Statistical Thermodynamics of Association Colloids: V.

Critical Micelle
Concentration, Micellar Size and Shape

F R A N S A. M. L E E R M A K E R S AND J A N M. H. M. S C H E U T J E N S
Department of Physical and Colloid Chemistry, Wageningen Agricultural University,
Dreijenplein 6, 6703 HB Wageningen, The Netherlands
Received August 2, 1988; accepted July 27, 1989

Recently, we generalized the lattice theory of Scheutjens and Fleer ( 1) for chain molecules in inho-
mogeneous systems to amphiphilic molecules in systems of nonplanar geometries (2-4). This theory is
used here to study surfactant micelle systems. In this paper it is shown that the critical micelle concentration
for surfactant micelles is theoretically well defined. The fact that in most experimental systems the
transition is not clearly observable is explained. The relation between chain architecture and overall
surfactant concentration on the size and shape of surfactant micelles is studied. Segment density profiles
through cross sections of spherical micelles are presented and are in accord with recent Molecular Dynamics
and Monte Carlo simulations. However,long range interactions seem not to be essential for the stabilization
of micelles if the interactions between head groups and tails are sufficiently unfavorable. © 1990Academic
Press, Inc.

INTRODUCTION tistical approach which successfully incorpo-

A b o v e the critical micelle concentration
amphiphilic molecules in aqueous solutions
form association colloids. This p h e n o m e n o n
is o f considerable theoretical and technological
interest. In 1976 Hall and Pethica (5) pub-
lished an extensive theoretical analysis o f mi-
cellisation in solutions o f nonionic surfactants,
based on the thermodynamics o f small systems
developed by Hill (6). This framework is used
here to present a detailed analysis of surfactant
systems over a wide concentration range. Sta-
tistical t h e r m o d y n a m i c s is used to give an in-
terpretation on a molecular level. For example,
the relation between the architecture o f the
amphiphiles and their aggregation structure is
worked out in some detail. Segment density
profiles for the association colloids are also
obtained. O u r approach is m o r e general than
other statistical mechanical theories ( 7 - 9 ) be-
cause no preassigned positions o f the amphi-
philes are required; i.e., the positions o f the
head groups are not a priori fixed onto certain
lattice sites in the system. This is the first sta-
rates the t h e r m o d y n a m i c s o f small systems.
C o m p l e m e n t a r y to our approach, Molecular
D y n a m i c s ( 10-15 ) and M o n t e Carlo (16)
simulations can also give detailed information
on surfactant-water systems. In these simu-
lation m e t h o d s the c o m p u t a t i o n time is m a n y
orders o f magnitude longer than for a statistical
one. Typically, our statistical approach needs
less than a C P U m i n u t e on a V A X 8700. In
principle our theory can be used to check the
line o f arguments first presented by Israelach-
viii et al. to predict the m o r p h o l o g y o f asso-
ciation colloids ( 1 7 - 2 0 ) .
Previous articles in this series have dealt
with bilayer m e m b r a n e s (21 ), lipid vesicles
(2), the gel-to-liquid phase transition ofbilayer
m e m b r a n e s (22), and i n h o m o g e n e o u s m e m -
brane systems (23).
In the following section the theory is briefly
reviewed. A m o r e detailed discussion is given
elsewhere (2). In a subsequent section the sta-
bility and structure of micelles is analyzed. See
also Ref. (3) for m o r e results on surfactant
micelles.

231
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 232 LEERMAKERS AND SCHEUTJENS

