4880 Langmuir 2003, 19, 4880-4883

Fine-Tuning the Wetting Behavior of Polyelectrolyte

Films with Sodium Dodecyl Sulfate
Rita J. El-Khouri and Malkiat S. Johal*
Division of Natural Sciences, New College of Florida, 5700 North Tamiami Trail,
Sarasota, Florida 34243
Received January 31, 2003. In Final Form: April 6, 2003

Charge-alternating polyelectrolyte multilayers containing the anionic surfactant sodium dodecyl sulfate
(SDS) were constructed by adsorption from aqueous solution. The polyelectrolyte films contained the
polycation PEI (poly(ethylenimine)) and the polyanion PAZO (poly[1-[4-(3-carboxy-4-hydroxyphenylazo)-
benzenesulfonamido]-1,2-ethanediyl, sodium salt]). SDS adsorption on the PEI/PAZO/PEI trilayer was
studied using dynamic tensiometry and single wavelength ellipsometry. Advancing contact angle
measurements of SDS adsorption onto PEI surfaces indicate that surfactant adsorption is complete within
1 min. The contact angle increases with surfactant concentration, from 30 (0 mM SDS) and plateaus to
a constant value of 80 beyond 0.01 mM SDS. Constructing films from varying concentrations of PEI
allowed the degree of PAZO interpenetration to be qualitatively measured. Contact angle and ellipsometric
thickness studies indicate that PAZO interpenetrates 32 into the terminal PEI layer, above which the
surface is composed entirely of PEI. Maximum SDS adsorption is observed above the interpenetrated
region, consistent with maximum electrostatic interaction between the terminal PEI layer and SDS.

Introduction polycation surface is generated by sequential adsorption

Varying the surface properties of polymer films is
important in a wide range of applications.1-3 In particular,
taking advantage of electrostatic adsorption of surfactants
onto polyelectrolyte surfaces provides a convenient method
of fine-tuning the wetting behavior of polymer films. Due
to displacement of small counterions, the association
between polyelectrolytes and ionic surfactants is entropi-
cally and electrostatically driven, with little contribution
from hydrophobicity.4-8 The polycation PEI (poly(ethylen-
imine)) has the highest known charge density of all
polyelectrolytes and a strong tendency to form complexes
with anionic surfactants.9,10 In fact Van der Berg and
Staverman first suggested complex formation between
PEI and the common anionic surfactant sodium dodecyl
sulfate (SDS) over 30 years ago.11 As the charge density
of the polycation increases, greater amounts of anionic
surfactant are adsorbed to the polymer. Degree of pro-
tonation often determines the charge density of cationic
polyelectrolytes. Approximately 75% of the amino groups
of PEI are protonated at pH 2 with the degree of
protonation decreasing linearly to zero charge at pH
11.12 This work investigates the wetting behavior of a PEI
surface containing various amounts of adsorbed SDS. The
* To whom correspondence should be addressed. E-mail: johal@
ncf.edu. Fax: (941) 359-4396.
(1) Contact Angle, Wettability and Adhesion; Mittal, K. L., Ed.; V.S.P.
Intl Science: Utrecht, The Netherlands, 2003.
(2) Jones, R.; Richards, R. W. Polymers at Surfaces and Interfaces;
Cambridge University Press: Cambridge, 1999.
(3) Garbassi, F.; Morra, M.; Occhiello, E. Polymer Surfaces: From
Physics to Technology; John Wiley & Son Ltd.: Chichester, 1998.
(4) Satake, I.: Yang, J. T. Biopolymers 1976, 15, 226.
(5) Bronich, T. K.; Cherry, T.; Vinogradov, S. V.; Eisenberg, A.;
Kabanov, V. A.; Kabinov, A. V. Langmuir 1998, 14, 6101.
(6) Thunemann, A. F. Langmuir 2000, 16, 824.
(7) Wallin, T.; Linse, P. J. Phys. Chem. 1996, 100, 17873.
(8) Wallin, T.; Linse, P. Langmuir 1996, 12, 305.
