Journal of Colloid and Interface Science 362 (2011) 382–388

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Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

Solvation forces between molecularly rough surfaces

Kan Yang a,b, Yangzheng Lin b, Xiancai Lu a, Alexander V. Neimark b,⇑
a
State Key Lab for Mineral Deposit Research, School of Earth Sciences and Engineering, Nanjing University, 22 Hankou Road, Nanjing 210093, PR China
b
Chemical and Biochemical Engineering, Rutgers University, 98 Brett Road, Piscataway, NJ 08854, USA

a r t i c l e i n f o a b s t r a c t

Article history: Surface heterogeneity affects significantly wetting and adhesion properties. However, most of the theo-
Received 25 April 2011 ries and simulation methods of calculating solid–fluid interactions assume a standard thermodynamic
Accepted 23 June 2011 model of the Gibbs’ dividing solid–fluid interface, which is molecularly smooth. This assumption gives
Available online 30 June 2011
rise to a layering of the fluid phase near the surface that is displayed in oscillating density profiles in
any theories and simulation models, which account for the hard core intermolecular repulsion. This lay-
Keywords: ering brings about oscillations of the solvation (or disjoining) pressure as a function of the gap distance,
Solvation pressure
which are rarely observed in experiments, except for ideal monocrystal surfaces. We present a detailed
Surface roughness
QSDFT
study of the effects of surface roughness on the solvation pressure of Lennard-Jones (LJ) fluids confined
Adsorption and Adhesion by LJ walls based on the quenched solid density functional theory (QSDFT). In QSDFT, the surface rough-
ness is quantified by the roughness parameter, which represents the thickness of the surface ‘‘corona’’ –
the region of varying solid density. We show that the surface roughness of the amplitude comparable
with the fluid molecular diameter effectively damps the oscillations of solvation pressure that would
be observed for molecularly smooth surfaces. The calculations were done for the LJ model of nitrogen
sorption at 74.4 K in slit-shaped carbon nanopores to provide an opportunity of comparing with standard
adsorption experiments. In addition to a better understanding of the fundamentals of fluid adsorption on
heterogeneous surfaces and inter-particle interactions, an important practical outcome is envisioned in
modeling of adsorption-induced deformation of compliant porous substrates.
Ó 2011 Elsevier Inc. All rights reserved.

1. Introduction in aqueous solution oscillates at separations 1.5 nm with a mean

periodicity of 0.25 ± 0.03 nm, roughly the diameter of water mole-
Interactions between solid surfaces separated by thin liquid lay- cule. They proposed that the origin of these oscillations is primarily
ers are characterized in terms of disjoining, or solvation pressure, due to the ordered layering of water molecules at mica surfaces.
which depends on the state of fluid in the gap between the surfaces Similar oscillations of the solvation pressure as a function of the
and the gap width. The notion of disjoining pressure was first film thickness have been found for various polar and non-polar sol-
introduced by Derjaguin in 1936, who found that two mica sur- vents and complex fluids [5–13].
faces in water repel each other, and this ‘‘disjoining’’ effect in- The oscillating behavior of fluid density and solvation pressure
creases as the gap width decreases from 1 to 0.04 lm [1]. Later, in thin layers was confirmed in various thermodynamic models
with the progress in experimental techniques and the develop- and molecular simulations performed assuming ideal ‘‘mathemat-
ment of the modern surface force apparatus and atomic force ically’’ smooth solid surfaces [14–17]. This traditional approach
microscope, the spatial resolution was extended down to the stems from the Gibbs definition of dividing solid–fluid interfaces,
sub-nanometer scale [2,3]. It was established that the pressure ex- which provides zero excess of solid density [18]. The density oscil-
erted by fluid films onto confining solid surfaces is not always po- lation in confined films is caused by the hard-core repulsion be-
sitive; it may be negative or co-joining, depending on the specifics tween the fluid molecules and between the fluid molecules and
of solid–fluid intermolecular interactions. In this respect, the term the surface that facilitates packing of fluid molecules near the sur-
‘‘solvation pressure’’ is better suited for the following discussion, face in layers similarly to the layering of billiard balls compressed
since it does not bear a connotation that thin films should always between two parallel bars. This effect was studied extensively in
‘‘disjoin’’ the confining surfaces. Moreover, Israelachvili and Pash- the works of Henderson [19] and others. It was shown that intro-
ley [4] showed that the solvation pressure between mica surfaces ducing soft solid–fluid interactions [19–21] or imposing various
defects or irregularities on the surface [22,23], the layered order
⇑ Corresponding author. can be frustrated and, thus, the density oscillations damped.
E-mail address: aneimark@rutgers.edu (A.V. Neimark). At the same time, as shown by Schoen and Dietrich [24] and

