Langmuir 1992,8, 838-847

Effect of Surfactant on the Solution Properties of

Hydrophobically Modified Polyacrylamide
S.Biggs, J. Selb, and F. Candau*
Institut Charles Sadron (CRM-EAHP), 6 Rue Boussingault, 67083 Strasbourg Cedex, France
Received September 26,1991. In Final Form: December 24,1991

The interactions, in aqueous solution, of sodium dodecyl sulfate (SDS)with copolymers of acrylamide
(AM) and N-(4-ethylphenyl)acrylamide (e$AM; [e$AMI/([AMl + [e$AMl) between 1and 1.3 mol 5%)
have been examined in the semidilute concentration range by rheology, fluorescence, and conductometry.
Data are discussed with regard to changes in the hydrophobe content, the molecular weight, and the
microstructure of the copolymers. The hydrophobic groups of such copolymer chains, in pure water
solution, are associated by either inter- or intrachain liaisons. The presence of interchain liaisons leads
to apparent viscositiesmuch greater than those seen for corresponding polyacrylamides. Addition of SDS
to these aqueous copolymersolutions was seen to causedramatic increasesin the viscosityat concentrations
below that of the critical micelle concentration (cmc). Examination of the viscosity both as a function
of shear rate and as a function of time (fixed shear rate) showed these solutions to have shear thickening,
rheopexic, and thixotropic behavior. This complex behavior is explained in terms of the balance between
inter- and intrachain liaisons and their effects on chain dimensions. Fluorescence and conductometric
data have shown that the SDS associates with the hydrophobicregions of the copolymers in a noncooperative
continuous binding process.

Introduction investigated:-" there are relatively few communications

The interaction of hydrophobically associating water-
soluble copolymers with small molecule surfactants, for
example sodium dodecyl sulfate (SDS), is of fundamental
importanke for many industrial applications such as
tertiary oil recovery and latex paint technology.' This
interest stems from the need to accurately control the
solution viscosity under a variety of shear conditions. As
a consequence,nonionic water-soluble copolymersof acryl-
amide prepared with low amounts of a hydrophobic
comonomer (<1mol %) have recently received a great
deal of attention in the specific Interchain
associations of the hydrophobe units, which are dispersed
along the polyacrylamide backbone, lead to solutions of
high viscosity at low concentrations and low shear rates.
In general, these solutions are shear thinning, as the shear
rate is increased the interactions are disrupted and the
viscosity decreases. If the shear is halted, the associations
between the polymer chains re-form and the solution
viscosity returns to its original value. While the properties
of these copolymers in pure solution have been thoroughly
* To whom correspondence should be addressed.
(1) (a) Polymers in Aqueous Media; Glass, J. E., Ed.; Advances in
Chemistry Series 223;American Chemical Society: Washington, DC, 1989.
(b) Evani, S.; Rose, G. D. Polym. Mater. Sci. Eng. 1987,57,477.
(2) (a) Peer, W. J. Polym. Mater. Sci. Eng. 1987,57,492. (b) Peer, W.
J. in ref la, p 381.
(3) (a) Valint, P. L., Jr.; Bock, J.;Schulz, D. N.Polym. Mater. Sci. Eng.
1987,57, 482. (b) Valint, P. L., Jr.; Bock, J.; Schulz, D. N. in ref la, p
399.
(4) (a) Bock, J.; Siano, D. B.; Valint, P. L., Jr.; Pace, S. J. Polym.
Mater. Sci. Eng. 1987.57, 487. (b) Bock, J.; Siano, D. B.; Valint, P. L.,
Jr.; Pace, S. J.<n ref l a , p 411.
(5) (a) Siano, D. B.; Bock, J.;Myer, P.; Valint, P. L., Jr. Polym. Mater.
Sci. Ene. 1987. 57. 609. (b) Siano, D. B.: Bock, J.: Mver, P.: Valint, P.
L., Jr. ref l a , p 425.
(6) Dowling, K. C.; Thomas, J. K. Macromolecules 1990, 23, 1059.
(7) Evani, S. U S . Patent 4 432 881, 1984.
(8) Mc Cormick, C. L.; Nonaka, T.; Johnson, C. B. Polymer 1988,29,
731.
(9) Schulz, D. N.; Kaladis, J. J.; Maurer, J. J.; Bock, J.; Pace, S. J.;
Schulz, W. W. Polymer 1987, 28, 2110.
(IO) Hill, A.; Candau, F.; Selb, J. Prog. Colloid Polym. Sci. 1991, 84,
61.
(11)Flynn, C. E.; Goodwin, J. W. In Polymers as Rheology Modifiers;
Schulz, D. N . , Glass, J. E., Eds.; ACS Symposium Series 462; American
Chemical Society: Washington, DC, 1991; Chapter 11, p 190.
on the interaction of hydrophobically associating co-
polymers and surfactants. In contrast, the interaction of
nonionic water-aoluble homopolymers with surfactants
in solution has been extensively investigated. An excellent
comprehensive review12 of such systems has been previ-
ously published and therefore only a brief review of the
major points will be presented here.
The interaction of poly(ethy1eneoxide) (PEO) with SDS
has been of particular interest to many research groups.
Studies of this interaction have been performed with a
wide range of techniques including vis~osity,'~ surface
tension,14dialysis equilibrium,15NMR,16 ESR,17neutron
scattering,'& and f l u ~ r e s ~ e n As
~ e a. ~result
~ ~ ~of~these
studies it has been concluded that PEO interacts with
SDS by inducing micellization of the surfactant onto the
polymer chains at concentrations below that of the cor-
responding critical micelle concentration (cmc) in pure
water. The existence of two critical surfactant concen-
trations, viz. C1 and CZ,in the system SDS/PEO was first
reported by Jones.14 C1 was defined as the surfactant
concentration at which interaction with the polymer first
occurs while C2 is that concentration at which all the
polymer sites available for interaction are saturated and
any further surfactant will form classic micelles free in
solution. C1 and C2 are always located below and above
the corresponding cmc, respectively. The micelles which
are formed at C1 have a smaller aggregation number, a
higher degree of charge delocalization, and a more open
structure19 than those of a regular SDS micelle. The
polymer chain is believed to envelope the micelles with
the hydrophilic regions of the chain associated with the
ionic head groups and the hydrophobic regions protecting
(12) Goddard, E. D. Colloids Surf. 1986,19, 255.
(13)Francois, J.; Dayantis, J.; Sabbadin, J. Eur. Polym. J. 1985, 21,
165.
(14) Jones, M. N. J. Colloid Interface Sci. 1967, 23, 36.
