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Thermodynamics of capillary adhesion between rough surfaces
M.P. de Boer
a,∗
, P.C.T. de Boer
b
a
MEMS Technologies Department, Sandia National Laboratories, Albuquerque, NM 87185, USA
b
Sibley School of Mechanical and Aerospace Engineering, Cornell University, Ithaca, NY 14853, USA
Received 10 October 2006; accepted 13 February 2007
Available online 23 February 2007
Abstract
According to the Dupré equation, the work of adhesion is equal to the surface energy difference in the separated versus the joined materials
minus an interfacial energy term. However, if a liquid is at the interface between two solid materials, evaporation or condensation takes place under
equilibrium conditions. The resulting matter exchange is accompanied by heat ﬂow, and can reduce or increase the work of adhesion. Accounting
for the energies requires an opensystem control volume analysis based on the ﬁrst law of thermodynamics. Depending on whether evaporation
or condensation occurs during separation, a work term that is negative or positive must be added to the surface energy term to calculate the work
of adhesion. We develop and apply this energy balance to several different interface geometries and compare the work of adhesion to the surface
energy created. The model geometries include a sphere on a ﬂat with limiting approximations and also with an exact solution, a circular disc,
and a combination of these representing a rough interface. For the sphere on a ﬂat, the work of adhesion is one half the surface energy created if
equilibrium is maintained during the pulloff process.
© 2007 Elsevier Inc. All rights reserved.
Keywords: Adhesion; Thermodynamics; Control volume; Pendular ring; Surface roughness; Capillarity; Energy balance; Fracture mechanics
1. Introduction
Liquids can penetrate porous media, greatly affecting the
mechanical properties of solids. Resulting capillary forces must
be taken into account in studies of granular materials [1,2], fric
tion [3], insect adhesion [4], soil mechanics [5] and concrete
mechanics [6]. Capillary forces are also important at techno
logical interfaces such as in the head/disk system[7] where they
cause stiction, and in microelectromechanical systems (MEMS)
[8,9] where they can trigger permanent adhesion. As liquid
ﬁlls a rough interface, the area that can sustain tensile forces
increases dramatically and the associated capillary forces can
dominate the work of adhesion between the materials.
The surface roughness of technologically fabricated ﬁlms,
often deposited by vapor deposition processes on <1 nm root
mean square (rms) substrates, is often on the scale of nanome
ters. The Kelvin radius r
K
, which is the effective radius of a liq
uid meniscus in equilibrium with a vapor of partial pressure
p/p
s
, is also on the nanometer scale for 0.1 < p/p
s
< 0.95.
*
Corresponding author.
Email address: mpdebo@sandia.gov (M.P. de Boer).
Therefore, we might expect a strong interaction between capil
lary adhesion and p/p
s
for technologically fabricated surfaces.
The work of adhesion can be measured with a fracture me
chanics test specimen. The Grifﬁth energy balance, G= Γ , is
applied to obtain to obtain the work of adhesion when a crack is
in mechanical equilibrium [10,11]. G, the energy release rate,
is associated with the release of potential energy as a crack ad
vances. If there are no dissipation terms in the bulk materials
surrounding the crack walls, the adhesion per unit area Γ is as
sociated with the Dupré work of adhesion [12], according to
(1) Γ =γ
1
+γ
2
+γ
12
,
where γ
1
and γ
2
are the surface energies of the upper and γ
12
lower surfaces, respectively, and is the interfacial energy. If like
materials are separated, the equation reduces to Γ =2γ . More
generally, the adhesion Γ is the integral of the interface trac
tions beginning from the equilibrium separation D
0
. Accord
ingly,
(2) Γ =
∞
_
D
0
F(D)
A
p
dD,
00219797/$ – see front matter © 2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2007.02.051
172 M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185
where F is the attractive interface force over the projected inter
face area A
p
, and D is the interface separation. Measured values
of Γ are often much larger than the Dupré work of adhesion,
and this is attributed to dissipative processes such as disloca
tion motion or phonon excitation in the bulk of the material.
Thermodynamically, this irreversible crack growth is associated
with entropy production [13].
When a liquid wets two ﬂat surfaces that are to be separated,
the Dupré work of adhesion equates with 2γ
l
cos θ, where γ
l
is
the liquid–vapor surface energy and θ is the contact angle that
the liquid makes with the surface. However, when the interface
is rough, we must consider the geometry in more detail. The
contact mechanics [14] and adhesion of dry rough interfaces
[15,16] has received much attention. The general result of this
work is that the work of adhesion is proportional to the area of
real contact, which is difﬁcult to ascertain with known conﬁ
dence. Models of increasing complexity have been applied to
calculate this area [17–19].
When the interface is wetted and rough, the work of ad
hesion will depend also on how much the liquid evaporates
(or condenses) as the two materials are separated. In this work,
we shall consider two extremes. Before separation, the initial
condition for the capillary volume will be established by the
Kelvin radius, which corresponds to thermodynamic equilib
rium. In the ﬁrst extreme, the volume of the liquid will remain
constant. This corresponds to rapid separation of the two sur
faces, and we shall refer to this as the constant volume case.
In the second extreme, the Kelvin radius remains constant and
therefore the Laplace pressure remains constant. This corre
sponds to thermodynamic equilibrium (i.e., constant chemical
potential) and is achievable by very slowly separating the mate
rials. We shall refer to this as the constant pressure case. In the
example experiment below, we contend that each case is rele
vant in a fracture mechanics experiment. To maintain constant
pressure, matter exchange with the surrounding vapor through
evaporation or condensation is required. Neither the Grifﬁth
approach nor the Dupré approach considers this process. There
fore, we shall expect an energy balance that is fundamentally
different from these criteria.
In our treatment, we shall consider the effects of capil
lary forces only. We shall derive an energy balance based on
a controlvolume analysis and apply it to different geometries
to determine the trend for adhesion versus p/p
s
in rough in
terfaces. The effects of solute precipitation which can result in
solid bridging [20], of disjoining pressure and its effect on the
meniscus volume and shape [21,22], of contact angle hysteresis
which can affect the capillary F(D) path [23], of liquid viscos
ity [24] and the rate at which menisci nucleate [25] all deserve
attention but are beyond the scope of this work.
We brieﬂy consider the circumstances, from a fracture of
materials viewpoint, under which capillary forces dominate. In
tersolid forces in brittle materials are responsible for adhesion
energies from ∼1 to ∼100 J/m
2
[11]. It is well known that
environmental species can reduce the adhesion of a brittle ma
terial. For example, stress corrosion cracking of materials such
as glass [26] and sapphire [27] increase crack velocities at sub
critical stress intensities when water vapor is introduced (stress
Fig. 1. Array of asperities bridged by capillaries of areal density n
asp
.
corrosion velocities can be analyzed thermodynamically using
a modiﬁed Grifﬁth criterion, G > 2γ [28]). Likewise, a di
electric layer of liquid such as water can decrease adhesion
due to charge screening of mica surfaces [29]. Capillary forces
can contribute strongly to adhesion if the intersolid forces are
reduced, for example by misorienting the virgin surfaces of
mica [30], even though in this case the real contact area ap
proaches the apparent area of contact. In a rough interface the
real area is much smaller than the apparent contact area. Fur
thermore, when solids formed separately are later brought to
gether the lattices will be incoherent, which will also reduce
adhesion. Dispersion forces exist between such solids, but as
we shall show, their adhesion contribution is much smaller than
that due to capillary force. Therefore, capillary forces can dom
inate the adhesion between solids when the interface is rough,
the real contact area is small and the surfaces are wetted by liq
uids.
1.1. Interface description
In Fig. 1, a model of a simple rough interface, in which rigid
spherical asperities of radius R that protrude a maximum dis
tance z
max
from a ﬂat surface, is presented. The areal asperity
density n
asp
is inversely related to z
max
. We shall assume a cap
illary bridge of equilibrium Kelvin radius r
K
has condensed
around each sphere. The force–displacement (F–D) law of the
individual asperity is necessary to calculate the expected adhe
sion. Because the asperities are at the same height and they are
rigid, we will take D
0
= 0 in (2). Of course, this is no longer
valid when there is a distribution of asperity heights [14]. In the
absence of capillary forces, only dispersion forces exist, and the
treatment will then be that of DMT [31] contacts. The point at
which these become dominant is considered in Section 7.
For noninteracting asperities, the integrated F–D curve,
W
asp
times n
asp
, will determine the adhesion value Γ . The case
of interacting asperities (asperity saturation) will also be con
sidered.
1.2. Adhesion measurement in the sample geometry
Although we imagine the substrate and the asperities to
be rigid, we suppose that the asperities are attached to an
elastic cantilever as in Fig. 2. The sample could be a dou
ble cantilever beam (DCB) sample as has been used in many
studies [11,32]. Micromachined cantilevers with micrometer
scale thickness are also well suited to the capillary adhesion
range [33]. Their deﬂections can be accurately measured using
interferometry [34]. From an experimental determination of the
crack length s, knowledge of the ﬁlm thickness t , the gap h
and the elastic modulus E
m
of the cantilever material, the en
ergy release rate G, is known [35]. Typically, t ≈ h ≈ 2 µm.
M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 173
Fig. 2. (a) Geometry of the adhered cantilever, (b) closeup of the crack tip, (c) idealized surface roughness in the crack region.
With t z
max
,
(3) G=
3
2
E
m
h
2
t
3
s
4
.
We now consider the effect of surface separation rate. Suppose
that, while keeping the value of p/p
s
constant, we actuate the
cantilever electrostatically such that G and consequently s are
decreased. As shown in Fig. 2a, this is accomplished by placing
an electrically isolated actuation pad of length a near the sup
port post. While keeping both the cantilever and the substrate at
ground potential [36–38], an electric potential is applied. If an
approximation is made that the distributed force due to the elec
tric ﬁeld has a uniform value q, the energy release rate is [37]
(4) G=
3
2
E
m
h
2
t
3
s
4
+
a
6
q
2
(4s −3a)
2
24E
m
s
4
t
3
−
qa
3
h
2s
4
(4s −3a).
According to (4), an increase of q corresponds to smaller s
for constant Γ , and is analogous to retraction of the wedge in
a DCB sample. (An accurate treatment of the nonuniform dis
tribution of q is developed in [37].)
With s held at a smaller value, we mark time until capillaries
equilibrate around the asperities in the new crack tip position.
Then we remove the actuation load by reducing the electric ﬁeld
to zero (akin to reinsertion of the wedge in the DCB sam
ple), thereby increasing G. The surfaces separate rapidly and
s will soon reach a new length. If no liquid evaporation occurs,
the volume of each capillary is constant during the separation
process. This is the constant volume case. However, this initial
crack length is unstable because the meniscus radius r
e
 (de
ﬁned in Section 2) is larger than r
K
. Evaporation will occur,
which will reduce the capillary volume of the asperities in the
vicinity of the crack tip. The capillary force will decrease and
the crack length will increase incrementally, with G decreasing
according to (3). This process will continue until an equilib
rium crack length associated with menisci of radii r
e
 =r
K
 is
established. This is the constant pressure case.
2. Capillarity basics
We wish to calculate the adhesion values of two nominally
ﬂat surfaces for the constant volume and pressure cases. The
initial state of each is taken to be deﬁned by thermodynamic
equilibrium. Moreover, the constant pressure case remains in
equilibrium. To establish this equilibrium, we review the basics
of capillaries in this section.
The fundamental equation of capillarity, the Young–Laplace
equation, is derived from a surface curvature argument [39].
Accordingly, a curved surface has a pressure difference
(5) P =γ
l
/r
e
across the liquid–vapor interface. Here, the liquid vapor energy
is γ
l
and the effective radius of curvature of the surface is r
e
as
deﬁned by
(6) 1/r
e
=1/r
a
+1/r
m
,
where r
a
(the azimuthal radius) and r
m
(the meridional radius)
are the principal radii of curvature of the surface. These quan
tities are positive when the center is inside the meniscus and
negative when outside. The liquid is assumed to be isobaric at
each instant in time. This means that r
e
is constant along the
meniscus surface, while r
a
and r
m
will vary along this surface.
As mentioned above, in the case of evaporative equilibrium,
r
e
equals the Kelvin radius r
K
.
The Kelvin equation is derived from thermodynamic equa
tions and the Young–Laplace equation [39]. First, for a re
versible process at constant temperature, the effect of a change
in mechanical pressure on the free energy G
f
of a substance is
(7) G
f
=
_
V
m
dP.
Assuming constant molar volume of the liquid substance V
m
,
and applying the Young–Laplace equation we get
(8) G
f
=γ
l
V
m
/r
e
,
174 M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185
where V
m
is the liquid molar volume. Thermodynamics relates
the free energy of a substance to its vapor pressure. Assuming
the vapor to be ideal,
(9) G
f
=R
u
T ln(p/p
s
).
Equating (8) and (9), and assuming thermodynamic equilib
rium, the Kelvin equation [40] is found.
(10) r
K
=
γ
l
V
m
[RTln(p/p
s
)]
=
0.53
ln(p/p
s
)
nm.
The value of 0.53 nm assumes that the substance is water
at room temperature (γ
l
= 0.072 N/m, V
m
= 0.018 L/mol,
T = 300 K, and R
u
= 0.082 Latm/(mol K)). Equation (10) is
graphed in Fig. 3. Gravity signiﬁcantly inﬂuences the curvature
only if the Bond number (gL
2
ρ/γ
l
, where g is the acceler
ation due to gravity, L is a characteristic length of the system
and ρ is the density difference of the ﬂuids on adjacent sides
of the interface) approaches 1. In the examples below, the Bond
number is typically 10
−12
or smaller.
As represented in Fig. 4, the Young equation describes
a force balance between the surface tension of the solid–vapor
interface (γ
s
), the solid–liquid interface (γ
ls
), and the liquid–
vapor interface, such that
(11) γ
l
cos θ =γ
s
−γ
ls
,
where θ is the contact angle between the solid and the liquid.
According to (11), the difference in surface energy between
a surface in contact with a vapor versus a liquid is γ
l
cos θ.
The Kelvin radius is negative for 0 < p/p
s
< 1, indicat
ing that a condensed liquid coexists in narrow channels with
an undersaturated vapor. In turn, signiﬁcant negative (tensile)
Fig. 3. The Kelvin radius (for water) versus p/p
s
. The approximate diameter
of a water molecule (0.3 nm) and a roughness range over which many techno
logical surfaces may vary are also indicated.
Fig. 4. The Young geometry.
pressure exists in the liquid, which gives rise to the strong cap
illary forces and adhesion in micrometerscale structures and in
porous materials. Liquids are metastable in tension and are sus
ceptible to spinodal decomposition. However, in the absence of
cavitation, very high negative pressures can be sustained by the
van der Waals or hydrogen bonding forces between adjacent
liquid molecules. Indeed, pressures of −140 MPa have been
measured for bulk water [41], in good agreement with vapor
nucleation theory [42]. From (5) and (10), −140 MPa would
give a lower limit on the partial pressure at p/p
s
=0.37. How
ever, the critical vapor nucleus radius at a given pressure, as
can be calculated from nucleation theory, is then larger than the
Kelvin radius. Therefore, this consideration may not limit the
applicability of (10). However, as r
K
 decreases, it reaches the
size of individual molecules (a water molecule is ∼0.3 nm in
diameter [43]) and the applicability of continuum theory must
reach a limit.
