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We report on the statics and dynamics of long and flexible wormlike micelles made from cationic
surfactants (cetylpyridiniumions) diluted in brine (0.5M NaC1) with stronglybinding counterions (salicylate
ions). This survey was performed at ambient temperature by combining light scattering and rheology
regimes were studied. Above the crossover concentration 4* -
measurements. Varying the weight percent, 4, of surfactants from 0.1 5% to 105% ,both dilute and semidilute
0.3 5% , the viscoelastic properties are
described by an almost ideal Maxwell relaxator. The overall rheological data are found to scale with the
surfactant concentration with exponents close to those predicted from a recent stress relaxation model
applied to living polymers. In addition, at high angular frequency, the complex elastic modulus results
are interpreted in terms of crossover between the regimes of reversible scission and of breathing of the
-
polymer-like chains. Contrary to earlier reporb, the total average length of the micellar aggregates is
found to increase with surfactant concentration as: E(4) 4°.2m0.4.
Flexible elongated surfactant micelles can be considered scission, breathing and Rouse motions of the chains were
as model systems for the study of reversibly breakable taken into account to determine the overall stress relax-
polymers, sometimes called “living” polymers. It is now ation function G(t), or its dynamical counterpart, the
well established that the static and quasi-static properties complex elastic modulus G*(w) = G’(w) + iG”(w). The
of these surfactant systems show strong similarities with essential features of this model are the following:
those of polymers in solutions. In the semidulute regime, In the semidilute regime of entangled network, well
e.g., the micelles form a disordered entangled network, characterized scaling laws are predicted for the rheological
and one process for the flexible chains to relax external properties, e.g. for the static (defined at zero shear or zero
stress is reptation. frequency) and for the dynamic shear viscosity g(w) =
Equilibrium polymers exhibit however fundamental IG*b)l/w.
differences with respect to ordinary polymers: (i) The In the so-called C o l d o l e representation, which consists
length of the flexible chains are broadly distributed, and in plotting the imaginary part G”(w) of G * ( w ) as afunction
determined by the thermodynamical equilibrium of the of its real part G’(o), a more or less semicircular behavior
surfactant solution. (ii) There exists another crucial is expected, depending on the ability for the system to
process for stress relaxation (in addition to reptation): relax faster through unimolecular scission and/or reptation.
the reversible breaking and recombination of the chain. The important parameter is then the ratio between the
During the last years, the dynamical behavior of relaxation times of each mechanism, n and T ~respec- ~ ~ ,
wormlike micellar solutions have attracted much attention tively. At higher frequency, the crossover to the breathing
from theoreticians’“ and e~perimentalists.”~~ A model regime manifests itself as a minimum in the Cole-Cole
of stress relaxation in living polymers (essentially based plot. The crucial point of the Cates model is that the
on the theory of polymer dynamics14) was recently height of this dip is directly related to the average number
proposed by Cates and c o - ~ o r k e r s .In
~ ~addition
~ to the of entanglements along the chain. It allows moreover to
already mentioned processes of reptation and reversible calculate the totalaverage length of the micelles, a quantity
which cannot be derived from measurements of static
+ The Groupe de Dynamique des Phases Condens6es is associated properties.
with the Centre National de la Recherche Scientifique. In this paper, we combine light scattering and rheology
* Abstract published in Advance ACS Abstracts, September 15, measurements, so that we can investigate the connection
1993. between the static and dynamic properties of long flexible
(1) Cates, M. E. Macromolecules 1987,20,2289;J. Phys. (Paris)1988,
49,1593; J. Phys. Chem. 1990,94,371. wormlike micelles. The system considered here consists
(2) Cates, M. E.; Candau, S. J. J. Phys.: Condens. Matter 1990, 2, of a cationic surfactant (cetylpyridinium ions) diluted in
6869. brine (0.5 M NaC1) with strongly binding counterions
(3) Granek, R.; Cates, M. E. J. Chem. Phys. 1992,96, 4758.
(4) Lequeux, F. Europhys. Lett. 1992,19,675.
(5) Rehage, H.; Hoffmann, H. J. Phys. Chem. 1988, 92, 4712; Mol.
Phys. 1991, 74,933.
(salicylate ions). Measurements are performed at ambient
temperature. Above the crossover concentration cf~*
0.35% ,the viscoelastic properties of the entangled micellar
-
(6) Shikita, T.; Hirata, H.; Kotaka, T. Langmuir 1988, 4, 354. network vary as power laws as a function of concentration
(7) Kern, F.; Zana, R.; Candau, S. J. Langmuir 1991, 7,1344.
(8) Clausen, T. M.; Vinson, P. K.; Minter, J. R.; Davis, H. T.;Talmon, with exponents close to those predicted by the Cates model.
Y.; Miller, W. G. J . Phys. Chem. 1992,96, 414. Furthermore the total average length could be derived
(9)Appell, J.; Porte, G.; Khatory, A.; Kern, F.; Candau, S. J. J.Phys.
ZI 1992, 2, 1045.
(10) Kern, F.; Lemarechal, P.; Candau, S. J.; Cates, M. E. Langmuir
1992,8, 437.
from complex elastic modulus data and was found to
increase with surfactant concentration as - 4°.256.4.
(11) Terech, P.;Schaff’hauser,V.; Maldivi, P.; Guenet, J. M.Langmuir Experimental Section
1992,8, 2104.
