CAPILLARITY 1

CAPILLARITY
(Revised 09/13/2003)

Dani Or, Department of Civil and Environmental Engineering
University of Connecticut, Storrs, Connecticut, USA

Markus Tuller,

Department of Plant, Soil & Entomological Sciences
University of Idaho, Moscow, Idaho, USA

Introduction
The coexistence of gaseous, liquid, and solid phases in soil pores gives rise to a variety
of interfacial phenomena that, for example, lead to spreading of liquid droplets on solid
surfaces, liquid rising in capillaries and soil pores, or the entrapment of liquid in
crevices. These phenomena, partially attributed to capillarity, determine retention and
movement of water and solutes through soils. Hence they are of great importance in a
variety of environmental and agricultural problems.
Liquid Properties
The phenomenon of capillarity in porous media results from two opposing forces, liquid
adhesion to solid surfaces that tends to spread the liquid, and the cohesive surface
tension force of liquids that acts to reduce liquid-gas interfacial area. The resulting
liquid-gas interface configuration under equilibrium reflects a balance between these
forces. The phenomenon of capillarity is thus dependent on solid and liquid interfacial
properties such as surface tension, contact angle, and solid surface roughness and
geometry.
Surface Tension: At the interface between water and solids or other fluids (e.g., air),
water molecules are exposed to different forces than are molecules within the bulk fluid.
For example, water molecules in the bulk liquid are subjected to uniform cohesive
forces whereby hydrogen bonds are formed with neighboring molecules on all sides. In
contrast, molecules at the air-water interface experience net attraction into the liquid
because of lower density of water molecules on the air side of the interface, with most
hydrogen bonds formed at the liquid side. The result is a membrane-like water surface
having a tendency to contract and reduce the amount of its excess surface energy
(Hillel, 1998). The surface tension reflects the amount of interfacial energy per unit area,
or the energy required to bring molecules from the bulk liquid to increase the surface (it
is also useful to express surface tension as force per unit length of interface). Different
liquids vary in their surface tension (Table 1).

2 CAPILLARITY
Table1: Liquid-vapor interfacial tensions for various liquids (Adamson, 1990).
Liquid
Temp.
[
o
C]
Surface
Tension
[mN/m]
Liquid
Temp.
[
o
C]
Surface
Tension
[mN/m]
Water 20 72.94 Butyric acid 20 26.51
25 72.13 Carbon tetrachloride 25 26.43
Organic Compounds Butyl acetate 20 25.09
Methylene iodide 20 67.00 Diethylene glycol 20 30.9
Glycerin 24 62.6 Nonane 20 22.85
Ethylene glycol 25 47.3 Methanol 20 22.50
Dimethyl sulfoxide 20 43.54 Ethanol 20 22.39
Propylene carbonate 20 41.1 Octane 20 21.62
1-Methyl naphthalene 20 38.7 Heptane 20 20.14
Dimethyl aniline 20 36.56 Ether 25 20.14
Benzene 20 28.88
Perfluoromethylcycl
ohexane
20 15.70
Toluene 20 28.52 Perfluoroheptane 20 13.19
Chloroform 25 26.67 Hydrogen sulfide 20 12.3
Propionic acid 20 26.69 Perfluoropentane 20 9.89

Surface tension also depends on temperature, usually decreasing linearly as the
temperature rises. Thermal expansion reduces the density of the liquid, and therefore
also reduces the cohesive forces at the surface of (as well as inside) the liquid phase.
Soluble substances can increase or decrease surface tension. If the affinity of the solute
molecules or ions to water molecules is greater than the affinity of the water molecules
to one another, then the solute tends to be drawn into the solution and to cause an
increase in the surface tension. This is the effect of electrolytic solutes. For example, a
1% NaCI concentration increases the surface tension of an aqueous solution by 0.17
mN/m at 20C. If, on the other hand, the cohesive attraction between water molecules is
greater than their attraction to the solute molecules, then the latter tend to be relegated
toward the surface, reducing its tension. That is the effect of many organic solutes,
particularly detergents.
Contact Angle: When a liquid drop is placed on a solid surface, the angle formed
between the solid-liquid (S-L) interface and the liquid-gas (L-G) interface (see Fig. 1) is
referred to as the equilibrium (or static) contact angle (). Two equivalent approaches
are commonly used to describe the equilibrium contact angle on smooth and chemically
homogeneous planar surfaces: (1) a force balance approach, and (2) an interfacial free
energy minimization (McHale and Newton, 2002). The force balance formulation
considers interfacial tensions (
ij
) as forces per unit length; hence the force balance at
the contact line of a drop resting on a solid surface under equilibrium requires the vector
sum of the forces acting to spread the drop (outward) to be equal to opposing cohesion
and viscous forces. Free energy minimization regards interfacial tension as energy per
CAPILLARITY 3