THEORY consecutive segments, numbered s = 1 , . . . ,

To facilitate the counting of conformations
of chain molecules a lattice is introduced. The
lattice is designed to have shells of L (z) lattice
sites of constant volume on which the seg-
ments of the chain molecules and the solvent
molecules are placed. The lattice layers are
numbered z = 1. . . . . M, where 1 is the center
of the lattice and M a layer in the bulk solution.
In general the volume of the lattice from layer
n u m b e r 1 up to a layer z is (in units of lattice
sites)
V ( z ) = 2Asz + zchz 2 + (4zr/3)z 3
( Z > 0, h 2 >~ 7rAs),
where the parameters As and h determine the
geometry of the lattice. For a spherical lattice,
As and h are zero. For rods of length h, with
a hemisphere at each end, As is zero. For planar
parts we assume that an area As is surrounded
by a curved half of a cylinder. A disk of radius
Rd would have an area As = 7rR~ and a contour
length 2h = 2~rRa; for all other structures h 2
> zrAs.
The number of lattice sites in layer z is given
by the simple expression
L ( z ) = V ( z ) - V ( z - 1). [2]
r, are situated. This implies that when one of
the segments of conformation c is fixed on the
lattice all other segments have specified posi-
tions. Segments along the chain are connected
with each other by chemical bonds. End seg-
ments have only one bond; other segments
have two (or more) bonds. It is convenient to
n u m b e r the bonds of a segment. We will de-
note the first bond of a segment s (linking it
to segment s - 1 ) by s~ and the second bond
(linking it to s + 1 ) by s2.
In a lamellar lattice the degeneracy o~c of a
conformation c is L, because only the first
[1] segment can choose between L lattice sites.
The degeneracy of a conformation c in a
curved lattice is slightly more complicated,
since the degeneracy should not depend on
which segment is placed first. When segment
n u m b e r 1 of conformation c is free to choose
its position in the lattice layer the degeneracy
is given by
wc = LC(z, 1) ]5i ?tc(z, Sl), [5]
s=2
where U ( z , sl)equals ~ l(Z)/)tbl if segment
s -- 1 is in layer z -- 1, equals ~o(Z)/~ b if s
1 is in z, and equals X l ( z ) / ~ b i f s - 1 is in
-

The contact area S ( z ) (in units of the surface
area of a face of an unperturbed lattice site)
between layer z and z + 1 is given by
S ( z ) = 2As + 27rhz + 4~-z 2.
z + 1. The superscript c indicates segment po-
sitions of conformation c. In a planar lattice
U ( z , Sm) = 1. Realizing that the n u m b e r of
steps from z to z + I must be equal to the
[3] n u m b e r of steps from z + 1 to z, i.e.,

Eqs. [ 2 ] and [ 3 ] determine Xz'-z(z), the frac- ~ ( z ) L ( z ) = )~-l(Z + 1 ) L ( z + 1), Eq. [5] can
be transformed in order to start with any seg-
tion of contacts of a site in layer z with sites
m e n t other than segment n u m b e r 1.
in layer z', where z' is z - 1, z, or z + 1:
The conformations are generated by a Mar-
X_~(z) = )~b_IS(z- 1 ) / L ( z ) kov-type approximation (2). In this procedure
we accept chains which can intersect with
~k0(Z ) = 1 -- ~k_l(Z ) - - ~ I ( Z ) themselves or with other molecules in the lat-
)t,(z) = ) t b S ( z ) / L ( z ) . [4] tice. The structure of the molecules (branch-
ing, chain length etc.) determines the n u m b e r
Here, Xb_l = xb are the fractions of contacts a of allowed conformations. The main advan-
site has in a planar lattice, i.e., in the bulk tage of this approximation is that the confor-
solution, with either of its neighboring layers. mations can be generated using a recurrence
A spatial conformation of a chain molecule relation. Very efficient computation schemes
is specified by the lattice sites in which the have been developed to generate all confor-

