Advances in Colloid and Interface Science 210 (2014) 7277

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Advances in Colloid and Interface Science

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

Role of self-assembled surfactant structure on the spreading of oil on at

solid surfaces
Bingquan Li, Ponisseril Somasundaran, Partha Patra
Langmuir Center for Colloids and Interfaces, Columbia University, NY 10027, United States

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

Available online 22 April 2014 Uniform spreading of oil on solid surfaces is important in many processes where proper lubrication is required
and this can be controlled using surfactants. The role of oilsolid interfacial self-assembled surfactant structure
Keywords: (SASS) in oil spreading is examined in this study for the case of hexadecane-surfactant droplet spreading on a
Oil spreading at horizontal copper surface, with triphenyl phosphorothionate surfactants having varying chain lengths
Surfactants (0 to 9). It is shown that the frictional forces (FSASS) as determined by the SASS regulate droplet spreading rate
Self-assembled structures
according to surfactant chain length; surfactants with longer chains led to higher reduction in the spreading
Tanner's law
Frictional forces
rate. The extent of such forces, FSASS, depends on the surfactant density of the evolving SASS, and specic cong-
uration the evolving SASS exhibit as per the orientations of the surfactant chains therein. Thus, FSASS = [k1 + k2(t)]
(t), where (t) is the surfactant adsorption density of SASS at time t during evolution, and, k1 and k2(t) are the
force coefcients for (t) and orientations (as a function of spreading time) of the surfactant chains respectively.
As a SASS evolves/grows along with adsorption of surfactants at the spreading induced fresh interface, the k1(t)
component of FSASS increases and contributes to reduction in the net spreading force (S). With a decrease in the
net spreading force, the existence of a cross-over period, during which the transition of the spatial dynamics of
the chains from disordered to realignment/packing induced ordered orientation occurs, has been inferred from
the FSASS vs. chain length relationships. Such relationships also suggested that the rate of realignment/packing
is increased progressively particularly due the realignment/packing induced decrease in the net spreading
force. Therefore, the realignment process is a self-induced process, which spans a measurable period of time
(several minutes), the cross-over period, during which the net spreading force decreases essentially due to
such self-induced process.
2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2. Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.1. Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.2. Imaging and analysis of oil droplet spreading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.3. Rheological measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
3. Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.1. Effect of surfactant chain length on spreading rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
4. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.1. Macroscopic force balance accounting for frictional forces at SASSoil interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

1. Introduction

Corresponding author. Tel.: +1 212 854 2925. An understanding of the mechanisms by which oilsolid interfacial
E-mail address: pp2295@columbia.edu (P. Patra). self-assembled surfactant structures (SASS)surfactant lmimpart

http://dx.doi.org/10.1016/j.cis.2014.04.004
0001-8686/ 2014 Elsevier B.V. All rights reserved.
 B. Li et al. / Advances in Colloid and Interface Science 210 (2014) 7277 73