unit area, and calculates changes in surface free energy (F) due to infinitesimal
displacement (A):

LG GS SL
cos A ) ( A F + = (1)
The result is identical whether considering the minimization of free energy with
F/A=0, or taking a balance of forces tangential to the solid surface; both cases yield
the Young equation (Adamson, 1990):
0 cos
GS SL LG
= + (2)
with L,G, and S indicating liquid, gas, and solid, respectively, and
ij
the respective
interfacial surface tensions. The equilibrium contact angle is therefore:

LG
SL GS
cos

= (3)
Liquids that are attracted to solid surfaces (adhesion) more strongly than to other liquid
molecules (cohesion) exhibit a small contact angle, and the solid is said to be "wettable"
by the liquid (Fig.1a). Conversely, when the cohesive force of the liquid is larger than
the adhesive force, the liquid "repels" the solid and is large (Fig.1b).

Figure 1: Liquid-solid-gas contact angles, (a) hydrophilic surface (<90
o
) where liquid wets the surface,
(b) hydrophobic surface (>90
o
) where liquid repels the surface.
Figure 2 illustrates differences in wettability of a silt soil (Bachmann et al., 2000). In
Fig.2b a water droplet is resting on a soil surface that was treated to become water
repellent (=70

). n contrast, Fig.2a depicts a wettable soil surface. In general, the

contact angle of water on clean glass, and presumably on most soil minerals, is small,
and for mathematical convenience is often taken as =0

.
4 CAPILLARITY

Figure 2: (a) Wettable silt soil surface ( ~ 0
o
). (b) Treated water-repellant silt soil surface ( = 70
o
)
(Bachmann et al., 2000).
Curved Surfaces and Capillarity: When the forces that spread the liquid (adhesion and
spreading on solids, or gas pressure within a bubble) are in balance with surface
tension that tends to minimize interfacial area, the resulting liquid-gas interface is often
curved. In porous media, the liquid-gas interface shape reflects the need to form a
particular contact angle with solid(s) on the one hand, and the tendency to minimize
interfacial area within the pore. A pressure difference forms across the curved interface,
where the pressure at the concave side of the interface is greater by an amount that is
dependent on the radius of curvature and the surface tension of the fluid. For a
hemispherical liquid-gas interface having radius of curvature R, the pressure difference
is given by the Young-Laplace equation:

R
2
P

= (4)
where P=P
liq
-P
gas
when the interface curves into the gas (e.g., water droplet in air); or
P=P
gas
-P
liq
when the interface curves into the liquid (e.g., air bubble in water, water in
a small glass tube). In many instances a bubble may not be spherical, or an element of
liquid may be confined by irregular solid surfaces resulting in two or more different radii
of curvature such as water held in pendular rings between two spherical solid particles
(Fig.3). The Young-Laplace equation for this case is given by:

|
|
.
|

\
|
+ =
2 1
R
1
R
1
P (5)
Note that this equation reduces to Eq. 4 for spherical geometry with R
1
=R
2
, and the sign
of R is negative for convex interfaces (R
2
<0) and positive for concave interfaces (R
1
>0).
For an interface forming in a linear crevice or within a fracture, we can consider R
2
,
hence Eq. 5 reduces to:
1
R / P = where R
1
= half the fracture aperture.
CAPILLARITY 5


