501

Conclusions
In the rst three chapters of this book, we have shown that all equilibrium and
kinetics properties of liquids in contact with solid substrates can be described
using a unifying approach by considering the simultaneous action of disjoining
and capillary pressure (save cases where gravity or other external elds apply).
Using this approach the overall equilibrium liquid prole can be subdivided into
three parts: (i) the bulk of the liquid (meniscus or drop), where only capillary
(and, eventually gravity) forces act, (ii) thin equilibrium lms in front, where the
surface forces dominate (in the form of disjoining pressure action), and (iii) a
transition region in-between, where both capillary and surface forces are equally
important. The main conclusion of Chapter 1 through Chapter 3 is that true
progress in the area demands the consideration of disjoining pressure action in
a vicinity of the apparent three-phase contact line. Though roughness and heter-
ogeneity (chemical or otherwise) of the solid substrate affects wetting conditions,
further progress in understanding of wetting and spreading must be based on the
inclusion of surface forces action into consideration.
The major dominant quantity used to describe the liquid-solid substrate inter-
action is the disjoining pressure isotherm and its dependence on the thickness of
the layer. The latter dependence has been experimentally investigated only for a
limited range of liquid lm thicknesses and only for at liquid lms or layers.
Further experimental work needed to get such dependence of the disjoining pres-
sure isotherm on the thickness in the whole range of thickness (including over-
saturation and the region of unstable at lms). Theory needed to really understand
the structural component of the disjoining pressure isotherm, and to understand
how the disjoining pressure is expressed in the case of non-at liquid layers.
We have shown that in the case of complete wetting there is a reasonable
agreement between the theory predictions and the progress is related to the fact
that in such a case the disjoining pressure isotherm is well understood. The
situation is drastically different in the case of partial wetting. We believe that the
lack of progress in this case is related to the lack of understanding of the
importance of disjoining pressure in those circumstances. Note, in colloid and
interface science substantial progress was achieved only after the importance of
surface forces action was understood. Hence, consideration of wetting and spread-
ing processes on real, rough, and heterogeneous (chemical or otherwise) surfaces
taking into account surface forces action in the case of partial wetting appears
as the most challenging problem. In Chapter 2 some problems in this area were
considered.
In Chapter 4 we have provided results about the kinetics of spreading and
imbibition when liquids are in contact with porous solid materials. An important
conclusion is that the behavior of liquids in contact with porous materials is
2007 by Taylor & Francis Group, LLC
502 Wetting and Spreading Dynamics
substantially different from the corresponding processes with non-porous mate-
rials. We also deduced the novel universal laws in this chapter. However, the latter
universal dependencies have been deduced only in the case of spreading over thin
porous layers and kinetics of wetting and imbibition in the case of thick porous
layers is still a challenge. The latter is especially true if surfactants are involved.
In Chapter 5 we have considered how the spreading of aqueous surfactant
solutions is affected by the presence of surfactants. It is difcult to imagine our
present-day life without surfactants (soaps, shampoos, detergents, washing liq-
uids, etc.). Although some understanding has been accumulated in the case of
surfactants acting on liquid-air interfaces where the transport processes are deter-
mined by the Marangoni effect, much less is known about the behavior of
surfactants in the vicinity of the three-phase contact line. Here we are very far
from the level of understanding offered in Chapter 1 through Chapter 3. It is the
reason why we used a semi-empirical model to understand the role of surfactants
in a vicinity of the three-phase contact line. In some cases such an approach leads
to predictions and explanations of available experimental data. However, under-
standing of the real mechanism of surfactants transfer in the vicinity of the three-
phase contact line demands further research efforts. Recently new surfactants like
trisiloxanes have attracted the attention of scientists and industrialists due to their
unusual properties that have led to call them superspreaders. We did not touch
the subject in this book, however, as understanding the nature of superspreading
behavior is still a challenging open problem.
FREQUENTLY USED EQUATIONS
NAVIERSTOKES EQUATIONS
NavierStokes equations in cylindrical coordinate system (r, , z) are

v
v
r
v
r
v
v
v
z
v
r
p
r
r
r r
z
r

_
,

2
+

2
2 2
2
2
2
2
1 1 2 v
r r
v v
z r
v
r r
r r r r
22 2

_
,

v
v
r
r

v
v
r
v
r
v
v
v
z
v v
r r
p
r z
r

_
,

=
1

2
2 2
2
2
2
2
1 1
v
r r
v v
z r
v
r
++

_
,

2
2 2
r
v
v
r
r

,
2007 by Taylor & Francis Group, LLC
Conclusions 503
If the Reynolds number is small, then the latter equations become the Stokes
equations:
In any case, we have four equations for four unknown functions,
The viscose stress tensor is:

v
v
r
v
r
v
v
v
z
p
z
r
z z
z
z

_
,

_
,

2
2 2
2
2
2
2
1 1 v
r r
v v
z r
v
r
z z z z

..

