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Article history: Spatial connement modies the microscopic structure of dense uids, thereby inducing for example structural
Received 29 January 2016 forces between the conning walls. However, connement also modies the uids' density uctuations, resulting
Received in revised form 14 February 2016 in more elusive but equally important effects. In this brief review it is shown that both of these phenomena are
Accepted 15 February 2016
naturally analyzed using the conned uid's pair densities, which have recently become also experimentally ac-
Available online 23 February 2016
cessible. Two particular topics are discussed, namely, the mechanisms of oscillatory density proles and ensuing
Keywords:
solvation forces in dense conned uids as well as the behavior of liquids in solvophobic connement.
Conned uids 2016 The Author. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
Pair densities (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Density uctuations
Solvophobicity
http://dx.doi.org/10.1016/j.cocis.2016.02.005
1359-0294/ 2016 The Author. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
K. Nygrd / Current Opinion in Colloid & Interface Science 22 (2016) 3034 31
Fig. 1. Schematic of a dense uid conned between planar solid walls at short separation. Having introduced pair densities in dense conned uids, I turn
The uid orders into layers parallel to the conning walls, which can be quantied by the to the rst example of this brief review a conceptually simple and
density prole n(z) across the conning slit as shown to the right. The yellow sphere formally exact approach for mechanistic analysis of oscillatory density
depicts a central particle at position r, and the pair density describes the local density at
position r around the central particle.
proles and solvation forces.
Let us begin by considering again the schematic presentation of
Fig. 1. The central particle at r interacts with the conning walls and
where the local density is measured, and z the coordinate of r perpen- all other particles in the system. These interactions can be cast in the
dicular to the conning walls. Note that whereas in bulk the pair density form of the potential of mean force, which is the free energy of interac-
is isotropic and only depends on the distance from the central particle, tions. By denition the potential of mean force w(z) is related to the
in connement it is both anisotropic and dependent on the central number density prole n(z) across the slit via n(z) = nb exp[w(z)],
particle's position in the slit (see, e.g., Refs. [4,9] for illustrative exam- with nb denoting the bulk number density, = (kBT)1, kB Boltzmann's
ples). As a consequence ng is signicantly more complex in connement constant, and T the absolute temperature. The uid in the slit geometry
than in bulk, explaining why the former has been studied explicitly only exhibits isotropy parallel to the conning walls. For mechanistic analy-
seldom. sis of the density prole, it is thus sufcient to consider the normal com-
The theoretical schemes for explicit studies of conned uids at the ponent of the mean force, F(z) = dw/dz = kBTd ln n/dz, which can be
level of pair densities ng are rather mature, including integral-equation determined using the principal components of the mean force in the
theories [4,10,11], classical density functional theory [12,13], and mode- upward (F) and downward (F) directions, F(z) = F F [13,29]. A
coupling theory [14,15]. Simulations of pair densities in dense con- key observation here is that we can determine the principal mean
ned uids have also recently become feasible [13]. However, since force components F and F using the conned uid's pair densities,
the practical computations have been conceived as complicated and ex- and hence analyze the mechanisms of oscillatory density proles and
pensive, it is only recently that theoretical studies at this level of sophis- solvation forces.
tication have become more common. Studies of interest to the colloid To illustrate the concept of principal mean force components, I ex-
and interface community include, but are not limited to, ionion corre- emplify them in Fig. 2(a) for a dense hard-sphere uid conned be-
lations in electrolytes near charged surfaces [16], depletion potentials tween hard planar walls. For theoretical details and more examples,
[17], tunable assembly of charged uids between dielectric walls [18], see Ref. [29]. Since F(z) = F F d ln n/dz, maxima and minima
reentrant glass transitions in conned uids [19], and uid inclusions in n(z) are observed for vanishing F(z) (i.e., F = F) and a positive
in porous matrices [20]. (negative) F(z) corresponds to a positive (negative) dn/dz. By integrat-
The traditional experimental approach to study pair densities of ing the net force F(z) of panel (a) one thus obtains the density prole
dense uids is scattering, as already alluded to in the introduction, n(z) of panel (b). From n(z) one can further determine the pressure in
which provides the pair density in reciprocal space in terms of a struc- the slit, and hence the net force acting on the conning walls. However,
ture factor [1]. However, while studies on bulk systems have been rou- by analyzing the force components separately one can also understand
tinely carried out for about half a century, experiments on conned the mechanisms leading to the oscillatory density prole, and subse-
uids have been hampered by minute sample volumes and the quently the oscillatory solvation force by carrying out the analysis as a
presence of the conning walls. This problem was recently overcome, function of slit width [29]. Note that this scheme is formally exact and
when we reported the rst scheme for probing pair densities of con- can also be applied to simple uids exhibiting soft interactions, such
ned uids, based on x-ray scattering from colloid-lled nanouidic as Lennard-Jones or screened Coulomb potentials.
