PHYSICAL REVIEW E 87, 032307 (2013)

Phase transitions and phase equilibria in spherical confinement

Alexander Winkler, Antonia Statt, Peter Virnau, and Kurt Binder
Institut für Physik, Johannes Gutenberg-Universität Mainz, Staudinger Weg 7, D-55099 Mainz, Germany
(Received 7 December 2012; published 20 March 2013)
Phase transitions in finite systems are rounded and shifted and affected by boundary effects due to the surface
of the system. This interplay of finite size and surface effects for fluids confined inside of a sphere of radius R
is studied by a phenomenological theory and Monte Carlo simulations of a model for colloid-polymer mixtures.
For this system the phase separation in a colloid-rich phase and a polymer-rich phase has been previously studied
extensively in the bulk. It is shown that spherical confinement can strongly enhance the miscibility of the mixture.
Depending on the wall potentials at the confining surface, the wetting properties of the wall can be controlled, and
this interplay between preferential adsorption of one species to the confining surface and bulk unmixing leads to
very special shapes of the loops observed for the chemical potential of the colloids as a function of their packing
fraction. We also discuss the extent to which concepts used for phase transitions in macroscopic systems, such
as critical exponents of the order parameter distinguishing the phases, or the Kelvin equation describing the shift
of the chemical potential at phase coexistence with the radius R, are applicable.

DOI: 10.1103/PhysRevE.87.032307 PACS number(s): 64.75.Xc, 82.70.Dd, 47.57.J−, 64.60.an

I. INTRODUCTION formation of (macroscopically thick) wetting or drying layers,

The recent interest in exploring nanomaterials and nanoflu-
idic devices [1–3] urgently emphasizes the need for a better
understanding of the phase behavior of materials when one
constrains them to exist in nanoscopic dimensions. While some
aspects of the general problem have received longstanding
attention (e.g., it is well-known that very small ferromagnetic
particles can exist in monodomain states and behave as
superparamagnets [4–6], and near the Curie temperature their
phase transition to the standard paramagnetic phase is rounded
[7]), phase separation of fluids in spherical confinement has
received attention only recently; e.g., progress in the prepara-
tion of miniemulsions as “containers” for polymer blends [8,9]
allows for the production polymer nanoparticles that exhibit
phase separation [10]; both “Janus particles” [11–13] and
core-shell nanoparticles [14] are clearly of interest.
While the general aspects of the phase behavior of simple
fluids or of binary mixtures of small molecules in the bulk
is well understood [15,16], progress has also been made in
clarifying phase diagrams and critical phenomena in various
complex fluids, such as binary polymer blends [17,18], poly-
mer solutions [19,20], colloid-polymer mixtures [21,22], etc.,
clarifying properties of such systems in confined geometries
is still an active field of research; see, e.g., Refs. [22–27]. The
special case that is best understood are systems that have finite
linear dimensions but no surfaces, e.g., a cubic L × L × L
box with periodic boundary conditions; this case is relevant
for computer simulations [28–30], and the finite-size scaling
theory [29] accounts for the corresponding rounding and
shifting of phase transitions. The finite-size effects on phase
coexistence for such systems have also been analyzed recently
[31–35]. However, for systems of experimental interest in
reduced geometry always both finite-size effects and surface
effects due to the constraining walls are present. When a bulk
fluid is exposed to a wall (i.e., a semi-infinite geometry),
the interactions of the fluid with the wall may give rise to a
wealth of interesting wetting and layering phenomena [36–39].
Confining the fluid in a slit pore (e.g., Refs. [22–25]), the
finite distance D between the confining walls precludes the
and hence wetting transitions [37–39] are also rounded [22].
Note that such a system is still infinite in two spatial
dimensions, and hence sharp phase transitions still occur,
which are predicted to fall in the universality class of the two-
dimensional Ising model (see, e.g., Ref. [22]). If we consider
cylindrical pores of diameter D instead, the system is quasi-
one-dimensional (if the cylinder length Lcyl tends to infinity).
This fact implies the absence of “true” phase transitions (in the
sense of sharp singularities of the thermodynamic potentials),
but for finite Lcyl , one still may find rather sharp transitions
between monodomain and multidomain structures [26]. For
spherical confinement, however, no length scale larger than
the sphere diameter can evolve, of course, and hence all phase
transitions are rounded off. Nevertheless, away from criticality
interfacial widths may be much smaller than the sphere
diameter, and thus rather well-defined two-phase coexistence
inside the sphere becomes possible. The resulting morphology
of the system depends on the interplay between the interfacial
free energy between the coexisting phases (in the bulk) and
their surface excess free energies due to the wall, analogous to
the case of wetting phenomena at planar surfaces [37,39].
In the present study, we aim to contribute to the under-
standing of this problem by Monte Carlo simulations of a
simple model, supported by a brief outline of the appropriate
phenomenological theory (Sec. II). The model that is studied
here (Sec. III) is the Asakura-Oosawa (AO) model [40] of
colloid-polymer mixtures. In this model, colloids are modeled
as hard spheres of radius Rc , which must not overlap with each
other nor the polymers. The latter, however, are modeled as
soft spheres of radius Rp , which may overlap with no energy
cost, and provide the entropic attraction between the colloid
particles causing the phase separation in a colloid-rich and
a polymer-rich phase. Despite its simplicity, this model is a
rather good description of real colloid-polymer mixtures [21],
which also are a very suitable experimental model system for
the study of interfacial phenomena [41], wetting layers [42],
etc. Experimental evidence [43] and simulations [44,45] show
that the critical behavior of this system falls in the universality

1539-3755/2013/87(3)/032307(13) 032307-1 ©2013 American Physical Society

WINKLER, STATT, VIRNAU, AND BINDER
class of the three-dimensional Ising model [15]. Since colloidal
particles have radii of about 1 μm, the direct experimental
counterpart to our simulation results (Sec. IV) would require
us to confine such systems in cavities with radii 10 to 100 μm.
Presumably, such studies will be difficult, and one might
ask why we do not use models for polymer mixtures (e.g.,
Refs. [46,47]) in view of the fact that first experiments to study
phase separation of polymer blends confined in miniemulsions
(of diameters in the 100-nm range) are available [10]. However,
since such studies would require huge computational effort
(unlike the case of colloid-polymer mixtures the internal
conformational degrees of freedom of the polymers need to be
accounted for [46,47]) and the existence of another large length
scale, namely the correlation length at which the mean-field
to Ising crossover [17,46] occurs, complicates the quantitative
understanding of this system. However, we feel that the case of
the AO-model in spherical confinement can serve as a generic
model for the interplay of finite-size and surface effects of
all fluids and fluid mixtures separating into coexisting phases
under spherical confinement.
II. PHENOMENOLOGICAL CONSIDERATIONS
A. The order parameter distribution near criticality
A basic quantity often used to discuss finite-size effects on
systems exhibiting phase transitions from a homogeneous state
toward phase coexistence is the distribution function PL (M)
of the “order parameter” M used to distinguish the phases. In
an Ising ferromagnet, M would be the magnetization per spin,
while in a binary polymer blend (A,B) it would be the relative
monomer concentration of one of the species. In the colloid-
polymer mixture, we may take M = ηc − ηccrit , ηc being the
colloid packing fraction in the considered volume V and ηccrit
its value at the critical point, Nc being the number of colloids
of radius Rc in the system
  