0021-9797/$ - see front matter Ó 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2011.06.056
 K. Yang et al. / Journal of Colloid and Interface Science 362 (2011) 382–388 383

Henderson et al. [25], the surface corrugations or grooves of the The density q(r) of the adsorbate, confined in a pore at given
supra-molecular scale (larger than 5–10 fluid molecular diameters) chemical potential l and temperature T, is determined by the
do not obscure the molecular layering. The solvation pressure minimization of the grand thermodynamic potential: X½qðrÞ ¼
R
oscillations induced by supra-molecular corrugations on crystal F½qðrÞ  l m qðrÞdr. Helmholtz free energy F[q(r)] is a functional
surfaces, scale of which is comparable with the size of the AFM of the fluid density q(r) as prescribed in Rosenfeld fundamental
tip, can be probed with AFM as considered in by O’Shea et al. measure theory [43]. Equilibrium density profile qðr; l; V; TÞ is
[26]. A detailed discussion on how the size of surface corrugations determined from the solution of the Euler equation l ¼ @@Fq [36].
and tiling affects the pressure oscillating was given by Fink and van In NLDFT model, the adsorption stress is calculated by as a
Swol [23]. derivative of the grand thermodynamic potential with respect to
The conclusion that confined fluid layers of molecular thickness the pore width at given external thermodynamic parameters,
 
possess an ordered layered structure causing the oscillating behav- ra ¼  A1 @@HX T;l;A , where A is the surface area and H is the pore
ior of the solvation pressure has been widely adopted in the liter- width [17].
ature. However, it is worth noting that all experiments showing The density profiles at saturation conditions are presented in
oscillating solvation pressures were performed with molecularly Figs. 1 and 2 respectively for commensurate and non-commensu-
smooth surfaces like mica, so that the ordering of adsorbed mole- rate pores of different widths. Commensurate pores are defines
cules was not frustrated by chemical or geometrical surface heter- as the pores that possess maximally dense packings of integer
ogeneities of the molecular scale. At the same time, most of the numbers of layers. These pores correspond to maxima of the aver-
non-crystalline surfaces of practical interest, such as amorphous age fluid density as a function of the pore width, Fig. 3. Minima of
oxides and carbons, are molecularly rough as shown by molecular the average density are achieved in non-commensurate pores,
simulations [27–29] and directly by XRD experiments [30–33]. In where the molecular packings are loose. The density profiles in
particular, the density of amorphous silica at the surface decreases commensurate pores show pronounced oscillations from layer to
from its bulk value to null within a certain layer of varying density layer with almost equal distance between the maxima that can
called ‘‘corona’’. The corona thickness is of the order of molecular be associated the mean layer positions. Thus defined inter-layer
diameters, and depending on the material, it may extend from frac- distance constitutes 0.95rff in the commensurate pores, which
tions to a few nanometers, accounting for the molecular level accommodate 2 layers and more. The distance between the first
roughness of the solid surface [30,33,34]. layer position and the wall is 0.45rff. The density profiles in
In this work, we analyze the effects of molecular level rough-
ness, drawing on the example of Lennard-Jones (LJ) fluid confined
by parallel LJ walls. We study the dependence of the fluid density
and the solvation pressure on the pore width and the degree of sur- 26
face roughness, as well as, the variation of the solvation pressure in 24 δ= 0 σff

pores during the process of adsorption and capillary condensation. 22 0.73σff (0.26 nm)
20 1.82σff (0.65 nm)
The latter problem has practical implications in the phenomena of 18 2.78σff (0.99 nm)
adsorption-induced deformation of adsorbents, which is discussed 16 3.75σff (1.33 nm)
also. For these purposes, we adopted the quenched solid density 14
3
ρσff