From surface force apparatus (SFA) experiments, the Lap
lace pressure term dominates for p/p
s
> 0.7 for cyclohexane,
nhexane and water vapors on mica surfaces [44]. This implies
that the Kelvin equation is valid at least to 1.5 nm for water
on mica. The Kelvin radius can be obtained more directly by
measuring the surface separation near pulloff [45] and here
for cyclohexane, agreement with the Kelvin equation was also
found for p/p
s
down to 0.7, with experimental error limiting
this lower bound. In a MEMS cantilever experiment, adhesion
spontaneously increased from 0.02 mJ/m
2
at p/p
s
< 0.05 to
0.5 mJ/m
2
in water vapor on an oxidized silicon surface at
p/p
s
=0.3 [33]. There, the average value of R was estimated
to be 250 nm. Recently, capillary forces at the remarkably low
value of p/p
s
= 0.15 were detected for silicon tips in atomic
force microscopy (AFM) experiments with R ranging from 50
to 400 nm [46].
The discrepancy between the SFA and AFM results may be
resolved by the theory due to Fogden and White [47], which
clariﬁes that the SFA experiment [44] does not necessarily mea
sure the lower limit to the Kelvin radius. They developed a di
mensionless parameter
(12) k =
_
3
4
_
π
2
__
K
γ
l
_
[r
K
(1 −D
0
/2r
K
)]
3/2
√
R
,
where K = (4/3)(E/[2(1 − υ
2
)]), υ is Poisson’s ratio, and
D
0
atomic spacing when the surfaces are in contact. The
parameter k is related to the inverse of the Tabor parame
ter [48], which describes the transition from the Johnson–
Kendall–Roberts (JKR) [49] regime to the Derjaguin–Muller–
Toporov (DMT) [31] regime. Small k (1) corresponds to
large spheres at low vapor pressures. This extreme is JKRlike
and the expected force at zero displacement is 3πRγ
l
cos θ.
Large k (1) applies to small hard spheres at high vapor pres
sures. This extreme is DMTlike and the expected force at
zero displacement is 4πγ
l
R. A calculation shows that k ≈1
at p/p
s
= 0.7 in Christenson’s [44] work, and below this
value of p/p
s
the measured force is less than 4πRγ
l
cos θ.
For the MEMS experiment [33], k = 27 with R = 260 nm at
p/p
s
=0.3 (assuming D
0
2r
K
). This is consistent with the
assumption of a rigid sphere during withdrawal of the sphere
M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 175
from the substrate, as in the DMT model. For the AFM ex
periment [46], k = 0.75 for R = 400 nm and p/p
s
= 0.15,
and the assumption of a rigid sphere becomes questionable.
Nonetheless, a capillary model agreed reasonably well with the
measured F–D curve [46].
Although its valid range is not ﬁrmly established, the present
treatment assumes a continuum material, i.e., we use the Kelvin
equation (10).
3. Energy balance for constant volume and pressure cases
Let us consider an arbitrary rough surface in contact with
a ﬂat substrate as represented in Fig. 5. We shall suppose it has
a proﬁle that allows a condensed capillary liquid to ﬁll a contin
uous volume as the surfaces are separated. We wish to develop
an energy balance for a control volume V encompassing the
liquid for the constant volume and pressure cases.
The differential energy dE of the control volume consists of
bulk and surface components. Accordingly,
(13) dE =d(U
b
+U
s,cv
),
where the bulk liquid energy is U
b
and the control volume sur
face energy is U
s,cv
. For a change in relative displacement D of
the surfaces, we write the ﬁrst law for this open system [50] as
(14) dE =dH +δQ+δW −dU
s,ocv
−P dV.
The differential enthalpy of the material entering the control
volume is dH, the differential heat supplied to the control vol
ume is δQ and the differential work done on the control volume
is δW. Differential surface energy created outside the control
volume is represented by dU
s,ocv
. The P dV term is required
because the analysis is in terms of absolute pressure (for ex
ample, volume lost due to evaporation will reduce the work
required). Equations (13) and (14) hold for either evaporation
or condensation.
For constant volume, dU
b
= ρ
l
u
l
dV = 0 in (13), where ρ
l
is the density of the liquid and u
l
is its speciﬁc internal energy.
Likewise, dH =0 in (14) because no liquid enters or leaves the
volume. Because this case is adiabatic, δQ=0 in (14). Equat
ing (13) and (14), and assigning the total system differential
surface energy dU
s
= dU
s,cv
+ dU
s,ocv
, yields the Grifﬁth en
ergy balance
(15) δW =dU
s
(constant volume).
Fig. 5. Object (surface 1) surrounded by a capillary meniscus as it is separated
from the substrate (surface 2). The restriction placed on the shape is that the sur
face separation from the substrate continuously increases (or remains constant)
from the point of closest approach as deﬁned by D.
For constant pressure, Eq. (13) becomes
(16) dE =dU
s,cv
+ρ
l
u
l
dV.
A control volume about the liquid–vapor interface is considered
to ﬁnd the heat δQ in Eq. (14), which is supplied by the walls
and causes a phase change in the liquid. The result is
(17)
δQ=(u
v
+P/ρ
v
)(−dm) −
_
u
l
+(P +P)/ρ
l
_
(−dm).
Here, −dm is the mass of the material exiting the control vol
ume, while u
v
and ρ
v
are the vapor internal energy and density,
respectively. The differential enthalpy is
(18) dH =dH
in
−dH
out
=−(u
v
+P/ρ
v
)(−dm).
Equating (13) and (14) now results in
δW =dU
s
−P dV =dU
s
−
γ
l
r
K
dV
(19) (constant pressure).
This deﬁnes the energy balance in the constant pressure situ
ation. Compared to the Grifﬁth energy balance (15), the work
done on the liquid in (19) is changed by a P dV term, where
P = γ
l
/r
K
. For 0 < p/p
s
< 1, r
K
< 0. If capillary liquid
evaporates as D increases, dV is negative and hence δW is
less than dU
s
. Energy is conserved, but the work of adhesion
will be less than the surface energy created. From an energy
releaserate point of view, the P dV term is analogous to
stored energy being released, thereby reducing W. It occurs by
heat transfer through the liquid to reduce the meniscus volume.
If liquid condenses as D increases, dW >dU
s
and the converse
statements can be made.
To quantify the heat δQ, a value for the liquid enthalpy
at negative pressure is required. This is not generally found
in thermodynamic tables. However, liquid enthalpies depend
strongly on temperature but only weakly on pressure. Further
more, the effect of curvature on the heat of vaporization is small
(less than 10% for r
e
 = 1 nm [51]). Therefore, we approxi
mate
(20) δQ≈h
lv
dV,
where h
lv
is the speciﬁc heat of vaporization of the liquid.
For water at room temperature and atmospheric pressure, h
lv
≈
2.5 attoJ/nm
3
. In general, δQ is much larger (order 10 times)
than the energy terms in (19). It should be noted that the sign of
δQ is opposite when condensation occurs.
The force (positive is taken to be attractive) is obtained
from
(21a) F(D) =
dW
dD
.
Then,
(21b) F(D) =
dU
s
dD
(constant volume)
and
(21c) F(D) =
dU
s
dD
−
γ
l
r
K
dV
dD
(constant pressure).
176 M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185
The adhesion is the rate of change of work with respect to the
creation of solid–vapor area. Accordingly,
(22) Γ =
dW
−dA
2w
,
where −dA
2w
is the differential increase in unwetted area of the
lower surface (the area A
2
is in the plane of the crack). Then,
(23a) Γ =
dU
s
−dA
2w
(constant volume)
while
(23b) Γ =−
_
dU
s
dA
2w
−
γ
l
r
K
dV
dA
2w
_
(constant pressure).
The effective adhesion is
(23c)
˜
Γ =
W
−A
2w
,
where −A
2w
is the change in unwetted substrate surface area
from D = D
0
to D →∞ and W is the corresponding work
done. In the following sections, we shall apply the energy bal
ances (15) and (19) to model geometries of interest.
4. Sphere on a ﬂat (with R r
e
 and r
a
r
e
)
In this section we ﬁnd the separation work (W
asp
), the force–
separation (F–D) curve and the adhesion (Γ
asp
) of an isolated
asperity under the assumption that R r
e
 for the cases of
constant volume and pressure for the geometry illustrated. We
also take the disc radius x
d
r
m
, i.e., r
e
 =r
m
. This means
that the meniscus has a circular proﬁle. We further take the con
tact angle to be the same on the top and bottom surfaces.
4.1. Geometry
For the sphere on ﬂat geometry as in Fig. 6,
(24)
_
R −
_
2r
e
 cos θ −D
__
2
+x
2
d
≈R
2
.
We expand (24) in powers of r
e
/R, leaving out higherorder
terms, with the result
(25) x
2
d
=4Rr
e
 cos θ
_
1 −
D
2r
e
 cos θ
_
.
The volume of the capillary bridge is
(26) V =
x
d
_
0
2πrη(r) dr,
where the height of the disk is given by η(r) = D +r
2
/(2R).
Working out the integral and using (25) results in
(27)
V =πx
2
d
_
D+
x
2
d
4R
_
=4πRr
2
e
cos
2
θ
_
1 −
D
2
4r
2
e
cos
2
θ
_
.
4.2. Case of constant volume
In this case, the separation is rapid enough that no evapo
ration occurs. Because the surface tensions γ
s
and γ
ls
are un
changed, the contact angle θ remains constant. Therefore, as D
increases, the values of the meniscus radius r
e
and the disk ra
dius x
d
change. The rate of change of x
2
d
follows from taking
the derivative of V with respect to D. Then
(28)
dV
dD
=0 =π
_
x
2
d
+D
dx
2
d
dD
+
x
2
d
2R
dx
2
d
dD
_
,
so that
(29)
dx
2
d
dD
=−
_
x
2
d
D+x
2
d
/(2R)
_
.
The total surface energy U
s
of the system in Fig. 6 (of solid
surface area A=A
1
+A
2
, the area of the upper and lower sur
faces, respectively) is the energy of the liquid–solid interface,
the energy of the solid–vapor interface and the energy of the
liquid–vapor interface. Approximately,
(30) U
s
≈2γ
ls
πx
2
d
+γ
s
_
A−2πx
2
d
_
+γ
l
2πx
d
2r
K
.
The liquid–vapor term is small and therefore
(31) U
s
=−2πx
2
d
γ
l
cos θ +constant,
where we have used Young’s equation (11). Recalling (15),
(21b), (29), and (31),
F =
dU
s
dD
=−2πγ
l
cos θ
dx
2
d
dD
Fig. 6. Geometry of the capillary disk with R r
e
and R r
a
.
M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 177
Fig. 7. Normalized F–D curve for the constant volume and pressure cases (with
R r
K
).
(32) =4πRγ
l
cos θ
_
1 −
D
2r
e
 cos θ
_
.
We consider the situation in which a capillary bridge of radius
r
K
has formed while the sphere and the plate are in contact
(D =0). The volume of the disk follows from (27) as
(33) V =V
0
=4πRr
2
k
cos
2
θ.
The sphere then is withdrawn. Using (27) and (33), the condi
tion of constant volume yields the dependence of r
e
on D as
(34) r
e
=
_
r
2
K
+D
2
/(4cos
2
θ).
Inserting (34) into (32), we ﬁnd
(35) F =4πRγ
l
cos θ
_
1 −
D
_
4r
2
K
cos
2
θ +D
2
_
,
which is plotted in Fig. 7. The expression (35) is equivalent to
the one given in Chapter 15 of [43], but is written explicitly in
terms of D. The work to remove the asperity from the substrate,
W
asp
, is
(36) W
asp
=
∞
_
0
F(D) dD =8πγ
l
Rr
K
cos
2
θ.
The same result is obtained by combining (25) and (31). The
asperity adhesion is
(37)
Γ
asp
=
d(−2πγ
l
cos θx
2
d
)
−d(πx
2
d
)
=2γ
l
cos θ (constant volume),
which is independent of D. Using (36) and (23c), the effective
asperity adhesion
˜
Γ
asp
also equals 2γ
l
cos θ.
4.3. Case of constant pressure
In this case, r
e
=r
K
and V generally decreases due to evap
oration as D increases. Therefore we replace r
e
with r
K
in (27)
and (25). The rate of decrease in volume is given by
(38)
dV
dD
=−2πRD
and the rate of decrease of x
2
d
is
(39)
dx
2
d
dD
=−2R.
Noting that dU
s
is unchanged with respect to D, the force is
now
F(D) =
dW
dD
=
dU
s
dD
−
γ
l
r
K
dV
dD
(40) =4πRγ
l
cos θ
_
1 −
D
2r
K
 cos θ
_
,
which is also plotted in Fig. 7. This equation can also be derived
fromforce considerations [52]. The work to remove the asperity
from the substrate is now
(41) W
asp
=
2r
K
cos θ
_
0
F(D) dD =4πγ
l
Rr
K
cos
2
θ,
and is one half the result for the constant volume case (36). The
rate of change of V with respect to −A
2w
is
(42)
dV
−dA
2w
=
1
−π
dV
dx
2
d
=
1
−π
dV
dD
dD
dx
2
d
=−D.
Using (23b), we then have
Γ
asp
=−
_
dU
s
dA
2w
−
γ
l
r
K
dV
dA
2w
_
=2γ
l
cos θ
_
1 −
D
2r
K
 cos θ
_
(43) (constant pressure).
That is, Γ
asp
decreases as D increases. Now the effective as
perity adhesion
˜
Γ
asp
equals γ
l
cos θ, one half the result of the
constant volume case. Yet, the change in surface energy is the
same as in the constant volume case. The work done on the sys
tem is responsible for only one half of the surface energy the
system has gained, 2γ
l
cos θ(−A
2w
), while the second half
of the surface energy gained is due to P dV work effectively
done by evaporation.
5. Exact geometry—the pendular bridge analysis
The above analysis used the approximations that the merid
ional curvature is circular, that R r
e
 and x
d
≈r
a
r
e
 and
that the liquid–vapor term can be ignored. While the simpli
ﬁcations allow insight into physical processes, they are clearly
inaccurate over parts of the F–D curve. Orr et al. [53] have used
the pendularbridge geometry to solve the problem without ap
proximation. We have applied (15) and (19) to this geometry
and describe the approach and results in this section. Our moti
vation is that asperity radii of curvature in MEMS surfaces, as
well as in AFM measurements, can be 50 nm or smaller, and
therefore the approximations become poor. The main result of
this section is that the relatively crude approximations used in
Section 4 overestimate the work of adhesion by up to a factor
of 2 or more.
The pendularbridge geometry is shown in Fig. 8. Both r
a
(the azimuthal radius) and r
m
(the meridional radius) vary lo
cally but for an isobaric meniscus, (6) still holds. As R de
creases, ¯ r
a
decreases because of the sharp asperity curvature.
178 M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185
Fig. 8. Pendular ring geometry.
Because r
a
is positive while r
m
is negative,  ¯ r
m
 must decrease
to keep r
e
the same. At D =0, this already reduces the area of
the meniscus relative to the approximation used in Section 4,
and hence F will decrease. As D increases, ¯ r
a
decreases fur
ther. Consequently  ¯ r
m
 decreases more, and so F will decrease
more rapidly than in the analysis of Section 4.