Journal of Colloid and Interface Science, Vol. 136,No. 1, April 1990

 EQUILIBRIUM MICELLES
mations (2). Using them, the n u m b e r of op-
erations needed to generate all conformations
is reduced from about 3 r-I to about r. We
refer to Ref. (2) for more details of our method
of computation.
To calculate the statistical weight of each
conformation, the potential of each confor-
mation must be known. Three contributions
are identified. First, the potential of a given
conformation depends on the n u m b e r of seg-
ment ( x ) - s e g m e n t (y) and segment-solvent
contacts. We will use a m e a n field approxi-
mation to calculate the average interaction
each segment in the molecule has with the
surrounding molecules. Second, differences
between gauche and trans configurations are
accounted for. To do this, a third order Mar-
kov process, the rotational isomeric state (RIS)
scheme, and a diamond lattice are used to
generate the various conformations of the
chains. In the RIS scheme the " m e m o r y " of
the r a n d o m walk type of conformations is two
bonds long. A third bond can only have three
different directions. Two of them result in a
gauche and a third in a trans configuration. A
third contribution to the potential of a con-
formation, u'(z), originates from hard-core
interactions. This contribution is chosen such
that all lattice sites are filled, i.e., Ex q~x(z) = 1
for each layer z, and is independent of the
type of segment or solvent molecule. Here the
average segment density of segments of type
x in layer z is given by 4~x(Z) : n x ( z ) / L ( z ) ,
where nx (z) is the n u m b e r of segments of type
x in layer z. The segment types which will be
considered are water (x = W), apolar segments
(x = A), and polar segments (x = B). The
potentials u ' ( z ) are defined with respect to the
bulk solution, where u 'b = 0.
The potential u Cof conformation c is given
by
U c = HCgU g + ~ u C ( z , S ) , [6]
s--1
where n cg is the n u m b e r of gauche bonds in
conformation c and u g the energy difference
between a gauche and a trans configuration.
233
The parameter uC(z, s) is the potential of seg-
m e n t s. The layer n u m b e r z where segment s
is located depends on conformation c. If s is
of type x, uC(z, s) is substituted by
Ux(Z)
= u'(z) + k T ~ Xxy((chy(z)> - 4~by). [7]
y
In Eq. [7] the well known Flory-Huggins pa-
rameters Xxy occur. They are only nonzero
when x v~ y, because the energetic effect of
any xy contact is taken with respect to the pure
phases x and y. The angular brackets in Eq.
[7] indicate an averaging over three consec-
utive layers in order to account for the fraction
of contacts with segments in these layers:
(~(z)) = ~ ~(z)~(z- I)
"4- ) k o ( Z ) f f ) ( Z ) ~- )kl(Z)(~(Z-~- 1 ) . [8]
The n u m b e r of chains in conformation c is
now given by
n c : CoSe -uc/k~. [9]
Realizing that a solvent molecule is a "chain"
of only one segment, a similar equation applies
for solvent molecules. In Eq. [9 ] C is a nor-
malization constant which is found either from
the n u m b e r of molecules in the system, or
from the bulk concentration.
Summation over all segments in each con-
formation results in the segment density dis-
tributions. With these segment density profiles,
new statistical weights of each conformation
can be calculated. In general a self-consistent
set of conformations can only be found iter-
atively, a process which is initiated by a suit-
able segment density profile (2). As soon as a
self-consistent micelle profile is found which
satisfies the boundary condition that all lattice
sites are filled by either a chain segment or a
solvent molecule, the thermodynamic prop-
erties can be evaluated.
THERMODYNAMICS OF SMALL SYSTEMS
For surfactant micelles, the excess free en-
ergy plays a key role in determining the sta-
Journal of Colloid and InterfaceScience, Vol. 136,No. 1, April 1990
234 LEERMAKERS AND SCHEUTJENS

bility of a given arrangement of molecules. We translational entropy, and, more importantly,

showed before (3) that for a micelle with a relatively constant. A constant term in the free
fixed center of mass the excess free energy A ~ energy shifts the CMC, but all trends remain
is given by the rather forbidding equation the same. At high concentrations (which we
do not consider in this paper) the interactions
A ~ / k T = - ~ n~ + ~ L ( z ) l n ( ~ ) between micelles will dominate the free en-
i z ergy.
From a mass balance we know that
1
+ Z Z Z {(Xxw + Xyw - ×xy)L(z)
z X y nzr2 _ ~2 n~r2
Vs = ~ + ~bb' [12]
× [ 4 A z ) ( 4 ~ y ( z ) ) - ~bx~yb]}, [10]
where 32 is the overall surfactant concentra-
where the molecule type is indicated by a sub- tion in the system. Combining Eqs. [111 and
script i = 1 (water), 2 (amphiphile) . . . . . the [ 12] we find the useful formula
superscript b indicates the bulk solution value,
and the superscript a indicates that the quan- 32 ~- e x p ( - A ~ / k T ) + d~b2
tity is counted as an excess value with respect (A ~ ~> lkT), [13]
to the bulk solution. The subscripts x, y, and
W refer to segment types. As water has only which gives us the overall surfactant concen-
one segment, both the subscripts W and 1 refer tration of the system at given A ~(~bb). We note
to water molecules. Eq. [ 10 ] contains an os- that our present model is only valid for low
motic, an ideal mixing, and an interaction micelle concentrations, i.e., as long as the mi-
term. The excess free energy given in Eq. [10] celles do not interact with each other.
is identical to the subdivision potential for
RESULTS
fixed center of mass defined by Hill (6). Hall
and Pethica (5) showed that in equilibrium First, the behavior of an unbranched sur-
A ~ must be compensated for by terms not in- factant A j2 B3, with 12 tail segments and three
cluded in Eq. [ 10 ]. The most important term head group segments, is discussed. The inter-
of this kind is the translational entropy of the action parameters are found from solubility
micelle, for the computation of which the vol- data and by fitting known CMC values for a
ume fraction of micelles in the system must series of surfactants with different tail lengths
be known. Let V~ be the volume of the small (3). How to obtain CMC values with the pres-
system in which one micelle is present. Real- ent theory will be discussed below. The fol-
izing that n~r2 is a good approximation for the lowing set is used throughout this paper: XAw
volume of the micelle we find for the equilib- = 1.6, XBw = -0.5, XAB 1.5. The high value
=