4.71σff (1.67 nm)

functional theory (QSDFT) that was recently introduced to model 12 5.66σff (2.01 nm)
10
adsorption at the rough surfaces [35]. 6.62σff (2.35 nm)
8 7.57σff (2.69 nm)
The rest of the paper is structured as follows. In Section 2, we 6 8.52σff (3.02 nm)
set a stage for the analysis of surface roughness effects by present- 4 9.50σff (3.37 nm)
ing a detailed account of fluid behaviors in the pores with smooth 2 10.45σff (3.71nm)
walls given with the non-local density functional theory (NLDFT). 0
0 2 4 6 8 10
This data serves as a reference for the QSDFT studies of the damp- z, σff
ing of the density and solvation pressure oscillations as the surface
roughness increases, which are presented in Section 3. Special Fig. 1. Density profiles in commensurate pores with smooth walls. Curves are
attention is paid to the investigation of adsorption in slit-shaped shifted by 2qr3ff .
micropores and mesopores, which shows a variety of different
non-monotonic solvation pressure isotherms. The conclusions are
summarized in Section 4.
22
δ= 0 σff
20
2. Confined fluid density and solvation pressure in pores with 18
1.27σff (0.45 nm)
smooth walls 16
2.30σff (0.82 nm)
14 3.27σff (1.16 nm)
To demonstrate the specifics of the density distribution and sol- 12 4.20σff (1.50 nm)
3
ρσff

vation pressure obtained with the models of smooth pore walls, we 10 5.19σff (1.84 nm)
employ the conventional NLDFT approach that is widely used to 8 6.14σff (2.18 nm)
study the fluid density distribution in nanopores [17,36–39]. In 7.10σff (2.52 nm)
6
the NLDFT approach, the adsorption and desorption isotherms in 8.05σff (2.86 nm)
4 9.01σff (3.20 nm)
pores are calculated based on the intermolecular potentials of
2 9.98σff (3.54 nm)
fluid–fluid and solid–fluid interactions. Fluid–fluid interactions
0
are modeled by a pair-wise LJ potential in the WCA approximation
0 2 4 6 8 10
[40], and fluid–solid interactions are modeled by an external Steele
Pore width, σff
potential [41]. We consider slit pores and employ the fluid–fluid
and fluid–solid LJ interaction parameters suggested for N2 adsorp- Fig. 2. Density profiles in non-commensurate pores with smooth walls. The width
tion on carbons, eff/kB = 95.77 K, rff = 0.3549 nm; esf/kB = 150 K, of non-commensurate pore is determined by the average of pore widths of adjacent
rsf = 0.269 nm [42]. commensurate pores. Curves are shifted by 2qr3ff .
384 K. Yang et al. / Journal of Colloid and Interface Science 362 (2011) 382–388

1000 1.4 22
solvation pressure smooth surface δ= 0.56 σff
900 20
average fluid density P/P0 =1
800 18 0.73σff (0.26 nm)
1.2

Average fluid density, ρσff

3
Solvation pressure, MPa

700 16 1.82σff (0.65 nm)

600 14 2.78σff (0.99 nm)
1.0 3.75σff (1.33 nm)
500 12

ρσ ff
4.71σff (1.67 nm)

3
400 10
5.66σff (2.01 nm)
300 8 6.62σff (2.35 nm)
0.8
6 7.57σff (2.69 nm)
200
4 8.52σff (3.02 nm)
100 9.50σff (3.37 nm)
0.6 2
0 10.45σff (3.71nm)
0
-100 0 2 4 6 8 10
-200 0.4 Pore width, σff
0 1 2 3 4 5 6 7 8 9 10 11
Pore width, σff Fig. 5. Density profiles in commensurate pores with rough walls of the same
roughness parameter d = 0.2 nm (0.56rff). Curves are shifted by 2qr3ff . Compare
Fig. 3. Plot of average densities and solvation pressure at smooth surface condition. with Fig. 1.