+ =
v
r r
v
v
z
v
r
r z r
1
0

.
0
1 1
2
2 2
2
2
2
2
=

p
r
v
r r
v v
z r
v
r
r r r r

_
,

2
2 2
r
v
v
r
r

,
0
1 1 1
2
2 2
2
2
2
2
=

+

r
p
v
r r
v v
z r
v

_
,

r r
v
v
r
r
2
2 2

,
0
1 1
2
2 2
2
2
2
2
=

p
z
v
r r
v v
z r
v
r
z z z z

_
,

+ =
v
r r
v
v
z
v
r
r z r
1
0

.
v r z v r z v r z p r z
r z
( , , ), ( , , ), ( , , ), ( , , ).

rr
r
r
r
p
v
r r
v
v
r
v
r
= +

_
,

2
1
,

= +

_
,

+

p
r
v
v
r
v
z r
v
r
z
2
1 1
,
zz

_
,

2007 by Taylor & Francis Group, LLC

504 Wetting and Spreading Dynamics
where
r
is the tangential stress in the case of pure rotational ow,
zr
is the
tangential stress in the case of pure axial ow, and
zz
in the normal stress to the
at surface.
NAVIER-STOKES EQUATIONS IN THE CASE OF TWO-DIMENSIONAL FLOW
In the case of a low Reynolds number, the latter equations become the Stokes
equations:
In any case, these are three equations for three unknown functions, v
x
, v
y
, p.
The viscose stress tensor appears as
The last component is the tangential stress in the case of a plane parallel ow.

zz
z
zr
z r
p
v
z
v
r
v
z
= +

_
,

2 ,
v
v
x
v
y
v
y
p
x
v
x
v
x
x x x x

_
,

2
2
2
yy
v
v
x
v
v
y
p
y
v
x
y
y
y y
2
2

_
,

_
,

_
,

=
x
v
y
v
x
v
y
y
x
y
2
2
2
0
0
0
2
2
2
2
2
=

_
,

+

p
x
v
x
v
y
p
y
v
x x
y

_
,

=
x
v
y
v
x
v
y
y
x
y
2
2
2
0

xx
x
yy
y
xy yx
x
p
v
x
p
v
y
v
= +

= +

= =

2 2 , ,
yy
v
x
y
+

_
,

2007 by Taylor & Francis Group, LLC

Conclusions 505
CAPILLARY PRESSURE
Capillary pressure is determined as K, where is the interfacial tension (liq-
uidair or liquidliquid), and K is the mean curvature of the interface.
Let h be the equation that describes the interface. Following are expressions
for the mean curvature:
The general case in the Cartesian coordinate system, the interface prole, is
h(x,y):
.
The axisymmetric case on the inner or outer surface of the cylindrical capillary
of the radius a, the interface prole, is h = h(x), where x is the axial coordinate
,
Here, the upper sign corresponds to the outer surface, and the lower sign corre-
sponds to the inner surface; means the differentiation with x.
The axisymmetric droplet on the plane substrate, the interface prole, is h(r),
where r is the radial coordinate:
means the differentiation with r.
LIST OF MAIN SYMBOLS USED
GREEK
Interfacial tension
Contact angle
Excess free energy
Dynamic viscosity
Disjoining pressure
K
h
x
h
x
h
y
=

_
,

_
,

1
]
1
1
2
2
2 2
3
1
/22
2
2
2 2
3
1
+

_
,

_
,

1
]
1
1
h
y
h
x
h
y
//2
K
h
h
h
a h h
=

+
( )

+
( )
1 1
2
3 2
2
1 2 / /
( )

K
r
d
dr
rh
h
=

+
( )
1
1
2
1 2 /
2007 by Taylor & Francis Group, LLC
506 Wetting and Spreading Dynamics
LATIN
g Gravity acceleration
P Excess pressure
p Pressure
S Surface
T Absolute temperature in K
V Volume
SUBSCRIPTS
v Vapor
s Solid
l Liquid
* Characteristic scale or initial value
a Ambient air
e Equilibrium
s Surface forces or saturated
c Capillary
2007 by Taylor & Francis Group, LLC