The pendularbridge solution involves writing the axisym
metric Young–Laplace differential equation and solving it sub
ject to boundary conditions that are derived at the points where
the bridge meets the sphere and the substrate in Fig. 8. The
pendular bridge coordinates are found in terms of incomplete
elliptic integrals of the ﬁrst and second kinds (F and E, respec
tively), and their values are found numerically. The solution
is ambiguous in that “±” signs appear. Four different solu
tion cases, each corresponding different shapes (nodoids and
unduloids of up or down concavity) arise. Also, over part of
the solution space, the concave up and down unduloids must
be combined because r
m
changes sign, i.e., there are inﬂection
points in the meridional curvatures. Singularities appear in the
elliptic integrals when the unduloids must be combined. Ad
ditionally, three special solutions, corresponding to a catenoid
(1/r
e
=0), a cylinder (1/r
m
=0) and a sphere (1/r
m
=1/r
a
),
exist. Orr et al. [53] detail the possible solutions and discuss
meniscus stability with respect to small ﬂuctuations.
1
Several workers [54–56] have developed numerical integra
tion methods that solve the meniscus shapes by an iterative
approach to arrive at identical solutions to Orr et al. Willett et
al. [54] also conducted macroscale experiments that fully vali
1
Note that in the Orr et al. notation, 1/r
e
= 2H, not to be confused with
enthalpy.
date the theoretical results for the constant volume case, which
is relevant for large volumes and short experiment times. Capil
larity theory using the constant volume assumption was used
to model the force–displacement curves for R = 50 nm and
R = 400 nm silicon tips in water vapor, and good agreement
was observed [46]. Equilibration of a Kelvin meniscus for con
tacting tips was achieved on the order of seconds. The F–D
curves were rateindependent for withdrawal times from 0.01
to 10 s. The withdrawal time is hence much longer to achieve
the constant pressure assumption. Our contribution in this sec
tion is to apply both (15) and (19) to the pendular bridge and
present results for small R. Our method is outlined here and
sample calculations are presented, while the method is detailed
and generalized in [57].
In the pendularbridge geometry, we have
U
s
=(A
1
−A
1w
)γ
s1
+A
1w
γ
ls1
+(A
2
−A
2w
)γ
s2
(44) +A
2w
γ
ls2
+A
m
γ
l
,
where the numbered subscripts refer to the upper and lower sur
faces, the “w” subscript refers to the wetted area of that surface,
and the “m” subscript refers to the meniscus. Hence,
(45) dU
s
=−γ
l
[dA
1w
cos θ
1
+dA
2w
cos θ
2
−dA
m
].
The energy balance for the constant volume and constant pres
sure cases can now be written from (15) and (19). Then
δW =−γ
l
[dA
1w
cos θ
1
+dA
2w
cos θ
2
−dA
m
]
(46) (constant volume)
and
δW =−γ
l
[dA
1w
cos θ
1
+dA
2w
cos θ
2
−dA
m
] −
γ
l
r
K
dV
(47) (constant pressure).
For a given p/p
s
, the initial r
e
is assigned according to the
Kelvin equation and D is set to zero. The included angle Ψ
and the volume V are now found by iterating on the incomplete
elliptic integral solutions. From this, the meniscus coordinates
and area terms are determined; in turn the energies are found.
For constant volume, Ψ is ﬁrst decremented in the iterative
solution. With V held constant, new values of r
e
and D are
found, from which the meniscus coordinates and energies are
found. In some cases (large R), when decrementing Ψ, there
are no longer continuous values of D. To obtain continuous
values, the iteration control must be changed by incrementing
1/r
e
to ﬁnd D and Ψ rather than by decrementing Ψ. There
after, it is necessary to return to decrementing Ψ again. For
constant pressure, D is incremented and with r
e
held constant,
Ψ is found and the coordinates and energies can then be deter
mined.
For each case, the F–D curve was found in two ways. First,
according to [53]
(48) F =2πγ
l
R
_
sinΨ sin(θ
1
+Ψ) −Rsin
2
Ψ/2r
e
_
.
Here, the ﬁrst term represents the axial component of the sur
face tension while the second term is the Laplace pressure
contribution. From (48), the force (attractive if positive) can be
M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 179
calculated as a function of D. Second, we took the total work as
a function of D, using only the U
s
term for constant volume and
including the P dV term for constant pressure. The force was
then determined as the numerical derivative of the work with
respect to D, i.e., the numerical form of (21a). That is
(49) F(D) =
W(D+D) −W(D)
D
.
Within numerical error, results from this work approach are
identical to the force approach, as expected.
We applied (46) and (47) to the pendular bridge using the
surface tension of water (with γ
l
=72 mN/m) for:
(i) R/r
K
 = 100, 30, 10, 3, and 1 (to establish initial values
for the bridge volume),
(ii) θ
1
=θ
2
=0
◦
, θ
1
=θ
2
=40
◦
.
The pendular bridge solutions are in terms of the quantity
R/r
e
. Hence, small values of r
K
 and R/r
K
 (e.g., r
K
 =1 nm
and R/r
K
 =1, implying R = 1 nm) may be physically unre
alistic (as discussed above for r
K
 and in [58] for R). However,
the R/r
K
=1 curve also applies for values such as R =30 nm
and r
K
 =30 nm in Figs. 10 and 11.
The constant pressure case is reasonably straightforward to
solve because it involves only one pendular bridge solution
case corresponding to r
e
= r
K
. The constant volume case is
more complicated in that r
e
changes. Two different solution
cases must be traversed if θ
1
> 0, and over part of the prob
lem two of the unduloid cases must be combined because the
meridional curvature changes sign. The singularities appearing
at the integral limits (as mentioned above) were handled with
the openended Romberg algorithm.
In Fig. 9 with R = 10 nm and r
K
 = 1 nm, we show
meniscus shapes for constant volume with θ
1
= θ
2
= 0
◦
and
θ
1
=θ
2
=40
◦
(Figs. 9a and 9b, respectively), and for constant
pressure with θ
1
=θ
2
=0
◦
and θ
1
=θ
2
=40
◦
(Figs. 9c and 9d,
respectively). For each of the graphs, the uppermost sphere is at
the point of pulloff. From these ﬁgures, it is clear that r
m
varies
locally for a given value of D, especially for constant volume.
The inﬂection points in the meridional curvature, which are as
sociated with theoretically accessible but physically unstable
solutions, are indicated.
(a) (b)
(c) (d)
Fig. 9. (a) Constant volume meniscus shapes with r
e
=−1 nm initially, R =10 nm, θ
1
=θ
2
=0
◦
. (b) Same as (a) except θ
1
=θ
2
=40
◦
. ("symbols mark the change
from concave down to concave up.) (c) Constant pressure meniscus shapes with r
e
=−1 nm, R =10 nm, θ
1
=θ
2
=0
◦
. (d) Same as (c) except θ
1
=θ
2
=40
◦
.
180 M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185
We plot normalized F–D curves for values of R/r
K
 = 1,
10, and 100 in Fig. 10a for θ
1
= θ
2
= 0
◦
. Equations (35)
and (40) where R/r
K
 →∞are also plotted for reference.
Let us consider Fig. 10a in the context of single asperity pull
off experiments. For constant volume as D increases, a “nose”
develops. The tip of this nose is the point of rupture in a ﬁxed
grip experiment, as can be conducted in principle by an inter
facial force microscope [59,60]. Rupture occurs at a nonzero
tensile force. Unless p/p
s
→1, the rupture force does not de
crease to zero. For very large R, (33) and (40) represent the ex
act solution very well. For constant volume and R/r
K
 =3000,
the error is less than 5% over the majority of the range of D.
At large values of D, the error increases up to 20%, but here
the force here is already quite low. Likewise, for constant pres
sure and R/r
K
 =3000, the error is less than 5% over most of
the range, but grows rapidly beyond this point. These errors are
again only when the force is quite low. The dotted lower branch
of the constant volume solutions in Figs. 10a and 10b corre
spond to the dotted meniscus lines in Figs. 9a and 9b. Bestﬁt
expressions for the F–D curve and the rupture distance for the
constant volume case over a range of R/r
K
 values have been
reported [54].
As D increases in the constant pressure case, there is again
no longer a stable solution at some distance signiﬁcantly less
than 2r
K
cos θ. Hence there is also an abrupt pulloff of the
meniscus. (For this case, unstable solutions also exist but are
not plotted in Figs. 9 or 10 because they are not in equilibrium.
Hence, the mechanical stability of the F–D curve need not be
considered to rule them out.)
At D = 0, the force is equal for the two cases. In a load
control experiment, the force would be measured only at D =0.
If there is ﬁnite stiffness in the experimental apparatus, as for
example in an atomic force microscope pulloff experiment,
a load line reﬂecting the spring constant must be considered,
as discussed for example by Greenwood [48] and Carpick et
al. [61]. For small R with constant volume and for all values of
R with constant pressure, the F–D curves are concave down.
Pulloff will occur at D = 0 if the apparatus is compliant. If
the compliance decreases, pulloff will occur before the max
imum value of D is reached. As R increases for the constant
(a) (b)
Fig. 10. (a) Normalized F–D curves for increasing values of R/r
K
. Here θ
1
= θ
2
= 0
◦
. (" symbols mark the pulloff point in a ﬁxed grip experiment. For
R/r
K
 =100, the pulloff is at the coordinates (9.88, 0.69).) (b) Same as (a), except θ
1
=θ
2
=40
◦
.
(a) (b)
Fig. 11. (a) Normalized adhesion normalized asperity radius of curvature. Here θ
1
=θ
2
=0
◦
. (b) Same as (a), except θ
1
=θ
2
=40
◦
. Symbols indicate calculated
points.
M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 181
(a) (b)
Fig. 12. (a) Energies for constant volume and pressure cases with R =100 nm, r
K
=−1 nm, and θ
1
=θ
2
=0
◦
. (Note that the slope of W with respect to D is F.
Also Q
in
= Q
out
is divided by 10.) (b) Same as (a) except now R = 1 nm (the axis scales have also changed). The P dV contribution shows evaporation is
relatively smaller compared to (a), and hence that the work is closer to the surface energy change.
volume case, the F–D curves change to being concave up. For
a compliant load apparatus, it is possible to have a point of in
stability at D =0 after which force equilibrium would be found
at a larger value of D. A second instability would occur then
shortly before the maximum value of D. On the other hand,
a low compliance apparatus would sample most or all of the
curve.
Some details of the F–D curve change for Fig. 10b, where
θ
1
= θ
2
= 40
◦
. In particular for constant volume, the nose
extends further out. The reason for this is geometric. When
θ
1
> 0
◦
, the meniscus geometry allows the meridional curva
ture to be concave down at the point of departure from the
substrate as D increases. This in turn allows more of the pen
dular ring solutions to be accessed. When θ
1
= 0
◦
in the case
of constant volume, the meridional curvature cannot be con
cave down (this would correspond to the meniscus going into
the substrate), so only one solution is needed. It is also inter
esting to note that as D increases, r
e
> 0 before rupture and
hence the Laplace pressure contribution becomes repulsive but
remains smaller than the attractive axial component of the sur
face tension. Meanwhile, for the constant pressure case, only
the concaveup nodoid solution is used independent of the con
tact angle because r
e
= r
K
< 0, so the normalized constant
pressure curves are much more similar in Figs. 9a and 9b.
The integrated area under the F–D curve up to the ﬁxedgrip
point of rupture is W
asp
, the work of adhesion. Anormalized ad
hesion energy
ˆ
Γ
asp
=
˜
Γ
asp
/(γ
l
cos θ
2
) is plotted versus R/r
K

in Fig. 11a, where θ
1
= θ
2
= 0
◦
. In these calculations, we set
A
2w
as equal to the initial A
2w
; i.e., the ﬁnal A
2w
is set to
equal zero. Although at rupture A
2w
>0, the liquid will spread
over the surface and evaporate without any further work being
required, so that eventually none of the originally wetted area
remains wetted. In Fig. 11,
ˆ
Γ
asp
decreases as R/r
K
 decreases,
as explained in the introductory comments in this section. For
large R/r
K
,
ˆ
Γ
asp
= 2 and 1 the constant volume and pres
sure cases, respectively. At R/r
K
 = 10,
ˆ
Γ
asp
= 1.25 and 0.6
for Cases I and II, respectively. For very small R/r
K
 = 1,
ˆ
Γ
asp
is almost the same for the two cases. In Fig. 11b, where
θ
1
= θ
2
= 40
◦
, the decrease in
ˆ
Γ
asp
with R/r
K
 is not as se
vere. The reason is again because of the geometrical constraints
as explained before.
We can gain more physical insight by tracking the relative
contributions of surface energy (dU
s
) and heat (−P dV ) to
the total work as a function of. In Fig. 12, we plot the dU
s
term
for constant volume and the dU
s
and −P dV terms for con
stant pressure with R = 100 nm or 10 nm and r
K
= −1 nm.
Fig. 12 also plots (20) to show that Q
in
= Q
out
W
asp
. As
can be concluded from (43), Γ
asp
is a function of D for con
stant pressure. This is because dV/(−dA
2w
) ∼ D according
to (42). Consequently the −P dV term becomes larger in
Fig. 12a as D increases, so that progressively less work need
be done as the asperity reaches the pulloff condition. As R
decreases as in Fig. 12b, the −P dV term becomes smaller
relative to the dU
s
term. This is because the capillary volume
always initially increases due to condensation; this effect is en
hanced for small R. Hence the values of Γ
asp
in Fig. 11 for
constant pressure decrease more slowly with R than for con
stant volume where dW = dU
s
, especially for θ
1
= θ
2
= 0
◦
.
Correspondingly, Q
in
is negative for small D in Fig. 12b.
6. Case of two nominally ﬂat surfaces
In the previous sections, we obtained the constitutive laws
for an individual asperity. That treatment is easily extended to
multiple noninteracting asperities. However, we ﬁrst discuss
a different extreme, in which the interface is completely satu
rated. We assume the surfaces are nominally ﬂat, but initially
separated by some nonzero spacing, as might be established by
asperities that are distantly spaced from each other. For conve
nience, we choose a disk rather than a rectangular geometry. We
repeat the analysis of Section 4 for this geometry, and ﬁnd that
in both cases the adhesion can approach 2γ
l
cos θ.
6.1. Force–displacement and adhesion laws for constant
volume case
Consider a ﬂat disk of radius x
d
separated by widely spaced
nanometerscale asperities of height D
0
, as in Fig. 13a. Let us
182 M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185
(a) (b)
Fig. 13. (a) Disk geometry. (b) Flat plate with protruding asperities. (Note that the horizontal scale is signiﬁcantly compressed in both ﬁgures.)
Fig. 14. Normalized F(D) curves for parallel surfaces, with D
0
=
0.1 ×(2r
K
 cos θ).
assume that the interface is initially ﬁlled, with D
0
x
d
. The
volume is approximately
(50) V =V
0
=πx
2
d
D
0
=πx
2
D,
where x now represents the meniscus radius and D the plate
separation. Then
(51)
dx
2
dD
=−x
2
d
D
0
D
2
.
The surface energy is
(52) U
s
≈γ
s
A−πx
2
2γ
l
cos θ.
Application of (21b) to the control mass of the liquid gives
(53) F =−2πγ
l
cos θ
dx
2
dD
=
πx
2
d
D
0
2γ
l
cos θ
D
2
,
as graphed in Fig. 14. This result is in agreement with [62] for
contactangle controlled bridges. The work to separate the disk
from the substrate is now
(54) W
disk
≈
∞
_
D
0
F(D) dD =πx
2
d
2γ
l
cos θ.