ηc = 4π Rc3 3 Nc /V . (1)
Strictly speaking, the optimum choice for the order param-
eter actually is a linear combination [48] of ηc − ηccrit and
ηp − ηpcrit , ηp being the packing fraction of the polymers,
defined analogously [ηp = (4π Rp3 /3)Np /V , with Np being
the number of polymers in the system]. However, this
complication is not essential for what follows and, hence, shall
be ignored here.
In the distribution function PL (M), the index L stands for
the linear dimension of the considered volume V [we take L =
V 1/3 for a cubic box, but L = R = (3V /4π )1/3 for a spherical
cavity]. If one disregards any effects due to the surface of this
volume V , which is appropriate only for the case of periodic
boundary conditions, of course, PL (M) near the critical point
can be written as [28–30]
PL (M) = Lβ/ν P̃ (MLβ/ν , H L(β+γ )/ν , L/ξ ), L → ∞, (2)
where β and γ are the standard critical exponents of the
order parameter M and the susceptibility kB T χ , ν is the
critical exponent of the correlation length ξ of order parameter
fluctuations, P̃ is a scaling function, and H the thermodynamic
variable conjugate to the order parameter. For the Ising
magnet, H would simply be the magnetic field; for the
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PHYSICAL REVIEW E 87, 032307 (2013)
symmetric polymer blend, H is a chemical potential difference
between the species; for the colloid-polymer mixture, H is the
difference between the colloid chemical potential μ and its
value μcoex (ηpr ) at two-phase coexistence, H = μ − μcoex (ηpr ).
Here, we have noted the fact that in systems lacking any
symmetries between the coexisting phases, such as colloid-
polymer mixtures, phase coexistence occurs at a nontrivial
value of the chemical potential (unlike the Ising magnet where
symmetry requires phase coexistence at magnetic field H =
0), which depends on the temperature-like control variable, ηpr .
The latter is given by the product of fugacity exp(μp /kB T )
of the polymers (μp being their chemical potential) and the
polymer volume, ηpr = (4π Rp3 /3) exp(μp /kB T ). Varying this
so-called “polymer reservoir packing fraction”, the density
of polymers in the suspension is controlled. In the Ising
magnet, ηpr would correspond to inverse temperature (kB T )−1 ,
and in the polymer blend the corresponding variable is the
Flory-Huggins parameter [17]. Following a path H = 0,
the quantities defined above exhibit the well-known critical
behavior in the bulk [15]
 β  −ν
M ∝ ηpr − ηp,critr
, ξ ∝ ηpr − ηp,crit
r  , (3)
 −γ
kB T χ = V (M 2  − M2 ) ∝ ηpr − ηp,crit
r  (4)
and the critical exponents describing these singularities have
their well-known values [49] β ≈ 0.325, ν ≈ 0.63, and γ ≈
1.24.
As has been said above, in the finite system these singular-
ities are rounded off, and one has instead (for H = 0 we need
to take |M| rather than M in the finite system [50])
|M| = L−β/ν M̃(L/ξ ), χ = Lγ /ν χ̃ (L/ξ ), (5)
where M̃ and χ̃ are scaling functions, with M̃(0), χ̃(0) being
constants. Thus, |M| does not vanish in the finite system at
criticality, and χ does not diverge but reaches a maximum of
finite height (proportional to Lγ /ν ). Considered as a function
of ηpr , both |M| and χ (and any moments M k  of the order
parameter distribution function) are analytic. Nevertheless, the
location of the critical point can be inferred from suitable
ratios, such as [50] M 4 /M 2 2 . As an example, Fig. 1
shows corresponding data for the choice Rp /Rc = 0.8 and
three choices of V : one sees that any such ratio M 4 /M 2 2
is a smooth function of ηpr (actually a straight line for ηpr
r r
close enough to ηp,crit ), but ηp,crit is well defined nevertheless
r
from the intersection point of these curves at ηp,crit , since
the ratio U = M 4 /M 2 2 = Ũ (L/ξ ) = Ũ (0) when ξ → ∞,
so at criticality there is no longer L dependence. Figure 1
also illustrates that the order parameter distribution PL (M)
of the AO model at criticality converges to that of the
three-dimensional Ising model, but this still is a double-peaked
distribution: if we would locate criticality from the value
ηpr where the shape of the distribution changes from double
peak to single peak (far in the one phase region PL (M) is
always a simple Gaussian, see, e.g., Ref. [50]), we would
r
underestimate ηp,crit systematically. Thus, while for ηpr 
r
ηp,crit one may simply estimate the packing fractions of the
two coexisting phases from the peak positions of PL (M),
r
this gives systematically wrong results near ηp,crit : we find
a distance between the peak positions of order L−β/ν still for
PHASE TRANSITIONS AND PHASE EQUILIBRIA IN . . .
FIG. 1. (Color online) (a) Plot of the moment ratio M 4 /(M 2 )2
of the AO-model with Rp /Rc = 0.8 versus ηpr for different volumes
as indicated, yielding an estimate of the critical point from the unique
r
intersection point at ηp,crit = 0.7670, consistent with values from
literature [44]. Lengths are measured in units of the colloid 
Rc = 1. (b) Rescaled order parameter distribution P (M)/ M 2 
versus M/M 2 , with M = ηc − ηc,crit , taken at ηp,crit
r
, for the largest
volume included in (a). The result for the three-dimensional Ising
model is included for comparison.
ηpr  ηp,crit
r
. Fitting the power law M ∝ (ηpr − η̃p,crit
r
)β to the
r r
data, using η̃p,crit as the value of ηp , where the minimum in
PL (M) disappears, one automatically must find the mean field
value β = 1/2, since for finite volume PL (M) is an analytic
function of ηpr [51].
Unfortunately, it is not straightforward to obtain any simple
results in the case of a finite system with surfaces. Then the
generalization of Eq. (2) involves an additional “field” H1 ,
which describes the preferential attraction of one of the species
to the surface [52,53]
PL (M) = Lβ/ν P̃ (MLβ/ν ,H L(β+γ )/ν ,H1 L 1 /ν ,L/ξ ),
L → ∞,
where the associated critical exponent 1 ≈ 0.47 ± 0.03 [51].
While in an Ising ferromagnet H1 is a local magnetic field
acting only on the surface layer of the system, and for small
magnetic particles such a field normally will not be present, we
do expect some preferential attraction (which we assume to be
of short range here) of one species of a mixture to the surface,
both in the case of polymer blends and of colloid-polymer
mixtures. In the latter case, an entropic attraction of colloids
to a wall occurs if the wall is purely repulsive for both colloids
and polymers (see, e.g., Ref. [22]); however, if one adds a soft
repulsive potential acting on the colloids [27], one can change
the behavior of a planar wall from complete wetting conditions
to partial wetting or even drying. Thus, in an experiment it
is likely that one can control the parameter H1 by suitable
coating of the wall to some extent, but it is not likely that one
realizes the special case H1 = 0 over an extended regime of
the temperature-like control parameter (ηpr )−1 .
To clarify the physical effects of H1 , we recall that the free-
energy density f of a system in the presence of a surface (or
surfaces, respectively) can be split into bulk (fb ) and surface
(fs ) contributions, in the limit L → ∞
C
f (H,H1 ,L) = fbulk (H ) + fs (H,H1 ), L → ∞,
L on ηpr , but to simplify our notation this dependence is not
where C is a geometrical factor (C = 2 for a thin film with
two equivalent surfaces, while C = 3 for a sphere of radius
PHYSICAL REVIEW E 87, 032307 (2013)
R = L). Just like bulk order parameter and susceptibil-
ity follow from the derivatives M = −(∂fb /∂H )T , χ =
−(∂ 2 fb /∂H 2 )T , keeping the temperature (or temperature-like
variable ηpr , respectively) constant, one finds also the local
order parameter M1 and surface excess order parameter Ms
from analogous derivatives:
M1 = −(∂fs /∂H1 )T ,H ; Ms = −(∂fs /∂H )T ,H1 . (8)
Noting that the free-energy density f can also be expressed
in terms of the order parameter distribution PL (M) as