(15) Shirahama, K. Colloid Polym. Sci. 1974, 252, 978.
(16) Cabane, B. J. Phys. Chem. 1977,81, 1639.
(17) Shirahama, K.; Tohdo, M.; Murahashi, M. J. Colloid Interface
Sci. 1982, 86, 282.
(18)Cabane, B.; Duplessix, R. J.Phys. (Paris) 1987, 48, 651.
(19) Zana, R.; Lianos, P.; Lang, J. J.Phys. Chem. 1985, 89, 41.
(20) Turro, N. J.; Baretz, B. H.; Kuo, P.-L. Macromolecules 1984,17,
1321.

0 1992 American Chemical Society

Hydrophobically Modified Polyacrylamide
the exposed hydrophobic areas of the micelle. Such a
conformation which limits the contact of the hydrophobic
regions of the micelles with water is obviouslyenergetically
favorable and therefore the micelles form at a lower sur-
factant concentration, i.e. C1. These findings led Shira-
hama et to propose the so-called "necklacen model of
the complex in which the beads are the SDS clusters and
the string is the polymer chain. In such a model the chain
is elongated to reduce the electrostatic repulsion between
the clusters, a proposal which is supported by viscosi-
metric data which show polyelectrolyte behavior for the
~omp1exes.l~ There is no evidence at present to suggest
aggregates comprising more than one chain for such ho-
mopolymer/surfactant systems in the range of concen-
trations studied. Other homopolymers investigated for
their interaction behavior in aqueous surfactant solution
include poly(vinylpyrro1idone) poly(viny1 acetate) ,24
,22923
and p~lyacrylamide.~~ In the case of polyacrylamide it
has been shown that there is no interaction with SDS in
aqueous solution.
Studies of the solution properties of hydrophobically
modified copolymers with surfactant are much less ex-
tensive. For such systems it is necessary to consider the
microstructure of the copolymer, the presence of charge
either in the chain backbone or on the pendant hydro-
phobic groups, and the size of these pendant groups. I t is
also important to consider the chemical nature (anionic,
cationic, or nonionic), size, and structure of the surfac-
tant.26127The interplay of two or more of these factors can
lead to widely differing properties. For instance, addition
of surfactant, particularly nonionic or cationic, to an
aqueous solution of hydrophobically modified poly(s0-
dium acrylate) has been shown to cause a marked viscosity
enhancement2* However, results for a copolymer of acryl-
amide and an N-alkylacrylamide in the presence of anionic
surfactant suggest that the surfactant disrupts interchain
liaisons causing a decrease in solution viscosity.*l0
As outlined above, the presence of hydrophobic groups
along the copolymer backbone may allow, dependent upon
the chain flexibility,both inter- and intrachain associations
which are in many ways analogous to micellar aggregates.
Small molecule surfactants, when added to such a system,
can interact with these hydrophobic groups leading to the
formation of mixed micelle-like These
mixed micelles either may promote chain cross-linking by
acting as a bridge between two polymer chains or may
disrupt such linkages by solubilizing each hydrophobic
group of a polymer chain into a single micelle. It has been
previously reporteds32 that, for a hydrophobically mod-
(21)Shirahama, K.;Tsujii, K.; Takagi, T. J. Biochem. 1974,75, 309.
(22)Fishman, M. L.; Elrich, F. R. J. Phys. Chem. 1975,79,2740.
(23)Arai, H.; Murata, M.; Shinoda, K. J. Colloid Interface Sci. 1971,
37,223.
(24)Tadros, Th.F. J. Colloid Interface Sci. 1974,46,528.
(25)Sabbadin,J.;Le Moigne, J.;Franpis, J. In SurfactantsinSolution;
Mittal, K. L., Lindman, B., Eds.; Plenum Publishing: New York, 1984;
Vol. 2,p 1377.
(26)Ruckenstein, E.; Huber, G.; Hoffmann, H. Langmuir 1987,3,382.
(27)Nagarajan, R. J. Chem. Phys. 1989,90,1980.
(28)Wang, K. T.; Iliopoulos, I.; Audebert, R. In Water-Soluble
Polymers. Synthesis, Solution Properties and Applications; Shalaby,
S.W., McCormick,C. L., Butler, G. B., Eds.; ACS Symposium Series467,
American Chemical Society: Washington, DC, 1991;Chapter 14,p 218.
(29)Sau, A. C.; Landoll, L. M. in ref 1, Chapter 18,p 353.
(30)Hulden, M.;Sjoblom,E. In64thACSColloidandSurfaceScience
Symposium Abstracts; American Chemical Society: Washington, DC,
1990.
(31) Dualeh, A. J.; Steiner, C. A. Macromolecules 1990,23,251.
(32)Steiner, C. A. J. Appl. Polym. Sci. 1991,42, 1493.
(33)(a) Lundberg, D.J.; Glass, J. E. Polym. Mater. Sci. Eng. 1989,61,
533. (b) Karunasena, A.; Brown, R. G.; Glass, J. E. in ref la, p 495. (c)
Lundberg, D. J.; Ma, Z.; Alahapperuna, K.; Glass, J. E. in ref 11,Chapter
14,p 234.
(34)Iliopoulos, I.; Wang, K. T.; Audebert, R. Langmuir 1991,7 , 617.
Langmuir, Vol. 8, No. 3, 1992 839
Table I. Physical Properties of the Copolymers
~
copolymer % monomers hydrophobe) mol wt,'
sample code conversiona mol % Mw (Xl0-9
M 51 44.8 1.30 3.13
M 52 52.6 1.25 3.12
M 53 62.7 1.12 2.90
M 54 73.5 1.09 2.67
M 55 83.0 1.03 2.60
M 56 87.8 1.03 2.57
a Monomers conversion as a percentage of total initial monomers
*
feed in polymerization. Mol % = [hydrophobe]/([acrylamide] +
[hydrophobe]). Determined from light scattering measurements.
ified hydroxyethyl cellulose copolymer in SDS solution,
both increases and decreases in solution viscosity were
observed as a function of increasing SDS concentration
below the cmc. The increase in viscosity observed at low
SDS concentrations was attributed to an increase in chain
cross-linking by the formation of mixed micelles. As the
surfactant cmc is approached, however, there is sufficient
surfactant to solubilize each hydrophobe separately and
so the viscosity falls. Similar behavior, in SDS solution,
has also been reported both for hydrophobically modified
ethoxylated urethane (HEUR) copolymers33and for a hy-
drophobically modified poly(sodium acrylate) in SDS
solution.34
In this paper we report the results of investigations into
the effects of SDS on the semidilute solution properties
of copolymers of acrylamide and N- (4-ethylpheny1)acryl-
amide at surfactant concentrations ranging from below to
above the cmc in pure water solution. The effects of
varying the hydrophobe content of the copolymer samples
in this region of enhanced solution viscosity will be
discussed. Rheological behavior as a function of (i) the
shear rate and (ii) the shear time at constant shear rate,
in this region, is investigated. Complementary data
obtained by fluorescence and conductometry will also be
presented. In the light of these data the relative impor-
tance of inter- and intramolecular interactions for the
copolymers as a function of shear conditions will be
discussed.