non-commensurate pores display less pronounced oscillations X½qs ðrÞ; qðrÞ ¼ F id ½qðrÞ þ e
F ex ½qs ðrÞ; qðrÞ
Z Z
compared to those in commensurate pores. The layered structure 1
þ drdr0 qðrÞqðrÞ0 uff ðjr  r0 jÞ
is leveled due to packing disordering in the pore center beyond 2
the first 2–3 ordered layers at the pore walls.
Z Z
The solvation pressure as a function of the pore width exhibits þ drdr0 qðrÞqs ðrÞ0 usf ðjr  r0 jÞ
oscillation correlated with the oscillation of the mean density. That Z
is the solvation pressure maxima corresponded to the most  l drqðrÞ ð1Þ
ordered states in commensurate pores and minima – to the least
ordered states in non-commensurate pores. This behavior is typical
Here, eF ex ½qs ðrÞ; qðrÞ ¼ F ex ½qs ðrÞ; qðrÞ  F ex ½qs ðrÞ; qðrÞ  0 is the ex-
for any theories of solvation pressure in the gap between smooth
cess Helmholtz free energy of the reference hard sphere fluid, Fid
surfaces [2,17,20,44,45].
and Fex are the ideal and excess components of the Helmholtz free
energy, l is the fluid chemical potential, and uff(|r  r0 |) and
3. The effect of surface roughness on confined fluid distribution usf(|r  r0 |) are the attractive parts of the fluid–fluid intermolecular
and solvation pressure potential and the solid–fluid intermolecular potential. Both the so-
lid–fluid and fluid–fluid interactions are split into hard-sphere
Using the NLDFT results for smooth surfaces as a reference, we repulsive and mean-field attractive parts with the WCA approxima-
demonstrate the effects of surface roughness by means of the tion similarly to the fluid–fluid interactions in NLDFT. Hard-sphere
QSDFT model [35,42]. The QSDFT model is based on the multicom- interactions are treated with the multicomponent fundamental
ponent density functional theory, in which the grand thermody- measure theory (FMT) functional for quenched-annealed systems
namic potential X is defined as a functional of the solid qs(r) and [43]. The equilibrium density distribution of fluid is determined
fluid q(r) densities by minimizing the grand thermodynamic potential with respect

6 6
solid density
fluid density
pore edge A solid density
fluid density
pore edge B
5 Pore width=5σff, δ=0 nm 5 Pore width=5σff, δ=0.2nm

4 4

3 3
ρσff3
ρσff3

2 2

1 1

0 0
0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Distance, σff Distance, σff

Fig. 4. Density profiles in the pore of width H = 5rff at the saturation conditions for the LJ model of N2 adsorption on carbon at 77.4 K. (A) Smooth pore walls, (B) molecularly
rough pore walls with the roughness parameter d = 0.2 nm (0.56rff). The solid density profile is given by Eq. (3). The pore diameter is defined from the Gibbs condition of zero
excess solid density that implies the equality of the shaded areas separated by the vertical line denoting the ‘‘theoretical’’ pore edge.
 K. Yang et al. / Journal of Colloid and Interface Science 362 (2011) 382–388 385

1.5 pore wall edge, and, as such, to consider the molecular level surface
roughness in the form of corona. In our calculation, the surface
1.4
roughness is modeled as a corona of linearly reducing density
1.3 (Fig. 4), which is described by the following equation [42]:
δ=0.56 σff
1.2 δ=0.45 σff 8 0
> q 0 6 z < h0
<ρσff>

δ=0.37 σff >

< s  
3

1.1 δ=0.25 σff zh0

qs ðzÞ ¼ 0:75qs  1  2d
0
h0 6 z < h0 þ 2d ð3Þ
δ=0.17 σff >
>
1.0 :
δ=0.08 σff 0 z P h0 þ 2d
0.9 δ=0 σff

0.8 Here, qs = 0.114 Å3 is the density of bulk solid; h0 is the thickness
of the solid wall assumed to be equal to h0 = 2  0.34 nm, in accord
0 2 4 6 8 10 with [34]. The roughness parameter d, defined as the half-thickness
Pore width, σff of the corona, is used to characterize the surface roughness. Pore
diameter is defined from the Gibbs condition of zero excess solid
Fig. 6. Pore width dependence of average density at P/P0 = 1 in pores with different density (Fig. 4B).
roughness. Curves are shifted by 0:1qr3ff .
A typical example of calculated density profiles with NLDFT and
QSDFT models is presented in Fig. 4. Even with such small rough-
ness parameter as d = 0.2 nm (0.56rff), the density fluctuations are
1000 significantly leveled, compared to the reference density between
smooth walls. Fluid penetrates into the outer part of the corona
Solvation pressure, MPa