f (H,H1 ,L) = −(kB T /V ) ln dMPL (M) + const, (9)
it is easily seen that the singular parts of f and fs satisfy
radius, similar scaling properties as written in Eq. (7), in particular
fs (H,H1 ,L) = ξ −2 f˜s (H L(β+γ )/ν ,H1 L 1 /ν ,L/ξ ), L → ∞.
(10)
From Eqs. (8) and (10), one finds that the critical behavior
of the surface excess order parameter is
Ms (H,H1 ) ∝ ξ β/ν−1 M̃s (H1 ξ 1 /ν ,H ξ (γ +β)/ν ), (11)
where M̃s is another scaling function. From Eq. (11), one
concludes that Ms diverges as one approaches criticality, and
its response to H1 is also divergent, implying that the order
parameter in the finite system must deviate very strongly from
its value in the bulk, since Eq. (7) also implies
C
M(H,H1 ,L) = Mbulk (H ) + Ms (H,H1 ). (12)
L
While the divergence of Ms (0,0) in the finite system again
will be rounded off, it is clear that the interplay of finite-size
(6)
effects on bulk and surface excess properties at criticality must
lead to a rounding and shifting of the singularities, which
strongly depends on H1 .
B. Interplay of finite-size and surface effects
on phase coexistence
We now focus on the regime where two-phase coexistence
occurs in the bulk, i.e., ηpr  ηp,crit
r
, and hence one reaches
easily the limit L  ξ , which means that Eqs. (7)–(10) are
useful for the interpretation of the actual simulation data. As
a first step, we ignore the finite-size effects completely and
take only the surface effects into account. Denoting the phase
rich in colloids as “liquid” () and the phase rich in polymers
(and hence poor in colloids) as “vapor” (v), we note that at
phase coexistence the free-energy densities fv and f of the
two coexisting phases are equal, and using Eq. (7), this implies
(we now use L = R here for spherical geometry)
3
fv (H,H1 ,R) = fb,v (H ) + fs,v (H,H1 )
R
3
= f (H,H1 ,R) = fb, (H ) + fs, (H,H1 ).
R
(13)
(7) Of course, all these bulk and surface free energies depend
explicitly written here. A more subtle point is the fact that
for finite R one must also expect a curvature dependence
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WINKLER, STATT, VIRNAU, AND BINDER PHYSICAL REVIEW E 87, 032307 (2013)

of the wall excess free energies fs,v , fs, . Such a curvature

dependence is familiar from the problem that spherical liquid
droplets coexist with surrounding vapor [54]. If we generalize
the standard expression for the vapor to liquid transition [33]
to the present case, we obtain

fs (H,H1 ,R) = fs (H,H1 ,∞)/[1 + 2δ/R + 2(/R)2 ], (14)

where fs (H,H1 ,∞) is nothing but the surface excess free

energy due to a planar wall, δ is the analog of a Tolman [54]
length, and  is another characteristic length appearing in the
FIG. 2. Schematic colloid density profiles ρc (r) versus r of
higher correction 1/R 2 . However, to the two leading orders in
coexisting vapor-like and liquid-like states in a spherical cavity of
1/R, for which we wish to study the shift of the location of
radius R, assuming that the wall exhibits a preferential attraction to
the transition, this term does not yet enter. Since in all known
the colloids rather than the polymers. Note that the actual colloid
cases of interest the Tolman length δ is very small, we thus density profiles of colloids will exhibit layering close to the wall of
neglect it here as well. the cavity. For detailed discussion see text.
We then use the expansions (remember that H = μ − μcoex
when we deal with a colloid-polymer mixture) of the transition, it predicts for H = Ht a sharp jump from

fb,v (H ) = fb,v (0) − ρc,v H − 12 χv H 2 , 3

(15) ρc,v (Ht ,R) = ρc,v + χv Ht + ρs,v (0,H1 ) + · · · (19)
R
fb, (H ) = fb, (0) − ρc, H − 12 χ H 2 , (16) to
fs,v (H,H1 ) = fs,v (0,H ) − ρs,v (H1 )H, 3
ρc, (Ht ,R) = ρc, + χ Ht + ρs, (0,H1 ) + · · · . (20)
(17) R
fs, (H,H1 ) = fs, (H,H1 ) − ρs, (H1 )H.
3
For simplicity, only terms in first order in R
will be kept
Here, ρc,v , ρc, denote the colloid densities of the bulk here, so that
coexisting phases. In the Ising magnet, when H denotes a
magnetic field, we would instead have ±msp , the spontaneous ρc, (Ht ,R) − ρc,v (Ht ,R)
magnetization. In analogy to the Ising system, we denote the
coefficients χv , χ of the higher-order terms as “susceptibil-
ities.” Using now the fact that for bulk phase coexistence
fb,v (0) = fb, (0), Eqs. (15)–(17) and (13) yield, to order 1/R 2
3 fs, (0,H1 ) − fs,v (0,H1 )
Ht ≈
R ρc, − ρc,v
 rounded over a finite interval H around Ht . To estimate this
3 ρs, (H1 ) − ρs,v (H1 )
× 1−
R ρc, − ρc,v
2
 at H = H1 can jump back and forth between both coexisting
χ v − χ 3 fs, (0,H1 ) − fs,v (0,H1 ) 2
+ .
2(ρc, − ρc,v ) R ρc, − ρc,v
(18)
Thus, any difference in the surface excess free energy due to
the wall of the spherical container shifts the chemical potential
μ at which phase coexistence occurs away from its bulk value
μcoex . This is the analog of the phenomenon of “capillary
condensation,” familiar from slit pores and cylindrical pores
[23–25]. To leading order this shift is proportional to 1/R,
but in the regime of interest for our simulations the next
order term (proportional to 1/R 2 ) must not be neglected. Note
that the last term on the right-hand side of Eq. (18) does not
occur for the Ising model, where χv = χ due to spin reversal
symmetry. Note that this transition is not a transition between
homogeneous states, like in the bulk, but rather between
different density profiles (Fig. 2). The detailed features of
these density profiles will be discussed at the end of Sec. IV.
Equation (18) is our first important result of this section,
and it will be put to a numerical test in Sec. IV. However, our
treatment so far completely neglects the finite-size rounding
032307-4
 