specic oil spreading behavior is fundamentally important to many chain lengths [triphenyl phosphorothionate (TPPT), butylated
applications including engine oil lubrication, coating, painting, oil re- triphenyl phosphorothionate (butylated TPPT), nonylated triphenyl
covery, micro-uidics, and drug delivery [16]. Depending on the con- phosphorothionate (nonylated TPPT)] were obtained from Ciba (Fig. 2).
centration of surfactants and their molecular architecture (polarity of Solutions of these surfactants were prepared in hexadecane at desired
the head group, and chain length and branching), interfacial surfactant concentrations.
lms attain form such as uniform monolayer or irregular hemicelles
[7,8]. SASS formation is not necessarily a spontaneous event but struc- 2.2. Imaging and analysis of oil droplet spreading
turally evolves along with adsorption of surfactants at the fresh oil
solid interface generated during spreading and, alignment/packing of The substrate was placed on the stage of a microscope (Nikon) and
the surfactants in the SASS. In spite of interference from structural and a 2 L droplet of the surfactant solution was gently placed onto a stage
congurational dynamics associated with evolution of SASS, possibly using a syringe and taking care to avoid any effect due to the loading
spanning the entire spreading duration, the spreading behavior has impact. The ambient temperature was controlled at 25 C. The images
been seen to follow Tanner's power law [9]. of the droplet during the spreading process were captured by a Hitachi
CCD camera from the top and recorded by a Labview program at
3 1
Rt 10 =10 t 10
1
1 preset intervals. The base contact area values of the droplets were
analyzed from the images with software ImageJ (National Institutes of
Health). The droplet area was measured as soon as a pure hexadecane
where, R is the radius of a droplet on a surface, t is the spreading time, droplet was placed on the Cu metal surface. This area was accounted
represents surface tension, refers to the droplet viscosity, and is for in the estimation of the normalized areas of the droplets during
the droplet volume. Here, the spreading behavior of the hexadecane spreading.
droplet (having triphenyl phosphorothionate (TPPT) type surfactants
of varying chain lengths) on a at horizontal copper surface was studied 2.3. Rheological measurements
to determine the role of the surfactant structure on spreading behavior.
Self-assembly of the surfactants upon their adsorption at the solidoil Kinematic viscosity values of hexadecane-surfactant solutions were
(s/o) interface and along the solid/oil/air (s/o/a) contact line can be measured using an Anton Paar DSR rheometer. 100 mL of solution was
viewed microscopically as a exible soft SASS tray electrochemically poured into a glass cylinder and measurements were taken using a
glued to the interface and having wedges at the s/o/a contact line vane type probe, and at 25 C. Hexadecane density was considered to
(Fig. 1). The forces (FSASS)frictional forces at the SASSoil interface be 0.77 g/cm3. Kinematic viscosity values were determined within the
which vary with structural evolution are governed by surfactant density shear rate range of 0.1100 s1, and using Cannon viscosity standards.
and alignment/packing of surfactants. In order to determine the pro-
gressive effects of an evolving SASS on the spreading rate (determined
as n = ln (normalized base area of a droplet)/ln t, area/time), particular-
ly with emphasis on structural evolution being unique as per surfactant
structures that constitute a SASS, this study focuses on the how varia-
tions in surfactant chain lengths from 0 to 9 regulate spreading rate.
Typically, for surfactants having similar head groups, adsorption density
and alignment of the chains in the SASS are dependent on the surfactant
chain length [10].

2. Experimental

2.1. Materials

The non-aqueous solvent used was hexadecane (N99%, Sigma). The

copper metal surface of 100 nm thickness was prepared by thermal
evaporation (Edwards BOC Auto 306) of 99.99% pure copper (Kurt J.
Lesker Co.) from a tungsten boat followed by deposition on a silicon
wafer (University Silicon) at a rate of 2 /s and at 5 107 Torr pressure.
The surface tension of solid copper is about 1300 mN/m [11].
Triphenylphosphorothionate type surfactants having different

Hexadecane + Surfactants SASS - A Flexible Tray

FSAASSS
FVISC
V C VIS
SC

Fig. 1. Illustration of the forces contributing to spreading of a hexadecane-surfactant drop-

let on a at horizontal copper substrate. SASSresembling a exible tray (blue in color) Fig. 2. Molecular structures of triphenyl phosphorothionate (TPPT), butylated triphenyl
can be seen at the substrate Cudroplet interface; viscous forces (FVISC) are in the phosphorothionate (butylated TPPT), and nonylated triphenyl phosphorothionate
spreading direction and FSASS towards the droplet center. (nonylated TPPT) surfactants.
74 B. Li et al. / Advances in Colloid and Interface Science 210 (2014) 7277