(9) Claesson, P. M.; Bergstrom, M.; Dedinaite, A.; Kjellin, M.; Legrand,
J.-F.; Grillo, I. J. Phys. Chem. B 2000, 104, 11689.
(10) Thunemann, A. F.; Kubowicz, S.; Pietsch, U. Langmuir 2000,
16, 8562.
(11) Van den Berg, J. W. A.; Staverman, A. J. Recl. Trav. Chim.
Pays-Bas 1972, 91, 1151.
(12) Reveda, T.; Petkanchin, I. J. Colloid Interface Sci. 1997, 196,
87.
of polyelectrolytes of opposite charge onto a glass substrate,
with the outer layer as PEI.13-15
The surface wettability of charge-alternating polyelec-
trolyte layers is determined primarily by the outermost
layer.16,17 Rubner has shown that wettability can be fine
tuned by varying the pH of the adsorbing polyelectrolyte.16
In that work, changes in pH resulted in layers with
different thicknesses and surface wettabilities. These
changes were attributed to varying degrees of layer
interpenetration. In fact, certain layer combinations have
yielded water contact angles as low as <5 and as high
as 100.16,17 In this study, we report contact angle
measurements of polyelectrolyte films containing an
adsorbed outer layer of SDS. The polycation used was
PEI and the polyanion was PAZO (poly[1-[4-(3-carboxy-
4-hydroxyphenylazo)benzenesulfonamido]-1,2-ethane-
diyl, sodium salt]). Trilayer patterns of PEI/PAZO/PEI
were assembled on a glass substrate (Figure 1). Adsorption
of SDS on the surface of the trilayer films was measured
using dynamic tensiometry and single wavelength ellip-
sometry. Dynamic contact angle measurements were used
to determine the surface wettability as a function of the
amount of SDS adsorbed, the kinetics of SDS adsorption
onto PEI, and the degree of interpenetration in the PEI/
PAZO/PEI/SDS system.
Experimental Section
The sequential adsorption of PEI (MW 70000) and PAZO, and
the preparation of the glass substrate, is described elsewhere.18-21
SDS (Aldrich, A.C.S. reagent, >99%) was recrystallized twice
(13) Decher, G. Science 1997, 277, 1232.
(14) Decher, G.; Hong, J. D.; Schmit, J. Thin Solid Films 1992, 210/
211, 831.
(15) Handbook of Polyelectrolytes and Their Applications, Volume 1:
Polyelectrolyte-Based Multilayers, Self-Assemblies and Nanostructures;
Tripathy, S. K., Jayant, K., Singh, N. H., MacDiarmin, A. G., Ed.;
American Scientific Publishers: Stevenson Ranch, CA, July 2002.
(16) Yoo, D.; Shiratori, S. S.; Rubner, M. F. Macromolecules 1998,
31, 4309.
(17) Chen, W.; McCarthy, T. J. Macromolecules 1997, 30, 78.
(18) Casson, J. L.; Wang, H.-L.; Roberts, J. B.; Parikh, A. N.; Robinson,
J. M.; Johal, M. S. J. Phys. Chem. B 2002, 106, 1697.
(19) Casson, J. L.; Johal M. S.; Roberts, J. B.; Wang, H.-L.; Robinson,
J. M. J. Phys. Chem. B 2000, 104, 11996.

10.1021/la034174g CCC: $25.00 2003 American Chemical Society

Published on Web 05/10/2003
Letters
Figure 1. Schematic of the PEI/PAZO/PEI trilayer film,
containing adsorbed SDS. The thickness of the interpenetrated
region was estimated from contact angle and ellipsometric
thickness measurements (see text). Structures of both PEI and
PAZO are also shown.
from ethyl acetate before use. PEI and PAZO were used as
received from Aldrich. Polydispersity data for these polyelec-
trolytes are not available. Ultrapure water (resistivity >18 M
cm) was used in all solution and substrate preparations. The
concentration of aqueous PEI and PAZO was fixed at 1 mM,
based on the molecular weight of the repeat unit. The pH values
of the SDS, PAZO, and PEI solutions were approximately neutral.