3 ρb, (0,M1 ) − ρs,v (0,H1 )
= (ρc, − ρc,v ) 1 +
R ρc, − ρc,v
(χ − χv )(fs, − fs,v )
+ . (21)
(ρc, − ρc,v )2
In typical cases the correction term is negative, and so
the magnitude of the density jump is reduced. But it also is
interval, we note that in the finite volume 4π R 3 /3, the system
phases with densities ρc, (Ht ,R) and ρc,v (Ht ,R), and hence
the fluctuation relation of the order parameter susceptibility
yields [cf. Eq. (4)]
kB T χ (H = Ht ) = (4π R 3 /3)[(ρc, (Ht ,R) − ρc,v (Ht ,R)]2 .
(22)
Thus, the isotherm ρ(H ) as function of H has at H = Ht a
very steep slope, which scales linearly with the volume of the
sphere. In the interval H around Ht , the variation of H takes
the system from ρc,v (Ht ,R) to ρc, (Ht ,R), and hence we have
ρc, (Ht ,R) − ρc,v (Ht R) = H χ , (23)
and using Eq. (22) this yields a rounding that scales inversely
with the volume,
H /kB T = {(4π R 3 /3)[ρc, (H1 ,R) − ρc,v (H1 ,R)]}−1 . (24)
While for systems with periodic boundary conditions,
rounding and shifting of a first order transition both scale
inversely with the system volume, in the case of spherical
confinement the situation is different, the shift (∝1/R) is in
general much larger than the rounding (∝1/R 3 ).
PHASE TRANSITIONS AND PHASE EQUILIBRIA IN . . .
(a)
(b)
FIG. 3. Schematic comparison of phase coexistence in a spherical
cavity, as predicted in the grand-canonical ensemble (a) and the
canonical ensemble (b). In (a) the colloid density ρc is obtained as a
statistical average as function of the chemical potential μ, while in
(b) the chemical potential μ and the free-energy difference f (ρc )
are plotted as a function of ρc , treating ρc as the fixed thermodynamic
variable. Only for R → ∞ is μ = μ(ρc ) simply the inverse function
of ρc = ρc (μ). Dash-dotted curves refer to finite R. Broken horizontal
straight lines in (b) indicate the Maxwell construction (left part) or
double-tangent construction (right part), respectively. Free-energy
differences f (ρc ) refer to H = 0(R → ∞) or H = Ht (finite R),
respectively. For further explanations cf. text.
Figure 3 gives a qualitative sketch of the situation, where the
reader is also reminded of the fact that the observed finite-size
effects depend upon the statistical ensemble that is chosen. In
the grand canonical ensemble, with the chemical potential μ
as an independently fixed thermodynamic variable controlling
the system, the conjugate variable (the colloid density ρc ) is
a monotonically increasing function of μ. If we choose the
conjugate statistical ensemble, in the thermodynamic limit the
existence of a Legendre transformation implies that nothing
changes, ensemble equivalence implies that all what happens
is an interchange of ordinate and abscissa, the jump from ρc,v
to ρc, at μ = μcoex becomes a horizontal plateau for μ in the
region ρc,v  ρ  ρc, , at a value μcoex . Still, ρ as a function of
increasing μ also increases monotonically. This is not true in
finite systems, however: now we obtain a loop in the μ versus
ρ curve (Fig. 3). In the finite system, the curve μ as function
of ρ (ρ being given and μ a fluctuating observable) is not the
inverse function of the ρ versus μ curve (μ being given and
ρ a fluctuating observable). As we shall see later, the detailed
shape of the loop in the canonical ensemble reflects interfacial
contributions to the free energy of the finite system. Due to
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these interfacial contributions, the difference f (ρ) of the free
energy f (ρ) and its value at phase coexistence, f (ρc,v (R))
has a double-minimum shape, but the hump in between the
vapor-like phase [at colloid density ρc,v (R)] and the liquid
phase [at colloid density ρc, (R)] also scales like 1/R, and
hence f (ρc ) smoothly converges toward the double-tangent
construction that results for R → ∞, where f (ρc ) = 0 for
ρc,v  ρc  ρc, . In Fig. 3(b), f (ρc ) for finite R has been
shifted upward for the sake of clarity.
Finally, we address the interesting issue of the crossover
of the results of Eqs. (18) and (24) to the scaling description
based on Eq. (6). We note that near criticality we may write
ρc, − ρc,v ∝ ξ −β/ν and using the hyperscaling relation 3 =
2β/ν + γ /ν, one readily concludes from Eq. (24) that near
criticality a rounding results:
H ξ (γ +β)/ν ∝ (ξ/R)3 . (25)
Thus, when ξ is of order R(= L), we recover the scaling
dependence written in Eq. (6), as it should be. Recalling the
scaling of surface excess free energies [53], f˜s being a suitable
scaling function,
fs = ξ −2 f˜s [H ξ (γ +β)/ν ,H1 ξ 1 /ν ], (26)
we recognize from Eq. (18) that to leading order near criticality
the shift becomes, with f˜s = f˜s, − f˜s,v ,
ξ
Ht ξ (γ +β)/ν ∝ f˜s (H1 ξ 1 /ν ), (27)
R
where putting ξ of order R(=L), a scaling behavior compatible
with Eq. (6) indeed is found. In any case, for R  ξ , the fact
that the shift scales like ξ/R while the rounding scales like
(ξ/R)3 is maintained. However, a detailed test of Eqs. (25)–
(27) will be left to future work.
III. COMMENTS ON THE SIMULATED MODEL
We here use the standard Asakura-Oosawa model [40],
where colloids are represented as hard spheres of radius Rc = 1
(being our unit of length), while polymers are soft spheres of
radius Rp = 0.8, which may overlap with each other without
energy cost, while the overlap of polymers with colloids is also
strictly forbidden. As has already been stated in Sec. II A, in
the simulations it is convenient to work in the grand-canonical
ensemble with the chemical potentials μp and μ of polymers
and colloids as thermodynamic parameters that are varied.
Note that there does not occur any energy parameter in this
model; the effective interactions between the particles are
purely entropic in origin. However, one can use the “polymer
reservoir packing fraction” ηpr = (4π Rp3 /3) exp(μp /kB T ) as
a parameter playing the role of inverse temperature, when we
compare the phase behavior of this system to other models.
One motivation for the choice of this model is the fact that its
bulk properties have been studied extensively in previous work,
r
the critical point occurs at ηp,crit = 0.767 (see also Fig. 1),
and the phase diagram in the bulk is also known with good