800 and its distribution across the pore is, in overall, more homoge-
neous. The destruction of layering reflects a disordered packing
600 δ=0.56 σff
of molecules confined by rough walls.
δ=0.45 σff
The density profiles in commensurate pores with rough walls of
400 δ=0.37 σff
the same roughness parameter d = 0.2 nm (0.56rff) are presented in
δ=0.25 σff
δ=0.17 σff
Fig. 5. They should be compared with those given in Fig. 1. The den-
200 sity oscillations are damped in all pores that accommodate two and
δ=0.08 σff
δ=0 σff more layers. Note that the surface roughness effect destructs layer-
0 ing to a lager extent than the pore size mismatch, Fig. 2.
In Figs. 6 and 7, we present the dependences of the mean fluid
-200
density and the solvation pressure on the pore width for different
0 2 4 6 8 10
roughness parameters at the saturation conditions. The correlated
Pore width, σff
mean density and solvation pressure oscillations characteristic for
the pores with smooth walls, are gradually damped as the roughness
Fig. 7. Pore size dependence of solvation pressure at P/P0 = 1 in pores with different
roughness. Curves are shifted by 100 MPa. parameter increases. The oscillations of the solvation pressure dis-
appear for the roughness parameter exceeding d = 0.37rff
to the fluid density q(r) keeping the solid density qs(r) fixed (this (0.13 nm). It is worth noting that this value of the roughness param-
is where the term ‘quenched’’ stems from). This yields the Euler– eter was used earlier in [42] to model adsorption on carbons. It was
Lagrange equation, shown that the adsorption of N2 and Ar on non-porous carbon Vul-
dX½qs ðrÞ; qðrÞ=dqðrÞ ¼ 0 ð2Þ can is adequately described by the QSDFT model with d = 0.13 nm.
When pore wall roughness d P 0.37rff (0.13 nm), the solvation force
that is solved in an iteration fashion [42]. at the saturation conditions monotonically decays with the pore
Thus, in contrast with NLDFT, QSDFT accounts for the fluid–so- width. The solvation pressure is disjoining and, as such, the porous
lid interactions through pair wise intermolecular potentials rather sample should exhibit swelling upon saturation with the adsorbate.
than through an effective external potential. This approach allows However, as shown below, the solvation pressure may vary non-
one to take into account the in homogeneous solid density at the monotonically in the process of adsorption–desorption cycles.

0.9 0.73σ (0.26 nm) 0.9

A δ=0 σ B δ=0.37σ
ff 0.73σ (0.26 nm)
ff
ff 1.82σ (0.65 nm) ff 1.82σ (0.65 nm)
ff ff
0.8 2.78σ (0.99 nm)
ff 0.8 2.78σ (0.99 nm)
ff
3.75σ (1.33 nm) 3.75σ (1.33 nm)
ff ff
0.7 4.71σ (1.67 nm)
ff 0.7 4.71σ (1.67 nm)
ff
5.66σ (2.01 nm) 5.66σ (2.01 nm)
ff ff
0.6 6.62σ (2.35 nm) 6.62σ (2.35 nm)
ff 0.6 ff
7.57σ (2.69 nm) 7.57σ (2.69 nm)
ff ff
<ρfluidσff>

8.52σ (3.02 nm)

<ρfluidσff>

0.5 8.52σ (3.02 nm)

ff
0.5 ff
3
3

9.50σ (3.37 nm) 9.50σ (3.37 nm)

ff ff
10.45σ (3.71 nm) 10.45σ (3.71 nm)
0.4 ff
1.27σ (0.45 nm) 0.4 ff
ff 1.27σ (0.45 nm)
ff
2.30σ (0.82 nm) 2.30σ (0.82 nm)
ff
0.3 3.27σ (1.16 nm) 0.3 3.27σ
ff
(1.16 nm)
ff ff
4.20σ (1.50 nm) 4.20σ (1.50 nm)
ff ff
0.2 5.19σ (1.84 nm)
ff 0.2 5.19σ (1.84 nm)
ff
6.14σ (2.18 nm) 6.14σ (2.18 nm)
ff ff
0.1 7.10σ (2.52 nm)
ff 0.1 7.10σ
ff
(2.52 nm)
8.05σ (2.86 nm) 8.05σ (2.86 nm)
ff ff
0.0 9.01σ (3.20 nm) 9.01σ
ff 0.0 ff
(3.20 nm)
9.98σ (3.54 nm) 9.98σ (3.54 nm)
1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1 ff 1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1 ff