Fig. 3: (a) Definition sketch of radii of curvature and shape of water held in pendular space between two
spherical grains [note that for two equal spheres with radius a, the relationships between R
2
and
R
1
is given as: R
2
=R
1
2
/2(a-R
1
)]; (b) photographs of water menisci held between three spherical
glass beads at different capillary pressures.
The Capillary Rise Model
When a cylindrical glass tube of small diameter (a capillary) is dipped into free water, a
meniscus forms in the tube due to the contact angle between water and the tube walls,
and minimum surface energy requirements. The smaller the tube radius, the larger the
degree of curvature and the pressure difference across the air-water interface (Fig.4).
The pressure at the water side (P
W
) is lower than atmospheric pressure (P
0
). This
pressure difference causes water to rise into the capillary until the upward capillary
force is balanced by the weight of the water column. In a cylindrical tube, the radius of
meniscus curvature (R) is related to the tube radius r by r=R/cos, consequently the
equilibrium height of capillary rise in a cylindrical tube with contact angle is:
6 CAPILLARITY

r g
cos 2
h
w

= (6)
where g is the acceleration of gravity, and
w
is the liquid density. For water at 20
0
C in
a glass capillary with =0
0
the capillary rise equation simplifies to: h(mm)=15/r(mm).

Figure 4: Capillary rise in cylindrical tubes with different radii.
Capillarity in Soils
The complex geometry of soil pore space creates numerous combinations of interfaces,
capillaries, and wedges in which water is retained, and results in a variety of air-water
and solid-water configurations. Water is drawn into and/or held by these interstices in
proportion to the resulting capillary forces. In addition, water is adsorbed onto solid
surfaces with considerable force at close distances. Due to practical limitations of
present measurement methods, no distinction is made between the various
mechanisms affecting water in porous matrices (i.e., capillarity and surface adsorption).
Common conceptual models for water retention in porous media and matric potential
rely on a simplified picture of soil pore space as a bundle-of-capillaries (see article on
Retention of Water in Soil and the Soil Water Characteristic Curve in this
Encyclopedia). The primary conceptual steps made in such models are illustrated in
Fig.5. The representation of soil pores as equivalent cylindrical capillaries greatly
simplifies modeling and parameterization of soil pore space and relies heavily (capillary
rise).
CAPILLARITY 7



Figure 5: Idealization of the soil pore space as cylindrical capillaries.
Capillarity in Angular Pores:
Cursory inspection of scanning electron micrographs of soils and other natural porous
media (Fig.6) shows that pore spaces formed by aggregation of primary particles and
mineral surfaces tend to be angular and slit-shaped, rarely resembling cylindrical tubes.
Such observations and other shortcomings of the cylindrical capillary model have led
to development of new models for capillarity in angular and slit-shaped pores (Tuller et
al., 1999).

Figure 6: (a) Thin section of Devonian Sandstone [Roberts and Schwartz, 1985] revealing angular
pore space. (b) Scanning electron micrograph (SEM) of calcium-saturated montmorillonite
clay.
Capillarity in angular pores is quite different from the behavior in cylindrical pores with
equivalent cross-sectional area. For example, when angular pores are drained, a
fraction of the wetting phase (water) remains in the pore corners (Fig.7a). This aspect of
dual occupancy of wetting and non-wetting phases (Morrow and Xie, 1998), not
possible in cylindrical tubes, more realistically represents liquid configurations and the
mechanisms for maintaining hydraulic continuity in porous media (Dullien et al., 1986).
8 CAPILLARITY
Liquid-filled corners and crevices play an important role in displacement rates of oil
(Blunt et al., 1995) and in other transport processes in partially saturated porous media.
Tuller et al. (1999) have shown that for all (regular and irregular) polygons with n
corners, the total water filled area (A
wt
) at a given matric potential is simply the sum of
the water-filled areas in each corner (Fig.7a). This sum is given by the simple equation:
( ) F ) ( r Aw
2
t
= (7)
with
( )
( )