3. Results
3.1. Effect of surfactant chain length on spreading rate
The effects of TPPT surfactants having 0, 4 and 9 alkyl groups on the
spreading behavior of hexadecane droplets were studied in the concen-
tration range of 0.01 to 2 wt.%. Particle size measurement was carried
out to investigate surfactant aggregation in the oil phase and surfactant
aggregation was not observed in the concentration range from 0.01 to
2 wt.%. Ideally, it can be inferred from numerous studies that a SASS
exhibits a conguration where the head groups are contact with the
substrate and the chains being buried in the oil phase (Fig. 1) [7].
Fig. 3 indicated that irrespective of the surfactant concentrations
in the droplets the spreading rate decreased (smaller droplet areas)
with an increase in the chain length: 0 b 4 b 9. Complete wetting of
a pure hexadecane droplet on a at copper surface (surface tension
1300 mN/m) [11] was observed with the droplet areas A scaling with
time, t, as A ~ t0.2. For a droplet having TPPT at 0.01 wt.%, the spreading

1st min 26th min 51st min

n = 0.2

TPPT

n = 0.019

n = 0.009

n = 0.2

Butylated
n = 0.015
TPPT

n = 0.009

n = 0.04

n = 0.008
Nonlylated
TPPT

n0

Fig. 3. Optical images of hexadecane-surfactant droplets at 1st, 26th and 51st min during spreading, with droplets having varying (0.01, 0.1 and 2 wt.%) concentrations of TPPT, butylated
TPPT, and nonylated TPPT. The spreading rate, n, at 51 min is shown.
 B. Li et al. / Advances in Colloid and Interface Science 210 (2014) 7277 75

rate was n ~ 0.2 (Fig. 4a). The spreading rate decreased further spreading regimes respectively. As similar to the effect of TPPT surfac-
at higher TPPT concentration (0.1 wt.%) and exhibited two regimes, tants at 2 wt.%, with butylated TPPT type surfactant, droplet pinning
the rst regimen being faster than the second; in comparison to n was observed in less than 1 min (Fig. 4c) at 2 wt.%. With nonylated
~ 0.2 at 0.01 wt.%, n was 0.11 in the faster regime (0th to 8th min) TPPT (9 alkyl groups), even at a lower (0.01 wt.%) concentration, the
and n ~ 0.019 in the slower regime (from 8th min to droplet pinning) spreading rate reduced considerably in comparison to that with TPPT
at 0.1 wt.% TPPT (Fig. 4b). At 2 wt.% of TPPT, droplet pinning was or butylated-TPPT, i.e., n values were 0.13 and 0.04 (Fig. 4b) respective-
observed in less than 1 min (Figs. 3 and 4c). The spreading rate with ly in faster and slower spreading regimes (compared to n ~ 0.2 for both
butylated TPPT (4 alkyl groups) at 0.01 wt.% was similar to that of TPPT and butylated TPPT). The marked contribution of the 9 alkyl
TPPT, i.e., n ~ 0.2. With an increase in the concentration of butylated groups to the reduction in spreading rate was evident when the droplet
TPPT from 0.01 to 0.1 wt.% the spreading rate decreased with n values exhibited signicantly slower spreading rate (n = 0.008)almost
as 0.08 and 0.015 (n ~ 0.11/0.019 for TPPT) in faster and slower pinningat lower concentration (0.1 wt.%).

4. Discussion
(a) TPPT, 0.01%
0.5 Butylated TPPT, 0.01% 4.1. Macroscopic force balance accounting for frictional forces at SASSoil
Nonylated TPPT, 0.01% interface
Log(Normalized Base Area)

0.4
0.2
t The interfacial tension of either s/o (solid/oil) or o/a (oil/air) inter-
0.3
face decreases with an increase in surfactant chain length; in particular,
0.04 the s/o interfacial tension s/o decreases signicantly with an increase
0.2 t in chain length [12]. The spreading power which is a parameter for
the measure of wetting is determined as [13]:
0.1
0.13 S s=a o=a s=o 2
0.0 t
where, S indicates spreading power, and s/a, o/a and s/o indicate
-0.1
0.0 0.4 0.8 1.2 1.6 2.0
solidair, oilair and solidoil interfacial tensions respectively. If s/o
Log (Time), min. and o/adecrease with an increase in chain length, it suggests in accor-
dance with Eq. (1) that the spreading power S is less negative with an
increase in chain length, suggesting wetting, and an increase in the
(b) spreading rate. On the contrary, a reduction in the spreading rate
0.5
TPPT, 0.1% with an increase in chain length indicated that there exist forces that
contribute to the reduction in the spreading rate which are opposite in
Log(Normalized Base Area)