The sequence of adsorption on the substrate was first PEI (1
mM), followed by PAZO (1 mM), followed by PEI (1 mM), and
finally SDS (variable concentration). The resulting film is denoted
PEI/PAZO/PEI/SDS. In some experiments the concentration used
to adsorb the second (outer) PEI layer was varied. The adsorption
time for all species in all experiments was 5 min, except in kinetic
measurements where SDS adsorption time was varied from 0 to
200 s.
Dynamic advancing contact angles (a) were obtained using
the Wilhelmy plate method. In this method, the force (F) acting
on the glass substrate of dimension lwt (length, width, thickness)
submerged in water to a height h is given by F ) (Fglwt)g -
(FLhwt)g + 2(w + t) cos a. Fg and FL are the densities of the glass
substrate and water, respectively, and is the surface tension
of pure water (72.8 mN/m). By zeroing the weight of the substrate
((Fglwt)g), F then depends only on surface tension, contact angle,
substrate dimensions, and the upthrust term (FLhwt)g. Both
dynamic advancing and receding contact angles were determined
as a function of h using the Nima Technology dynamic surface
tensiometer (DST9005). The surface tension of pure water was
determined using the Du Nouy ring method, and this value was
then used to determine the contact angle. One inch square glass
(20) Chiarelli, P. A.; Johal, M. S.; Holmes, D. J.; Casson, J. L.;
Robinson, J. M.; Wang, H.-L. Langmiur 2002, 18, 168.
(21) Chiarelli, P. A.; Johal, M. S.; Casson, J. L.; Roberts, J. B.;
Robinson, J. M.; Wang, H.-L. Adv. Mater. 2001, 13, No. 15, August 3,
1167.
Langmuir, Vol. 19, No. 12, 2003 4881
substrates were immersed into water at a speed of 5 mm/min to
a depth of 15 mm below the liquid level. Approximately 1000
contact angle measurements were taken for a single immersion,
and the average advancing macroscopic contact angle is reported
here. The precise dimensions of the plate were determined by
optimizing the width to the precise surface tension determined
for water and optimizing the thickness so that the contact angle
was constant for all immersion depths. In practice, it was not
necessary to adjust thickness, since a constant contact angle
was always obtained for all immersion depths.
Film thickness measurements were collected on a Rudolph
Instruments Inc. (439L633P) single-wavelength manual pho-
toelectric ellipsometer. Single-sided polished silicon wafers (1
in. round) were used as substrates. Data were collected at a
beam incidence angle of 70 and a wavelength of 632.8 nm. A
refractive index of 1.5 + 0i was used to manually calculate the
ellipsometric film thicknesses from and parameters. The
substrate measurements (the native oxide layer) were subtracted
from the film measurements to determine total ellipsometric
film thickness. The native oxide layer on silicon is identical to
the surface of etched glass.1 Furthermore, others have reported
a common substrate effect using both substrate types.20
Results and Discussion
The advancing water contact angle of a freshly cleaned
(hydrophilic) glass side was determined to be 10 ( 1. In
the adsorbed polyelectrolyte film, the contact angle was
found to systematically and reproducibly alternate from
a value of 58 ( 2 to a value of 30 ( 2 as the terminal
layer was changed from PAZO to PEI. SDS was adsorbed
on the PEI/PAZO/PEI trilayer rather than on a single
PEI layer (Figure 1). Advancing contact angles of SDS
adsorbed on a single PEI layer show lack of reproducibility
and suggest a substrate effect as reported by others.16,18-21
The terminal (outer) PEI layer in the PEI/PAZO/PEI
trilayer is at least 40 from the glass substrate, and
advancing contact angle measurements are reproducible.
Figure 2a shows the change in the advancing contact
angle of the PEI/PAZO/PEI/SDS system as the concentra-
tion used to adsorb SDS is increased. Very small con-
centrations (<10-6 M) used to adsorb SDS cause large
changes in the measured contact angle of the film surface.