Applying (23a),
(55) Γ
disk
=2γ
l
cos θ,
similar to the sphere on a ﬂat. The work done on the system is
again entirely absorbed as surface energy, i.e., the Dupré equa
tion applies. The result is independent of the initial spacing D
0
.
6.2. Force–displacement and adhesion laws for constant
pressure
To maintain constant Kelvin radius, liquid will condense be
tween the disk and the substrate as the disk is pulled away. The
volume is approximately
(56) V =πx
2
d
D.
Then
(57)
dV
dD
=πx
2
d
.
The differential surface energy of the control volume is approx
imately
(58) dU
s
=0.
Applying (21c), we have
(59) F =−
γ
l
r
K
πx
2
d
,
a positive quantity. The force, as graphed in Fig. 14, is now
independent of D. It is also independent of the contact angle
because the force is applied purely against the liquid surface
tension. The work of adhesion is
W
disk
=
2r
K
 cos θ
_
D
0
F(D) dD
(60) =2γ
l
cos θπx
2
d
_
1 −
D
0
2r
K
 cos θ
_
.
Here work is done against surface tension only without a change
in area. Applying (23c),
(61)
˜
Γ
disk
=2γ
l
cos θ
_
1 −
D
0
2r
K
 cos θ
_
.
For constant pressure,
˜
Γ
disk
is not equal to 2γ
l
cos θ unless
D
0
/r
K
 → 0. The possible range of values is 0 <
˜
Γ
disk
/
γ
l
cos θ < 2. As D increases, the walls absorb the heat of con
densation. Up until capillary pulloff, the interfacial energy re
mains unchanged. After, excess liquid will wet the surfaces.
The walls will resupply the absorbed heat and the liquid will
revert to vapor. At that point, the change in surface energy will
be again equal to 2γ
l
cos θ.
Note that at D =D
0
, the force values must be the same for
the two cases because the pressures are the same. This result can
be obtained by considering the volume of liquid just outside the
disk. Accordingly, we set F (D
0
) to be the same for the two
cases in Fig. 14.
M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 183
7. Combination of the asperity array and the ﬂat plate
We are now in position to consider the situation as posed in
Section 1.1, namely an array of asperities attached to a ﬂat plate
as a function of p/p
s
. Similar to Sections 4 and 6, we will make
estimates using limiting approximations.
If the array of asperities has a maximum height z
max
as in
Fig. 1 and we assume a square array of spheres, then
(62) n
asp
=
1
8Rz
max
.
7.1. Constant volume
If 2r
K
 cos θ < z
max
, i.e., an undersaturated interface, we
have
(63a) Γ =n
asp
W
asp
=n
asp
8c(θ, R)πRr
K
γ
l
cos
2
θ.
The factor c corrects for R and θ. In the subsequent calcula
tions, we take R/r
K
 30, and approximate c ≈1, as justiﬁed
by Section 5. Using (62) and the Kelvin equation (10) (with the
constants for water), allowing z
max
=εR where ε 1, we can
rewrite this explicitly as a function of p/p
s
:
(63b) Γ ≈γ
l
π
_
0.53 nm
εR
_
cos
2
θ
 ln(p/p
s
)
.
We now consider the transition from the undersaturated to
the saturated interface. As p/p
s
increases, 2r
K
 cos θ ap
proaches z
max
. The interface will not ﬁll completely when the
menisci ﬁrst merge because z
max
depends on direction. How
ever, for constant volume we saw for both the sphere on ﬂat and
ﬂatonﬂat geometries that Γ =2γ
l
cos θ. Therefore, once (63b)
reaches 2γ
l
cos θ, we have very nearly attained the maximum
value of adhesion. Equation (63b) is plotted in Fig. 15 for vari
ous values of R with ε =0.03 and θ =0
◦
. Notionally reﬂecting
the expected behavior of progressively smoother interfaces, the
limiting value of Γ = 2γ
l
cos θ is reached at lower values of
(p/p
s
) at smaller values of R because z
max
is assumed to be
proportional to R. Although the transition from (64) to 2γ
l
cos θ
Fig. 15. Γ vs p/p
sat
(with z
max
=0.03R, γ
l
=146 mJ/m
2
, and θ =0
◦
). The
marks the delineation between (64) and (66) for the constant pressure case.
is not captured precisely because of the details of the ﬁllin
process, this will have only a small effect in Fig. 15.
7.2. Constant pressure
For an undersaturated surface (2r
K
 cos θ < z
max
) and for
R/r
K
 30,
(64a) Γ =n
asp
W
asp
≈4πRr
K
γ
l
cos
2
θn
asp
,
which can be recast as
(64b) Γ ≈γ
l
_
π
2
__
0.53 nm
εR
_
cos
2
θ
 ln(p/p
s
)
.
As saturation occurs, the geometry becomes that of a ﬂat plate.
The work of adhesion is the work to separate the plane of the
ﬂat plate to 2r
K
 cos θ, plus the remaining work to separate the
menisci from the protruding asperities (Fig. 13b). Then,
Γ ≈
_
γ
l
r
K
 cos θ
_
_
2r
K
 cos θ −z
max
_
(65) +n
asp
2r
K
 cos θ
_
2r
K
 cos θ−z
max
F(D
) dD
.
Using (40) and (62), we obtain for an initially saturated inter
face
(66) Γ ≈γ
l
_
2cos θ
_
1 −
z
max
2r
K
 cos θ
_
+
_
π
8
__
z
max
r
K

__
.
With z
max
=εR (ε 1) and recasting in terms of p/p
s
,
Γ ≈γ
l
_
2cos θ
_
1 −
εR ln(p/p
s
)
2(0.53 nm) cos θ
_
(67) +
_
π
8
_
εR ln(p/p
s
)
0.53 nm
_
.
Again assuming ε = 0.03, γ
l
= 73 mJ/m
2
and θ = 0
◦
, (63b)
and (67) are plotted versus in Fig. 15. For low values of p/p
s
where (65) applies, Γ is one half of the constant volume case.
For large values of p/p
s
, Γ strictly reaches 2γ
l
cos θ only at
p/p
s
=1. The transition vapor pressure, [p/p
s
]
tr
, deﬁning the
transition from (64b) to (67) is
(68) [p/p
s
]
tr
=exp
_
−
2(0.53 nm) cos θ
εR
_
.
This is indicated by asterisks in Fig. 15. Again the region near
the transition is an approximation because this simple analysis
does not capture the details of the meniscus merging process.
Given the results of Section 5 (cf. Fig. 11), (67) is an upper
bound.
For comparison, the work of adhesion between a rigid sphere
and a substrate due to van der Waals forces is [43]
(69) W
vdW
=
A
H
R
6D
0
,
where A
H
is the Hamaker constant and D
0
is the minimum
approach between molecules. Assuming A
H
= 5 × 10
−20
J
(representing a silica surface) and D
0
= 0.2 nm (equivalent to
184 M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185
γ
s
=33 mJ/m
2
), and using (62) we have
(70) Γ
vdW
=W
vdW
n
asp
=
A
H
1.44RD
0
,
which is also plotted in Fig. 15. Note that capillary adhesion
dominates over van der Waals adhesion for any reasonable p/p
s
value (for p/p
s
>8 ×10
−6
), because the liquid force does not
fall off with separation as quickly as van der Waals forces. Also,
dielectric screening due to the liquid will reduce A
H
in (69)
and (70) as p/p
s
increases. Experimentally, of course, the van
der Waals limit may extend to a much larger value of p/p
s
be
cause capillary nucleation is ﬁrst required.
8. Concluding remarks
We have used thermodynamics to determine capillary adhe
sion laws in two extreme cases—constant volume and constant
pressure for different geometries (spheres of arbitrary size, ﬂat
plates and asperity arrays). As rough interfaces are separated
under constant pressure, evaporation or condensation can occur
depending on geometrical details of the surface. Our most im
portant result is that even though the change in surface energy
is the same, the work of adhesion depends strongly on the sep
aration rate and can be less than the surface energy created. It
is a factor of two smaller for the case of constant volume rela
tive to constant pressure when R r
K
. The physical reason is
that heat is capable of doing P dV work, while concomitantly
matter is exchanged with the environment. Further reductions in
the adhesion energy per unit area can be achieved by reducing
R/r
K
, as shown in Fig. 11. Another important result is that
for constant pressure in the ﬂat plate geometry, Γ approaches
2γ
l
cos θ only as D
0
/(2r
K
 cos θ) approaches zero. The present
work has been extended to the case of an elastic rough surface
consisting of summits of uniform radius R with a distribution
of summit heights [33].
As stated in the Introduction, we have not considered the
effect of the disjoining pressure [21,22]. If this quantity is at
tractive, no adsorbed layer is on the surface and the theory
presented is applicable at the nanometer scale. When this quan
tity is repulsive, an adsorbed liquid layer will be present on the
surface. The energy balances for the constant volume and pres
sure cases are not affected, but the control volume is changed.
The adsorbed layer thickness depends on p/p
s
, and will tend
to increase the volume of the capillary. Then the calculations
presented here are a lower bound for the work of adhesion
and serve as a benchmark for calculating the effect of disjoin
ing pressure, as recognized by Mate et al. [63]. To ﬁrst order,
(40) becomes
(71) F(D) =4πRγ
l
_
1 +
t
d
r
K

__
1 −
D
2(r
K
 +t
d
)
_
,
where t
d
is the thickness of a liquid disjoining layer assumed to
wet both surfaces. For simple substances, the disjoining pres
sure depends only on van der Waals interactions, and is re
pulsive if A
H
< 0. It is then straightforward to calculate the
adsorbed layer thickness [43]. It can also be determined from
AFM measurements [63,64]. For other substances electronic
and structural components must also be considered to ﬁnd A
H
.
For water on quartz A
H
< 0 according to calculations, but the
actual thickness of the water layer can also depend on double
layer and hydration forces [43].
Acknowledgment
Sandia National Laboratories is a multiprogram laboratory
operated by Sandia Corporation, a Lockheed Martin Com
pany, for the United States Department of Energy’s National
Nuclear Security Administration under Contract DEAC04
94AL85000.
Appendix A. Nomenclature
a actuation pad length (m) (Fig. 2a)
h cantilever gap (m) (Fig. 2a)
h
lv
speciﬁc heat of vaporization (J/g)
k Fogden–White parameter (Eq. (12))
m mass (kg)
n
asp
density of asperities on the rough surface (1/m
2
)
p/p
s
partial pressure of the vapor
q distributed force (N/m
2
) (Fig. 2a)
r
e
effective radius of capillary meniscus (m) (Eq. (6))
r
a
azimuthal radius of capillary meniscus (m) (Eq. (6),
Fig. 8)
r
m
meridional radius of capillary meniscus (m) (Eq. (6),
Figs. 6 and 8)
r
K
Kelvin radius (m) (Eq. (10))
s crack length (m) (Fig. 2)
t cantilever thickness (m) (Fig. 2a)
u speciﬁc internal energy of the liquid (kJ/kg)
x
d
disc radius (m) (Fig. 6)
z
max
maximum height in a simple model rough surface (m)
A area (m
2
)
A
p
projected interface area (m
2
)
A
H
Hamaker constant (J)
D distance between surfaces (m) (Figs. 5, 6, 8, and 12)
D
0
equilibrium separation (absent external forces) (m)
E total energy (J)
E
m
elastic modulus (N/m
2
)
F force (attractive taken as positive) (N)
G energy release rate (J/m
2
)
G
f
Gibbs free energy (J)
H enthalpy (J)
P pressure (Pa)
Q heat (J)
R radius of curvature of asperity (m) (Figs. 1, 6, and 8)
R
u
universal gas constant (Latm/(mol K))
T temperature (K)
U
b
bulk liquid energy (J)
U
s
surface energy (J)
V volume (m
3
)
V
m
molar volume (L/mol)
W work done on the control volume (J)
W
asp
work to remove an individual asperity from the sub
strate (J)
M.P. de Boer, P.C.T. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 185
ε ratio of z
max
to R
γ surface energy (J/m
2
)
γ
l
surface energy (tension) of liquid–vapor interface
(J/m
2
)
γ
s
surface energy (tension) of solid–vapor interface
(J/m
2
)
γ
ls
interfacial energy (tension) of liquid–solid interface
(J/m
2
)
ρ density (kg/m
3
)
θ contact angle (radian)
Γ work of adhesion per unit area (J/m
2
)
˜
Γ effective adhesion (J/m
2
) (Eq. (23c))
References
[1] L. Bocquet, E. Charlaix, S. Ciliberto, J. Crassous, Nature 396 (1998) 735.
[2] T.C. Halsey, A.J. Levine, Phys. Rev. Lett. 80 (14) (1998) 3141.
[3] J. Crassous, L. Bocquet, S. Ciliberto, C. LaRoche, Europhys. Lett. 47 (5)
(1999) 562.
[4] J. Qian, H. Gao, Acta Biomater. 2 (2006) 51.
[5] J. Bachmann, R.R. van der Ploeg, J. Plant Nutr. Soil Sci. 165 (2002) 468.
[6] D. Bentz, P. Dale, Mater. Construct. 28 (182) (1995) 450–458.
[7] C.M. Mate, J. Appl. Phys. 72 (2) (1992) 3084.
[8] C.H. Mastrangelo, C.H. Hsu, J. Microelectromech. Syst. 2 (1) (1993) 33.
[9] C.H. Mastrangelo, C.H. Hsu, J. Microelectromech. Syst. 2 (1) (1993) 44.
[10] H.L. Ewalds, R.J.H. Wanhill, Fracture Mechanics, Edward Arnold and
Delftse Uitgevers Maatschapij, London, 1991.
[11] B.R. Lawn, Fracture of Brittle Solids, second ed., Cambridge Univ. Press,
New York, 1993.
[12] A. Dupré, Théorie méchanique de la chaleur, Gauthier–Villars, Paris,
1869.
[13] J.R. Rice, J. Mech. Phys. Sol. 26 (1978) 61.
[14] J.A. Greenwood, J.B.P. Williamson, Proc. R. Soc. London A 295 (1966)
300.
[15] K.N.G. Fuller, D. Tabor, Proc. R. Soc. London A 345 (1975) 327.
[16] D. Maugis, J. Adhesion Sci. Technol. 10 (2) (1996) 161.
[17] W.R. Chang, I. Etsion, D.B. Bogy, J. Trib. Trans. ASME 109 (1987) 257.
[18] B.N.J. Persson, J. Phys. Condens. Matter 17 (44) (2005) 1071–1142.
[19] Y.F. Gao, A.F. Bower, Proc. R. Soc. London A 462 (2065) (2006) 319.
[20] D.H. Roach, S. Lathabai, B.R. Lawn, J. Am. Ceram. Soc. 71 (2) (1988)
97.
[21] B.V. Derjaguin, N.V. Churaev, V.M. Muller, Surface Forces, Consultants
Bureau, New York, 1987.
[22] C. Gao, Appl. Phys. Lett. 71 (13) (1997) 1801.
[23] C.D. Willett, M.J. Adams, S.A. Johnson, J.P.K. Seville, Powder Tech
nol. 130 (2003) 63.
[24] O. Pitois, P. Moucheront, X. Chateau, Eur. Phys. J. B 23 (1) (2001) 79.
[25] N. Maeda, J.N. Israelachvili, M.M. Kohonen, Proc. Natl. Acad. Sci.
USA 100 (3) (2003) 803.
[26] T.A. Michalske, S.W. Freiman, J. Am. Ceram. Soc. 66 (4) (1983) 284.