0.4 Butylated TPPT, 0.1%

direction of the forces which promote spreading, namely the viscous
Nonylated TPPT, 0.1%
and/or capillary forces [14]. As such forces led to reduction in the
0.3
spreading rate with an increase in surfactant chain length, the extent
of these forces owe to chain length dependent structural forms of the
0.2
0.019
SASS, and variations in and are assumed negligible. It has been re-
t ported that self-assembled surfactant structures impart frictional forces
0.1 0.11 0.015 (FSASS), and thereof, modulate the oil spreading rate [13,15,16]. General-
t t ly, in assessment of the contributions of the forces that govern droplet
0.0 spreading, the capillary forces balance with the viscous forces [18,19].
0.08
t
-0.1 2d
0.0 0.4 0.8 1.2 1.6 2.0 S F VISC 3
2
Log (Time), min.
The left hand side of the equation includes capillary forces, where
(c) and d indicate interfacial tension and oil droplet contact angle respec-
0.5 tively. The right hand side of Eq. (2) indicated forces owing to viscous
TPPT 2% forces (FVISC). In corroborating this relationship with the chain length
Log(Normalized Base Area)

0.4 Butylated TPPT 2% dependent reduction in the spreading rate, balancing of the contribu-
Nonylated TPPT 2% tions from the viscous and capillary forces theoretically predict faster
0.3 spreading with an increase in chain length, and thus, these forces fail
to account for the observed reduction in the spreading rate. Hence, it
0.2 is further clear that the contributions of the frictional forces, FSASS,
during structural evolution of SASS are measurable enough to cause re-
0.1 duction in spreading, where the frictional forces vary according to chain
length dependent SASS types and their evolving forms in the course of
0.0 spreading.
!
-0.1 2
0.0 0.4 0.8 1.2 1.6 2.0 S d F VISC F SASS F VISC 4
2
Log (Time), min.

Fig. 4. Spreading behavior (droplet area as a function of spreading time) of hexadecane

Here, Table 1 shows that with an increase in the TPPT chain
droplets having TPPT, butylated TPPT, and nonylated TPPT type surfactants at different length the changes in the kinematic viscosity values of hexadecane-
concentrations: (a) 0.01 wt.%, (b) 0.1 wt.% and (c) 2 wt.%. surfactant solutions are negligible. Thus, the contributions of the chain
76 B. Li et al. / Advances in Colloid and Interface Science 210 (2014) 7277

Table 1 Faster Spreading Regimen

Kinematic viscosity of hexadecane as a function of chain-length (09) and concentration Slower Spreading Regimen
(0.012 wt.%). 0.20

FSASS, measured as: [-noil-nsurf.]

Chain length Kinematic viscosity (centistokes, cs) vs. surfactant
concentrations

0.01 wt.% 0.10 wt.% 2 wt.%

0 4.458 4.698 5.158 0.15 [(k2) (t)) ]