rium condition of the micelle,
V~
A ~/kT ~- In n~--~2 "
In a not too concentrated system the transla-
tional entropy is the same for all micelles, in-
dependent of their individual aggregation
number. Hence for a polydisperse system we
should use average values for the volumes in
Eq. [ 11 ]. Size fluctuations would add an extra
term in Eq. [ 11 ], but in dilute solutions that
term would be small in comparison with the
for the tail-water interaction promotes phase
separation between tails and water. The head
[11] group-water interaction is negative, repre-
senting an attraction between these two spe-
cies. This attraction is responsible for hydra-
tion of the head groups. A negative XBw is also
equivalent to a repulsive force between head
groups (positive eBB)because by definition XBw
= Z { ~ w - 0.5(eBB + Eww)}/kT, where Z i s
the number of nearest neighbors and exyis the
potential energy of interaction of an x - y con-
tact. Further, the tail-head interaction is fairly

Journal of Colloid and Interface Science, Vol. 136, No. 1, April 1990
 EQUILIBRIUM MICELLES 235

repulsive, promoting the partitioning of head 2O

groups and tail segments. This increases the

t5
stability of the micelles. The flexibility of the A°/kT
acyl chain is reduced due to steric hindrance. i0

This is modeled by an energy difference be-

5
tween a gauche and trans configuration of u g
= 0.8 k T ( T = 300 K ) . Owenson and Pratt 0

(16) have argued that long-range interactions

are necessary in order to find stable micelles -5-

of finite size at concentrations far below the

-t0
concentration where macroscopic liquid-liq- 50 100 t50

uid phase separation occurs. Our model does surfoctant molecules/mice, lie

not support this view. We find that unfavor-
able contact energies between head groups and
tails are sufficient to stop the growth of the
aggregates. Long-range electrostatic interac-
tions can be accounted for in the present the-
ory, but are not considered in this paper. M D
simulations show that electrostatic potentials
are very low, at least in bilayers ( 11 ).
Figure 1 gives the excess free energy A ~ of
a micelle (with fixed center of mass) as a func-
tion of the excess n u m b e r of surfactants ag-
gregated. The curve where A ~ is negative is
physically irrelevant. In that region, other mi-
cellar shapes, like rods or disks, may dominate
and we have indicated an alternative curve by
a dashed line. The part of the curve with a
FIG. 1. The excess free energy A" as a function of n~
for a surfactant A 12B3 in a spherical aggregate. The dashed
curve is expected when shape variations would be taken
into account. Flory-Huggins energy parameters: XAw
= 1.6, XBw = -0.5, XA8 = 1.5.
positive slope leads to micelles that are meta-
stable because for a given composition another
micelle system with a lower free energy can
always be found (see Fig. 2). The very first
thermodynamically stable micelles are found
at the m a x i m u m in Fig. 1. The corresponding
size of the small system is determined by the
equilibrium condition given in Eq. [11]. We
conclude that micelles cannot exist below a

-2.25 -

-2.30

log ~'
-2.35

-2.40

-2.45 • • , , I • , , ' i , , , , I
50 100 150
surfactant m o l e c u l e s / micetle

FIG. 2. Log 4~ as a function of the excess number of surfactants A12B3 aggregated in the globular micelle
of Fig. 1. Two arbitrary points of equal overall surfactant concentration are indicated.