Experimental Section
Materials. Copolymers of acrylamide andN-(4-ethylphenyl)-
acrylamide were prepared by free-radical copolymerization in
an aqueous micellar medium. All the copolymer samples
examined here were prepared during a single copolymerization
reaction. The termination of aliquots of this reaction at different
degrees of total monomers conversion led to copolymer samples
with differing degrees of average hydrophobe content.35 Data
for the hydrophobe content and the degree of total monomers
conversion for these copolymers are given in Table I. The
copolymers chosen for study here varied in their average
hydrophobic monomer content between 1 and 1.3 mol %
([monomer]/ [monomers]). The distribution of the hydrophobe
units along the acrylamide backbone has not been determined.
However, the use of a micellar reaction medium is believed to
lead to copolymers with a structure in which small blocks of
hydrophobe are dispersed along the polymer chain. A full
discussion of the effects on the copolymer structure of using a
micellar reaction medium is given in a previous publication from
this l a b ~ r a t o r y . ~The
~ molecular weights, determined from
classical light scattering measurements, varied in the range (2.5-
3.2) X 108.
Before being used in the preparation of solutions, each
copolymer was dried for 24 h a t 50 "C to eliminate any residual
moisture. Samples were then weighed immediately and sealed
prior to measurement.
(35)Biggs, S.;Hill, A.; Selb, J.; Candau, F. J. Phys. Chem. 1992,96,
1505.
840 Langmuir, Vol. 8, No. 3, 1992 Biggs et al.
Sodiumdodecylsulfate (SDS) (TouzartandMatignon, >99.5%
pure) was used as received without further purification. The
critical micelle concentration (cmc) determined by conductivity
was 8 X 10-3 mol L-l and by fluorescence was 8.2 X mol L-l.
Pyrene was zone refined and kindly supplied by Dr. A. Mal-
liaris, NRC Democritos, Athens, Greece.
All water used here was doubly distilled from an all-glass
apparatus.
;'Ouo
W t
Methods. (1) Conductometry. Samples of the copolymer,
at appropriate concentrations, were dissolved in 20 cm3 of water
with gentle agitation over 24 h. These stock solutions were divided
into two lo-cm3 aliquots. SDS was then added to one of these
.-
VI
,x 75t
.- 50t
0

fractions to give a solution of polymer a t 1% (w/w) surfactant
concentration in water.
The conductivity measurements at a fixed concentration of
copolymer, as a function of surfactant concentration, were then
performed by titrating the portion a t 1% SDS into the nonsur-
factant containing portion in small aliquots. Conductivities were
recorded using a Universal Bridge B905 (Wayne-Kerr) and a
conductivity cell (Tacussel CM02/550).
(2) Fluorescence. From a filtered stock solution of water
saturated with pyrene, copolymer/SDS solutions were prepared
at appropriate copolymer and surfactant concentrations. Com-
plete dissolution of all the components was performed with gentle
agitation for 24 h. Before measurement, the solutions were left
without agitation a further 24 h.
Steady-state fluorescence measurements of the emission
spectra for all samples were performed using a Hitachi F-4010
spectrophotometer. The excitation wavelength used was 335 nm
with a bandwidth of 1.5nm. The ratio 13/11of the intensities of
the third and the first vibronic peaks for the emission spectrum
for pyrene provides an estimate of the local environment, i.e.
hydrophobic or hydrophilic, sensed by the fluorescent probe.36
In general, for the spectra, the first and third vibronic peaks
were situated a t 374 and 385 nm, respectively.
(3) Rheological Measurements: Viscosity-time measure-
menta were performed using a Contraves Low Shear 30 instrument
interfaced to a personal computer and driven by a software
package supplied by the manufacturers.
Viscosity-shear data were obtained using a Carri-Med con-
trolled stress rheometer with a cone-plate geometry: (acrylic cone,
diameter 6 cm, angle lo).
Copolymer/surfactant solutions were prepared by dissolution
of the copolymers, at appropriate concentrations, in stock aqueous
solutions of SDS. These stock solutions were pre-prepared at a
range of concentrations between 0.01% and 0.4% (w/w). No
agitation was applied during dissolution of the copolymers which
was usually complete a t between one and two days. For certain
samples of high viscosity a slow tumbling procedure was applied
to ensure complete homogeneity of the final solution.
Results and Discussion
(1) Solution Properties of the Copolymers in the
Absence of Surfactant, Apparent viscosities, measured
at a single shear rate (y = 1 s-l), as a function of average
hydrophobe content, in the absence of SDS, are shown in
Figure 1. Details of the hydrophobe contents and mo-
lecular weights of all the copolymers investigated here are
given in Table I. Clearly, the viscosity at a constant
copolymer concentration is directly related t o the average
hydrophobe content of the copolymer samples. A typical
example of the viscosity variation as a function of shear
rate, for copolymer sample M51, is presented in Figure 2.
It should be noted that all the copolymer samples
investigated here exhibited shear thinning behavior in
solutions free of surfactants.
Before considering the results of this study in detail, it
is necessary to define why hydrophobic groups interact in
aqueous solution and at what concentration of copolymer
such interchain associations may occur'.
(36) Kalyanasundaram, K.; Thomas, J. K. J.Am. Chem. SOC.1977,99,
2039.
>
25 t i
0 1
1.0 1.1 1.2 1.3 1.4
percentage hydrophobe
Figure 1. Variation of the apparent viscosity as a function of
hydrophobe content (mol % ) for copolymers of acrylamide and
N-(4-ethylpheny1)acrylamide in aqueous solution at a concen-
tration of 1%(w/w) (shear rate, y = 1 s-l).
1
1 10 100 1000
shear rate s-'
Figure 2. Effect of shear rate on the apparent viscosity for an
aqueous solution of copolymer sample M 51 at a concentration
of 0.5% (w/w).