P/P0 P/P0

Fig. 8. (A and B): Equilibrium adsorption isotherms in pores with smooth (d = 0) and rough (d = 0.37rff) walls. The pore sizes are given in the right panels.
386 K. Yang et al. / Journal of Colloid and Interface Science 362 (2011) 382–388

800 A 0.73σff (0.26 nm)

δ=0 σff 800 B δ=0.37 σff
700 700 0.73σff (0.26 nm)
1.27σff (0.45 nm)
600 600 1.27σff (0.45 nm)
Solvation pressure, MPa

Solvation pressure, MPa

1.82σff (0.65 nm)
500 500 1.82σff (0.65 nm)
2.30σff (0.82 nm)
400 400 2.30σff (0.82 nm)
2.78σff (0.99 nm)
300
2.78σff (0.99 nm)
300
200 200
100 100
0 0
-100 -100
-200 -200
-300 -300

1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1 1E-9 1E-8 1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1
P/P0 P/P0

Fig. 9. Solvation pressure variation in the process of adsorption in pores of different size with smooth (A) and rough (B) walls.

1.0 120
A H=1.82σff (0.65 nm)
100 B δ=0 σff
δ=0.08 σff
80
0.8 δ=0.17 σff
Solvation pressure,MPa

60
δ=0.25 σff
40
δ=0.37 σff
0.6 20
δ=0.45 σff
<ρfluidσff>

δ = 0 σff 0
3

δ=0.56 σff
δ = 0.08 σff -20
0.4 δ = 0.17 σff -40
δ = 0.25 σff
-60
δ = 0.37 σff
0.2 -80
δ = 0.45 σff
-100
δ = 0.56 σff
-120 H= 1.82σff (0.65 nm)
0.0
1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1 1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1
P/P0 P/P0

1.0 120
C H= 2.30σff (0.82 nm)
100 D δ=0 σff
δ=0.08 σff
80
0.8 δ=0.17 σff
Solvation pressure, MPa

60
δ=0.25 σff
40
δ=0.37 σff
<ρfluidσff>

0.6 20
δ=0.45 σff
3

δ = 0 σff 0
δ=0.56 σff
δ = 0.08 σff -20
0.4 δ = 0.17 σff -40
δ = 0.25 σff
-60
δ = 0.37 σff
0.2 -80
δ = 0.45 σff
-100
δ = 0.56 σff
-120 H= 2.30σff (0.82 nm)
0.0
1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1 1E-7 1E-6 1E-5 1E-4 1E-3 0.01 0.1 1
P/P0 P/P0

Fig. 10. Equilibrium adsorption isotherms and variation of solvation pressure in micropores: of size 1.82rff (0.65 nm) (A and B) and 2.30rff (0.82 nm) (C and D) with different
surface roughness.

3.1. Dependence on the vapor pressure, different regimes in smooth (d = 0) and rough (d = 0.37rff) walls. The pore widths were
micropores and mesopores varied from 0.73rff to 10.45rff (0.26–3.71 nm). This range of pore
sizes includes micropores and small mesopores, in which the
3.1.1. Micropores – no capillary condensation experimental adsorption isotherms of N2 at 77.4 K are reversible
In Fig. 8A and B, we present the equilibrium adsorption iso- and do not reveal hysteresis [46]. The calculated equilibrium
therms in commensurate and non-commensurate pores with isotherms in pores wider than 4rff (1.42 nm) possess a step that
 K. Yang et al. / Journal of Colloid and Interface Science 362 (2011) 382–388 387

10 4
A δ=0 σff
2
B δ=0 σff
0
0
Solvation pressure, MPa

-10

Solvation pressure,MPa
-2
3.27σff (1.16 nm)
-20 -4
3.75σff (1.33 nm)
-30 4.23σff (1.50 nm) -6
7.57σff (2.69 nm)
4.71σff (1.67 nm) -8 8.05σff (2.86 nm)
-40
5.19σff (1.84 nm) -10 8.52σff (3.02 nm)
-50 5.66σff (2.01 nm) 9.01σff (3.20 nm)
-12
6.14σff (2.18 nm) 9.50σff (3.37 nm)
-60 -14
6.62σff (2.35 nm) 9.98σff (3.54 nm)
7.10σff (2.52 nm) -16
-70 10.45σff(3.71 nm)
-18
1E-4 1E-3 0.01 0.1 1 1E-4 1E-3 0.01 0.1 1
P/P0 P/P0

Fig. 11. Variation of the solvation pressure in the course of adsorption in mesopores with smooth walls. The values of pore width are given in the graphs.