accuracy [44,45]. As a potential between the particles and
confining walls, we use a hard-core repulsion as well, both for
WINKLER, STATT, VIRNAU, AND BINDER
colloids (Ucw ) and polymers (Upw ),
Ucw (z) = ∞, z < σcw , Ucw (z) = 0, z > σpw
Upw (z) = ∞, z < σpw , Upw (z) = 0, z > σpw ,
where z is the normal distance between the center of mass
position of a particle and the wall. We only consider the
special case where the ratio of the repulsion ranges σpw /σcw
is the same as the ratio of particle’s radii, σpw /σcw = 0.8.
For this special case, the range σwc has been varied over a
wide range, and for one value of ηpr , where the system in
the bulk is well separated, namely ηpr = 0.94, the wetting
properties of planar walls have been studied [27]. At this value
of ηpr , the coexistence packing fractions of the colloids have
been estimated as ηc,v = 0.0077 and ηc, = 0.3117 [27], while
the interfacial tension fint between both coexisting phases is
fint = 0.2029 (note that a factor 1/kB T has been absorbed
in all interfacial and surface excess free energies throughout)
[27]. Using the so-called “ensemble switch method” [27], the
difference fs between the surface excess free energies of
the vapor-like phase and the liquid-like phase at a planar wall,
where the potentials Eqs. (28) and (29) act, can be found. Since
this difference is related to the contact angle θ via Young’s
equation [36–39],
cos θ = fs /fint , fs = fs,v − fs, ,
the ratio at the right-hand side of this equation is plotted versus
the range of the wall potential σwc in Fig. 4. One can see
that the wetting transition occurs for σwc = 0.59, while the
drying transition occurs for σwc = 0.78. Thus, a relatively
small variation of σwc suffices to change the state of the
(planar) wall from wet to dry. For σwc ≈ 0.6755, we have
the special case of neutral walls, fs = 0: Then, the contact
angle θ = π/2 implies that vapor-liquid interfaces have to be
1.5
sim. results
fit
1
0.5
Δ fs / fint
0 for ηpr = 1.40 the effective free energy F (Nc ) as function of
-0.5
-1
-1.5
0.5 0.6 0.7 0.8
σw
FIG. 4. (Color online) Normalized surface free-energy difference
fs /fint of the AO model at ηpr = 0.94 plotted vs. the range σwc of
the colloid-wall potential. When fs /fint < −1, complete “drying”
occurs (i.e., polymers form a wetting-like layer at the wall in the
colloid-rich phase). For −1 < fs /fint < +1, the wall is partially
wet. Therefore, the cases fs /fint = ±1, where the (first-order)
wetting or drying transition takes place, are highlighted by horizontal
straight lines.
PHYSICAL REVIEW E 87, 032307 (2013)
oriented perpendicular to the wall. This special case of “neutral
walls” is also of particular interest since then in Eq. (18) the
(28) coefficient of the leading 1/R term of the shift of the transition
(29) vanishes, and a much weaker shift (∝1/R 3 ) remains.
Since the methodology yielding the data shown in Fig. 4
has been explained elsewhere [27], we immediately turn to the
results obtained for the AO model in spherical confinement,
using radii in the range 5  R  10. In Fig. 2, schematic
colloid density profiles for spherical confinement are shown.
Phase coexistence in the cavity is shifted to a value of
the chemical potential μ at which the bulk system is off
coexistence in the vapor-like phase [Ht < 0, ρc (Ht ) < ρc,v ]. A
liquid-like wetting layer at the wall, the average colloid-density
ρc,v (Ht ,R) in the cavity typically will exceed ρc,v . This
wetting-like layer is separated by a vapor-like interface (of
thickness 2 ξ ) from the central vapor region. On the other
hand, in the corresponding liquid-like state, the average colloid
density in the pore, ρc, (Ht ,R), still can be less than the bulk
coexistence density ρc, : As coexistence occurs at Ht < 0, the
liquid density ρ (ms) (Ht ), which would correspond to a bulk
metastable (ms) state, because at Ht < 0 only the vapor-like
state is stable, is less than ρc, .
IV. SIMULATION RESULTS FOR SPHERICALLY
(30) CONFINED COLLOID-POLYMER MIXTURES
The first case that shall be considered is σwc = 0.5 (and,
consequently, σwp = 0.4), a case which, according to Fig. 4,
for ηpr = 0.94 is far away from the wetting transition, deep
inside the region when for a planar wall at phase coexistence
complete wetting of the colloid-rich phase occurs. From the
general theory of wetting phenomena [37–39], it then follows
that for all smaller values of ηpr (closer to the critical point)
the system is also in the complete wetting regime. Although
one might expect that for very large ηpr one encounters the
wetting transition, where the state of the planar wall changes
from complete to partial wetting, it is not clear whether or not
this regime has been reached in our simulations, which were
restricted to ηpr < 1.5 (note that the cluster algorithm [44,45]
that is needed for the implementation of the grand-canonical
ensemble simulation becomes inefficient for larger ηpr ). As
an example for the data that can be obtained, Fig. 5 shows
the number Nc of colloidal particles in a sphere of radius
R = 10. The chemical potential μ of the colloids was adjusted
according to the equal weight rule [55,56], so there occurs
phase coexistence between the state containing Nc = 177
colloids and the state containing Nc = 2909 colloids. Indeed,
in the vapor-like state (Nc = 177) all colloidal particles are
very close to the confining surface, but clearly their total
number is far too small to enable the formation of a precursor
of a wetting layer: the latter is only seen deep inside of the
two-phase coexistence regime, such as Nc = 877. The state at
the top of the barrier is characterized by a kind of core-shell
structure, where the polymer-rich phase forms the core and
the colloid-rich phase forms the shell. While we expect that on
average the structure exhibits spherical symmetry, this is not
so for individual microstates of the system, of course, since
entropy favors that the center of mass of the polymer-rich core
coincide with the center of the sphere, in average only, but not
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PHASE TRANSITIONS AND PHASE EQUILIBRIA IN . . . PHYSICAL REVIEW E 87, 032307 (2013)