4 4.558 4.498 5.258
9 4.498 4.598 5.158

length dependent variations in the capillary forces to the reduction in 0.10

spreading are negligible, and therefore, the FVISC predominantly regu-
lates the droplet spreading behavior. Thus, the force balance for oil
0 4 8
spreading can be written as:
Chain (Alkyl) Length
S F VISC F SASS 5
Fig. 5. Realignment/packing induced frictional forces as a function of surfactant chain
length for hexadecane droplets having TPPT type surfactants in the intermediate concen-
where S is the spreading power. The term FSASS is negative as the direc- tration range (0.1 wt.%).
tion of these forces is opposite to that of the spreading direction
viscous forces. The FSASS depends on the SASS surfactant density at the
increase in the forces that led to such reduction in the spreading rate
solidoil interface and is derived as:
is predominantly due to changes in the structural conguration of
G  SASS. Such congurational changes occur through the process of
0
lC 0 e RT 6 realignment/packing of surfactants in the SASS, where the outcome
of this process was contributive to the reduction in the spreading rate
[12],where, denotes adsorption density, l represents surfactant only under conducive oil spreading dynamics at the end of the faster
chain length and C0 as the concentration of surfactants in an oil droplet. spreading regimen. While the realignment process features surfactants
As the interfacial area A0 (spontaneous area as soon as a droplet is attaining uniformity in terms of their spatial orientations (relative to the
placed on the copper surface) increases during spreading, the adsorp- horizontal substrate base), in packing, the intermolecular chains tend be
tion density, (t), depends on normalized (interfacial area wise) bulk at closer proximity [17,18]. A few research investigations reporting the
surfactant concentration at time t, Ct, where Ct changes with an in- effect of SASS on oil spreading behavior infer that realignment of chains
crease in the interfacial area A as [C0 A0] / [(A0 + (A)]. If A is derived could lead to changes in the spreading rate [17]. Here, accounting for
from Tanner's law, then the realignment/packing of surfactant in the SASS, the frictional forces
G  G  increase as: k2(t)(t), where k2(t) is the force coefcient owing to the
0 A 0
t lC t e RT lC 0   0   1  e RT 7 realignment/packing of surfactants in the SASS. Thus, under scenarios
3

A0 10 t
10 n
where chain length induced variations in the interfacial tensions have
a negligible effect on the spreading behavior, which is seen here, the
net spreading power at time t can be written as:
As and values can reasonably be considered as constant here
for the hexadecane-surfactant system, the 3/10(1/) 1/10 term equates h  i
St F VISC k1 k2t t 9
to a constant value K. Thus, with initial surfactant concentration as C0
and droplet area A0 at time t = 0, the adsorption density, (t), at any
time t is a function of n, and l as: Fig. 6 shows that there exists a measurable (several minutes) period
2 3 of time in the entire spreading duration during which the spreading
G  rate, represented as n, progressively reduces to an equilibrium value.
RT 4
0 A0 5
t l C0e h 1
i 8
A0 K 10 t n

With increase in chain length (t) is higher and correspondingly the 0.2
Spreading rate Coeffcient, n

frictional forces FSASS. Due to signicantly higher (t) at higher (2 wt.%)