The contact angle increases from 30 (no SDS) to a
constant value of 80 beyond 0.01 mM. Even at much
higher SDS concentrations, the contact angle remains the
same (0.1 mM, 80 ( 2; 5.0 mM, 82 ( 2; 20 mM 82 (
2). Thus, saturation coverage is reached well below 8
mM, the critical micelle concentration (cmc) of SDS.22
Favorable electrostatic interactions of the anionic sur-
factant with positive sites in the outermost PEI layer likely
causes SDS saturation at a much smaller concentration
than the cmc. In fact, the critical aggregation concentration
(cac) of a polyelectrolyte-surfactant complex is generally
orders of magnitude smaller than the cmc.23,24 It is clear
from Figure 2a that the surface wettability can be
conveniently fine-tuned, from relatively hydrophilic (30)
to relatively hydrophobic (80), by simply adsorbing SDS
from very dilute solution. The observed increase in contact
angle is consistent with the anionic SDS headgroups
buried into the PEI layer, with the hydrophobic tail groups
exposed at the surface. Recent bulk phase studies indicate
that at large SDS concentrations, the polymer-surfactant
aggregate may become negatively charged, indicating that
the excess SDS is located at the surface of the aggregate.9
There was no evidence of excess SDS in our films, since
(22) Rosen, M. J. Surfactant and Interfacial Phenomena, 2nd ed.;
John Wiley & Sons: New York, 1989.
(23) Goddard, E. D. Colloids Surf. 1986, 19, 255.
(24) Lindman, B.; Thalberg, K. In Interactions of Surfactants with
Polymers and Proteins; Goddard, E. D., Ananthapadmanabhan, K. P.,
Eds.; CRC Press: Boca Raton, FL, 1993; p 203.
4882 Langmuir, Vol. 19, No. 12, 2003
Figure 2. (a) Advancing contact angles of the PEI/PAZO/PEI/
SDS surface as a function of concentration used to adsorb SDS.
(b) Advancing contact angles of the PEI/PAZO/PEI/SDS surface
as a function of adsorption time of SDS. The concentration used
to adsorb both the PEI layer and the PAZO layer in the PEI/
PAZO/PEI trilayers was fixed at 1 mM. The concentration used
to adsorb SDS in (b) was fixed at 0.001 mM.
any tail-to-tail adsorption at very high SDS concentration
would cause a decrease in contact angle.
The temporal stability of these films was tested by
keeping them in pure water for a period of 24 h and then
remeasuring both the UV-visible absorbance (PAZO has
a max ) 360 nm) and the contact angle. Both measure-
ments were identical before and after extended immersion
in water. Furthermore, contact angles of the same film
left in air for a few days remained unchanged.
Contact angles were measured as function of time.
Figure 2b shows the time-halted contact angles, from 0
to 200 s as SDS is adsorbed from a 0.001 mM solution.
The contact angle does not change beyond 100 s, suggesting
that equilibrium with respect to amount adsorbed has
been established by 100 s. Even when adsorbing from a
solution as high as 1 mM SDS, the time to reach
equilibrium is only marginally greater than 100 s. It is
interesting to compare this value to the equilibrium
adsorption times for PAZO (1 mM) and PEI (1 mM), both
of which are approximately twice as long.18
Letters
Figure 3. (O) Advancing contact angle of the PEI/PAZO/PEI
surface as a function of concentration used to adsorb PEI. (4)
Ellipsometric thickness measurements as a function of con-
centration used to adsorb PEI. The concentration used to adsorb
both the first (inner) PEI layer and the PAZO layer in the PEI/
PAZO/PEI trilayers was fixed at 1 mM.
As clearly seen above, the water contact angle is
sensitive to the composition of the surface layer. In fact,
it is possible to ascertain if fragments of the previously
adsorbed layer have penetrated into the surface of the
terminal adsorbed layer. It has been established that
whenever a thin layer is deposited onto a much thicker
layer, a large number of chain fragments from the
underlying thicker layer can penetrate into the outer
terminal layer; forming polycation/polyanion ion pairs.16,25
The extent of interpenetration can be determined by
measuring the contact angle. Figure 3 (open circles) shows
how the contact angle changes as PEI is adsorbed from
solutions of increasing concentration, onto an underlying
PAZO layer. The system is still the PEI/PAZO/PEI trilayer.