[27] S.M. Wiederhorn, Mechanical and Thermal Properties of Ceramics,
vol. 303, 1969.
[28] D. Maugis, J. Mater. Sci. 20 (1985) 3041.
[29] K.T. Wan, D.T. Smith, B.R. Lawn, J. Am. Ceram. Soc. 75 (3) (1992) 667.
[30] K.T. Wan, B.R. Lawn, Acta Mater. 38 (11) (1990) 2073.
[31] B.V. Derjaguin, V.M. Muller, Y.P. Toporov, J. Colloid Interface Sci. 53 (2)
(1975) 314.
[32] J.W. Obreimoff, Proc. R. Soc. London A 127 (1930) 290.
[33] M.P. de Boer, Exp. Mech. (2006), submitted for publication.
[34] M.B. Sinclair, M.P. de Boer, A.D. Corwin, Appl. Opt. 44 (36) (2005)
7714–7721 (cover article).
[35] M.P. de Boer, T.A. Michalske, J. Appl. Phys. 86 (2) (1999) 817.
[36] M.P. de Boer, J.A. Knapp, T.A. Michalske, U. Srinivasan, R. Maboudian,
Acta Mater. 48 (18–19) (2000) 4531.
[37] J.A. Knapp, M.P. de Boer, J. Microelectromech. Syst. 11 (6) (2002) 754.
[38] F.W. DelRio, M.P. de Boer, J.A. Knapp, E.D. Reedy, P.J. Clews,
M.L. Dunn, Nat. Mater. 4 (8) (2005) 629–634.
[39] A.W. Adamson, Physical Chemistry of Surfaces, Wiley, New York, 1990.
[40] W. Thomson, Proc. R. Soc. Edinburgh 7 (1870) 63.
[41] Q. Zheng, D.J. Durben, G.H. Wolf, C.A. Angell, Science 254 (1991) 829.
[42] J.C. Fisher, J. Appl. Phys. 19 (1948) 1062.
[43] J. Israelachvili, Intermolecular and Surface Forces, Academic Press, New
York, 1992.
[44] H.K. Christenson, J. Colloid Interface Sci. 121 (1) (1988) 170.
[45] L.R. Fisher, J.N. Israelachvili, J. Colloid Interface Sci. 80 (2) (1981) 528.
[46] L. Sirghi, R. Szoszkiewicz, E. Riedo, Langmuir 22 (3) (2006) 1093.
[47] A. Fogden, L.R. White, J. Colloid Interface Sci. 138 (2) (1990) 414.
[48] J.A. Greenwood, Proc. R. Soc. London A 453 (1961) (1997) 1277.
[49] K.L. Johnson, K. Kendall, A.D. Roberts, Proc. R. Soc. London A 324
(1971) 301.
[50] K. Wark, Thermodynamics, third ed., McGraw–Hill, New York, 1977.
[51] R. Defay, I. Prigonine, A. Bellemans, D.H. Everett, Surface Tension and
Adsorption, Longmans, Green, London, 1966.
[52] L.J. Douglas Frink, F. van Swol, J. Chem. Phys. 106 (9) (1997) 3782.
[53] F.M. Orr, L.E. Scriven, A.P. Rivas, J. Fluid Mech. 67 (part 4) (1975) 723–
742.
[54] C.D. Willett, M.J. Adams, S.A. Johnson, J.P.K. Seville, Langmuir 16
(2000) 9396.
[55] R. Aveyard, J.H. Clint, V.N. Paunov, D. Nees, Phys. Chem. Chem.
Phys. 1 (1) (1999) 155.
[56] G. Lian, C. Thornton, M.J. Adams, J. Colloid Interface Sci. 161 (1993)
138.
[57] P.C.T. de Boer, M.P. de Boer, Rupture work of pendular bridges (2007),
submitted for publication.
[58] B.Q. Luan, M.O. Robbins, Nature 435 (7044) (2005) 929.
[59] J.E. Houston, T.A. Michalske, Nature 356 (6366) (1992) 266.
[60] R.C. Thomas, J.E. Houston, R.M. Crooks, T. Kim, T.A. Michalske, J. Am.
Chem. Soc. 117 (13) (1995) 3830.
[61] R.W. Carpick, J.D. Batteas, M.P. de Boer, in: B. Bhushan (Ed.), Springer
Handbook of Nanotechnology, second ed., Springer Verlag, Berlin, 2006,
pp. 951–979.
[62] M.A. Fortes, J. Colloid Interface Sci. 88 (2) (1982) 338.
[63] C.M. Mate, M.R. Lorenz, V.J. Novotny, J. Chem. Phys. 90 (12) (1989)
7550.
[64] A.P. Bowles, Y.T. Hsia, P.M. Jones, J.W. Schneider, L.R. White, Lang
muir 22 (2006) 11436.
Wasp times nasp . The sample could be a double cantilever beam (DCB) sample as has been used in many studies [11. in which rigid spherical asperities of radius R that protrude a maximum distance zmax from a ﬂat surface. . constant chemical potential) and is achievable by very slowly separating the materials. which corresponds to thermodynamic equilibrium. This corresponds to thermodynamic equilibrium (i. From an experimental determination of the crack length s. knowledge of the ﬁlm thickness t . The point at which these become dominant is considered in Section 7. from a fracture of materials viewpoint. In the second extreme. Dispersion forces exist between such solids. t ≈ h ≈ 2 µm. In this work. a dielectric layer of liquid such as water can decrease adhesion due to charge screening of mica surfaces [29]. when the interface is rough.1. The areal asperity density nasp is inversely related to zmax . However. and D is the interface separation. we suppose that the asperities are attached to an elastic cantilever as in Fig. the Kelvin radius remains constant and therefore the Laplace pressure remains constant. 1. 2. Array of asperities bridged by capillaries of areal density nasp .T. The effects of solute precipitation which can result in solid bridging [20]. capillary forces can dominate the adhesion between solids when the interface is rough. 1. Before separation. In the ﬁrst extreme. a model of a simple rough interface. and the treatment will then be that of DMT [31] contacts. only dispersion forces exist.172 M. Micromachined cantilevers with micrometerscale thickness are also well suited to the capillary adhesion range [33]. Models of increasing complexity have been applied to calculate this area [17–19].32]. Intersolid forces in brittle materials are responsible for adhesion energies from ∼1 to ∼100 J/m2 [11].2. the gap h and the elastic modulus Em of the cantilever material. To maintain constant pressure. of disjoining pressure and its effect on the meniscus volume and shape [21. 1. Measured values of Γ are often much larger than the Dupré work of adhesion. Their deﬂections can be accurately measured using interferometry [34]. de Boer. we contend that each case is relevant in a fracture mechanics experiment. the Dupré work of adhesion equates with 2γl cos θ . when solids formed separately are later brought together the lattices will be incoherent. where γl is the liquid–vapor surface energy and θ is the contact angle that the liquid makes with the surface. under which capillary forces dominate. the real contact area is small and the surfaces are wetted by liquids. We shall assume a capillary bridge of equilibrium Kelvin radius rK has condensed around each sphere. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 where F is the attractive interface force over the projected interface area Ap . but as we shall show. we shall expect an energy balance that is fundamentally different from these criteria. Interface description In Fig. the work of adhesion will depend also on how much the liquid evaporates (or condenses) as the two materials are separated. Therefore. The contact mechanics [14] and adhesion of dry rough interfaces [15.e. In a rough interface the real area is much smaller than the apparent contact area. The case of interacting asperities (asperity saturation) will also be considered. we must consider the geometry in more detail. For example. We shall refer to this as the constant pressure case. the volume of the liquid will remain constant. The general result of this work is that the work of adhesion is proportional to the area of real contact. we shall consider two extremes. In our treatment. In the example experiment below. It is well known that environmental species can reduce the adhesion of a brittle material. is known [35]. is presented. For noninteracting asperities. Likewise. and this is attributed to dissipative processes such as dislocation motion or phonon excitation in the bulk of the material. P. the energy release rate G. We brieﬂy consider the circumstances. which will also reduce adhesion. Because the asperities are at the same height and they are rigid. the initial condition for the capillary volume will be established by the Kelvin radius.16] has received much attention. Neither the Grifﬁth approach nor the Dupré approach considers this process.P. this irreversible crack growth is associated with entropy production [13]. this is no longer valid when there is a distribution of asperity heights [14]. of liquid viscosity [24] and the rate at which menisci nucleate [25] all deserve attention but are beyond the scope of this work.. stress corrosion cracking of materials such as glass [26] and sapphire [27] increase crack velocities at subcritical stress intensities when water vapor is introduced (stress Fig. we shall consider the effects of capillary forces only. When the interface is wetted and rough. their adhesion contribution is much smaller than that due to capillary force. of contact angle hysteresis which can affect the capillary F (D) path [23]. Adhesion measurement in the sample geometry Although we imagine the substrate and the asperities to be rigid. Typically. Therefore. Capillary forces can contribute strongly to adhesion if the intersolid forces are reduced. matter exchange with the surrounding vapor through evaporation or condensation is required. and we shall refer to this as the constant volume case.C. The force–displacement (F –D) law of the individual asperity is necessary to calculate the expected adhesion.22]. In the absence of capillary forces. corrosion velocities can be analyzed thermodynamically using a modiﬁed Grifﬁth criterion. we will take D0 = 0 in (2). 1. When a liquid wets two ﬂat surfaces that are to be separated. which is difﬁcult to ascertain with known conﬁdence. G > 2γ [28]). This corresponds to rapid separation of the two surfaces. will determine the adhesion value Γ . Of course. Furthermore. Thermodynamically. We shall derive an energy balance based on a controlvolume analysis and apply it to different geometries to determine the trend for adhesion versus p/ps in rough interfaces. for example by misorienting the virgin surfaces of mica [30]. even though in this case the real contact area approaches the apparent area of contact. the integrated F –D curve.
The fundamental equation of capillarity. the liquid vapor energy is γl and the effective radius of curvature of the surface is re as deﬁned by 1/re = 1/ra + 1/rm . However. re equals the Kelvin radius rK . de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 173 Fig.C. Accordingly. in the case of evaporative equilibrium.) With s held at a smaller value. Evaporation will occur. As mentioned above. a curved surface has a pressure difference P = γl /re (5) 3 h2 t 3 G = Em 4 . This process will continue until an equilibrium crack length associated with menisci of radii re  = rK  is established. To establish this equilibrium. Capillarity basics We wish to calculate the adhesion values of two nominally ﬂat surfaces for the constant volume and pressure cases. we actuate the cantilever electrostatically such that G and consequently s are decreased. Moreover. The surfaces separate rapidly and s will soon reach a new length. for a reversible process at constant temperature. and is analogous to retraction of the wedge in a DCB sample. (8) . P. The initial state of each is taken to be deﬁned by thermodynamic equilibrium. is derived from a surface curvature argument [39]. These quantities are positive when the center is inside the meniscus and negative when outside. Here. we mark time until capillaries equilibrate around the asperities in the new crack tip position. while ra and rm will vary along this surface. which will reduce the capillary volume of the asperities in the vicinity of the crack tip. This is the constant pressure case. while keeping the value of p/ps constant. The capillary force will decrease and the crack length will increase incrementally. G = Em 4 + 2 s 24Em s 4 t 3 2s 4 (4) across the liquid–vapor interface. (An accurate treatment of the nonuniform distribution of q is developed in [37]. an electric potential is applied. (c) idealized surface roughness in the crack region. de Boer. (7) Assuming constant molar volume of the liquid substance Vm . the Young–Laplace equation. 2. The liquid is assumed to be isobaric at each instant in time.P. With t zmax . 2a. While keeping both the cantilever and the substrate at ground potential [36–38].M. This is the constant volume case. this is accomplished by placing an electrically isolated actuation pad of length a near the support post. this initial crack length is unstable because the meniscus radius re  (deﬁned in Section 2) is larger than rK .T. (a) Geometry of the adhered cantilever. Suppose that. an increase of q corresponds to smaller s for constant Γ . the constant pressure case remains in equilibrium. with G decreasing according to (3). thereby increasing G. and applying the Young–Laplace equation we get Gf = γl Vm /re . (6) According to (4). Then we remove the actuation load by reducing the electric ﬁeld to zero (akin to reinsertion of the wedge in the DCB sample). As shown in Fig. the energy release rate is [37] h2 t 3 a 6 q 2 (4s − 3a)2 qa 3 h 3 − (4s − 3a). If no liquid evaporation occurs. the volume of each capillary is constant during the separation process. The Kelvin equation is derived from thermodynamic equations and the Young–Laplace equation [39]. 2. we review the basics of capillaries in this section. (3) 2 s We now consider the effect of surface separation rate. If an approximation is made that the distributed force due to the electric ﬁeld has a uniform value q. First. the effect of a change in mechanical pressure on the free energy Gf of a substance is Gf = Vm dP . (b) closeup of the crack tip. where ra (the azimuthal radius) and rm (the meridional radius) are the principal radii of curvature of the surface. This means that re is constant along the meniscus surface.
agreement with the Kelvin equation was also found for p/ps down to 0. √ γl R (12) Fig. k = 27 with R = 260 nm at p/ps = 0. −140 MPa would give a lower limit on the partial pressure at p/ps = 0.5 mJ/m2 in water vapor on an oxidized silicon surface at p/ps = 0. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 where Vm is the liquid molar volume. which gives rise to the strong capillary forces and adhesion in micrometerscale structures and in porous materials. which describes the transition from the Johnson– Kendall–Roberts (JKR) [49] regime to the Derjaguin–Muller– Toporov (DMT) [31] regime.P. From surface force apparatus (SFA) experiments. However. and the liquid– vapor interface. In a MEMS cantilever experiment. in the absence of cavitation. The Kelvin radius can be obtained more directly by measuring the surface separation near pulloff [45] and here for cyclohexane.53 = nm.02 mJ/m2 at p/ps < 0. in good agreement with vapor nucleation theory [42]. However. very high negative pressures can be sustained by the van der Waals or hydrogen bonding forces between adjacent liquid molecules. and assuming thermodynamic equilibrium.018 L/mol.3 [33]. The Kelvin radius is negative for 0 < p/ps < 1. Assuming the vapor to be ideal. The approximate diameter of a water molecule (0. indicating that a condensed liquid coexists in narrow channels with an undersaturated vapor. For the MEMS experiment [33]. the average value of R was estimated to be 250 nm. and Ru = 0. Gf = Ru T ln(p/ps ).7 in Christenson’s [44] work. Thermodynamics relates the free energy of a substance to its vapor pressure. This is consistent with the assumption of a rigid sphere during withdrawal of the sphere . capillary forces at the remarkably low value of p/ps = 0. The Young geometry. In turn. nhexane and water vapors on mica surfaces [44]. signiﬁcant negative (tensile) pressure exists in the liquid. as rK  decreases. de Boer. Equation (10) is graphed in Fig.3 (assuming D0 2rK ). the Kelvin equation [40] is found.7 for cyclohexane. Therefore. There. the solid–liquid interface (γls ). L is a characteristic length of the system and ρ is the density difference of the ﬂuids on adjacent sides of the interface) approaches 1.37. Large k ( 1) applies to small hard spheres at high vapor pressures. However. and D0 atomic spacing when the surfaces are in contact. where g is the acceleration due to gravity. T = 300 K. This implies that the Kelvin equation is valid at least to 1. pressures of −140 MPa have been measured for bulk water [41]. the difference in surface energy between a surface in contact with a vapor versus a liquid is γl cos θ . rK = γl Vm 0. [RT ln(p/ps )] ln(p/ps ) (10) The value of 0. 3. Indeed.C.15 were detected for silicon tips in atomic force microscopy (AFM) experiments with R ranging from 50 to 400 nm [46]. is then larger than the Kelvin radius. as can be calculated from nucleation theory. Small k ( 1) corresponds to large spheres at low vapor pressures. adhesion spontaneously increased from 0. the Laplace pressure term dominates for p/ps > 0.3 nm) and a roughness range over which many technological surfaces may vary are also indicated. the critical vapor nucleus radius at a given pressure. such that γl cos θ = γs − γls . the Bond number is typically 10−12 or smaller. As represented in Fig.05 to 0. They developed a dimensionless parameter k= 3 4 π 2 K [rK (1 − D0 /2rK )]3/2 . υ is Poisson’s ratio. According to (11). (9) Equating (8) and (9). Recently.53 nm assumes that the substance is water at room temperature (γl = 0. A calculation shows that k ≈ 1 at p/ps = 0. (11) where θ is the contact angle between the solid and the liquid. The discrepancy between the SFA and AFM results may be resolved by the theory due to Fogden and White [47].5 nm for water on mica. This extreme is DMTlike and the expected force at zero displacement is 4πγl R. 4. The Kelvin radius (for water) versus p/ps .7. P. In the examples below. Fig.082 L atm/(mol K)). this consideration may not limit the applicability of (10). From (5) and (10). 3. This extreme is JKRlike and the expected force at zero displacement is 3πRγl cos θ .072 N/m. it reaches the size of individual molecules (a water molecule is ∼0. Liquids are metastable in tension and are susceptible to spinodal decomposition. Vm = 0. where K = (4/3)(E/[2(1 − υ 2 )]). and below this value of p/ps the measured force is less than 4πRγl cos θ . with experimental error limiting this lower bound.174 M. 4. Gravity signiﬁcantly inﬂuences the curvature only if the Bond number (gL2 ρ/γl . which clariﬁes that the SFA experiment [44] does not necessarily measure the lower limit to the Kelvin radius. the Young equation describes a force balance between the surface tension of the solid–vapor interface (γs ).3 nm in diameter [43]) and the applicability of continuum theory must reach a limit. The parameter k is related to the inverse of the Tabor parameter [48].T.
