of Molecular Liquids 329 (2021) 115523
viscosity decrease of several orders of magnitude was even observed.
From our predictive model of SLES salt curves an increase of the number
of surfactant molecules in endcaps over a large range of salt concentra-
tions upon the addition of hydrocarbon oils has been predicted, corrob-
orating such a rod-to-sphere transition. Nevertheless, based on the salt
screening studies presented here, viscosity is governed by the match of
co-existing effects on the overall micellar curvature. Therefore the dis-
ruption of entangled micellar networks is not an irreversible conse-
quence of the addition of hydrocarbons, but the effect can be
counterbalanced by the amount of added salt. For example, n-decane
shifts the salt curve of SLES to the right by about 1% of NaCl, but leaving
the maximum viscosity almost unchanged. Depending on the original
position of a surfactant solution of SLES on the salt curve in the absence
of n-decane, either a viscosity decrease (at lower NaCl concentrations)
or a viscosity increase (at higher NaCl concentrations) can be achieved
by the addition of n-decane, and the shift of the curve maximum is
just a question of counterbalancing the impact of hydrocarbons on the
packing parameter by adding more salt.
In the past, we particularly focused on the impact of fragrance mol-
ecules on the viscosity of the surfactant system SLES. Fragrance mole-
cules often contain polar oxygenated functional groups, such as
alcohols, aldehydes, ketones, esters or ethers, and typically lead to the
first two effects, left shift and decrease, respectively (data not shown).
However, some terpene molecules such as limonene for example lack
any chemical functional groups and are therefore supposed to act like
hydrocarbons. Indeed, in our previous work, we observed that limonene
was an outlier compared to the other compounds studied, showing a
slight increase of the salt curve, which was not well reflected by our pre-
dictive model [24]. Based on the new findings in this present study, the
impact on the salt curve can be explained by similar molecular structure
or polarity to the one of n-hexane or cyclohexane.
In Table 1, a comparison of the different effects that small organic ad-
ditives can have on the salt curve of SLES is shown. Although completely
different in nature, we postulate that all four effects are based on differ-
ent mechanisms and are directly linked to the location of the molecules
within the surfactant film. In a first order approximation, this position is
supposed to be a consequence of the molecular polarity of the molecules
and the polarity match with the surrounding surfactant chains. There
are numerous studies in the past that assessed the location of small or-
ganic molecules, in particular fragrance molecules, within surfactant ag-
gregates [28,29,52–55]. Although different surfactant systems and
observation techniques have been used, the general findings are similar.
Low logPO/W molecules seem to be positioned close to the surfactant
headgroups. Molecules with higher logPO/W, but amphiphilic character
are located a bit deeper within the micelles, but still close to the micelle
interface between headgroups and alkyl tails. On the other hand, the
more the molecules become nonpolar, the deeper they solubilize
towards the micellar core, where finally for very nonpolar and long-
chain alkanes they separate from the surfactant film. The exact position-
ing will depend on additional factors such as size, shape or specific mo-
lecular interactions, though. The situation is different for charged
additives where due to electrostatic interactions with the surfactant
headgroups the molecules are kept closer to the interface compared to
non-charged counterparts, which penetrate deeper into the micellar
core [56]. There may be additional mechanisms that potentially have
an impact on the shift of the salt curve, for example the influence of
the molecules on the chain packing in the cylindrical region [30].
The molecules studied are composed of different structural moieties,
which can compensate each other, and where accurate predictions are
no longer possible. For example, the commonly used solvent in perfum-
ery applications, isopropyl myristate (IPM), was found to drastically de-
crease the surfactant viscosity in SLES type systems [29], and it was
hypothesized that due to its long alkyl chain the molecule partially
demixes from the surfactant chain environment, leading to a shortening
of the micelles. Indeed, according to our results presented here, we
would expect a shift of the salt curve to the right hand side, whereas
W. Fieber, A. Scheklaukov, W. Kunz et al.
Table 1
Effect on salt curve and proposed mechanisms of interactions of small, organic additives to viscoelastic systems of SLES. 1) From reference [31].
Effect on salt curve Molecular origin Location in surfactant film
Viscosity decrease 1) Co-solvent effect Close to headgroups
Left shift 1) Co-surfactant effect Micellar interface
Viscosity increase Interface stiffening Close to surfactant chain ends
Right shift Demixing Separated oil droplet in micellar core Increase of curvature
from experiments we observed a slight left shift, accompanied by a sig-
nificant viscosity decrease (data not shown). It suggests that the pres-
ence of one carbonyl group in the ester imparts sufficient polarity to
the molecule so that the dominant effect of the alkane group gets
counterbalanced. Therefore, we assume that exact predictions of the im-
pact of complex organic molecules is still challenging.
We have to point out that our studies and observations have been
made for SLES. There may be specific effects, due to interactions with
the PEG moiety of the headgroup, and the findings can be different for
PEG-free surfactants. But we hypothesize that Table 1 can serve as a
rule of thumb for other surfactants or mixtures of surfactants. Despite
the new insights into the mechanisms that govern the impact of fra-
grance or small organic molecules on viscosity and viscoelasticity of sur-
factant solutions, and the simulation models for single raw materials,
the prediction for mixtures will remain challenging. As was shown in
the present study, not only is the concentration effect non-linear and
different for each molecule, in addition, there are indications for mutual
interactions of the molecules within the micelle, leading to changes in
the solubilization environment and consequently in the location within
the micelles. This will make a precise prediction for mixtures very chal-
lenging, and further studies are necessary to gain more insight into the
complex interplay between various additives.
Funding
This research did not receive any specific grant from funding agen-
cies in the public, commercial, or not-for-profit sectors.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
We thank Lydia Zahnweh and Didier Touraud from the University of
Regensburg for supervision and fruitful discussions.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.molliq.2021.115523.
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