containers [21]. Within this scheme the pair densities are probed in For completeness I also present in Fig. 2(c) the potential of mean
terms of an anisotropic structure factor [9], force w(z), i.e., the free energy of interactions. The small values of
|w(z)| kBT directly imply that (i) the instantaneous local structures
Z
1 0 are continuously changing and (ii) the temporally averaged local struc-
Sq 1 nrnr0 g r; r0 1eiqrr drdr0 ; 1
N tures, and hence many of the conned uid's ensuing properties, are
rather sensitive to weak particle-wall interaction potentials comparable
where q is the scattering vector, N the number of particles in the slit, and to the thermal energy kBT.
the integrations are performed over the whole space between the walls. In the particular case of Fig. 2, namely a dense hard-sphere uid in
Most importantly, the thus obtained experimental structure factors hard planar connement, the principal force components are only
have been found to be in semi-quantitative agreement with ab initio slightly perturbed by the presence of the opposite wall; F (and F) is
theoretical calculations [22], providing experimental verication of to a good approximation given by the corresponding force component
the strong anisotropy in the pair densities of dense conned uids pre- at a single soliduid interface [29]. As a result, we can understand
dicted twenty years earlier [4]. I note in passing that this connement the slit-width dependence of n(z) qualitatively (or even semi-
scheme has also been used to control the assembly of anisotropic nano- quantitatively) simply by a translation of F with respect to F. This is a
particles [23]. rather surprising nding which provides a novel, conceptually simple
The experimental studies have to date been carried out using approach to understand oscillatory density proles and ensuing solva-
colloidal dispersions as model systems. While such an approach allows tion forces.
quantitative comparison with statistical mechanics calculations and Here I have discussed a model system a dense hard-sphere uid
facilitates mechanistic analysis, chemical specicity is inevitably between planar hard walls but eventually this kind of analysis should
sacriced by the use of model systems. A highly challenging but be extended to more realistic systems. For example, oscillatory solvation
extremely important continuation of these studies would thus be to forces in ionic liquids [24], which are determined by a complicated
32 K. Nygrd / Current Opinion in Colloid & Interface Science 22 (2016) 3034
a)
0D 2 E 1
N hNi2
@ A kB T nH
lim S q ; 2
q0 hNi nH H;T
H;T
experimentally? A possible solution is given by Eq. (2), according to [14] Lang S, Boan V, Oettel M, Hajnal D, Franosch T, Schilling R. Glass transition in con-
ned geometry. Phys Rev Lett 2010;105:125701.
which the long-wavelength limit of S(q) yields an integral of the local [15] Lang S, Schilling R, Krakoviack V, Franosch T. Mode-coupling theory of the glass
compressibility (z); for sufciently narrow slits limq 0S(q) is sensi- transition for conned uids. Phys Rev E 2012;86:021502.This paper describes an
tive to density uctuations near the conning walls, thus allowing extension of the mode-coupling theory to conned uids, making dynamic studies
feasible.
experimental verication of the theoretically predicted divergence of [16] Kjellander R. Intricate coupling between ionion and ion-surface correlations
density uctuations in hydrophobic (or solvophobic) connement. At in double layers as illustrated by charge inversion combined effects of
the moment such experimental studies could be carried out following strong Coulomb correlations and excluded volume. J Phys Condens Matter 2009;
21:424101.
Ref. [33] using liquid-like colloids, and I foresee experiments address- [17] Boan V, Pesth F, Schilling T, Oettel M. Hard-sphere uids in annular
ing the nature of solvophobicity in the near future. However, eventually wedges: density distributions and depletion potentials. Phys Rev E 2009;
this experimental approach will also be applicable to molecular liquids 79:061402.