Nc=177 Nc=877

Nc=2130 Nc=2711
(a)

0.5
Nc=2909
βμ

-0.5

-1
c)
(c)
c)
0 1000 2000 3000
(b)
Nc

FIG. 5. (Color online) (a) Effective free energy βF (Nc ) of a colloid-polymer mixture confined into a sphere of radius R = 10 with repulsive
wall potential ranges σwc = 0.5, σwp = 0.4 at ηpr = 1.40 plotted vs. the number of colloids Nc . The dots show the choices of Nc for the snapshots
in part (b). Note that the zero βF (Nc ) = 0 was arbitrarily chosen. (b) Snapshots showing typical particle configuration in the sphere (one half of
the sphere is cut off, so one looks on a cross section plane containing the center of the sphere). Colloids are shown as yellow spheres; polymers
are black. States refer to different numbers of colloids Nc , as indicated. (c) Chemical potential difference βμ = ∂(βF (Nc ))/∂Nc plotted vs.
Nc , for the data shown in (a).

in individual configurations. In addition, the interface between
colloid-rich and polymer-rich phases is rather rough, and
there occur significant shape fluctuation of the polymer-rich
“droplet” in the center of the system. This is also true for
Nc = 2711, where the polymer-rich phase takes only a very
small fraction of the total volume, and due to entropic reasons,
the probability that the droplet is in the center is rather small.
We emphasize that this description of phase coexistence
inside of a spherical cavity with a wall that favors one of
the phases is very different from what one sees when one
studies cubic boxes without walls but rather choosing periodic
boundary conditions (Fig. 6). While one finds spherical
droplets of the minority phases close to the coexistence
packing fractions of the colloids (and polymers), the peri-
odic boundary conditions also stabilize structures, such as
cylindrical droplets or slab-configurations, that one would
never find for the physically more realistic case of spherical
confinement. Since for the transition from the cylindrical
morphologies to the slab one has to overcome rather high
entropic barriers in configuration space, studies with periodic
boundary conditions are plagued with hysteresis effects, and
the accurate estimation where these morphological transitions
occur is difficult [31–35]. This problem is illustrated by
the deviations between the estimates for μ found directly
from the Widom [57] particle insertion method and from
the derivative of F (Nc ). For the gas-droplet transition, two
peaks in the energy emerge at the transition point [58], which
are separated by a barrier. Therefore, if one only applies
a one-dimensional order parameter (such as the number of
particles), the transition point can be obscured because the
simulation has to push the configuration over the barrier. This
may explain the differences between the two measurements of
the chemical potential, as seen for the cylinder-slab transition
in Fig. 6(a).
For spherical confinement, no evidence for the presence of
any entropic barriers was found, and hence we feel that our
data should be fully reliable.
Figure 7 now summarizes some basic findings of the
present study. While in fully grand-canonical representation
(ηpr versus μ) the capillary-condensation-type shift of phase
coexistence caused by the wall is rather regular and not very
large [Fig. 7(a)], the distortion of the phase diagram in the
(ηpr , ηc ) representation is rather dramatic [Fig. 7(b)]. Note that
the data included here are simply the minima recorded for the
potential βF (Nc ) versus Nc at the various choices of R and
ηpr , for the chemical potential μ at which phase coexistence
according to the “equal weight rule” occurs, as mentioned
above [Fig. 5(a)]. We caution the reader that in finite systems
the finite-size effects do depend on the type of statistical
ensemble that is chosen, as discussed in Sec. II. This means,
that in Fig. 7(a) only the transition line for R → ∞ is well
defined, while for finite values of R the transition is rounded.
However, on the scales of Fig. 7(a), the rounding, in fact, is
much less than the size of the symbols [recall that the shift

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WINKLER, STATT, VIRNAU, AND BINDER PHYSICAL REVIEW E 87, 032307 (2013)

(a)

(b)
(c)

FIG. 6. (Color online) (a) Effective free energy βF (Nc ) of a colloid-polymer mixture in a cubic L × L × L box with L = 26 and periodic
boundary conditions. The dots show the choices of Nc for the snapshots in panel (b). All data refer to ηpr = 1.30. (b) Snapshots showing typical
particle configurations in the cubic box (colloids are shown in yellow; polymers are dark). States refer to the choices Nc = 121 (colloidal
droplet of spherical shape), Nc = 426 (cylindrical droplet of colloids), Nc = 777 ( slab configuration), Nc = 1060 (cylindrical polymer-rich
droplet) and Nc = 1365 (spherical polymer-rich droplet). (c) Chemical potential μc as a function of Nc , taken as a derivative of the data from
part (a), red curve, and determined directly by the Widom particles insertion method. The maximum (minimum) of this curve corresponds to
the droplet (bubble) evaporation/condensation transition [31–35], while the steps signify the transitions in droplet (bubble) morphology.

μcoex (R) − μcoex (∞) ∝ R −1 , while the rounding scales
as R −3 ]. In the fully canonical representation of the phase
diagram, ηp versus ηc [Fig. 7(c)], size effects are somewhat
less pronounced than in Fig. 7(b).
Since we have seen that in the bulk the difference ηc, − ηc,v
should follow a power law [Eq. (3)] with the critical exponent
β = 0.325, and the actual data for the bulk (taken from [44,45])
that are included in Fig. 7(b) are nicely compatible with this
prediction, it is tempting to try such an analysis also with
the data shown in Fig. 7(b) for finite R. This is shown in
Fig. 8: while with three adjustable parameters reasonably good
fits can be obtained, one must not attribute much physical
significance to the effective critical exponents βeff (R) and
r
effective critical points ηp,c (R): in a finite volume, no true
critical behavior anywhere can occur, since the growth of
critical correlations is limited by the finite sphere diameter.

FIG. 7. (Color online) Phase diagrams for spherical confinement, comparing three radii R (R = 5, 7.5, and 10, respectively) to the
corresponding bulk behavior (R = ∞, as estimated from cubic boxes with periodic boundary conditions). The packing fraction ηc is defined
as usual via ηc = Nc (Rc /R)3 with Nc being the number of colloids in the sphere with radius R. Case (a) shows the phase boundary in the plane
of variables ηpr , βμ, case (b) shows the phase diagrams in the (ηpr , ηc ) plane, and case (c) in the (ηp , ηc ) plane. The full black circle marks the
critical point. All data are for the case σwc = 0.5 σwp = 0.4. One can see from (c) that spherical confinement strongly enhances miscibility for
ηc < 0.2.