(12) Khatory, A.; Kern, F.; Lequeux, F.; Appell, J.; Porte, G.; Morie, The surfactant solutions investigated here are the binary
N.; Ott, A.; Urbach, W. To be submitted for publication in Langmuir. mixtures made of cetylpyridinium chloride (CPy+Cl-) and sodium
(13) Khatory. A.; Leaueux, F.;Kern. F.: Candau. S. J. To be submitted
for publication. salicylate (Na+Sal-), diluted in brine 0.5 M (NaCl). The weight
(14)Doi. M.: Edwards, S. F. The Theorv -
- of. Polymer Dvnamics: percent $t of surfactants range from 0.1 % to 10%. Thii system
Clarendon Press: Oxford; 1986. is known to be a good candidate for forming elongated wormlike
0743-746319312409-2851$04.00/0 0 1993 American Chemical Society
2852 Langmuir, Vol. 9, No. 11, 1993 Berret et al.
micelle^.^ The ratio R = [Sal]/ [CPy] has been kept to a constant, Table I. Comparison between Predicted and Experimental
R = 0.5. This approach is similar to that followed by Kern et Exponents for the Scaling Laws Related to the Dynamical
al.l0 in a viscoelastic study of a parent compound. In order to and Static Properties of Reversibly Breakable Micelles
ensure a constant electrostatic screening length while varying under Dilution
the surfactant concentration, we choose to work with rather theory experiment
concentrated brine solutions (namely, 0.5 M NaCl).
Measurements of scattered light as function of wave vector q plateau modulus Go 914 2.18
= 3 X 1o-L to 3 X 1V A-l were performed at 25 OC on filtered terminal time m 514 1.13
solutions, using an experimental setup as described elsewhere.l5 static viscosity 70 3.5 3.3
Gffh 112 0.72
The linear viscoelastic properties of the CPy/Sal mixtures were G"&Go -714 -1.44
obtained on a Rheometrics fluid spectrometer (RFS 11)working correlation length t -314 -0.65, -0).72a
with controlled shear rate. Depending on the viscosity range, a total average length L 112 0.36,0.24a
cone-and-plate (for 70 > 0.1 Pa-s) or a couette (typically below
1 Pa& configuration was utilized. Dynamical measurements a Static value, dynamic value.
were carried out for angular frequency w = 0.1-100 rad/s at 7 ' 1 ' ' """I ' """I ' 1
5
7
Itwasalsodemonstratedthat 7~ -
frequency storage modulus and 7~ the terminal relaxation time.
Suchaviscoelastic
system (with a monoexponential decay time) is generally iden-
0.1 1
41 (weight percent)
10
0.5
f
2
0
0.4
0.3
- I
0.2
0.1
00
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
G/G,
k
Figure 2. Cole-Cole plot for CPy + Sal micellar solutions at @*
various surfactant concentrations, 4 = 0.98-4.0% (T= 20 O C ) .
G' and G" data have been normalized to Go, the plateau modulus.
The half-circle (dashed curve, eq 1) corresponds to an ideal 1
Maxwell element with a unique relaxation time.
I
0.1 1 10
9 (weight percent)
Figure 4. Correlation length for CPy + sal micellar solution
loo-: as determined from rheological data (i.e. using eq 3b and the Go
data of Figure 3) and from elastic light scattering measurements.
In the entangled regime (4 > 4*) both sets of data, labeled €dm
Q0.S __ and &, respectively, exhibit scaling laws as a function of
surfactant concentration.
E
i3 agreement for the ratio G"mdG0 should not be overes-
timated however; especially on the low-concentrated side
where 1$L approach unity, the previous model is not
appropriate.
To proceed further, we have now to estimate the
correlation length t appearing in eq 3a. It has been derived
according to two techniques: first using eq 3b from
rheological data, second by direct measurements through
elastic light scattering experiments. This approach allows
agreementwith theoretical predictions, (cf. Table I). This with a = -0.65 or -0.72 depending on how 5 was determined.
2854 Langmuir, Vol. 9, No. 11, 1993 Berret et al.
One gets finally in both cases an increase of the average confirm the predictions of a new model of stress relaxation
- from light scattering experiments and
t$o.3s -
chain length with increasing surfactant concentration,L(4)
4°.24
from rheological data. The whole set of exponenta is again
recently developed for living polymers.1s In particular,
the micellar mean length is found to increase with
surfactant concentration, as expected from statistical
summarized in Table I and compared to the theoretical equilibrium. This last finding contradicts recent reports,
ones. however, one by Granek and Cates3analyzing rheological
Moreover, assuming for the persistence len h of CPy/ data on CTAC/NaSal (in brine 0.25 MI7 and one by
f
Sal micelles the value usually admitted of I50 the mean
length L ranges between 1000 and 2000 A using the light
Khatory et aL13 on CTAB aqueous solutionsin the presence
of KBr. Both systems were analyzed in a similar way, as
-
scattering tatatdata. This is roughly one-tenth of what
can be calculated from the relationship 4 G0-IJ3or what
was previously reported in the literature3J3 (typically of
for the present one. In order to explain the anomalous
decrease of the average chain lengths with increasing
surfactant concentrations,the formation of a cross-linked
the order of few micrometers). The absolute value of L network resulting from intermicellar branching was pro-
falls probably between both extremes. posed. Contrary to this, the present data suggest that
In conclusion,we have studied the viscoelasticproperties CPy/Sal aqueous solutions (in brine 0.5 M NaC1) are
of aqueous surfactant solutions forming long and flexible prototypes for entangled but not branched wormlike
micelles (CPy/Sal diluted in brine 0.5 M). Our results micellar systems.