[18] Zwanikken JW, Olvera de la Cruz M. Tunable soft structure in charged uids con-
[28], and I look forward to experimental verication for water in hydro-
ned by dielectric interfaces. Proc Natl Acad Sci U S A 2013;110:53018.This
phobic connement. paper describes pedagogically the analysis of soft structures in conned charged
Finally, I conclude with a speculative open question. Tunable interac- uids, explicitly carried out at the level of pair densities.
tions allow controlled assembly of colloidal systems. As an illustrative [19] Mandal S, Lang S, Gross M, Oettel M, Raabe D, Franosch T, et al. Multiple reen-
trant glass transitions in conned hard-sphere glasses. Nat Commun 2014;5:
example, connement of binary liquid mixtures close to their bulk crit- 4435. As an example of how spatial connement alters the dynamics of uids,
ical point leads to highly temperature-sensitive critical Casimir forces this paper predicts multiple reentrant glass transitions in conned hard-
between the walls [43], which are today used for reversible assembly sphere uids.
[20] Lomba E, Bores C, Kahl G. Explicit spatial description of uid inclusions in porous
of colloidal particles [44]. The above discussion on solvophobicity raises matrices in terms of an inhomogeneous integral equation. J Chem Phys 2014;141:
an interesting question: is it possible to tune the solvophobic interac- 164704.
tions by a suitable choice of model uid [45], thereby providing an [21] Nygrd K, Satapathy DK, Buitenhuis J, Perret E, Bunk O, David C, et al.
Connement-induced orientational alignment of quasi-2D uids. Europhys Lett
alternative method for controlled colloidal assembly? 2009;86:66001.
[22] Nygrd K, Kjellander R, Sarman S, Chodankar S, Perret E, Buitenhuis J, et al. Aniso-
tropic pair correlations and structure factors of conned hard-sphere uids: an ex-
5. Summary and outlook perimental and theoretical study. Phys Rev Lett 2012;108:037802.This paper
reports the rst experimental verication of the strongly anisotropic pair densities
I have briey reviewed some recent research on conned uids at in conned uids predicted theoretically twenty years earlier.
[23] Agthe M, Hydalsvik K, Mayence A, Karvinen P, Liebi M, Bergstrm L, et al. Control-
the fundamental level of pair densities, with an emphasis on phenome- ling orientational and translational order of iron oxide nanocubes by assembly in
na of importance in the eld of colloid and interface science. These kind nanouidic containers. Langmuir 2015;31:1253743.
of studies are now entering a very exciting phase, since they can nally [24] Smith AM, Lovelock KRJ, Gosvami NN, Licence P, Dolan A, Welton P, et al. Monolayer
to bilayer structural transition in conned pyrrolidinium-based ionic liquids. J Phys
be carried out both theoretically and experimentally. While my discus- Chem Lett 2013;4:37882.
sion here focused on simple model systems, I expect that similar analy- [25] Sheehan A, Jurado A, Ramakrishna S, Arcifa A, Rossi A, Spencer ND, et al. Layering of
sis also can shed light on the behavior of more complicated uids, such ionic liquids on rough surfaces. Nanoscale 2016;8:4094106.
[26] Lum K, Chandler D, Weeks JD. Hydrophobicity at small and large length scales. J
as nanoscopically conned ionic liquids and water in hydrophobic
Phys Chem B 1999;103:45707.
connement. [27] Remsing RC, Xi E, Vembanur S, Sharma S, Debenedetti PG, Garde S, et al. Pathways
to dewetting in hydrophobic connement. Proc Natl Acad Sci U S A 2015;112:
81816.This paper describes in a clear manner how enhanced density uctuations
Acknowledgments in hydrophobic connement lead to hydrophobic interactions.
[28] Lippmann M, Ehnes A, Seeck OH. An x-ray setup to investigate the atomic order of
conned liquids in slit geometry. Rev Sci Instrum 2014;85:015106.This paper de-
I thank the Swedish Research Council for nancial support (Grant
scribes the rst experimental method for determining structure factors of conned
No. 621-2012-3897). molecular liquids.
[29] Nygrd K, Sarman S, Kjellander R. Packing frustration in dense conned uids. J
Chem Phys 2014;141:094501.
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