Journal of Colloid and Interface Science, Vol. 136, No. 1, April 1990
 236
given concentration; in other words, the small
system (which holds only one micelle) cannot
be arbitrarily large. At the CMC a micelle
comprises a minimum number of surfactant
molecules and the concentration of micelles
is finite (the size of the small system is limited).
Thus, theoretically, the CMC is well defined.
The same conclusion was reached by Ruck-
enstein and Nagarajan (24-26). We note that
the slope OA~/On~contains information on the
size fluctuations of micelles (5, 27). The
steeper the curve the sharper is the size distri-
bution. Near the maximum in A" large fluc-
tuations in micellar size must be expected.
Near the CMC the micelles change their ag-
gregation number rather than more micelles
being formed. See also the discussion of Fig.
4 below.
Figure 2 gives the relation between the
equilibrium volume fraction and the number
of aggregated surfactants. A" passes a maxi-
m u m when log q~b goes through a minimum,
in accordance with Gibbs' law; the corre-
sponding value of q~b is the CMC. At each
overall concentration ~2 beyond the CMC
there are two possible equilibrium concentra-
tions ~bb. In Fig. 2 one such combination is
indicated. As can be easily seen, the molecules
in the bigger micelle always have a lower
chemical potential and these micelles are
therefore thermodynamically more favorable.
For very small micelles very high equilibrium
concentrations are required, as would be
characteristic for nucleation phenomena. In
the physically realistic part of Fig. 2, beyond
the CMC and for bigger micelles, the chemical
potential rises with n ~ because gain in energy
of the tails upon micellization is counteracted
by the loss in energy of the repulsive head
groups. This repulsive force rises with increas-
ing aggregation number, as a larger number
of head groups is forced to enter the apolar
tail region. This mechanism is responsible for
the finite dimensions of the micelles, i.e., it
prevents the micelles from growing indefinitely
toward macroscopic dimensions.
We note that especially when the maximum
value of A ~(n ~) is low, the micelle concentra-
Journal of Colloid and Interface Science, Vol. 136, No. 1, April 1990
LEERMAKERS AND SCHEUTJENS
tion at the CMC is relatively high. Naturally,
the first micelles can only be formed by a sur-
plus of surfactants in the system. Thus there
can be supersaturation, a difference between
the volume fraction of surfactants in the sys-
tem in the absence of micelles and the theo-
retically defined CMC at the maximum in
A ~(n ~) in the presence of micelles.
In many experimental systems the overall
concentration is fixed. In Fig. 3 the equilib-
rium bulk concentration ~bb is related to the
overall concentration ~2. Obviously, below
the CMC ~2 = q~b as there are no micelles.
Surprisingly, the difference between q~b and
~2 remains undetectable over a considerable
concentration range just beyond the CMC.
Only at higher concentrations does q~b become
essentially independent of the overall concen-
tration. As given in Eq. [ 13 ], as long as A" is
high, no big difference between ~2 and 4~b can
be expected. The behavior changes dramati-
cally when e x p ( - A ~/kT) becomes of the or-
der of ~2b. As a consequence, the theoretical
CMC is difficult to determine experimentally.
In most cases, the point where 4~2 b and ~2
start to deviate is identified as the experi-
mental CMC.
The concentration of micelles as a function
of composition is given in Fig. 4. As antici-
pated in the discussion of Fig. 1, the micelle
concentration is not detectable initially, al-
though the concentration of micelles is finite
at the CMC. The presence of micelles often
defies experimental observation at the ther-
modynamic criterion for the CMC. Only when
the micelles are larger does their concentration
become linear with the overall surfactant con-
centration.
In Fig. 5a the segment density distribution
through a cross section of a micelle is given at
the CMC. The micelle consists of 45 A12B3
molecules. The layers are numbered, so that
the center of the micelle is between layers 20
and 21. As can be seen from the segment dis-
tributions, the head groups are not confined
to one layer but spread out over several layers.
This is corroborated by recent Molecular Dy-
namics ( 13, 15) and Monte Carlo simulations
 EQUILIBRIUM MICELLES 237

w10 -3

cb 4 CMC

0 !
' ' ' ' .I0 -Z
0 t 2 3 4 5

FIG. 3. The equilibrium surfactant A]aB3 volume fraction as a function of the overall surfactant A l z B 3
volume fraction. Parameters as in FIG. 1.