Object (surface 1) surrounded by a capillary meniscus as it is separated from the substrate (surface 2). 5. δQ is much larger (order 10 times) than the energy terms in (19).e. Eq. It occurs by heat transfer through the liquid to reduce the meniscus volume.cv + ρl ul dV . as in the DMT model. the present treatment assumes a continuum material. It should be noted that the sign of δQ is opposite when condensation occurs. From an energyreleaserate point of view. If liquid condenses as D increases. while uv and ρv are the vapor internal energy and density. (13) For constant pressure. 3.15. the P dV term is analogous to stored energy being released. Furthermore. Differential surface energy created outside the control volume is represented by dUs. and the assumption of a rigid sphere becomes questionable. The result is δQ = (uv + P /ρv )(−dm) − ul + (P + P )/ρl (−dm). To quantify the heat δQ. (14) The differential enthalpy of the material entering the control volume is dH . we write the ﬁrst law for this open system [50] as dE = dH + δQ + δW − dUs. Nonetheless. dE = d(Ub + Us. volume lost due to evaporation will reduce the work required). Equating (13) and (14).ocv . the effect of curvature on the heat of vaporization is small (less than 10% for re  = 1 nm [51]). If capillary liquid evaporates as D increases. The differential enthalpy is dH = dHin − dHout = −(uv + P /ρv )(−dm). Accordingly. We wish to develop an energy balance for a control volume V encompassing the liquid for the constant volume and pressure cases. de Boer.ocv . (18) (19) where the bulk liquid energy is Ub and the control volume surface energy is Us. −dm is the mass of the material exiting the control volume.cv + dUs. The P dV term is required because the analysis is in terms of absolute pressure (for example. (17) Here. liquid enthalpies depend strongly on temperature but only weakly on pressure. The force (positive is taken to be attractive) is obtained from dW . In general. This is not generally found in thermodynamic tables. Equating (13) and (14) now results in γl δW = dUs − P dV = dUs − dV rK (constant pressure). the differential heat supplied to the control volume is δQ and the differential work done on the control volume is δW . Energy is conserved. (13) becomes dE = dUs. which is supplied by the walls and causes a phase change in the liquid. where ρl is the density of the liquid and ul is its speciﬁc internal energy. Compared to the Grifﬁth energy balance (15). For constant volume. However.. For 0 < p/ps < 1. dV is negative and hence δW is less than dUs . F (D) = (21a) dD Then.5 attoJ/nm3 . The differential energy dE of the control volume consists of bulk and surface components. where P = γl /rK . (16) A control volume about the liquid–vapor interface is considered to ﬁnd the heat δQ in Eq. hlv ≈ 2. but the work of adhesion will be less than the surface energy created. yields the Grifﬁth energy balance δW = dUs (constant volume). Equations (13) and (14) hold for either evaporation or condensation.ocv − P dV .C. and assigning the total system differential surface energy dUs = dUs. δQ = 0 in (14). (21c) .M.cv ). 5. Likewise. We shall suppose it has a proﬁle that allows a condensed capillary liquid to ﬁll a continuous volume as the surfaces are separated. a value for the liquid enthalpy at negative pressure is required. For water at room temperature and atmospheric pressure. a capillary model agreed reasonably well with the measured F –D curve [46]. i.T. we approximate δQ ≈ hlv dV . dW > dUs and the converse statements can be made. the work done on the liquid in (19) is changed by a P dV term. (15) This deﬁnes the energy balance in the constant pressure situation. The restriction placed on the shape is that the surface separation from the substrate continuously increases (or remains constant) from the point of closest approach as deﬁned by D. For a change in relative displacement D of the surfaces.P. dH = 0 in (14) because no liquid enters or leaves the volume. P. rK < 0.75 for R = 400 nm and p/ps = 0. dUb = ρl ul dV = 0 in (13). and F (D) = γl dV dUs − dD rK dD (constant pressure). (20) where hlv is the speciﬁc heat of vaporization of the liquid. Although its valid range is not ﬁrmly established. Because this case is adiabatic. Therefore. respectively. For the AFM experiment [46]. (14). k = 0.cv . de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 175 from the substrate. F (D) = dUs dD (constant volume) (21b) Fig. thereby reducing W . Energy balance for constant volume and pressure cases Let us consider an arbitrary rough surface in contact with a ﬂat substrate as represented in Fig. we use the Kelvin equation (10).
4. Geometry For the sphere on ﬂat geometry as in Fig.P. (29) The total surface energy Us of the system in Fig. Γ = (22) −dA2w where −dA2w is the differential increase in unwetted area of the lower surface (the area A2 is in the plane of the crack). as D increases. i. Γ = (23c) − A2w where − A2w is the change in unwetted substrate surface area from D = D0 to D → ∞ and W is the corresponding work done. the values of the meniscus radius re and the disk ra2 dius xd change. we shall apply the energy balances (15) and (19) to model geometries of interest. 6. . dW . F= dx 2 dUs = −2πγl cos θ d dD dD D . de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 The adhesion is the rate of change of work with respect to the creation of solid–vapor area. dD dD 2R dD so that 2 2 dxd xd . (30) The liquid–vapor term is small and therefore (24) 2 Us = −2πxd γl cos θ + constant. We further take the contact angle to be the same on the top and bottom surfaces. Accordingly. leaving out higherorder terms. dUs −dA2w while Γ = (constant volume) (23a) The volume of the capillary bridge is xd V= 0 2πrη(r) dr. the separation is rapid enough that no evaporation occurs. Working out the integral and using (25) results in 2 V = πxd D + 2 xd 4R 2 = 4πRre cos2 θ 1 − D2 . the contact angle θ remains constant. 2 2 Us ≈ 2γls πxd + γs A − 2πxd + γl 2πxd 2rK .. 2re  cos θ (25) Fig. 6. with the result 2 xd = 4Rre  cos θ 1 − where we have used Young’s equation (11). respectively) is the energy of the liquid–solid interface. the area of the upper and lower surfaces. (23b) 4.176 M. the force– separation (F –D) curve and the adhesion (Γasp ) of an isolated asperity under the assumption that R re  for the cases of constant volume and pressure for the geometry illustrated. Then. 4. Because the surface tensions γs and γls are unchanged. The rate of change of xd follows from taking the derivative of V with respect to D. In the following sections. (21b). de Boer. Geometry of the capillary disk with R re and R ra . Sphere on a ﬂat (with R re  and ra re ) (28) In this section we ﬁnd the separation work (Wasp ). Approximately. Case of constant volume In this case.T. Recalling (15). (31) We expand (24) in powers of re /R. We also take the disc radius xd rm .1. (26) where the height of the disk is given by η(r) = D + r 2 /(2R). 6 (of solid surface area A = A1 + A2 . R − 2re  cos θ − D 2 2 + xd ≈ R 2 . Then dx 2 x 2 dx 2 dV 2 = 0 = π xd + D d + d d .e. This means that the meniscus has a circular proﬁle. P. and (31). 2 4re cos2 θ (27) dUs γl dV Γ =− − dA2w rK dA2w (constant pressure). the energy of the solid–vapor interface and the energy of the liquid–vapor interface. (29).C. re  = rm .2. =− 2 dD D + xd /(2R) The effective adhesion is W ˜ . Therefore.
P. (36) The same result is obtained by combining (25) and (31).M. we ﬁnd F = 4πRγl cos θ 1 − D 2 4rK cos2 θ + D 2 . but is written explicitly in terms of D. Orr et al.3. The expression (35) is equivalent to the one given in Chapter 15 of [43]. while the second half of the surface energy gained is due to P dV work effectively done by evaporation. Our motivation is that asperity radii of curvature in MEMS surfaces. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 2 and the rate of decrease of xd is 177 2 dxd (39) = −2R. and is one half the result for the constant volume case (36). (6) still holds. (37) which is independent of D. and therefore the approximations become poor. Yet. As R decreases. they are clearly inaccurate over parts of the F –D curve. we then have Γasp = − dUs γl dV − dA2w rK dA2w (constant pressure). Γasp decreases as D increases. the change in surface energy is the same as in the constant volume case.C. The volume of the disk follows from (27) as 2 V = V0 = 4πRrk cos2 θ. Wasp . dD Noting that dUs is unchanged with respect to D. 7.P. The asperity adhesion is Γasp = 2 d(−2πγl cos θ xd ) 2 −d(πxd ) = 2γl cos θ (constant volume). Case of constant pressure In this case. The work to remove the asperity from the substrate is now Fig. The main result of this section is that the relatively crude approximations used in Section 4 overestimate the work of adhesion by up to a factor of 2 or more. 2re  cos θ (32) We consider the situation in which a capillary bridge of radius rK has formed while the sphere and the plate are in contact (D = 0). Exact geometry—the pendular bridge analysis The above analysis used the approximations that the meridional curvature is circular. (35) which is plotted in Fig. ra decreases because of the sharp asperity curvature. that R re  and xd ≈ ra re  and that the liquid–vapor term can be ignored. 2γl cos θ (− A2w ). de Boer. ¯ Wasp = 0 F (D) dD = 8πγl RrK cos2 θ. the effective ˜ asperity adhesion Γasp also equals 2γl cos θ . While the simpliﬁcations allow insight into physical processes. 7. This equation can also be derived from force considerations [52]. 2rK cos θ Wasp = 0 F (D) dD = 4πγl RrK cos2 θ. Using (27) and (33). one half the result of the constant volume case. as well as in AFM measurements.T. Normalized F –D curve for the constant volume and pressure cases (with R rK ). 7. 5. Using (36) and (23c). The rate of change of V with respect to −A2w is 1 dV 1 dV dD dV = = = −D. Therefore we replace re with rK in (27) and (25). 4. (34) Inserting (34) into (32). Both ra (the azimuthal radius) and rm (the meridional radius) vary locally but for an isobaric meniscus. (41) = 4πRγl cos θ 1 − D . The pendularbridge geometry is shown in Fig. re = rK and V generally decreases due to evaporation as D increases. = 2γl cos θ 1 − D 2rK  cos θ (43) (42) (33) The sphere then is withdrawn. The work to remove the asperity from the substrate. 2rK  cos θ which is also plotted in Fig. 2 2 −dA2w −π dxd −π dD dxd Using (23b). [53] have used the pendularbridge geometry to solve the problem without approximation. is ∞ That is. The rate of decrease in volume is given by dV = −2πRD dD (38) . the condition of constant volume yields the dependence of re on D as re = 2 rK + D 2 /(4 cos2 θ ). The work done on the system is responsible for only one half of the surface energy the system has gained. the force is now dUs γl dV dW = − F (D) = dD dD rK dD D = 4πRγl cos θ 1 − (40) . 8. We have applied (15) and (19) to this geometry and describe the approach and results in this section. can be 50 nm or smaller. Now the effective as˜ perity adhesion Γasp equals γl cos θ .
[54] also conducted macroscale experiments that fully vali1 Note that in the Orr et al. the force (attractive if positive) can be . P. Willett et al. Thereafter. and so F will decrease r more rapidly than in the analysis of Section 4.C. ¯m  must decrease r to keep re the same. Capillarity theory using the constant volume assumption was used to model the force–displacement curves for R = 50 nm and R = 400 nm silicon tips in water vapor. this already reduces the area of the meniscus relative to the approximation used in Section 4. Our method is outlined here and sample calculations are presented. As D increases. corresponding to a catenoid (1/re = 0). while the method is detailed and generalized in [57]. the “w” subscript refers to the wetted area of that surface. With V held constant. Hence. From (48). de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 date the theoretical results for the constant volume case. new values of re and D are found. γl dV rK (47) (46) For a given p/ps . the iteration control must be changed by incrementing 1/re to ﬁnd D and Ψ rather than by decrementing Ψ . To obtain continuous values. Ψ is ﬁrst decremented in the iterative solution. D is incremented and with re held constant. not to be confused with e The energy balance for the constant volume and constant pressure cases can now be written from (15) and (19). In some cases (large R). Our contribution in this section is to apply both (15) and (19) to the pendular bridge and present results for small R.P. First. The withdrawal time is hence much longer to achieve the constant pressure assumption. Pendular ring geometry. For each case. the concave up and down unduloids must be combined because rm changes sign. dUs = −γl [dA1w cos θ1 + dA2w cos θ2 − dAm ]. de Boer. we have Us = (A1 − A1w )γs1 + A1w γls1 + (A2 − A2w )γs2 + A2w γls2 + Am γl . Additionally. according to [53] F = 2πγl R sin Ψ sin(θ1 + Ψ ) − R sin2 Ψ/2re . respectively). The included angle Ψ and the volume V are now found by iterating on the incomplete elliptic integral solutions. Consequently ¯m  decreases more. notation. For constant pressure. a cylinder (1/rm = 0) and a sphere (1/rm = 1/ra ).T. each corresponding different shapes (nodoids and unduloids of up or down concavity) arise. Orr et al. Singularities appear in the elliptic integrals when the unduloids must be combined.e. and the “m” subscript refers to the meniscus. Equilibration of a Kelvin meniscus for contacting tips was achieved on the order of seconds. ra decreases fur¯ ther. exist. Also. Fig. in turn the energies are found.178 M. the ﬁrst term represents the axial component of the surface tension while the second term is the Laplace pressure contribution. (45) Because ra is positive while rm is negative. At D = 0. (48) enthalpy. there are inﬂection points in the meridional curvatures. From this. i. when decrementing Ψ . and their values are found numerically. three special solutions. In the pendularbridge geometry. The solution is ambiguous in that “±” signs appear. Four different solution cases.01 to 10 s.. Ψ is found and the coordinates and energies can then be determined. it is necessary to return to decrementing Ψ again. and good agreement was observed [46]. Here. from which the meniscus coordinates and energies are found. the F –D curve was found in two ways. the initial re is assigned according to the Kelvin equation and D is set to zero. Then δW = −γl [dA1w cos θ1 + dA2w cos θ2 − dAm ] (constant volume) and δW = −γl [dA1w cos θ1 + dA2w cos θ2 − dAm ] − (constant pressure). [53] detail the possible solutions and discuss meniscus stability with respect to small ﬂuctuations. there are no longer continuous values of D. For constant volume. The F –D curves were rateindependent for withdrawal times from 0. and hence F will decrease. 1/r = 2H . the meniscus coordinates and area terms are determined. The pendularbridge solution involves writing the axisymmetric Young–Laplace differential equation and solving it subject to boundary conditions that are derived at the points where the bridge meets the sphere and the substrate in Fig. (44) where the numbered subscripts refer to the upper and lower surfaces.1 Several workers [54–56] have developed numerical integration methods that solve the meniscus shapes by an iterative approach to arrive at identical solutions to Orr et al. 8. which is relevant for large volumes and short experiment times. 8. over part of the solution space. The pendular bridge coordinates are found in terms of incomplete elliptic integrals of the ﬁrst and second kinds (F and E.