=
|
|
|
|
|
.
|

\
|

|
.
|

\
|
=
i
1 n
i
i
360
180
2
tan
1
F

(8)
where is the matric potential and F() is a shape factor dependent on pore angularity
(coner angles
i
) only (Tuller et al., 1999).
In contrast to a piston-like filling or emptying of circular capillaries, angular pores
undergo different filling stages and spontaneous displacement in the transition from dry
to wet or vice versa. Under relatively dry conditions (low chemical potentials) liquid
accumulates in corners due to capillary forces. An increase in chemical potential leads
to an increase of the capillary radius of interface curvature until the capillary corner
menisci contact to form an inscribed circle. At this critical potential, liquid spontaneously
fills up the central pore (pore snap-off). The radius of interface curvature at this critical
point is equal to the radius of an inscribed circle in the pore cross section (Tuller et al.,
1999). If an angular pore is drained, liquid is displaced from the central region first,
leaving some liquid behind in corners. Subsequent decrease in chemical potential
results in incrementally decreasing amounts of liquid in the corners. The critical
potentials at spontaneous liquid displacement differ for imbibition and drainage (see
article on Retention of Water in Soil and the Soil Water Characteristic Curve in this
Encyclopedia).

Figure 7: (a) Conceptual sketch of dual occupancy of wetting and non-wetting phases in triangular
pores. (b) An image of liquid-vapor interfacial configuration in a triangular glass pore (~2 mm
size).

For completeness, one must also consider the role of liquid films due to adsorption to
solid surfaces as described in article on Retention of Water in Soil and the Soil Water
Characteristic Curve in this Encyclopedia, and reviews by Tuller et al. (1999) and Nitao
and Bear (1996).
CAPILLARITY 9

Dynamic Aspects of Capillarity

Dynamics of Capillary Rise:
The equilibrium height of fluid rise in a capillary (Eq.6) does not contain any information
regarding the rate of rise and the associated time scale, which is often of significant
importance in many industrial and natural processes. Lucas (1918) and Washburn
(1921) employed a simple force balance between a driving capillary force F

) cos( R 2 F =

(9)
and a retarding viscous force F (assuming Poiseuille flow):

dt
dx
x 8 F =

(10)
to model the rate of capillary flow into a horizontal capillary. Rideal (1921) included
inertial effects according to:


F F
dt
x d
m
2
2
= (11)
where m is the mass of the liquid in the capillary, x is distance, and t is time.
Substitution of the forces (Eqs. 9 and 10) into Eq.11, and integration (neglecting higher
order terms) yields the so-called Lucas-Washburn-Rideal (LWR) equation:

t
2
) ( Cos R
x
|
|
.
|

\
|
=

(12)
that describes the rate of liquid penetration into a horizontal capillary with the
dependency of x on t . It is interesting to note that Washburns (1921) neglect of
inertial effects and Rideals (1921) truncation of higher order terms (r
-n
, n>2) in his
series solution yield the same solution (Eq.12). Rye et al. (1996) provide exact solutions
that fully account for inertial effects, and expand LWRs expression to consider flows
into horizontal grooves and other capillary shapes.
Analytical solutions for dynamic capillary rise with gravity present a mathematical
challenge. Several simplified analytical solutions for the rate of capillary rise in vertical
capillaries have been proposed such as the following implicit solution (Marmur, 1992):

(

=
e
e
2
z
) t ( z
1 ln z ) t ( z t
8
gR

(13)
The solution diverges as z(t) approaches the equilibrium capillary rise z
e
(Eq.6). Another
approximate solution was proposed by Hamraouni and Nylander (2002) based on the
introduction of a retardation coefficient ():
10 CAPILLARITY