The removal of any hydrophobic chain from aqueous
solution, into a micellar aggregate, is always associated
with both a large increase in entropy and a small enthal-
pic decrease.37 The entropy gain is the driving force,
therefore, for the aggregation of hydrophobic groups in
aqueous solution. This entropy gain originates from the
breakdown of a highly ordered structure of the water
around the hydrophobe as it is removed from solution.
Any aggregation of hydrophobic groups which leads to a
net decrease in the number of hydrophobe/water contacts
will therefore be favored due to a large decrease in the free
energy.
Data from fluorescence measurements of 13/11 as a
function of copolymer concentration (for sample M55) in
the absence of surfactant are given in Figure 3. The values
of Z3/11 are seen to rise steadily, as a function of copolymer
concentration, indicating that at all concentrations, or at
least those as low as 0.001 96 (w/w), hydrophobic regions
are found in the solutions. Asimilar increase of the solution
hydrophobicity, with copolymer concentration, has been
reported previously, for copolymers of acrylamide-alkyl-
acrylamide, when studied by fluorescence using either
pyrene" or 8-anilino-1-naphthalene~ulfonate~ as a probe.
(37) Tanford, C. The Hydrophobic Effect. Formation of micelles and
biological membranes, 2nd ed.; Wiley-Interscience: New York, 1980.
Hydrophobically Modified Polyacrylamide
0.7 c I
IP
I ,
0.0 0.5 1.0 1.5 2.0
copolymer concentration (wt.%)
Figure 3. Variation of Z3/Z1 for a pyrene fluorescent probe in
aqueous solutions of copolymer sample M 55, as a function of
copolymer concentration (wt 5% 1.
Thus, in hydrophobically associating copolymer solutions,
intrachain associations may be considered to occur at any
concentration. However, definition of the presence or
absence of a minimum concentration for interchain liaisons
is not at all clear. Winnik38has reported the presence of
interchain interactions at copolymer concentrations con-
siderably lower than the critical overlap concentration (e*),
a result supported by extensional flow data for copolymers
in solution.39 It is certain, therefore, that for copolymer
concentrations equal to or greater than e*, substantial
interchain liaisons may occur. In our case, the copolymer
concentration was always equal to or greater than 0.5%
(w/w). If we assume that c * [ d is of the order of 1 and
using a known value of the intrinsic viscosity’0 [TI = 700
for a polyacrylamide of M , = 2.5 X lo6, we calculate. a
value of c* = 0.14% (w/w). This is 4 times smaller than
our working concentration and so, even allowing for the
diminished values of the intrinsic viscosity4Jl (-2 times
smaller) seen for associating copolymers, we may expect
interchain liaisons to occur if they are energetically
favorable.
The copolymer samples investigated here exhibit a
relatively large viscosity change on passing from a sample
with an average hydrophobe content of 1.3 mol % to one
of 1.03 mol % (Figure 1). This change from 122 to 38 cP,
a t a copolymer concentration of 1 % (w/w) in water, is due
to a combination of factors: the hydrophobe content, the
copolymer molecular weight, and the distribution of this
hydrophobe within the copolymer samples. The effects
on the solution viscosity, in the semidilute concentration
range, of altering either the hydrophobe content or the
molecular weight have been previously i n v e ~ t i g a t e d . ~ ~ ~formed homopolymers28~29and will have therefore a
However, systematic studies of the effects of changes in
the hydrophobe distribution have not been reported. The
role of each of these three factors, in this system, will
therefore be considered separately.
(a) Hydrophobe Content. Previous reports have
shown that, at a fixed concentration, an increase in the
hydrophobe content causes an increase in the solution
v i s c o ~ i t y . ~ Direct
~ ~ J ~ comparisons with this work are
difficult, however, since for comparable acrylamideIN-
alkylacrylamidecopolymer systems no published data exist
at concentrations greater than 0.4% (w/w).~ Furthermore,
(38) Winnik, F.M. Macromolecules 1989,22, 734.
(39) Odell, J. A.; Keller, A.; Muller, A. J. in ref la,Chapter 11, p 193.
(40) Kulicke, W.M.; Kniewske, R.; Klein, J. Prog. Polym. Sci. 1982,
8,373.
Langmuir, Vol. 8, No. 3, 1992 841
I for those associating copolymer systems which have been
investigated at 1 % concentration,4l the molecular weights
were of the order of lo5 and not lo6 as here.
Flynn and Goodwinll have reported the presence of a
critical hydrophobe concentration cc, for similar copoly-
mers in solution, above which rapid increases in the number
of interchain associations are observed. Increases in the
hydrophobe content of their copolymers led to a decrease
of the critical concentration and a more rapid increase in
the viscosity with concentration after cc. At any constant
concentration above cc, therefore, an increase in hydro-
phobe content was seen to lead to an increase in solution
viscosity as observed here.
(b) Copolymer Molecular Weight. As shownin Table
I, the copolymer weight average molecular weights (M,)
decrease with increasing monomers conversion. A full
discussion of this point is given elsewhere35and will not,
therefore, be considered here. Instead, we will concentrate
on the differences in copolymer solution viscosities (at
constant concentration) when employing copolymers of
different molecular weights. It is known for polyacryla-
mide40that, at a solution concentration of 1 % (w/w), the
viscosity, TI,is approximately proportional to M,.2.5 Thus,
a change of 20% in the M , can lead to changes of up to
1.5 times in the apparent viscosity. While in the case of
hydrophobically modified copolymers of acrylamide the
inter- and intrachain liaisons will complicate such a
calculation, it is clear that the variation in M , of the
samples (Table I) will also play an important role in the
viscosity variations observed here.
( c ) Hydrophobe D i s t r i b u t i o n w i t h i n t h e
Copolymers. The distribution of hydrophobe units within
the copolymers used here has not, as yet, been absolutely
determined. The following points are, however, known to
be true.35 Micellar copolymerization has been shown to
give copolymers which, at low levels of monomer conver-
sion, have a composition very rich in hydrophobe, with
the hydrophobe being distributed along the acrylamide
backbone in small blocks. As the copolymerization
proceeds, the amount of hydrophobe incorporated into
each chain falls, with both the size of the blocks and their
number decreasing. It is important to recall that all the
copolymers used here were prepared during one copo-
lymerization reaction, therefore those copolymers recov-
ered at high levels of conversion contain a mixture of all
the samples at lower conversion levels plus further
copolymers at lower contents of hydrophobe. The average
hydrophobe content of the samples falls therefore with
increasing conversion (Table I). This polydisperse “blocky”
nature of the copolymers, characteristic of micellar co-
polymerization,contrasts with other associatingcopolymer
systems in which the hydrophobic moieties of the copol-
ymers are introduced by chemical modification of pre-
relatively regular distribution of single hydrophobe units
throughout the copolymer samples. These differences are
represented schematically in Figure 4.