0.8 A H= 9.5σff (3.37 nm) 2

H= 9.5σff (3.37 nm) B
0.332

0.328 Solvation pressure, MPa 0

0.324
0.6 -2
0.320
<ρfluidσff>

0.316
-4
3

δ = 0 σff
0.4
0.312
δ=0 σff
δ = 0.08 σff
0.308
0.504 0.506 0.508 0.510 0.512 -6 δ=0.08 σff
δ = 0.17 σff
δ=0.17 σff
δ = 0.25 σff -8 δ=0.25 σff
0.2 δ = 0.37 σff δ=0.37 σff
δ = 0.45 σff -10 δ=0.45 σff
δ = 0.56 σff δ=0.56 σff
0.0 -12
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
P/P0 P/P0

Fig. 12. Effect of the surface roughness of equilibrium adsorption isotherm and solvation pressure in the mesopore of width H = 9.5rff (3.37 nm). The roughness parameter
varies from 0 to 0.56rff.

corresponds to the capillary condensation transition. This transition to the increase of the solvation pressure. This behavior is typical
was determined from the condition of thermodynamic equilibrium for microporous carbon [49,50] and other microporous materials
between the adsorbed film and the filled pore given as the equality like zeolites [50–52].
of the respective grand thermodynamic potentials. The main qual- The effect of the surface roughness of the adsorption isotherm
itative difference between the adsorption isotherms in smooth and and solvation pressure is presented in Fig. 10 for two micropore
rough pores is that the effect of surface roughness eliminates the sizes, commensurate pore of H = 1.82rff and non-commensurate
layering transitions that are characteristic to smooth pores larger pore H = 2.3rff. It is worth noting that the roughness affects differ-
than six molecular diameters. This artifact of the smooth wall pore ently the solvation pressure in commensurate and non-commen-
models has been discussed in the literature with respect to the surate pores. As the roughness parameter increases, the solvation
problem of pore size calculations from adsorption isotherms pressure decreases in the commensurate pore and increases in
[47,48]. the non-commensurate pore. This means that the molecular level
The variation of the solvation pressure in the course of adsorp- roughness leads to a frustration of ordering in commensurate pores
tion is presented in Fig. 9 for micropores of width smaller than 3rff and a densification of packing in non-commensurate pores.
(1.06 nm). Two types of solvation pressure behavior depending on Behavior of the solvation pressure in mesopores is drastically
the pore size can be identified. In super-micropores that can different from that in micropores due to the importance of capil-
accommodate only one dense layer of guest molecules, the solva- lary forces. Fig. 11 shows the variation of solvation pressure in
tion pressure monotonically increases. Due to the extreme confin- the course of adsorption in smooth-wall mesopores of widths from
ing effect, adsorption of guest molecules is necessarily associated 3.27rff to 10.45rff. The solvation pressure drops step-wise as the
with pore expansion. In micropores, wider than one molecular capillary condensation occurs. After the capillary condensation,
diameter, the solvation pressure decreases at low gas pressures when the pore is filled the solvation pressure increases for all pore
and increases at high pressures. The decrease of the solvation pres- sizes. However, the behavior of the solvation pressure prior to the
sure is associated with attractive solid–fluid interactions, which capillary condensation depends on the pore size. It may either de-
take place when the packing of guest molecules is loose. With crease or increase that may lead either to adsorbent contraction or
the further increase of adsorption, the packing is densified and swelling. The solvation pressure isotherms with the step-wise drop
the hard-core repulsion interaction become dominant that lead at the capillary condensation transition and subsequent relaxation
388 K. Yang et al. / Journal of Colloid and Interface Science 362 (2011) 382–388

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