|
|
|
.
|

\
|
=
(

t
z
) cos(
e
e
exp 1 z ) t ( z


(14)
The solution converges to the equilibrium capillary rise z
e
(Eq.6) for long times. Figure.
8a depicts comparison of Eqs. (13) and (14) with capillary rise measurements of silicon
oil (PDMS 10) in a glass capillary with r=0.315 mm (=20.1 mN/m; =10 mPas, and
=0.935 kg/m
3
).
Hamraouni and Nylander (2002) have shown that the nondimensional retardation
coefficient for water in glass capillaries ranges from =0.5 in large radii (r>r
c
)
representing friction dissipation due to contact line motion and contact angle
adjustment; to =0.7 for small radii (r<r
c
) representing primarily viscous dissipation
(Hamraouni and Nylander, 2002). The critical radius r
c
is related to an interesting
feature of capillary rise in the presence of gravity, namely inertia-induced oscillations in
large capillaries (Quere et al., 1999) as depicted in Fig.8b and simulated by Hamraouni
and Nylander (2002). The inertial oscillations disappear in capillaries of radii smaller
than r
c
:

g
) g ) cos( ( 2
r
5 / 1 3 2 2
c

= (15)

Figure 8: (a), Comparison of measurements and theoretical models for capillary rise dynamics of
silicon oil (PDMS 10) in glass capillary with r=0.315 mm (calculated curve = Eq.14;
classical Washburn equation= Eq. 13); (b) Inertia-induced oscillations during capillary rise
of water in different glass capillary sizes (numerical simulations). Note inertial oscillations
vanish for capillaries smaller than r=0.474 mm according to Eq. 15 (Modified from
Hamraouni and Nylander, 2002)

CAPILLARITY 11

Dynamic Contact Angle
The contact angle formed between a flowing liquid front (advancing or receding) and a
solid surface is not constant but reflects the interplay between capillary and viscous
forces. The relative importance of these forces is often expressed by the so-called
capillary number v Ca = , with the liquid dynamic viscosity, and v the contact line
velocity. The dependency of the dynamic contact angle
D
on the velocity of the contact
line during complete wetting can be described by a nearly universal behavior according
to the so-called Tanners law:
Ca A
3
D
= (16)
where A is a constant (~94 for
D
in radians). Kistler (1993) has shown that Eq. (16) fits
the data of Hoffman (1975) for Ca<0.1 and
D
<130
0
(Fig.9). The complete range of
Hoffmans (1975) data fitted to the empirical expression:

(
(

|
|
.
|

\
|
+
=

706 . 0
99 . 0
1
D
Ca 31 . 1 1
Ca
16 . 5 tanh 2 1 cos ) rad (
(17)
is depicted by a continuous line in Fig.9.

Figure 9: Experimental results of Hoffmann (1975) fitted with Eq. 17, and approximations given by Eqs.
16 and 19 . Note that for water flow in soils Ca rarely exceeds the range of values between 10
-
6
to 10
-4
(for v = 1mm/s Ca=1x10
-5
) [Modified from Kistler, 1996]

For conditions of partial wetting (
S
>0), the relationships between contact angle and
12 CAPILLARITY
capillary number are less universal. Hoffman (1975) postulated that at low Ca the
apparent dynamic contact angle remains close to the static angle but rapidly deviates
when Ca exceeds the value for
S
(see Fig.9 above). This postulate is formalized by the
following expression:
Ca A
3
S
3
D
= (18)
Additional examples of advancing and receding contact angle dependency on capillary
number are shown in Fig.10 (Hirasaki and Yang, 2002). Note that for receding contact
angle, there is a critical Ca above which the contact angle vanishes.

Figure 10: Finite difference computation vs. Eq. (18) and parameters from Kislter (1996) for advancing
(left) and receding (right) contact angle as a function of Ca (Modified from Hirasaki and
Yang, 2002}

The theoretical basis for the postulate in Eq. (18) was first derived by Voinov (1976)
using hydrodynamic approximations near the moving contact line resulting in:
) Ym / Y ln( Ca 9
3
S
3
D
= (19)
where Y/Y
m
is a ratio of macroscopic length over which the contact angle is defined
(~mm) to molecular length where continuum theories fail (~nm). Application of Eq.19
with Y/Y
m
=10
5
to the data of Hoffman (1975) is depicted in Fig.9. A key shortcoming of
such hydrodynamic models for a dynamic contact angle is the lack of consideration of
the effects and interactions with solid surface properties (Sciffer, 2000).