concentration of TPPT type surfactants in a droplet, higher FSASS resulted
in droplet pinning at an early stage (Fig. 4c). A similar explanation
applies for spreading of droplets having lower (0.01 wt.%) surfactant
concentrations, where the droplet spreading rate changed moderately 0.1
due to lower adsorption density. In the intermediate concentration
(~0.1 wt.%) range, the spreading rate, as shown through Figs. 4, 5 and
6, demonstrated two spreading regimes. Two spreading regimes exhib-
ited different spreading rates, faster followed by slower. Fig. 5 shows
that in either of the two spreading regimens the FSASS (represented 0.0
as n = (noil nsurfactant)) from the evolving SASS is higher with an
0.4 0.8 1.2 1.6 2.0
increase in chain length. After a certain period of time, from the time
Spreading time (min), Log scale
spreading commenced, the faster spreading rate reduced markedly,
and progressively thereafter and, until an equilibrium spreading rate
Fig. 6. Spreading rate coefcient vs. spreading time relationship demonstrates time of ini-
value had been attained. Such marked reduction in the spreading rate tiation (vertical dotted lines) and time-span of the cross-over regimes (vertical bars). The
at certain time during spreading is not due to the spontaneous increase horizontal bars indicate cross-over periods for nonylated-TPPT (blue) at 0.01 wt.%, and
in the surfactant density in SASS, but, we propose that the marked TPPT (green) and butylated TPPT (red) at 0.1 wt.%.
 B. Li et al. / Advances in Colloid and Interface Science 210 (2014) 7277
The forces contributive to such reduction in the spreading rate corrobo-
rate the differences (Figs. 5 and 6) of the forces in the faster and slower
spreading regimes. These forces, k2(t)(t), measured as the differences
(Fig. 5) of the forces in the faster and lower spreading regimens are sig-
nicantly high enough and cannot be accounted to an increase in the
surfactant adsorption density, as in such a short period of time it is un-
likely that there will be a ux of surfactants adsorbing onto the surface
to consequence a signicant increase in the frictional forces. Thus, the
transitional (faster-to-slower) period, during which the FSASS increases,
attributes to realignment/packing of the surfactants in SASS. For aque-
ous surfactant solutions, similar spreading regimes have been demon-
strated, where the transitional/cross-over period is described as a
molecular kinetic regime followed by a hydrodynamic regime [1922],
and according to the power law shift from t1/7 to t1/10, with an asymp-
totic regime corresponding to a longer relaxation time to equilibrium.
Furthermore, the characteristic time at which the cross-over between
the regimes occurs is of the order of seconds [1922], much shorter
than the time in this study, where, it is ~6 min for 0.01 wt.% nonylated
TPPT solution and, 5 and 7 min for 0.1 wt.% TPPT and butylated TPPT
respectively. The exponent n in the power law is much smaller than
either 1/7 or 1/10, i.e., 1/50. The time period spans from the com-
mencement of the realignment/packing process to until an equilibrium
state (spreading rate, n, in the slower spreading regimen) is reached.
During this period, the realignment/packing induces an increase in
frictional forces, k2(t)(t), which contributes to the reduction in the
spreading rate until a steady value is reached. Fig. 6 shows that the
extent of the cross-over period has no particular relationship with
the surfactant chain length, where the extent spans several minutes
(~ 6 min) and the rate (slope of the line n vs. spreading time in the
cross-over period) at which k2(t)(t) increases is similar. Such regularity
also suggests that the reduction of the spreading rate in the cross-over
period is less dependent on the net spreading power and, there exist
other self-induced forces that govern chain realignment/packing. By
following the progression of the changes in the spreading rate, which
progressively decreases in the cross-over period, it can be inferred
that the realignment/packing event that occurred at time t promotes
the event that occurs at time t + t. It is notable that the spreading
rate at time t + t is less that that at t. Thus, the realignment/packing
event at time t, which resulted an increase in the frictional forces,
k2(t)(t), contributed towards an increase in the rate of realignment/
packing in the duration t. Thus, an increase in the rate of realignment/
packing is likely to increase during the cross-over period until an equilib-
rium spreading rate is attained. Thus, realignment/packing event is a
self-induced process.
5. Conclusions
For spreading of oil-surfactant droplets on at surfaces, depending
on surfactant adsorption density, (t), at the oilat surface interface,