032307-8
PHASE TRANSITIONS AND PHASE EQUILIBRIA IN . . .
0.4
R=10
R=7.5
R=5
0.3
Δ
0.2
0.1
0 0
0.8 1 1.2 1.4
ηp
r r
FIG. 8. (Color online) Order parameter ηc, − ηc,v plotted vs.
polymer reservoir packing fraction ηpr , for three choices of R as indi-
cated. The full curves through the data are phenomenological fits of
the form ηc, − ηc,v = const[ηpr − ηp,c
r
(R)]βeff with {ηp,c
r
(R),βeff } =
{0.876(5), 0.63(2); 0.830(1), 0.597(8); 0.816(1); 0.544(6)} for R =
5,7.5 and 10, respectively.
It is interesting, nevertheless, to observe that due to the wall
effects the effective critical exponent βeff (R) approaches the
mean-field value βMF = 1/2 from above. [Recall that when
the two minima of F (Nc ) merge the exponent βeff (R) must
take the mean-field value βMF = 1/2, since F (Nc ) is analytic
in both Nc and ηpr and hence a Landau theory-type expansion
applies.] Also, the convergence of the corresponding colloid
packing fraction at these pseudo- “critical points” (which for
the shown values of R is close to about ηc ≈ 0.21) to the critical
packing fraction in the bulk (ηccrit = 0.134) [44] is obviously
extremely slow.
As discussed in Sec. II B, the strong size effects on the
order parameter ηc, − ηc,v in the finite-size sphere are a
consequence of the fact that (for the wall potential studied
here so far) the colloids get enriched near the wall, and
this enrichment gradually increases as ηpr increases. In order
to provide an actual counterpart to the schematic sketch in
Fig. 2, Fig. 9 shows radial density profiles of the colloids,
as observed in our simulations. In the regime where colloids
and polymers are well miscible also in the bulk (ηpr = 0.5),
we see that ηc is independent of r, apart from the immediate
neighborhood of the wall, where two layering peaks are visible.
At ηpr = 0.8, the system would be demixed in the bulk but
is still miscible in the cavity: due to the vicinity of bulk
criticality, the packing fraction profile is not constant even
far away from the wall, however. For ηpr = 1.1, however,
the system is locally unmixed also in the confined system,
a core-shell-type structure with an interface centered near
r = 6 has been formed. This transition from almost uniform
density to core-shell structure is completely gradual, no
sharp transition point for this change can be identified, of
course.
In order to make contact with the phenomenological theory
of Sec. II, Fig. 10 shows plots of ηc  versus μ at various
radii, as obtained in the grand-canonical ensemble, and the
032307-9
PHYSICAL REVIEW E 87, 032307 (2013)
ηpr = 0.5
ηpr = 0.8
1.5
ηpr = 1.1
η(r)
0.5
0 2 4 6 8 10
FIG. 9. (Color online) Radial density profiles of the colloids
ηc (r) plotted vs. r for the case R = 10, ηwc = 0.5, ηwp = 0.4 and
an average colloid packing fraction ηc = 0.214, for three choices of
ηpr , as indicated.
corresponding loops, μ versus ηc , as they are found in
the canonical ensemble, for the choice ηpr = 0.94 already
highlighted in Fig. 4 as a situation of complete wetting. The
qualitative features of the phenomenological theory sketched
in Sec. II A are indeed recovered. We indeed see that the regime
of rounding is much smaller than the shift.
In order to test the theory more quantitatively, a variation of
the range of the potential σwc of the wall has been performed.
As an example, Fig. 11 shows the particularly interesting case
of “neutral walls,” i.e., σwc = 0.6755 (cf. Fig. 4). Indeed,
one can recognize from the snapshots that in bulk vapor
(Nc = 144) and bulk liquid (N = 2036), the minority particles
are randomly distributed and there is no strong attraction to
the surface of the sphere. At the top of the (almost symmetric)
free energy [Fig. 11(a)] the configuration corresponds to the
presence of one essentially planar interface through the system.
At other packing fractions, one has either a colloid-rich (Nc =
376) or polymer-rich (Nc = 1753) wall-attached droplet. So
the free-energy barrier in Fig. 11(a) arises from moving one
interface that cuts the sphere at a circle of radius Rint through
the system, which reaches its maximal area (π R 2 ) when
Rint = R. The loops of the isotherms [Fig. 11(c)] are already
qualitatively similar to those isotherms that one finds in the
bulk [Fig. 6(c)], and they develop in the center a linear part,
with a slope that rapidly decreases as R → ∞.
At this point we comment on the shape of the free-energy
barrier F (x) as as function of the volume fraction x of
one of the phases near its maximum. For periodic boundary
conditions, this maximum Fmax is given by two planar
interfaces (of area L2 each in a L × L × L simulation volume),
Fmax = 2L2 fint , and the free-energy barrier does not depend
on x near x = 1/2, as changing the volume fraction changes
the relative sizes of the two domains, but does not change the
total interfacial area, as long as we have the slab configuration
with two planar, noninteracting interfaces. However, for a
sphere with neutral walls, for a volume fraction of the minority
phase x < 1/2, we have a reduction of the interfacial area. If
WINKLER, STATT, VIRNAU, AND BINDER PHYSICAL REVIEW E 87, 032307 (2013)

FIG. 10. (Color online) (a) “Adsorption isotherm” ηc  plotted as a function of the colloid chemical potential β μ for the case ηpr = 0.94
and complete wetting conditions (σwc = 0.5, σwp = 0.4). Four values of R are shown, as indicated. Also the case of R → ∞ (as estimated
from the system with periodic boundary conditions) is included. Insert shows a log-log plot of the maximum slope versus R. The straight
line indicates the theoretical slope 3. (b) Loops of the chemical potential βμ plotted as function of ηc , for the same case as part (a). The
horizontal dashed lines indicate the estimates of the coexistence chemical potentials of the colloids μc (R). These estimates within numerical
error coincide with the positions of the inflection points in (a). (c) The difference β[μc (∞) − μc (R)] as a function of 1/R. The straight line
illustrates that the relation Ht ≈ 1/R [Eq. (18)] holds for R  10.

the vectors from the center of the sphere to the contact line (in occurs for x = 1/2, with Fmax = π R 2 fint ). For small α, one
a cross-section containing the sphere center) make an angle can show that
2α with respect to each other, one finds that the interface is


not flat but exhibits a radius of curvature Rc = R cos α/ sin α 3α 2
(for α → 0 the interface is flat, of course, and this situation F (α) ≈ π R fint
2
1− , (31)
4

(a)

(c) (b)

FIG. 11. (Color online) (a) Effective energy free energy βF (Nc ) vs. Nc of a colloid polymer mixture confined in a sphere of radius R = 10
with σwc = 0.6755, ηpr = 0.94. The dots show the choices of Nc for which snapshots are shown in (b). (b) Snapshots showing typical particle
configurations inside the sphere (one half of the sphere being cut off, as in Fig. 5). Colloids are shown in yellow, polymers in black. States
refer to different numbers of colloids Nc , as indicated. (c) Chemical potential βμ obtained as derivative of the free energy ∂F (Nc )/∂Nc , for
neutral walls at ηpr = 0.94. Four different choices R are included, as indicated. From F (Nc ), the chemical potentials μRc at coexistence were
also estimated but not included in the figure, for the sake of clarity.

