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the length distribution depend on the energy of formation of two micellar endcaps
during the scission reaction(7,#). However, constant shear measurements on these
solutions suggest that the micelles act as rigid rods below a certain length
scale(9,70). These two different points of view are not inconsistent - the threadlike
micelles can be thought of as chains consisting of discrete rigid segments of a fixed
persistence length (Figure 2). Since these segments are assumed to act
independently, the microstructure on small length scales can be modeled as a
collection of rigid rods with length equal to the persistence length.
Small angle neutron scattering (SANS) provides useful information about the
structure and shapes of micelles in solution(77). However, for nonspherical particles
this technique cannot provide unambiguous information about particle shape(77,72).
Analysis of particle structure can be simplified by alignment of the anisotropic
particles in electric(75), magnetic(73) or flow fields(9,70,73-76). The degree of
alignment depends on the axial ratio of the particles, and alignment removes some
ambiguity in the determination of the particle shape. Measurements of scattering in
the presence of an external field also provides information about the rotational
diffusion coefficient of elongated particles(77).
SANS Theory
The measured intensity from a system of rodlike colloidal particles can be written
as(70,77),
^(q) =
exp(iq R
\N=1M=1
N M
)F (q)F (q)^
N
(1)
or,
fd d ~) = ^
S(FN,)
)V ^(,
' /
2
N = 1 M = 1
, ,
M
RNM=N(.F J
N
(2)
where RNM is a vector connecting the center of mass of particles and M . The
volume of the rod is V and Ap is the difference between the scattering length
density of the rod and the solvent, q is the difference between the incident and
scattered intensity vectors and has magnitude q=(47cA.)sin(e/2), where is the
neutron wavelength and is the scattering angle. The brackets indicate averages
over the orientations of the rods.
For cylindrical particles F(q) is written(72)
r
sin -V-cosa L
, .
F(q)-F(q.) = 4 r
(3)
where a is the angle between the rod axis, represented by a unit vector, u, and the
scattering vector, q (Figure 3). The amplitude function depends on the radius R and
the length, L. The form factor is
122
1.5 H
(D
c .
S 0.5 H
(D
Rodlike Micelles
and \fe sides
Rodlike Micelles
1
1
1
100/0 98/2 96/4 94/6 92/8 90/10
weight ratio CTAT/SDBS
Figure 1: Schematic of the phase diagram of CTAT/SDBS showing the
progression from rodlike micelle, through a micelle/vesicle two phase region, to
a vesicle lobe on the CTAT rich side of the equimolar line. The circles indicate
the samples studied with SANS.
Figure 3: Scattering geometry for the shear flow experiment. Flow is in the xdirection, the shear gradient, and the neutron beam are in the z-direction. The
azimuthal and polar angles are and .
In Structure and Flow in Surfactant Solutions; Herb, C., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1994.
(F (q)) = J F ( q ) f (u)du =
2
123
J * F ( q , a ) f (,)8
(4)
The normalized orientational distribution function f(u) represents the probability that
a rod is pointing between u and du and is a function of the azimuthal, () and polar,
() angles of the rod.
The second term in equation 2 can be simplified by neglecting any
correlation between rod orientation and position. In this decoupling approximation
we have(70,7J)
2
(5)
where is the volume fraction of particles and P(r) is the angularly-dependent pair
distribution function. For spherical particles, P(r) is isotropic and depends only on
interparticle center-to-center distance. Given an interparticle potential, integral
equations or Monte Carlo simulations can be used to obtain the pair distribution
function(77). For rods, the interaction potential, and so P(r), depends on both rod
orientation and interparticle distance. Spherical harmonic expansions of integral
equations have been used to find the angularly dependent pair distribution function
for uncharged elongated particles(79). Rigid charged rods have been modeled using
Monte Carlo simulations and perturbation expansions around sphericalized reference
potentials(20).
If a shear field aligns the rods, the Smoluchowski equation provides the
distribution function for the orientation of the rods. Doi and Edwards(27) and
Larson(22,25) write the time evolution equation for the orientational distribution
function as
^
= 0
(6)
Y?(u)
f(u,t)= X
^=0
m=0
\ m ) , where, |An) =
for m = 0
m
form*0
^even
(7)
124
The particular form of \m) combines the spherical harmonic functions, Y(u), so
that the symmetry and boundary conditions of the problem are met. This expansion
is then substituted into the Smoluchowski equation and the inner product is taken
with respect to each member of the series. Using orthogonality and triple product
conditions yields a set of ordinary differential equations in time for the coefficients
/m-
m a
m a x
Sheared CTAT-SDBS
-1
125
126
solutions is isotropic and displays a single strong correlation peak (Figure 4a). This
indicates that the micelles are charged and highly interacting. The scattering patterns
become increasingly anisotropic with increasing shear rate, and show increasing
intensity in the direction perpendicular to the flow direction and decreasing intensity
in the direction parallel to the flow direction. This change provides clear evidence
that the rodlike micelles are aligning. The increase in anisotropy implies the rods
align like the rungs on a ladder, thereby reinforcing the correlation peak in the
direction perpendicular to the flow and weakening it in the direction parallel to the
flow.
Figure 5 shows scattering from sample 2 along lines perpendicular and
parallel to the flow direction. The solid and dashed lines are the model fits of the
form factor where the effective rotational diffusion coefficient is the only adjustable
parameter; the radius and length are determined from the zero shear data. The good
agreement between the shape of the experimental and fitted curves at high q suggests
that the length estimated from the q value of the intensity peak is a good estimate of
the persistence length of the micelles. Table I shows the results of this fit for the four
samples studied.
Table I. Rotational Diffusion Coefficients as a Function of Shear Rate
Shear
Rate
(s- )
1
5
10
20
50
100
-1
ro
Conclusions
Rodlike micelles that can be aligned in a shear flow are present on the CTAT rich
side of the CTAT/SDBS/D2O phase diagram. Modeling the neutron scattering data
provides information about the effective rotational diffusion coefficient of these
127
128
rodlike micelles. The results indicate that longer, more entangled micelles are
formed as the total surfactant concentration is increased at a constant ratio of
CTAT/SDBS. Increasing the amount of SDBS at a constant total surfactant
concentration leads to rodlike micelles which are much shorter and more mobile.
Shorter micelles signal a change in the structures present as the phase transition is
approached.
Acknowledgments
This work was supported by E.I. DuPont de Nemours & Co. The authors thank Dr.
R.G.Larson for supplying the FORTRAN code used in the calculation of the
orientational distribution function of rods in a shear flow. The authors also
acknowledge G. Straty and Dr. J. Barker for their help with the shear cell and SANS
measurements. We acknowledge the support of the National Institute of Standards
and Technology, U.S. Department of Commerce, in providing the facilities used in
this experiment. This material is based upon activities supported by the National
Science Foundation under Agreement No. DMR-9122444.
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