It is well-known that the strength, or more precisely the
free energy change, of any hydrophobic interaction de-
pends on both the number of hydrophobic units and their
relative hydrophobicity. For example, changing the size
of the hydrophobic monomers from an aliphatic CSto an
aliphatic C12 has been shown to substantially increase the
solution viscosity for otherwise identical copolymers.8
While the aromatic CShydrophobic monomers used here
may not have a high hydrophobicity when employed
(41) Jenkins, R.D.Ph.D. Thesis, Lehigh University, Bethlehem PA,
1990.
842 Langmuir, Vol. 8,No. 3, 1992
Micellar Chemical
copolymerisation modification
I increasing
conversion
chemical
reaction
Figure 4. Schematicrepresentation of (i) the changing average
distribution of hydrophobic monomer within any copolymer
sample as a function of micellar copolymerization time and (ii)
the distributionof hydrophobe units in copolymers prepared by
chemical modification: monomer units, 0 .
separately, if they are found as small blocks within the
polymer backbone their hydrophobicity can be considered
to be much greater and they will be more likely to form
either inter- or intrachain aggregates. It was previously
reported that copolymers with the same molar quantity
of hydrophobe but with one having a blocky structure and
the other a structure in which the monomer is dispersed
as discrete units will have very different viscosities in
solution.10 The blocky copolymer was shown to have much
higher viscosities in aqueous solution at all the concen-
trations examined.
At low levels of conversion virtually all of the hydro-
phobe is found in small blocks and will therefore prefer
to form either inter- or intrachain liaisons protected from
solution by the hydrophilic backbone. At higher levels of
conversion, those copolymer chains with the large blocks
are still present, although their concentration will be
decreased by dilution with chains containing fewer more
singly distributed hydrophobes. These single units are
more easily solubilized as discrete units, and therefore the
proportion of interchain liaisons will fall. Thus, the
decrease of viscosity with increasing monomers conversion
(Table I) or, in other words, decreasing hydrophobe content
(Figure 1) must also be due, in part, to the increasing
proportion of copolymers with both smaller and fewer
blocks at higher levels of monomers conversion.
It is clear, therefore, that each of these parameters plays
an important role in the viscosity of these hydrophobi-
cally modified copolymers in solution. The relative
importance of each, however, has yet to be determined.
(2) “Steady State” Solution Properties of the Co-
polymers in the Presence of Surfactant. Addition of
SDS to the aqueous copolymer solutions was seen to
dramatically alter their rheological behavior. In Figure 5
the apparent viscosities as a function of SDSconcentration,
for copolymers of differing average hydrophobe content,
Biggs et al.
? I 1
4
C
0 5
L
(d
a
2 0
0.0 0.1 0.2
.; .;
percentage SDS (w/w)
Figure 5. Apparent viscosities as a function of the SDS
concentration (wt 5% ) for copolymers of differing molar hydro-
phobe contents: M 51,O;M 52,O; M 53, 0 ;M 54, M 55,
M 56, A. (Concentration of copolymers = 0.5% (w/w);shear
rate, y = 0.5 s-l.)
measured at a single shear rate ($ = 0.5 s-l) are given. The
viscosity values shown are those observed when at equi-
librium with respect to shear time. For many of the
copolymer/surfactant systems, time-dependent shear be-
havior was seen initially (see later), although after a certain
period (usually 3-5 min) a constant value was always
attained. Since we discuss these constant equilibrium
values in this section, we use the term steady state to
describe the viscosity values given.
Three regions of behavior may be identified from these
curves: region I occurs at very low SDS concentrations
(<0.01% (w/w)) where the viscosity is not seen to change
greatly from that of the pure copolymer solution; region
I1is characterized by large viscosity enhancements; region
I11 is located at SDS concentrations equal to or greater
than the cmc where the viscosity is observed to be
approximately the same as the pure copolymer solution
and to show very little variation. From the measurements
performed here, differences in the relative size of each
region as a function of the average hydrophobe content
are not evident. It is clear, however, that the magnitude
of the peak viscosity is very sensitive to the amount of
hydrophobe in each sample. At the highest hydrophobe
contents measured, the absolute maximum in the apparent
viscosity was too large to be measured with the LS 30
rheometer. However, the points on either side were
recorded giving an indication of the peakmagnitudes. Data
on the exact position of the maxima were also not
determined due to the preclusive number of solutions
which would be required for each copolymer sample.
The results of Figure 5 appear to be in agreement with
previously reported data.24-34Once again, however, direct
comparison is difficult because of the very different nature
of the copolymer samples. Despite this, it should be noted
that the region of increased viscosity seen here was at
approximately the same concentrations of surfactant given
in these earlier reports.
Before discussion of the more complex rheological
behavior in section 3, it is necessary to consider why the
presence of surfactant causes an increase in these “steady-
state”solution viscosities. For a copolymer solution above
c*, in any hydrophobically modified copolymer chain there
will be both inter- and intrachain liaisons of the hydro-
phobe. The hydrophilic polymer chains of the copolymers
will then surround these hydrophobe regions in a highly
coiled conformation to protect them from the solvent.
Hydrophobically Modified Polyacrylamide Langmuir, Vol. 8, No. 3, 1992 843
Obviously such a highly coiled and restricted conformation
does not represent an energetically favorable state for the
hydrophilic chains. However, the gain in entropy of
removing the hydrophobe from solution is much greater
and therefore overrides this loss of chain entropy. The
presence of surfactant micelles allows the solubilization
of the hydrophobe and its protection from the water by
the surfactant head groups. This in turn liberates the
hydrophilic chains, enabling them to rearrange into a more
energetically favorable state. As the surfactant is initially
added, at a concentration of 0.5% (w/w) copolymer, there
is already a substantial quantity of hydrophobe in the
solution. It would seem feasible therefore that the sur-
factant associates directly with those hydrophobic regions
of the copolymer solution in a noncooperative process, a
hypothesis which is supported by the conductance and
fluorescence data (see later). Similar behavior has been
proposed for a variety of systems in which hydrophobic
domains exist in solution before the addition of any
~ u r f a c t a n t . ~As
~ - the
~ ~ concentration of surfactant in-
creases, a point is reached at which there is sufficient to
effectively solubilize the hydrophobes, forming mixed mi-
celles, without the assistance of the hydrophilic chains.