Heterogeneous Surfaces and Microscale Hysteresis
Contact angle on chemically heterogeneous and rough surfaces
Consider a chemically heterogeneous surface made up of patches of solids (or grains)
with two different equilibrium contact angles
a
and
b
, and with the fraction of the area
occupied by a solid given as f. The apparent equilibrium contact angle (
e
) for the
composite surface is given by the semi-empirical Cassies equation (McHale and
CAPILLARITY 13

Newton, 2002):

b a e
cos ) f 1 ( cos f cos + = (20)

Figure 11: Definition sketch for contact angle formation on (a) chemically heterogeneous surface and
(b) rough surface with r=A/A
0
where A
0
is the projected area over a smooth surface
[McHale and Newton, 2002].

An example of Cassies law for contact angle of water on a sand surface with increasing
amounts of hydrophobic grains is shown in Fig.12 (Bachmann et al., 2000). Cassies
law (Eq. 20) was in remarkable agreement with the experimental data of Bachmann et
al. (2000) for sand (Fig.12) and silt surfaces.

Figure 12: Application of Cassies law to (a) experimental results of contact angle with sand surfaces
containing different proportions of hydrophobic (treated) sand grains; and (b) an image of a
water droplet on nonwetting sand forming a contact angle of 95
0
[Modified from Bachmann et
al., 2000].

An interesting extension of Cassies law for porous surfaces (soil, fabric, etc) predicts
that the apparent contact angle (
e
) should be proportional to surface porosity (n)
according to (Adamson, 1990):
14 CAPILLARITY
n cos ) n 1 ( cos
a e
= (21)
The negative sign associated with porosity is due to the non-wetting properties of empty
pores (i.e., air with cos
air
=-1).
These concepts of mixed wettability can be incorporated into the capillary rise model
(Eq. 6 above) such as described by Ustohal et al. (1998) who derived expressions for
capillary rise in slits formed between two walls of different wettability. The same study
applies Cassies law to liquid retention in porous media and demonstrated these effects
on the hydraulic properties of unsaturated porous media with varying surface wettability.

In addition to surface chemical heterogeneity, the roughness of a surface is known to
alter its wettability properties by increasing the wettable surface area per unit projected
area, and by enabling a complex interplay between macroscopic contact angle and
microscale geometry leading to gas entrapment and a patchwork of micro-interfaces
underneath the wetting fluid (Bico et al., 2002). Onda et al. (1996) and Shibuichi et al.
(1996) provided a spectacular demonstration of surface roughness-induced super
hydrophobicity with a water drop resting on a fractal hydrophobic surface and forming a
contact angle of about 170
0
(Fig.13a). Such enhanced hydrophobicity is not only
important for a variety of engineering and industrial treatments aimed at water-proofing
of surfaces and fabrics, but it may also be important for explaining wettability properties
of natural soil surfaces.
Assuming that surface roughness only affects the solid-liquid and solid-vapor interfacial
areas, minimization of surface free energy results in the so-called Wenzels equation:
cos r cos
e
= (22)
where is the static contact angle for a smooth surface of similar chemical composition
(see scheme in Fig. 11b).
The scope of surface influence is more complicated than predicted by simple
expressions such as Cassies and Wenzels equations. Other factors such as details of
roughness geometry, interfacial pinning and air trapping conspire to accentuate surface
wetting properties as schematically shown in Figure 13b (Onda et al. 1996; and Bico et
al. 2002). The scheme depicted in Fig.13b is based on experimental results showing the
apparent contact angle on a rough surface plotted against the static contact angle on a
smooth surface with similar chemical composition (to isolate the influence of surface
roughness). Subsequent studies by Bico et al. (2002) have shown a range of behaviors
and asymmetry between the hydrophobic (cos <0) and hydrophilic (cos >0) sides of
Fig. 13b. It is interesting to note that certain roughness patterns induce formation of air
patches trapped underneath the liquid (similar to water drops resting on surfaces of
some plant leaves).
CAPILLARITY 15