e. (" symbols mark the change from concave down to concave up. the uppermost sphere is at the point of pulloff. 10. (ii) θ1 = θ2 = 0◦ . (d) Same as (c) except θ1 = θ2 = 40◦ . respectively). However. and 1 (to establish initial values for the bridge volume).. In Fig. θ1 = θ2 = 0◦ . respectively). Hence. we took the total work as a function of D. rK  = 1 nm and R/rK  = 1. it is clear that rm varies locally for a given value of D.P. Two different solution cases must be traversed if θ1 > 0. 30. We applied (46) and (47) to the pendular bridge using the surface tension of water (with γl = 72 mN/m) for: (i) R/rK  = 100. 9 with R = 10 nm and rK  = 1 nm. i.M. the numerical form of (21a). the R/rK = 1 curve also applies for values such as R = 30 nm and rK  = 30 nm in Figs. The inﬂection points in the meridional curvature.T. (b) Same as (a) except θ1 = θ2 = 40◦ .) (c) Constant pressure meniscus shapes with re = −1 nm. P. 9a and 9b. θ1 = θ2 = 40◦ . Second. especially for constant volume. . The force was then determined as the numerical derivative of the work with respect to D. θ1 = θ2 = 0◦ . From these ﬁgures. (a) (b) (c) (d) Fig. results from this work approach are identical to the force approach. R = 10 nm. implying R = 1 nm) may be physically unrealistic (as discussed above for rK  and in [58] for R). The constant pressure case is reasonably straightforward to solve because it involves only one pendular bridge solution case corresponding to re = rK . For each of the graphs. small values of rK  and R/rK  (e.C. The pendular bridge solutions are in terms of the quantity R/re . de Boer. The singularities appearing at the integral limits (as mentioned above) were handled with the openended Romberg algorithm.. 3. which are associated with theoretically accessible but physically unstable solutions. are indicated. and over part of the problem two of the unduloid cases must be combined because the meridional curvature changes sign. 9. and for constant pressure with θ1 = θ2 = 0◦ and θ1 = θ2 = 40◦ (Figs. using only the Us term for constant volume and including the P dV term for constant pressure. (a) Constant volume meniscus shapes with re = −1 nm initially. D (49) Within numerical error. 9c and 9d. we show meniscus shapes for constant volume with θ1 = θ2 = 0◦ and θ1 = θ2 = 40◦ (Figs.g. That is F (D) = W (D + D) − W (D) . The constant volume case is more complicated in that re changes. 10 and 11. as expected. R = 10 nm. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 179 calculated as a function of D.
P. For very large R.) (b) Same as (a). (33) and (40) represent the exact solution very well. The tip of this nose is the point of rupture in a ﬁxedgrip experiment. 10a for θ1 = θ2 = 0◦ . For constant volume as D increases. [61]. there is again no longer a stable solution at some distance signiﬁcantly less than 2rK cos θ . Equations (35) and (40) where R/rK  → ∞ are also plotted for reference. 10a in the context of single asperity pulloff experiments. These errors are again only when the force is quite low. (" symbols mark the pulloff point in a ﬁxed grip experiment. Hence. If there is ﬁnite stiffness in the experimental apparatus. Hence there is also an abrupt pulloff of the meniscus.P. 11.60]. At large values of D. 9a and 9b.88. and 100 in Fig. but here the force here is already quite low.C. . As D increases in the constant pressure case. de Boer. but grows rapidly beyond this point. (For this case. for constant pressure and R/rK  = 3000. For small R with constant volume and for all values of R with constant pressure.T. 10. In a loadcontrol experiment. 0. As R increases for the constant (a) (b) Fig. (b) Same as (a). a “nose” develops. the error is less than 5% over most of the range. unstable solutions also exist but are not plotted in Figs. pulloff will occur before the maximum value of D is reached. If the compliance decreases.69). the error increases up to 20%. The dotted lower branch of the constant volume solutions in Figs. the error is less than 5% over the majority of the range of D. the F –D curves are concave down. 9 or 10 because they are not in equilibrium. the force would be measured only at D = 0. (a) (b) Fig. For constant volume and R/rK  = 3000. a load line reﬂecting the spring constant must be considered. except θ1 = θ2 = 40◦ . the rupture force does not decrease to zero. Here θ1 = θ2 = 0◦ . Let us consider Fig. Bestﬁt expressions for the F –D curve and the rupture distance for the constant volume case over a range of R/rK  values have been reported [54]. (a) Normalized adhesion normalized asperity radius of curvature. 10a and 10b correspond to the dotted meniscus lines in Figs. Symbols indicate calculated points. except θ1 = θ2 = 40◦ . For R/rK  = 100. Likewise.180 M. Here θ1 = θ2 = 0◦ . the mechanical stability of the F –D curve need not be considered to rule them out. as for example in an atomic force microscope pulloff experiment. as discussed for example by Greenwood [48] and Carpick et al. as can be conducted in principle by an interfacial force microscope [59. the pulloff is at the coordinates (9. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 We plot normalized F –D curves for values of R/rK  = 1. 10. Unless p/ps → 1. Rupture occurs at a nonzero tensile force.) At D = 0. (a) Normalized F –D curves for increasing values of R/rK . the force is equal for the two cases. Pulloff will occur at D = 0 if the apparatus is compliant.
For a compliant load apparatus. 12. A second instability would occur then shortly before the maximum value of D. 9a and 9b. In Fig. Γasp is a function of D for constant pressure. Fig. We repeat the analysis of Section 4 for this geometry. (Note that the slope of W with respect to D is F .) (b) Same as (a) except now R = 1 nm (the axis scales have also changed). When θ1 > 0◦ . as in Fig. 12b. a low compliance apparatus would sample most or all of the curve. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 181 (a) (b) Fig. the F –D curves change to being concave up. In particular for constant volume. the meniscus geometry allows the meridional curvature to be concave down at the point of departure from the substrate as D increases. Case of two nominally ﬂat surfaces In the previous sections. it is possible to have a point of instability at D = 0 after which force equilibrium would be found at a larger value of D. where ˆ θ1 = θ2 = 40◦ . This in turn allows more of the pendular ring solutions to be accessed. Force–displacement and adhesion laws for constant volume case Consider a ﬂat disk of radius xd separated by widely spaced nanometerscale asperities of height D0 . The reason for this is geometric. the work of adhesion. Let us . In these calculations. we choose a disk rather than a rectangular geometry. (a) Energies for constant volume and pressure cases with R = 100 nm. so that eventually none of the originally wetted area ˆ remains wetted. we obtained the constitutive laws for an individual asperity. On the other hand. 13a. Hence the values of Γasp in Fig. Qin is negative for small D in Fig. Γasp decreases as R/rK  decreases. but initially separated by some nonzero spacing.M. this effect is enhanced for small R. It is also interesting to note that as D increases. for the constant pressure case. In Fig. The reason is again because of the geometrical constraints as explained before. The P dV contribution shows evaporation is relatively smaller compared to (a). For very small R/rK  = 1. The integrated area under the F –D curve up to the ﬁxedgrip point of rupture is Wasp . only the concaveup nodoid solution is used independent of the contact angle because re = rK < 0. respectively. 12 also plots (20) to show that Qin = Qout Wasp . we plot the dUs term for constant volume and the dUs and − P dV terms for constant pressure with R = 100 nm or 10 nm and rK = −1 nm. ˆ Γasp is almost the same for the two cases.e. In Fig. de Boer. At R/rK  = 10. where θ1 = θ2 = 0◦ . However. 11. Also Qin = Qout is divided by 10.1.. 6. Γasp = 1. For convenience. as might be established by asperities that are distantly spaced from each other.C. 12a as D increases. where θ1 = θ2 = 40◦ . in which the interface is completely saturated. i. the decrease in Γasp with R/rK  is not as se vere. Correspondingly. the ﬁnal A2w is set to equal zero. the liquid will spread over the surface and evaporate without any further work being required. 12. This is because the capillary volume always initially increases due to condensation. and θ1 = θ2 = 0◦ . 11b. we ﬁrst discuss a different extreme.P. Although at rupture A2w > 0. and ﬁnd that in both cases the adhesion can approach 2γl cos θ . so the normalized constant pressure curves are much more similar in Figs. re > 0 before rupture and hence the Laplace pressure contribution becomes repulsive but remains smaller than the attractive axial component of the surface tension. 12b. Γasp = 2 and 1 the constant volume and presˆ sure cases. the − P dV term becomes smaller relative to the dUs term. Consequently the − P dV term becomes larger in Fig.25 and 0. When θ1 = 0◦ in the case of constant volume. 6.6 for Cases I and II. We can gain more physical insight by tracking the relative contributions of surface energy (dUs ) and heat (− P dV ) to the total work as a function of. respectively. This is because dV /(−dA2w ) ∼ D according to (42). Meanwhile. the nose extends further out. Some details of the F –D curve change for Fig. A normalized adˆ ˜ hesion energy Γasp = Γasp /(γl cos θ2 ) is plotted versus R/rK  in Fig. We assume the surfaces are nominally ﬂat. the meridional curvature cannot be concave down (this would correspond to the meniscus going into the substrate). As R decreases as in Fig. and hence that the work is closer to the surface energy change. For ˆ large R/rK . P. That treatment is easily extended to multiple noninteracting asperities. especially for θ1 = θ2 = 0◦ . so only one solution is needed. 11a. As can be concluded from (43). as explained in the introductory comments in this section. volume case. so that progressively less work need be done as the asperity reaches the pulloff condition.T. 11 for constant pressure decrease more slowly with R than for constant volume where dW = dUs . rK = −1 nm. 10b. we set A2w as equal to the initial A2w .
we set F (D0 ) to be the same for the two cases in Fig. 14. 2rK  cos θ (61) as graphed in Fig. Force–displacement and adhesion laws for constant pressure To maintain constant Kelvin radius. the force values must be the same for the two cases because the pressures are the same. with D0 = 0. The work of adhesion is 2rK  cos θ (51) Wdisk = D0 F (D) dD D0 .P. (54) Applying (23a). 14.C. 13.182 M. the walls absorb the heat of condensation. Application of (21b) to the control mass of the liquid gives F = −2πγl cos θ 2 dx 2 πxd D0 2γl cos θ . dUs = 0. This result is in agreement with [62] for contactangle controlled bridges.2. = dD D2 a positive quantity. The force. i.T. The volume is approximately 2 V = πxd D. (55) similar to the sphere on a ﬂat. (53) ˜ Γdisk = 2γl cos θ 1 − D0 . The possible range of values is 0 < Γdisk / γl cos θ < 2. xd . dD The differential surface energy of the control volume is approximately Fig. 14. (56) Then dV 2 (57) = πxd . Normalized F (D) curves for parallel surfaces.1 × (2rK  cos θ). The work done on the system is again entirely absorbed as surface energy. the Dupré equation applies. Applying (23c). The result is independent of the initial spacing D0 . Applying (21c). The walls will resupply the absorbed heat and the liquid will revert to vapor. rK d (58) assume that the interface is initially ﬁlled. 14. is now independent of D. excess liquid will wet the surfaces. . Up until capillary pulloff. The (50) F =− (59) where x now represents the meniscus radius and D the plate separation. At that point. P. Then dx 2 2 D0 = −xd 2 . with D0 volume is approximately 2 V = V0 = πxd D0 = πx 2 D.. (Note that the horizontal scale is signiﬁcantly compressed in both ﬁgures. Γdisk is not equal to 2γl cos θ unless ˜ D0 /rK  → 0. Accordingly. the interfacial energy remains unchanged. It is also independent of the contact angle because the force is applied purely against the liquid surface tension. The work to separate the disk from the substrate is now ∞ Wdisk ≈ D0 2 F (D) dD = πxd 2γl cos θ. Note that at D = D0 . 2rK  cos θ (52) 2 = 2γl cos θπxd 1 − (60) Here work is done against surface tension only without a change in area. de Boer. (b) Flat plate with protruding asperities.) 6. dD D The surface energy is Us ≈ γs A − πx 2 2γl cos θ.e. we have γl πx 2 . as graphed in Fig. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 (a) (b) Fig. Γdisk = 2γl cos θ. (a) Disk geometry. the change in surface energy will be again equal to 2γl cos θ . As D increases. ˜ For constant pressure. This result can be obtained by considering the volume of liquid just outside the disk. After. liquid will condense between the disk and the substrate as the disk is pulled away.