This corresponds to the onset of the dramatic increases
in viscosity, region I1 in Figure 5. There is not, as yet,
sufficient surfactant to solubilize each region of hydro-
phobe separately, and so two or more regions, either of the
same chain or of others, are incorporated into the same
micelle. Obviously, as further surfactant is added and we
approach the cmc, each hydrophobe region may become
solubilized by a single micelle leading to a decrease in the
viscosity. These processes are represented schematically
in Figure 6.
The large increases in the observed viscosity for all the
samples in the presence of SDS suggest that in pure water Figure 6. Schematic representation of the interaction of the
copolymerswith SDS at three differentsurfactantconcentrations
solution the number of interchain liaisons is considerably correspondingto the three regions displayed in Figure 5. SDS,
smaller than those of an intrachain nature, a result --; hydrophobe blocks, 0.
predicted theoretically in a recent publication by Balazs
and H u . ~ ~ 1.0 I""''''\
The magnitude of the maxima (Figure 5 ) were, as in the
absence of surfactant, disproportionally larger with higher
levels of hydrophobe (cf. Figure 1). Addition of the sur-
factant facilitates interchain linking, as described above.
As discussed in section IC, the chains at low levels of
monomer conversion have a very blocky composition and
therefore an increased hydrophobicity (cf. Figure 4). Thus,
addition of surfactant will result in a large lowering of the
free energy both from the formation of mixed micelles
and also from the release of the restriction of the hydro-
philic chain motion. At higher levels of monomer con-
version there is an increased proportion of hydrophobe
units which are distributed as smaller blocks. These blocks
will not have the same tendency to form mixed micelles
due to the much smaller energy gain of forming a mixed
0.5 ' 0.00 1
I ,

0.01 0.1
I

micelle with less hydrophobe and the very small release
of chain restriction. The dominance of larger hydrophobe
blocks for the formation of mixed micelle interchain
liaisons therefore means that those samples with the hy-
drophobe distributed as blocks will have a much greater
viscosity increase due to the formation of disproportion-
ately more linkages.
(42) Winnik, F. M.; Ringsdorf, H.; Venzmer, J. Langmuir 1991,7,905.
(43) Winnik, F. M.; Ringsdorf, H.; Venzmer, J. Langmuir 1991,7,912.
(44) Benrraou, M.; Zana, R.; Varoqui,R.;Pefferkorn, E. Submitted for
publication in J. Phys. Chem.
(45)Hu, Y.-Z.;Zhao, C.-L.; Winnik, M. A.; Sundararajan,P. R. Lang-
muir 1990, 6, 880.
(46) Balazs, A. C.; Hu, J . Y. Langmuir 1989,5, 1230 and 1253.
Concentration SDS (mol/l)
Figure 7. Variation of 13/11 for a pyrene fluorescent probe in
aqueous copolymer solutions as a function of the SDS concen-
tration (log scale): (a) SDS, A; (b) M 54, 0;(c) M 52, 0.
Data of 13/11versus SDS concentration for two copolymer
samples are given in Figure 7. The curve for SDS in the
absence of copolymer is also given for reference. The
curves of SDS/copolymer solutions were seen to rise
gradually toward a plateau region which corresponded to
those SDS concentrations of maximum viscosity. After
this region the curves were seen to follow closely the
behavior for that of the pure SDS solution after the cmc.
Up to the cmc the difference in 13/11values in the presence

600
500 -
oomo-0%
9f
h .d'
3400 - %
; I
I 4-
al
:
2 300 -
omC
%
"
om! I
I
; E0
as 3 ? I a
C 0% I
8 200 - 4 I
I
I 1
100-
Pg
,f
I
I
I shear rate s-'
I
L? I Figure 9. Effect of the shear rate on the apparent viscosity for
I
8'
I CYC
I ,
01 '
and absence of copolymer can be interpreted as the
increased hydrophobic character of the copolymer solu-
tions.
The absence of a sharp cmc for the copolymer/surfac-
tant solutions (Figure 7) supports the previous hypothesis
of a continuous association process of the SDS with the
hydrophobicregions of the copolymers. These data agree
directly with a recent report by Winnik et al.42for hy-
drophobically modified copolymers of poly(N-isopropyl-
acrylamide) in the presence of SDS. Their fluorescence
results show a gradually increasing value of 1 3 / 1 1 with
increasing surfactant concentration which was attributed
to a noncooperativebinding mechanism of the surfactant
to the hydrophobic regions of the copolymers.
The conductance data as a function of SDS concen-
tration for two copolymer samples at a concentration of
0.5% (w/w) are presented in Figure 8. Data for one of
these copolymer samples at a lower concentration (0.1%
(w/w))are also given as is the curve for a pure SDS solution.
The presence of the copolymer, at a concentration of 0.5 5%
(wlw), is seen to cause a decrease in the conductance at
all concentrations of SDS due to association of the sur-
factant with the macromolecules. Below the surfactant
cmc the difference between the conductance values with
and without copolymer was seen to increase with increasing
surfactant concentrations. Increasing the hydrophobe
content of the copolymer was seen to cause a slight decrease
in the conductivity. At the two copolymer concentrations
for the same sample, the conductivity was lower at the
higher concentration. Above the cmc of the SDS each
curve was seen to be parallel with equivalent gradients,
the difference in conductance increasing from the values
of SDS with increasing contents of hydrophobe.
Further evidence for noncooperative binding is found
in these results. If the surfactant is initially free in solution,
as discrete molecules, it may be expected that the curves
in the presence of copolymer would correspond exactly
with that of the pure SDS solution at low surfactant
concentrations. A deviation of the curves would only be
seen at some concentration which correspondsto a mixed
micelle cmc. No such curves were obtained at all con-
centrations and hydrophobe contents examined here.
Biggs et al.
.
45.1
.-x
c
UI
0
.-0>
v)
C
0
n t
1
3
1 10 100 1000
an aqueous solution of copolymer sample M 52 (concentration
= 0.6% (w/w)) at three concentrations of SDS (w/w):(a) 0.01%;
(b) 0.02%; ( c ) 0.25%.
This continuous aggregation process contrasts with the
earlier studies on water-soluble homopolymers and sur-
factants in which a cmc was observed at some concentration
lower than the cmc of the surfactant in pure water solution.
While there is no lower critical surfactant concentration,
CI, as defined by Jones,14we might expect to see differences
in the upper critical concentration, CZ. However, a t the
different concentrations of copolymer and hydrophobe
contents measured here, no measurable differences in the
Cp values were recorded. This is probably due, however,
to the relatively low overall amounts of hydrophobe in the
system. In the case of homopolymers which interact with
surfactants, the number of interaction sites is very large.