(16). The local concentration of head groups
is low. This gives room for many tail-water
contacts. The distribution of segments of a
given rank in the surfactant molecule (not
presented) is also wide. This indicates that the
entropy of the chain molecules in the aggre-
gates is rather large. The profiles show that
some solvent is found in the core of the mi-
celle. Indeed, this must be expected for a sol-
vent consisting of simple unassociated isotro-

*10 -2

E
,o-
3

0 C , ' ' 1 0 -z
1 2 3 4 5
72
FIG. 4. The volume fraction of micelles as a function of the overall surfactant A12B 3 volume fraction.
Parameters as in FIG. 1.

Journal of Colloid and Interface Science, Vol. 136,No. 1, April 1990

238 LEERMAKERS AND SCHEUTJENS

t.0 1.0
0.9
0.8
\ tails / water
0.9
0.8
•'• tails S water

(z) 0.7 ~(z) 0.7

@ , @
0.6 0.6
0.5 0.5
0.4- 0.4
0.3- 0.3
0.2 0.2
0.1 head groups 0.! head groups
0.0 .... i .... i , ~ , * .... i .... i 0.0 . . . . i . . . . . i . . . . i
5 t0 15 20 25 30 35 40 5 t0 15 20 25 30 35 40
layer z Ioyer z

FIG. 5. Segment density distributions through a cross section of a globular micelle composed of (a) 45
molecules A I 2 B 3 (the equilibrium bulk volume fraction is 3.92 × 10 -3 (CMC), and A" = 16.51kT per
micelle), (b) 97 molecules A12B3 (the equilibrium solution volume fraction is 4.46 × 10-3, and A ~ = 7 . 5 k T
per micelle). Energy parameters XAw = 1.6, Xs~v = -0.5, XAS = 1.5.

pic monomers. For water this is not a good
model. Therefore, we believe that the amount
of solvent in the micelle is overestimated. In
Fig. 5b the segment distributions of a cross
section through a globular micelle of 97 sur-
factant molecules are given. These micelles are
found at an overall surfactant volume fraction
of ~2 = 0.005. The unfavorable inhomogene-
ities observed in the center of this micelle orig-
inate from the fact that the radius of the mi-
celle is too big. This indicates that other mi-
cellar shapes might be more favorable at this
surfactant concentration.
We showed that in more concentrated sys-
tems the micelles are larger, the corresponding
chemical potential of the surfactants is higher,
and the excess free energy of the micelles is
lower. In general, when A ~ approaches zero,
the system can change its surface area without
change in Gibbs energy. Thus we can expect
shape fluctuations in the concentrated regime.
In order to investigate this phenomenon, the
equilibrium bulk concentration at given com-
position has been calculated for micelles of
other geometries by changing h and As in Eqs.
[ 1] and [3]. Figure 6 shows how, for the sur-
factant A 11B3 near the CMC, the equilibrium
concentration is related to the shape varia-
tions. The straight line in the contour plot
represents the boundary h 2 = ~-As, which de-
termines the minimum value of h (see Eq.
[1 ]). As can be seen, the globular micelle has
the lowest free energy. (In Fig. 6 the most fa-
vorable micelle shape is indicated by an as-
terisk.) Therefore it is concluded that the very
first micelles are globular.
At very high overall concentration (micelles
with A ~ = 0; translational entropy can be ne-
glected) we see in Fig. 7 that for the same mol-
ecules disk-like structures have the lowest free
energy. Interestingly, Molecular Dynamics
simulations by Watanabe et al. (13) revealed
disk-like micelles at high surfactant concen-
tration with average ratios of the principal in-
ertial moments of the micelles being 1.7:1.5:
1. However, the variation in chemical poten-
tial as a function of micellar shape is small, so
that a homodisperse micelle system is very
unlikely. Consequently, the curve shown in
Fig. 1 is modified for small A" when we allow
shape variations. In this case a dashed curve
such as sketched in Fig. 1 will more likely be
followed.
Similar analysis for a lipid lecithin-like
molecule with two apolar tails of 8 (A) seg-
ments, a glycerol backbone, and three head
group segments (of type B) shows that the very
first association colloids are again globular
micelles. Increasing the concentration of the
lipids has the effect that the aggregates trans-
form into flat membrane-like structures. This
is illustrated in Fig. 8. This tendency is more