032307-10
PHASE TRANSITIONS AND PHASE EQUILIBRIA IN . . .
6.4
6.3
6.2
βμc
6.1
σwc = 0.74
σwc = 0.6755
6 σwc = 0.625
σwc = 0.6
σwc = 0.55
5.9 σwc = 0.5
0 0.05 0.1 0.15 0.2
1/R
FIG. 12. (Color online) Chemical potential μc (R) at phase coex-
istence plotted vs. 1/R at ηpr = 0.94 for 6 choices of σwc , as indicated.
Straight lines are fits to the form μc (R) = μc (∞) + a/R + b/R 2 ,
with a,b being fitting parameters. This form is suggested from
Eq. (18), since Ht ≡ μc (R) − μc (∞).
while the volume fraction scales as
x = 1/2 − 3α/16.
Thus, we find that F varies proportional to (x − 1/2)2 near
its maximum, for the case of neutral walls. The barrier is
symmetric around x = 1/2, of course. Since the radius of
curvature of F (x) in its maximum x = 1/2 diverges like R 2 ,
for R → ∞ a flat barrier (of relative order F /R 3 ∝ 1/R →
0) results, as expected.
For complete wetting, on the other hand, the situation is
completely different: the system has core shell symmetry, so
an interface occurs at a radius r < R, with a barrier F (α) =
4π r 2 fint . Since r = Rx 1/3 , with x the volume fraction of the
nonwetting phase, we see that (in the limit of R → ∞) we
simply have F / Fmax = x 2/3 , 0 < x < 1: the maximum of
the barrier moves toward x = 1 for R → ∞. For finite R,
we expect a smooth but distinctly asymmetric barrier shape,
consistent with observation [Fig. 5(a)].
We now present a test of the variation of μc (R) as a function
of R and σwc (Fig. 12). Indeed, the data are compatible
with the variation μc (R) = μc (∞) + a/R + b/R 2 , that one
expects from Eq. (18). Recalling that for ηpr = 0.94 we know
both ρc, − ρc, = 0.57442 [44] and the difference of surface
excess free energies fs, − fs,v [see Eq. (30)], a quantitative
test of the leading term in Eq. (18) actually becomes possible.
This is shown in Fig. 13. We emphasize that in Fig. 13 there
is no tunable parameter whatsoever, so the present theory is
quantitatively reliable, at least to leading order in 1/R, as
expected. Note that in the complete wetting regime the wall
excess free energy of the vapor phase indeed is [36–39]
fsv = fs + fint , complete wetting,
because then the surface is coated with a layer of the liquid-like
phase and, hence, a contact of the vapor-like phase with
the wall is avoided. Since there is a high barrier against
nucleation of such a liquid layer at a wall, when one applies
the ensemble switch method, such as in Ref. [27], the
PHYSICAL REVIEW E 87, 032307 (2013)
0.4
Ens. switch
± γlv
0.3
sph. conf.
0.2
fsv- fsl
0.1
0
-0.1
-0.2
0. 5 0. 6 0. 7 0.8
σwc
FIG. 13. (Color online) Surface free-energy difference fs,v − fs,
at ηpr = 0.94 plotted as function of σwc . Full curve are the data from
Fig. 4, while symbols with error bars show the data extracted from the
coefficient of the fits shown in Fig. 12. The horizontal straight lines
at ±fint ≡ ±0.2029 indicated where complete wetting or complete
drying occurs, respectively.
metastable continuations of fs beyond the wetting (or drying,
(32) respectively) transition could also be observed. The present
method using the extrapolation from small spheres avoids this
problem of metastability, but the first order wetting and drying
transitions in this finite geometry are somewhat rounded, of
course.
V. CONCLUSIONS
In this paper, systems undergoing a vapor-liquid-like
transition were studied for conditions of confinement within a
(mesoscopic) sphere of radius R. Phenomenological theoreti-
cal concepts were outlined and numerical tests by a simple
model were provided, namely the Asakura-Oosawa model
of colloid-polymer mixtures, with purely repulsive walls of
variable range σwc between the location of the sphere surface
and the colloid particles. While for small values of this
parameter σwc , one finds complete wetting of the wall by the
colloid-rich phase, for larger values partial wetting is found,
or even complete wetting of the wall by the colloid-rich phase
(from the point of view of the colloids, this is a “drying”
behavior of the wall).
We find that one must distinguish essentially between two
qualitatively different scenarios. For cases of complete wetting
or complete drying, the phase separation that develops in
the sphere exhibits (on average) a spherical core-shell-type
symmetry. For partial wetting, in particular, close to the
condition of neutral walls, a Janus-type morphology of phase
separation in the sphere develops.
In the case where the core-shell-structure develops, the
(33)
gradual transition from the homogeneously mixed phase in
the spherical cavity to the core-shell structure already shows
up in radial density profiles (as discussed schematically in
Fig. 2, ignoring possible layering effects at the walls, while
numerically layering can be rather pronounced, Fig. 9): in
the one-phase region (ηpr distinctly less than the critical value
032307-11
WINKLER, STATT, VIRNAU, AND BINDER
r
ηp,crit ) the surface enrichment of the component preferred by
the wall decays on the scale of the correlation length ξ (
R) profile is not very useful: the (almost) planar interface
to a constant value prevailing in the center of the sphere,
but there is no well-developed wetting-like layer. Only deep in
the two-phase region near the wall such a layer can be found
(Figs. 2 and 9). For ηpr close to ηp,crit
r
, however, ξ in the bulk
would be comparable to R, and then radial density profiles in
the sphere do not exhibit any constant parts, rather the densities
have a nontrivial radial dependence throughout the sphere.
We have paid attention to characterize the transition in
terms of the “adsorption isotherm” ηc  versus μ in the grand-
canonical ensemble, or in terms of the effective free energy
function F (ηc ) at phase coexistence in the canonical ensemble
(emphasizing the fact that for finite R no equivalence between
ensembles can be expected). The “adsorption isotherm” always
is a monotonously increasing function, in the one-phase region
its maximal slope χ scales like ξ γ /ν away from bulk criticality
but like R γ /ν near bulk criticality. In the two-phase coexistence
region, an even steeper variation proportional to R 3 is pointed
out, but this steep variation occurs only over a very small
region of the chemical potential (of width H ∝ 1/R 3 ).
This behavior is the rounded counterpart of the δ-function
singularity that occurs in the thermodynamic limit due to the
jump from ρc,v to ρc, in the isotherm. However, the shift
of the transition relative to its location in the bulk is much
larger (namely proportional to the inverse radius 1/R) than
the rounding. The effective free-energy density exhibits two
minima, the locations of which one can take to define an
effective order parameter of the system. Due to the combined
action of the shift of the corresponding chemical potential and
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is much smaller than its bulk counterpart; i.e., confinement
enhances the region of the parameter space where no demixing
occurs. We have also shown that fitting critical power laws
to this order parameter does not give physically meaningful
results. In between these minima, the effective free energy
exhibits an (asymmetrically) located maximum, of order 1/R,
which can be attributed to the core-shell interface.
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ACKNOWLEDGMENTS
We thank Richard Vink for providing bulk phase diagrams.
We are grateful to the Deutsche Forschungsgemeinschaft for
supporting this research under Grants No. TR6/A5, No. SPP
1296 VI 237/4-3, and No. SFB 625/A17. We also thank the
John von Neumann Institute for Computing (NIC Jülich) for a
generous grant of computing time.
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