Therefore a change in concentration of the polymer causes
a large and easily measurable change in the number of
interactions. It was already noted that polyacrylamide
does not interact with SDS,25and therefore in our case the
only possible sites of cooperationare with the hydrophobe
groups. Since these groups are considered to be grouped
along the polyacrylamide backbone in small blocks, at a
concentration of between 1 and 1.3 mol %, they will be
separated by relatively large blocks of acrylamide. Thus
any electrostatic interactions of associated micelles will
be very slight, contrary to the homopolymerlSDS systems
where the adsorption of micelles confers a polyelectrolyte
behavior on the polymer. So, the increased viscosities
seen here in the presence of SDS are caused solely by
changes in the numbers of chain-chain attractions and
not to increased coil dimensions as a result of polyelec-
trolyte charge repulsions.
(3) Viscosity of Copolymer/Surfactant Solutions
as a Function of Shear Rata and Shear Time. Viscosity
as a function of shear rate for a single copolymer sample,
but within the three regions of existence described above,
are shown in Figure 9. It can be seen that for regions I
and I11 (curves a and c) the copolymer/SDS mixtures
exhibit shear thinning with increasing shear rate, a
comportment seen also for the pure copolymer solutions
(cf. Figure 2). For the sample located in region I1 (curve
9b) the viscosity-shear rate behavior is very different, the
sample initially exhibiting shear thickening before be-
coming shear thinning at higher shear rates. The shear
rate range of this shear thickening region was seen to have
only a small dependence on the hydrophobe content of
the copolymer, while the height of the maximum was again
sensitive to the amount of hydrophobe in the copolymer.
A closer examination of those samples located in region
Hydrophobically Modified Polyacrylamide
’5 {;I I .%0.2
- 0 2 4 6 8 10
time (mins)
Figure 10. Apparent viscosity as a function of shear time, at a
constant shear rate (y = 0.5 s-l) for copolymer sample M51 at
three different concentrations of SDS: (a) 0.05%; (b) 0.1%; (c)
0.15%.
i the same sample at a shear rate of y = 1 s-l, but before
4 t
i1
$2
$ 0
4 o
2 3 4 5 1
time (mins)
Figure 11. Apparent viscosity as a function of shear time a t a
fixed shear rate of y = 5 s-l: copolymer sample, M 52;
SDS concentration = 0.02% (w/w).
concentration = 0.5% (w/w);
I1 reveals a number of interesting rheological properties.
The viscosity of the samples was measured as a function
of time at a variety of different shear rates between y =
0.5 s-l and y = 50 s-l. Rheopectic behavior (i.e. increasing
viscosity with time a t a fixed shear rate) was observed for
all samples, a t all shear rates examined, the viscosity
increasing with time to a plateau value (Figure 10). The
magnitude of the viscosity increases and the time required
to obtain the plateau value were dependent on the hy-
drophobe content of the copolymers, the concentration of
the SDS, and the shear rate. For certain samples, the
rheopectic effect was followed by a smaller thixotropic
effect (Le. decreasing viscosity with time at a constant
shear rate) before attainment of the plateau value of the
viscosity. An example of such a curve is given in Figure
11.
Rheopectic behavior was further investigated by sub;
mitting a sample to a series of alternate shear rates of y
= 1 s-l and y = 20 s-l and recording the viscosity as a
function of time. After each measure at y = 20 s-l (of
fixed 5 min duration) increasing periods of relaxation in
the absence of shear and before the measure at y = 1 s-l
were employed. The results obtained at the shear rate of
y = 1 5-l are presented in Figure 12 (curves a-c). As the
relaxation time is increased, the difference between the
Langmuir, Vol. 8, No. 3, 1992 846
T
0
0.6
4
x 0.5
n
a
50.4
h
20.3
0
3
C
co.1
2a t
20.0
0 2 4 6 8 1012
time (mins)
Figure 12. Apparent viscosity as a function of shear time at a
fixed shear rate of y = 1 s-1. Before each measure the sample
was subject to a shear rate of y = 20 s-l for 5 min duration,
followed by a relaxation time, t (at zero shear): (a) t = 30 a; (b)
t = 9 O s ; (c) t = 150s. For reference, curve d, is the initial measure
at y = 1 s-l before any shear at y = 20 s-l. (Copolymer sample,
M 52;concentration = 0.5% (w/w); SDS concentration = 0.05%
(w/w).)
initially recorded peak viscosity and that of the plateau
value decreases. At the shortest relaxation time, 30 s, the
initial peak viscosity value is approximately that recorded
for the higher shear rate. The viscosity-time profile for
it was subjected to a higher shear rate, is also given in
Figure 12 (curve d). The curves obtained both before and
after the higher shear rate appear to approach the same
equilibrium viscosity as a function of time.
The shear thinning behavior observed both for copol-
ymer solutions in the absence of surfactant (Figure 2) and
for those copolymer/surfactant solutions which do not show
any enhanced viscosification (Figure 9, curves a and c) is
comparable to the classic response of a polymer solution
to increased shear stress. In this case, such behavior can
be attributed both to the disentanglement of the isolated
coils and to the breakdown of hydrophobic interactions.
A previous study of copolymersof acrylamide and N-alkyl-
acrylamides? which had been partially hydrolyzed (18mol
%), suggested the presence of a critical copolymer con-
centration (0.2% (w/w)) and hydrophobe content (1.25
mol % 1, after which shear thickening is observed, even in
the absence of surfactants. Critical values of these
parameters leading to shear thickening were also observed
by Jenkins41for hydrophobically end capped poly(ethy1ene
oxide) (M,,= lo5). This behavior was seen for shear rates
of 1 s-l < y < 10 s-l in the absence of surfactants. No
critical hydrophobe content was observed here between
1.03 and 1.3 mol % ,at a copolymer concentration of 0.5%
(w/w). Also, a previous report on similar copolymers
showed no critical concentration at up to 3% (w/w) for a
hydrophobe content of 1 mol % .lo
Shear thickening was observed,however,within a certain
range of surfactant concentrations, for all the different
hydrophobe contents measured (Figure 9, curve b). The
shear.thickening occurred at low to moderate shear rates
(1 < y < 20 s-l) and its magnitude was dependent on the
amount of hydrophobe in the sample. Similar shear
thickening has also been reported for the HEUR copol-
y m e r with
~ ~ ~anionic surfactants although in this case at
shear rates of between 100 and 1000 s-l. This dilatant
behavior may be explained if we consider the relative
amounts of inter- and intrachain associations as a function
846 Langmuir, Vol. 8, No. 3, 1992
Figure 13. Schematic representation of the effectsof shear time, at a constant shear rate, on the interactions in an aqueous solution
of copolymer/SDS: SDS, --; hydrophobe blocks, 0.
of shear. As the copolymer chains are extended under
increased shear, the number of hydrophobic groups
available for interchain associations is increased due to
the breakdown of intramolecular associations which re-
quire a coiled polymer conformation. In the presence of
micelles, these newly liberated hydrophobic groups can
be solubilized, leading to an increase in the number of
interchain liaisons and hence the viscosity. As the shear
rate is increased further, however, this structure is broken
down in the shear flow and the solution becomes shear
thinning. This is further evidence therefore, that the
interactions between copolymer hydrophobic groups via
the mixed micelles are considerably stronger than those
seen in the absence of surfactant, since the same elongation
under shear of the copolymer coil is occurring but in the
second case no dilatant behavior is observed.