Journal of Colloid and Interface Science, Vol. 136,No. 1, April 1990

 EQUILIBRIUM MICELLES 239

204C

1 2 2048
048
As 1 2 As
FIG. 6. Stability domains for micelles of varying shapes. Given is the relative change in equilibrium
concentration 4)b for A11B3 micelles of different shapes, characterized by the parameters Asand h. The overall
surfactant volume fraction is near its CMC. In the graph with iso-4)2 b lines the fault line gives the limit of
the physically significant area (h 2 = 7rAs).Parameters as in Fig. 5.

p r o n o u n c e d w h e n the tails are longer. There-
fore, lecithin m o l e c u l e s are likely to prefer fiat
m e m b r a n e s over small micelles. A d d i t i o n a l
details o f the crossover f r o m a given associa-
t i o n structure into a n o t h e r as a f u n c t i o n o f
m o l e c u l a r architecture are given elsewhere (3).
T h e p r e d i c t i o n s o f m i c e l l a r shapes as a
f u n c t i o n o f the p r o p e r t i e s o f the a m p h i p h i l e s
f o u n d b y o u r a p p r o a c h are in g o o d a g r e e m e n t
with the t h e o r y o f Israelachvili et al. ( 1 7 - 2 0 ) ,
w h o base their p r e d i c t i o n s o f the shape o f the
association colloids o n the architecture o f the
a m p h i p h i l i c molecules. Indeed, a change in
the i n t e r a c t i o n p a r a m e t e r s shifts the absolute
value o f the C M C , b u t has little effect on the
qualitative t r e n d s t h a t we have shown. This
p r o m i s i n g result gives h o p e o f studying m o r e
c o m p l i c a t e d systems in future. E.g., it is
straightforward to study the effect o f additives
o n the C M C or o f specific groups in the a p o l a r
tails on the s e g m e n t distributions.
CONCLUSIONS
T h e t h e r m o d y n a m i c s o f small systems is
c o m b i n e d with a statistical t h e r m o d y n a m i c a l
Self-Consistent F i e l d T h e o r y a n d a p p l i e d to
a m p h i p h i l i c m o l e c u l e s in a q u e o u s solutions.

204~"

h
204~'

h ~,

2 jj' i 2o48
1 2 2048 1~ As
AS

FIG. 7. Stability domains for micelles of varying shapes. See also Fig. 6. In this case the overall surfactant
concentration is very high so that the micelles do not have any translational entropy (A" = 0).

Journal of Colloid and Interface Science, Vol. 136, No. 1, April 1990
240 LEERMAKERS AND SCHEUTJENS
2048
1 2
As
FIG. 8. Stability domains for micelles of varying shapes for the lipid molecule with a lecithin-like structure
at moderate overall volume fractions. See also Fig. 6.
The theoretical CMC is found to be a well
defined concentration, but is not easily found
experimentally because of the low concentra-
tion of the micelles at the CMC. We showed
that the very first micelles to form are globular
and have fluctuations in size. The general
structure of the micelles agree with recent M D
and MC simulations. However, we find that
long range interactions are not essential for
the stabilization of the aggregates, because un-
favorable nearest neighbor interactions be-
tween head groups and tails can limit the size
of micelles. At higher surfactant concentration
the micelles can change their shapes and large
fluctuations with respect to their shapes are
predicted. This behavior strongly depends on
the architecture of the molecules. Lecithin-like
molecules are shown to prefer membrane-like
structures, whereas short-chain surfactants will
form relatively small aggregates even at high
surfactant concentration.
ACKNOWLEDGMENTS
The work of F.A.M.L. is part of the research program
of the Sfichting Scheikundig Onderzoek Nederland
(S.O.N.), which is financially supported by the Nederlandse
Organisatie voor Wetenschappelijk Onderzoek (N.W.O.).
Journalof Colloidand InterfaceScience. Vol. 136,No. 1, April1990
2048
2048
2 As
2048
A8 - - B - - A
I
As - - B - - A
[
A--B3
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