the frictional forces (FSASS) at the interfacial self-assembled surfactant
structure (SASS)oil interface can be measurable enough over viscous
(FVISC) and capillary forces to regulate the spreading behavior. Such
forces increase progressively as a SASS structurally evolves along
with adsorption of surfactants at the spreading induced fresh inter-
face. The frictional forces act in a direction that is opposite to the
spreading direction, and the extent of such forces at time t during
spreading can be accounted as: FSASS = [k1(t)]. In addition, the extent
of such forces at any particular time during spreading also depend on
the surfactant adsorption kinetics, where, for surfactants which adsorb
spontaneously, e.g., amino acid based surfactants, FSASS = [k1(t)] will
be measurable enough early on in spreading. Thus, the extent of
77
frictional forces primarily depends on the adsorption density and ad-
sorption kinetics; accordingly, it is seen here that as the substrate af-
nity of surfactants having longer chains is higher the frictional forces
are higher. As spreading progresses, the frictional forces which restrict
spreading increase, and the effect of FVISC which promotes spreading de-
creases. Thus, in the entire spreading regime, depending on the relative
measure of both k1(t) and FVISC, the spreading behavior in term of the
spreading rate can be categorized as: 1) faster spreading rate, where
FVISC is signicantly higher than k1(t), which is due to lower adsorption
density, 2) signicantly slower spreading rate from the beginning,
almost pinning behavior, where k1(t) is signicantly higher than FVISC
due to faster adsorption kinetics and higher adsorption density, and,
3) mixed spreading behavior, where depending on the relative values
of FVISC and k1(t) the spreading rate is higher at the beginning
and slower in the later stage. Depending on the droplet volume the
spreading rate is likely to be regulated by the FVISC in the rst regime
[23], and, in the second regime, dewetting in separate regions across
the s/o interface could be a possibility due to formation of SASSs in
patches. For droplets exhibiting mixed spreading behavior, there exist
a cross-over period during which progressive transition in the spreading
rate from faster to slower occurs. At the beginning of the transition
period St (net spreading power) becomes signicantly less to promote
realignment/packing of the surfactants/chains in the SASS. As seen
here, realignment of chains is not a spontaneous event and spans several
minutes, particularly for spreading of oil-surfactant droplet, during
which there is a measurable increase in the frictional forces, especially
owing to the realignment/packing process. The process of realignment/
packing, which is favorable under quiescent spreading dynamics,
would typically include uncoiling of the chains, chains attaining similar
orientations, and packingreduction in the distances between the sur-
factants. A better understanding of how realignment process occurs
and the steps thereof, sought further investigation.
Acknowledgements
The authors are thankful to NSF I/UCR Center for Particulate and Sur-
factant Systems (Grant #: IIP-0749461) for supporting the research
program.
References
[1] Ananthapadmanabhan KP, Goddard ED, Chandar P. Colloids Surf 1990;44:281.
[2] Biebuyck HA, Whitesides GM. Langmuir 1994;10(12):45817.
[3] Wasan DT, Nikolov AD, Bierwagen GP. Nature 2003;423:156.
[4] Somasundaran P, Zhang L. J Pet Sci Eng 2006;52:198.
[5] De Coninck J, de Ruijter M, Voue M. Curr Opin Colloid Interface Sci 2001;6:4953.
[6] Monica CB, Schneidera JP. Acta Biomater 2009;5(3):817.
[7] Kavehpour HP, Ovryn B, Gareth McKinley H. Phys Rev Lett 2003;91(19):4.
[8] Martin JI, Wang ZG, Schick M. Langmuir 1996;12(20):49509.
[9] Tanner LH. J Phys D Appl Phys 1979;12(9):1473.
[10] Zhang R, Somasundaran P. Adv Colloid Interface Sci 2006;123126:21329.
[11] Brillo J, Egry I. J Mater Sci 2005;40:2213.
[12] Somasundaran P, Healy TW, Fuerstenau DW. J Phys Chem 1964;68(12):3562.
[13] de Gennes P-G. Wetting: statics and dynamics. Rev Mod Phys 1985;52(827).
[14] Bonn D, Eggers J, Indekeu J, Meunier J. Rev Mod Phys 2009;81(2):739805.
[15] Xiao X, Hu J, Charych DH, Salmeron M. Langmuir 1996;12:235.
[16] Brewer NJ, Beake BD, Leggett GJ. Langmuir 2001;17(6):1970.
[17] Liu Y, Evans DF. Langmuir 1996;12:1235.
[18] Small DM. The Physical Chemistry of Lipids. New York: Plenum Press; 1986
[Chapter 3].
[19] Biance AL, Clanet C, Quere D. Phys Rev E 2004;69:016301.
[20] Dussan EBV. Annu Rev Fluid Mech 1979;11:371.
[21] Lee S, Shon YS, Colorado Jr R, Guenard RL, Lee TR, Perry SS. Langmuir 2000;16:2220.
[22] Rojas OJ, Macakova L, Blomberg E, Emmer , Claesson PM. Langmuir 2002;18:8085.
[23] Heine David R, Grest Gary S, Webb III Edmund B. Phys Rev Lett 2005;95:107801.