The time required to reach an equilibrium value of the
apparent viscosity under a constant shear rate when not
in this shear thickening region is very short, usually of the
order of seconds. However, when within the region of
shear thickening, the copolymer relaxation times increase
substantially, observed values often being greater than 5
min. These samples exhibit rheopectic behavior generally
(Figure lo), with certain showing both rheopexy followed
by a smaller thixotropic effects (Figure 11). The rheopexy
may be explained with similar arguments to those em-
ployed for the shear thickening above, i.e. under a shear
the copolymer chain has an extended conformation and
more hydrophobe units are liberated for interchain as-
sociations. The time required to arrive at an equilibrium
value and the magnitude of this viscosity are very sensitive
to the amount of SDS for any one copolymer sample at
a fixed concentration. This is shown in Figure 10, where
increasing amounts of SDS are seen to lead to decreasing
equilibration times. The variation in the plateau values
of the viscosity with SDS concentration have already been
discussed in section 2 for the “steady state” values of the
viscosity (Figure 5). Therefore, no further discussion will
be given here.
The time required to obtain the plateau value can be
more easily understood if we consider the rheopectic
process to occur in three stages. In the first, the copolymer
chains undergo chain extension liberating a certain number
of hydrophobe units, from intrachain association, into
solution. This is followed by a rearrangement of the SDS
to solubilize the liberated hydrophobe forming mixed mi-
celles which may form a linkage between two or more
copolymer chains. In the final stage, the copolymer
undergoes a conformational rearrangement to remove from
solution any of those hydrophobes liberated in the first
stage which have not been solubilized into the mixed mi-
celles. These stages are shown schematically in Figure
13. The first stage, involving the elastic response of the
Biggs et al.
- Chain
re-coiling
chains to a suddenly imposed shear strain, is practically
instantaneous. The second will be relatively fast also, since
it concerns only the motion of the small molecule sur-
factants and their attainment of the minimum free energy
state in the mixed micelles with respect to aggregation
numbers and SDS/hydrophobe ratios. However, the third
stage which involvesthe relaxation of the copolymer chains,
in opposition to the imposed shear stress, in order to
remove excess hydrophobe from solvent contacts may be
considered to be a slow process. Therefore, for a copolymer
sample at a high level of SDS there is sufficient surfactant
to solubilize more of the initially liberated hydrophobe
than is the case at lower levels. Hence, the amount of
hydrophobe which must be protected from the solvent by
a rearrangement of the chain is lower and so the third
stage has a decreased importance. Thus the time required
to reach the equilibrium plateau viscosity decreases with
increasing amounts of surfactant.
In some cases, a small thixotropic effect was observed
after the rheopexy and before attainment of the equilib-
rium value of the viscosity. This may be explained using
similar arguments to those outlined above. The initial
extension of the chain is followed by the formation of mixed
micelles with the SDS which facilitates interchain liaisons
and hence causes a rise in viscosity. Those micelles formed
initially may be at a ratio of surfactant/hydrophobe which
does not give the lowest free energy for the system but
does give a free energy level which is very favorable
compared to the free hydrophobe in solution. These mi-
celles will be kinetically, but not thermodynamically,
stable, and so with time the surfactant will rearrange to
give surfactant/ hydrophobe ratios which offer a lower free
energy level at the same time as the copolymer chain relaxes
removing the excess hydrophobe from solution. Hence,
the viscosity undergoes a small decrease before attaining
equilibrium.
Conclusions
Rheological data on the interaction of hydrophobically
modified polyacrylamide copolymers in aqueous SDS
solutions have shown that the relative numbers of inter-
and intrachain hydrophobic liaisons are very sensitive to
the amount of surfactant and/or shear stress imposed on
the system.
SDS when added to an aqueous solution of copolymer
binds to the copolymeric regions in a noncooperative
process causing a shift from intra- to interchain liaisons.
This is evidenced by a peak in the apparent viscosity at
surfactant concentrations below that of the cmc. Above
the surfactant cmc intra- and interchain interactions are
destroyed, each hydrophobe region of each copolymer
chain being solubilized in a single micelle.
Hydrophobically Modified Polyacrylamide
In this region of enhanced solution viscosity, shear
thickening was observed at shear rates below 20 s-l. This
too is attributed to an increase in the number of inter-
chain liaisons as the copolymer chain is elongated under
the influence of the shear stress liberating further hy-
drophobe from intrachain liaisons. Solutions in this shear
thickening domain were seen to exhibit rheopectic and
thixotropic behavior. Such observations are attributed
to the delicate free energy balance in these systems which
is controlled by the entropy changes of removing or
replacing hydrophobic groups in aqueous solution and of
restrictions of the copolymer chain motion.
Contrary to homopolymer/surfactant systems none of
the rheological effects are attributed to a polyelectrolytic
effect as micelles become attached to the polymer. In the
case of hydrophobically modified copolymers, the attach-
Langmuir, Vol. 8, No. 3, 1992 847
ment sites are very specific and are considered to be
separated from each other by long chains of noninter-
acting polyacrylamide.
Acknowledgment. We thank Alain Hill for many
helpful discussions. S.B. expresses his gratitude to the
SERUNATO for the provision of a European post-
doctoral fellowship. The financial assistance of ARTEP
(Association de Recherches sur les Techniques
d'Exploitation du PBtrole) and PIRSEM (Programme In-
terdisciplinaire de Recherches sur les Sciences pour
l'Energie et les MatiBres PremiBres) is also gratefully
acknowledged.
Registry No. SDS, 151-21-3; (H&=CHCONH*)-
(H&=CHCONHCeHI-p-Et (copolymer), 112218-43-6.