then 1 . 7.03R. 15. Fig. Using (62) and the Kelvin equation (10) (with the constants for water). The work of adhesion is the work to separate the plane of the ﬂat plate to 2rK  cos θ .53 nm) cos θ . Γ vs p/psat (with zmax = 0. Γ ≈ γl rK  cos θ + nasp 2rK  cos θ−zmax The factor c corrects for R and θ . 15.. εR (68) This is indicated by asterisks in Fig. Notionally reﬂecting the expected behavior of progressively smoother interfaces. plus the remaining work to separate the menisci from the protruding asperities (Fig. de Boer. Equation (63b) is plotted in Fig. deﬁning the transition from (64b) to (67) is [p/ps ]tr = exp − 2(0.53 nm (67) Again assuming ε = 0. Similar to Sections 4 and 6. If the array of asperities has a maximum height zmax as in Fig. AH R . 15. Therefore. 11). The transition vapor pressure. εR  ln(p/ps ) (63b) 2rK  cos θ − zmax 2rK  cos θ F (D ) dD . (66) We now consider the transition from the undersaturated to the saturated interface. for constant volume we saw for both the sphere on ﬂat and ﬂatonﬂat geometries that Γ = 2γl cos θ . Then. In the subsequent calculations.1. we will make estimates using limiting approximations. the work of adhesion between a rigid sphere and a substrate due to van der Waals forces is [43] WvdW = Fig. εR  ln(p/ps ) (64b) (64a) As saturation occurs. P. and approximate c ≈ 1.2 nm (equivalent to . Γ is one half of the constant volume case. 6D0 (69) where AH is the Hamaker constant and D0 is the minimum approach between molecules.53 nm cos2 θ Γ ≈ γl π . an undersaturated interface. Again the region near the transition is an approximation because this simple analysis does not capture the details of the meniscus merging process. γl = 146 mJ/m2 .P. as justiﬁed by Section 5.53 nm) cos θ εR ln(p/ps ) . Although the transition from (64) to 2γl cos θ 1) and recasting in terms of p/ps .03 and θ = 0◦ . 13b). Combination of the asperity array and the ﬂat plate We are now in position to consider the situation as posed in Section 1. (67) is an upper bound. Constant volume If 2rK  cos θ < zmax . which can be recast as Γ ≈ γl π 2 0. The interface will not ﬁll completely when the menisci ﬁrst merge because zmax depends on direction. For low values of p/ps where (65) applies.03. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 183 7.53 nm cos2 θ . As p/ps increases. namely an array of asperities attached to a ﬂat plate as a function of p/ps . (65) Using (40) and (62).1. Assuming AH = 5 × 10−20 J (representing a silica surface) and D0 = 0. we have very nearly attained the maximum value of adhesion. The marks the delineation between (64) and (66) for the constant pressure case. 2rK  cos θ approaches zmax . εR ln(p/ps ) 2(0. i. (63a) (62) is not captured precisely because of the details of the ﬁllin process. Γ strictly reaches 2γl cos θ only at p/ps = 1. this will have only a small effect in Fig. Given the results of Section 5 (cf.T.C. 15. we obtain for an initially saturated interface Γ ≈ γl 2 cos θ 1 − With zmax = εR (ε Γ ≈ γl 2 cos θ 1 − + π 8 zmax 2rK  cos θ + π 8 zmax rK  . (63b) and (67) are plotted versus in Fig. we take R/rK  30. For comparison. once (63b) reaches 2γl cos θ . Γ = nasp Wasp ≈ 4πRrK γl cos2 θ nasp . allowing zmax = εR where ε 1. 15 for various values of R with ε = 0.M. the limiting value of Γ = 2γl cos θ is reached at lower values of (p/ps ) at smaller values of R because zmax is assumed to be proportional to R. [p/ps ]tr . and θ = 0◦ ).2. nasp = 8Rzmax 7. However. we can rewrite this explicitly as a function of p/ps : 0. we have Γ = nasp Wasp = nasp 8c(θ. For large values of p/ps . R)πRrK γl cos2 θ. 1 and we assume a square array of spheres. Constant pressure For an undersaturated surface (2rK  cos θ < zmax ) and for R/rK  30.e. the geometry becomes that of a ﬂat plate. γl = 73 mJ/m2 and θ = 0◦ . 0.
Acknowledgment Sandia National Laboratories is a multiprogram laboratory operated by Sandia Corporation. de Boer. Note that capillary adhesion dominates over van der Waals adhesion for any reasonable p/ps value (for p/ps > 8 × 10−6 ). as recognized by Mate et al. 5. (40) becomes F (D) = 4πRγl 1 + td rK  1− D . 2a) speciﬁc heat of vaporization (J/g) Fogden–White parameter (Eq. The adsorbed layer thickness depends on p/ps . 2a) effective radius of capillary meniscus (m) (Eq. (6). Figs. (10)) crack length (m) (Fig.C. Γ approaches 2γl cos θ only as D0 /(2rK  cos θ ) approaches zero. 2(rK  + td ) (71) where td is the thickness of a liquid disjoining layer assumed to wet both surfaces. 1. As rough interfaces are separated under constant pressure. the disjoining pressure depends only on van der Waals interactions. Then the calculations presented here are a lower bound for the work of adhesion and serve as a benchmark for calculating the effect of disjoining pressure.184 M. (12)) mass (kg) density of asperities on the rough surface (1/m2 ) partial pressure of the vapor distributed force (N/m2 ) (Fig. Another important result is that for constant pressure in the ﬂat plate geometry.T. Fig. Also. and using (62) we have ΓvdW = WvdW nasp = AH . 1. For simple substances. It can also be determined from AFM measurements [63. Nomenclature a h hlv k m nasp p/ps q re ra rm rK s t u xd zmax A Ap AH D D0 E Em F G Gf H P Q R Ru T Ub Us V Vm W Wasp actuation pad length (m) (Fig.44RD0 (70) and structural components must also be considered to ﬁnd AH . 2a) speciﬁc internal energy of the liquid (kJ/kg) disc radius (m) (Fig. but the actual thickness of the water layer can also depend on doublelayer and hydration forces [43].64]. For other substances electronic . we have not considered the effect of the disjoining pressure [21. Further reductions in the adhesion energy per unit area can be achieved by reducing R/rK . of course. When this quantity is repulsive. but the control volume is changed. It is then straightforward to calculate the adsorbed layer thickness [43]. The present work has been extended to the case of an elastic rough surface consisting of summits of uniform radius R with a distribution of summit heights [33]. [63]. 2) cantilever thickness (m) (Fig. Experimentally. dielectric screening due to the liquid will reduce AH in (69) and (70) as p/ps increases. 6. because the liquid force does not fall off with separation as quickly as van der Waals forces. and 12) equilibrium separation (absent external forces) (m) total energy (J) elastic modulus (N/m2 ) force (attractive taken as positive) (N) energy release rate (J/m2 ) Gibbs free energy (J) enthalpy (J) pressure (Pa) heat (J) radius of curvature of asperity (m) (Figs. 6.22]. while concomitantly matter is exchanged with the environment. for the United States Department of Energy’s National Nuclear Security Administration under Contract DEAC0494AL85000.P. and 8) universal gas constant (L atm/(mol K)) temperature (K) bulk liquid energy (J) surface energy (J) volume (m3 ) molar volume (L/mol) work done on the control volume (J) work to remove an individual asperity from the substrate (J) which is also plotted in Fig. 6) maximum height in a simple model rough surface (m) area (m2 ) projected interface area (m2 ) Hamaker constant (J) distance between surfaces (m) (Figs. ﬂat plates and asperity arrays). P. As stated in the Introduction. The physical reason is that heat is capable of doing P dV work. 2a) cantilever gap (m) (Fig. Concluding remarks We have used thermodynamics to determine capillary adhesion laws in two extreme cases—constant volume and constant pressure for different geometries (spheres of arbitrary size. as shown in Fig. 8. an adsorbed liquid layer will be present on the surface. a Lockheed Martin Company. (6)) azimuthal radius of capillary meniscus (m) (Eq. and is repulsive if AH < 0. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 γs = 33 mJ/m2 ). Appendix A. If this quantity is attractive. It is a factor of two smaller for the case of constant volume relative to constant pressure when R rK . the van der Waals limit may extend to a much larger value of p/ps because capillary nucleation is ﬁrst required. To ﬁrst order. 8) meridional radius of capillary meniscus (m) (Eq. no adsorbed layer is on the surface and the theory presented is applicable at the nanometer scale. evaporation or condensation can occur depending on geometrical details of the surface. and will tend to increase the volume of the capillary. Our most important result is that even though the change in surface energy is the same. 15. (6). the work of adhesion depends strongly on the separation rate and can be less than the surface energy created. For water on quartz AH < 0 according to calculations. 8. The energy balances for the constant volume and pressure cases are not affected. 6 and 8) Kelvin radius (m) (Eq. 11.
Qian. White. London A 345 (1975) 327.V. [26] T.P.J. J. 38 (11) (1990) 2073. Natl. 44 (36) (2005) 7714–7721 (cover article). second ed. M. B. Thomas. Corwin. DelRio. Colloid Interface Sci.W. Ceram. Chateau. Bocquet. third ed. C. K.R. 1977. J.Q. M. Matter 17 (44) (2005) 1071–1142. A. N. 121 (1) (1988) 170.T. Houston. F. U. de Boer. P. Phys. Plant Nutr.H. 1991. K.D. London A 127 (1930) 290. 130 (2003) 63.H. 303. J. [9] C.L. Colloid Interface Sci. J. Edward Arnold and Delftse Uitgevers Maatschapij. Bower. Am. Technol. Phys. Soil Sci. J. Opt.B. M.P. R. Proc. Gao.C. D. R. Ceram.V. Fluid Mech. submitted for publication. London A 453 (1961) (1997) 1277. 20 (1985) 3041. Powder Technol. Knapp.A. Luan. Churaev.R. Exp. J. Paris. Appl. Bentz. J.R. Eur. [62] [63] [64] D.P.R.R. R. Lett. 1869. Dupré. H.E.H. Bogy. Bellemans. A. C. Soc.A. Schneider. Nat. M. Wark. Wolf. [15] K. de Boer. R. Rice. Clint. 67 (part 4) (1975) 723– 742. Carpick. Trans. J. Surface Forces. Soc. [19] Y. J. J. pp. D. M. Clews. Acta Mater. Johnson.J. 1966. [20] D. Phys. Mater. I. New York. Batteas. Proc. R. Srinivasan. Adhesion Sci. C.C. New York.A. Proc.D.N.R. Colloid Interface Sci. J.D. de Boer. Zheng. Colloid Interface Sci. Jones. C.F. London A 324 (1971) 301. Nature 356 (6366) (1992) 266. in: B. R. B. Phys. [11] B. J. J. V. Science 254 (1991) 829. submitted for publication.T. 80 (14) (1998) 3141. Surface Tension and Adsorption. Hsia. Fogden.K. [6] D.H. R.. 75 (3) (1992) 667. Thermodynamics. Chem. McGraw–Hill. P. Maugis. M. London. E. T.E. Reedy.A.T. Mate. Sirghi.A. Appl. J. Maboudian. J. Adamson. S. 117 (13) (1995) 3830. 2 (1) (1993) 33. Academic Press. Hsu. S.P. Levine. J.P. Phys. Obreimoff. Moucheront. Proc. S.E.T. M. A. G. J. Fisher. Trib. B. Greenwood.W.A. T. Bowles. ASME 109 (1987) 257. Fracture of Brittle Solids. Chem. J. Fracture Mechanics. G. Greenwood. 106 (9) (1997) 3782. Rivas. Appl. Muller. Williamson.R. T.W. Toporov. Phys. 48 (18–19) (2000) 4531. [3] J. D. Mate. [27] S. Soc. L. Mechanical and Thermal Properties of Ceramics. vol. Michalske. Berlin. [8] C. R. Mater.H.A. Mech. R.G.R. A. Michalske. Phys. Lathabai. 10 (2) (1996) 161.A. L. Maeda. Colloid Interface Sci.J. J. Sci.B. Angell. second ed.C. F. Soc. Douglas Frink. Johnson. Riedo. D. Derjaguin. London A 462 (2065) (2006) 319. A. de Boer.H. [24] O. Soc. Lett. Europhys. Ceram. J. Michalske. S. Syst. Lawn. 138 (2) (1990) 414. Seville.J. V. Condens. Longmans. Springer Verlag.A. Colloid Interface Sci. Syst. Press. Fuller. Soc. Microelectromech. Halsey. Appl. de Boer.T. Construct. [4] J. M. Seville. B.J. Wiederhorn. L. Israelachvili. F. E. 1993.W. Acta Mater.M. Michalske. P..P. L. T. 47 (5) (1999) 562. C. V. (2006).). Houston. Roach. 80 (2) (1981) 528. Langmuir 22 (2006) 11436. Roberts. Johnson. A. Green. 88 (2) (1982) 338.P.M. Muller. 1 (1) (1999) 155. Y.K. Proc. Physical Chemistry of Surfaces. Freiman. Persson. Cambridge Univ. [22] C.R. J. Chem. Phys. [13] J. Szoszkiewicz. Tabor. J. Thomson.M. [25] N.N.C.A. J. van Swol.P. Lawn. LaRoche. Wiley. Michalske. Lian. Sci. New York. Knapp.J. V. J. 90 (12) (1989) 7550. Israelachvili. M. Nature 435 (7044) (2005) 929. J. London. Willett. [17] W. Orr. Sinclair.M. Chem. [2] T. J. New York. J. L. van der Ploeg.W..N.M. W. M.J. 71 (2) (1988) 97. 19 (1948) 1062. J.L. [10] H. Chem. [5] J. L. E. de Boer.B. Am. Springer Handbook of Nanotechnology. Lorenz. Théorie méchanique de la chaleur. Smith. Mastrangelo.M. Dunn. Gao.P. Soc. Mastrangelo. Phys. Wan. Crooks. J. 2006. P.T. R.W. de Boer. Crassous. Adams. M. J. J.D. J. H. M.J. Proc. Paunov. J. Israelachvili. Phys. J. Christenson.M. Knapp. 4 (8) (2005) 629–634. [18] B.J. Durben.M.H. Soc. de Boer. Mater. 26 (1978) 61. 1992.D.A. Lawn. R. C. [7] C. 11 (6) (2002) 754. B 23 (1) (2001) 79. Aveyard. Maugis. M. Proc. Ciliberto. J. Proc.R. A. Appl. R. M.M. New York. Rupture work of pendular bridges (2007). X. USA 100 (3) (2003) 803. Lett. R. [23] C. Y. Adams. 1987. Gao. Robbins. Kendall. de Boer. M. J. M.H. Derjaguin. Willett.C. Bocquet. Etsion. Dale. Acad. Am. Soc. 1969. R. Scriven. Nature 396 (1998) 735. Acta Biomater. C. 2 (2006) 51. A. [12] A.M.P. Crassous.P. 28 (182) (1995) 450–458. Wan. J. 72 (2) (1992) 3084. S. R. .P. S. 71 (13) (1997) 1801. K.O. A. 165 (2002) 468.H.A. de Boer.P. Bhushan (Ed. (23c)) [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40] [41] [42] [43] [44] [45] [46] [47] [48] [49] [50] [51] [52] [53] [54] [55] [56] [57] [58] [59] [60] [61] References [1] L. [21] B. Sol. J. Nees. Phys. Gauthier–Villars. Soc. I. J.K. R. P. White. Mech. J. 1990. J. Ewalds. Pitois.V. Microelectromech. Langmuir 22 (3) (2006) 1093. Rev. Phys. J.L. Prigonine. London A 295 (1966) 300. T. Hsu. Bachmann. P.J. M. D.A. Thornton. [14] J.N. Everett. Fortes. Am. Ciliberto. K. de Boer / Journal of Colloid and Interface Science 311 (2007) 171–185 185 ε γ γl γs γls ρ θ Γ ˜ Γ ratio of zmax to R surface energy (J/m2 ) surface energy (tension) of liquid–vapor interface (J/m2 ) surface energy (tension) of solid–vapor interface (J/m2 ) interfacial energy (tension) of liquid–solid interface (J/m2 ) density (kg/m3 ) contact angle (radian) work of adhesion per unit area (J/m2 ) effective adhesion (J/m2 ) (Eq. Chang.R.F. 951–979. Lawn. L. Novotny. Soc.N. Wanhill. Fisher. J. 2 (1) (1993) 44. Defay. Kim. Q. 53 (2) (1975) 314.P. K. Kohonen. D. 161 (1993) 138. Adams. Syst.A. Charlaix. 86 (2) (1999) 817.P. 66 (4) (1983) 284.D. Microelectromech. [16] D. Consultants Bureau. Intermolecular and Surface Forces. Edinburgh 7 (1870) 63. Langmuir 16 (2000) 9396. J. B.
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