Figure 13: (a) water drop (r=1 mm) resting on fractal rough surface with r=4.4 (Eq. 22); and (b) apparent
contact angles as a function of surface micro-roughness for a range of surfaces with different wettability
[Onda et al, 1996]

Hysteresis
The amount of liquid retained in a porous medium is not uniquely defined by the value
of matric potential but is also dependent on the history of wetting and drying. This
phenomenon, known as hysteresis, is closely related to various aspects of pore
geometry, capillarity, and surface wettability. The macroscopic manifestation of
hysteresis in soil water retention (or soil water characteristic) as discussed in the article
on Retention of Water in Soil and the Soil Water Characteristic Curve in this
Encyclopedia is rooted in several microscale mechanisms including: (i) differences in
liquid-solid contact angles for advancing and receding water menisci (Fig.14a, Hillel,
1998), that is accentuated during drainage and wetting at different rates (Friedman,
1999); (ii) the "ink bottle" effect resulting from nonuniformity in shape and sizes of
interconnected pores as illustrated in Fig.14b, whereby drainage of the irregular pores is
governed by the smaller pore radius r, and wetting is dependent on the larger radius R.
Additional effects stem from pore angularity discussed in the article on Retention of
Water in Soil and the Soil Water Characteristic Curve in this Encyclopedia; (iii)
differences in air entrapment mechanisms; and (iv) swelling and shrinking of the soil
under wetting and drying, respectively. From the early observations of Haines (1930) to
the present (e.g., Kool and Parker, 1987), the role of individual factors remain unclear,
and hysteresis is a subject of ongoing research.

16 CAPILLARITY

Figure 14: Two microscale mechanisms for hysteresis in capillary behavior: (a) differences between
advancing and receding contact angle; and (b) the ink bottle effect depicting two different
amounts of liquid retained in identical pores under the same matric potential (see text).

Further Reading
Adamson, A.W., 1990. Physical chemistry of surfaces, 5
th
edition, John Wiley and Sons, New
York.
Bico, J., U. Thiele and D. Quere, 2002. Wetting of textured surfaces. Colloids and Surfaces A
206, 41-46.
Blunt, M., and H. Scher, 1995. Pore-level modeling of wetting, Physical Review E, 52(6), 6387-
6403.
Bachmann, J., A. Elliesb, and K.H. Hartgea, 2000. Development and application of a new
sessile drop contact angle method to assess soil water repellency. J. Hydrology 231 66
75.
Dullien, F.A.L., F.S.Y. Lai, and I.F. Macdonald, 1986. Hydraulic continuity of residual wetting
phase in porous media, J. Colloid Interface Sci., 109:201-218.
Friedman, S.P., 1999. Dynamic contact angle explanation of flow rate-dependent saturation-
pressure relationships during transient liquid flow in unsaturated porous media, J.
Adhesion Sci. Technol. 13:1495-1518
Haines, W. B. 1930. Studies in the physical properties of soil. V. The hysteresis effect in
capillary properties, and the modes of moisture distribution associated therewith, J.
Agric. Sci., 20:97-116.
Hamraoui, A., and T. Nylander, 2002, Analytical Approach for the LucasWashburn Equation. J.
Colloid and Interface Sci., 250, 415421.
Hillel, D., 1998. Environmental Soil Physics, Academic Press, San Diego.
Hirasaki, G.J., and and S.Y. Yang, 2002. Dynamic contact line with disjoining pressure, large
capillary numbers, large angles and pre-wetted, precursor, or entrained films. Contact
Angle, Wettability and Adhesion, Mittal, K.L. (ed.). Vol. 2, pp. 130
Hoffman, R. L., 1975, A study of advancing interface: J. Colloid Interface Sci., 50:228-241.
Kistler, S. F., 1993. Hydrodynamics of wetting, in Wettability, J. C. Berg (Ed.), pp. 311-429,
CAPILLARITY 17

Marcel Dekker, New York.
Kool, J. B., and J. C. Parker. 1987. Development and evaluation of closed-form expressions for
hysteretic soil hydraulic properties, Water Resour. Res., 23:105-114.
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