The contact angle decreases from 60 (no PEI) to a
limiting value of 30 beyond 0.5 mM PEI, characteristic
of a pure PEI surface. Below the 0.5 mM PEI concentration,
the surface is characterized by an intermediate contact
angle, indicating a mixed PAZO/PEI surface composition.
As the concentration of PEI increases, the surface becomes
richer in PEI. These measurements suggest that the
underlying PAZO layer interpenetrates the outer PEI layer
below an adsorbed amount corresponding to 0.5 mM PEI.
Above this concentration, the surface layer is composed
of pure PEI. The open triangles in Figure 3 show the
ellipsometric thickness measurements at the correspond-
ing concentrations of PEI. Initially, at 0 mM PEI, the film
is 10 and corresponds to a PEI/PAZO bilayer. The
deposition of the first PEI layer on glass typically shows
an increase in thickness of only a few angstroms at most,
since most of the polycation probably adsorbs within the
crevices of the etched glass substrate.18,19 As the second
(outer) PEI layer is adsorbed onto the underlying PAZO
layer, the thickness of the film increases. On comparison
of the thickness and contact angle measurements, it can
be seen that of the total 38 increase due to the terminal
PEI layer, 32 corresponds to the interpenetrated zone.
Only the last 6 ( 2 correspond to pure PEI.
(25) Chen, J.; Luo, G.; Cao, W. J. Colloid Interface Sci. 2001, 238,
62.
Letters
Table 1. Advancing Contact Angles of the
PEI/PAZO/PEI/SDS Surface Filmsa
a ( 2 a ( 2
[SDS]/mM ([PEI], 1 mM) ([PEI], 0.1 mM)
0 30 44
0.0001 53 45
0.001 68 44
0.01 82 48
a The data are shown for SDS adsorbed at the various concen-
trations. The second (outer) PEI layer was adsorbed from 1 mM
(column 2) and 0.1 mM (column 3).
It is likely that the relatively thin (few angstroms) outer
layer of pure PEI drives the SDS adsorption. If this is the
case, then no or very little SDS adsorption would be
expected from a trilayer whose second PEI layer is
adsorbed from solutions less than 0.5 mM. Table 1 shows
how the contact angle of the PEI/PAZO/PEI/SDS system
varies as a function of SDS concentration. The table shows
the data for outer PEI layers adsorbed from 1 and 0.1 mM
solutions. As expected, the contact angle increases from
30 to about 80 when adsorbing from 0 mM SDS to 0.01
mM SDS, when the outer PEI layer is adsorbed from a 1
mM solution. When constructing the outer PEI layer from
a 0.1 mM solution, the contact angle only marginally
increases as SDS is adsorbed from progressively higher
concentrations. Under these conditions, the surface is
composed of PEI and PAZO. The formation of many PEI-
Langmuir, Vol. 19, No. 12, 2003 4883
PAZO ion pairs at the surface inhibits significant SDS
adsorption. The data in Table 1 suggest that electrostatic
forces primarily govern SDS adsorption into PEI layers.
Summary
In summary, the SDS adsorption from dilute aqueous
solution onto a PEI surface causes an increase in contact
angle as a function of SDS concentration. We have shown
that both amount of adsorbed SDS and the extent of
interpenetration can both be used to fine-tune surface
wettability. Constructing films from varying concentra-
tions of PEI allowed the degree of PAZO interpenetration
to be qualitatively measured. Contact angle and ellipso-
metric thickness studies indicate that PAZO interpen-
etrates 32 into the terminal PEI layer, above which the
surface is composed entirely of PEI. Maximum SDS
adsorption is observed above the interpenetrated region,
consistent with maximum electrostatic interaction be-
tween the terminal PEI layer and SDS.
Acknowledgment. This work was supported by the
New College Division of Natural Sciences, the Camille
and Henry Dreyfus Foundation, and the New College
Foundation. We also thank Dr. Paul Scudder for useful
discussions.
LA034174G