J. Fluid Mech. (1979), vol. 95, pan 3, pp.

539-565 539
printed in areat Britain

On the interpretation of dynamic contact angles

in capillaries
By FRED Y. KAFKAt ANO E. B. DUSSAN V.
Departmcnt of Chemica.l and Biochemical Engineering.

University of Pennsylvania. Philadelphia. Pennsylvania 19174

(Received 17 February 1978)

The motion of two immiscible fluids with arbitrary viscosities flowing through a
capillary with an almost flat fluid-fluid interface is investigated in the limit of small
capillary and Reynolds numbers. A complete description of t,he dynamics of the fluids
i8 presented . It. i8 shown that the motion of the fluid away from the moving contact
line can be completely determined in terms of one material parameter, and how t,he
capillary can be viewed as a device for measuring it. The dynamic behaviour ofvarious
contact angles, measured by ot,hers, is calculat,ed. It. is shown that they al! depend on
the radius of the capillary; hence, they do not represent properties of only the materials
of the system.

1. Introduction
West (1911) and vVashburn (1921) were the first to successfully analyse the dis
placement of one immiscible fluid by another through a circular capillary. West,
interested in developing a viscomet,er, studied the speed at which an entrapped index
ofliquid moves through a capillary when a fixed pressure drop is maintained between
its ends. Washburn examined the unsteady rate at which a liquid penetrates a hori
zontal or vertical capillary in the hopes that it would lead to a better understanding of
flow thl'ough porous media. Although both were interested in different problems, their
methods of analysis were the same. Their two main assumptions were: (i) the liquids
undergo Poiseuille flow; (ii) the pressure drop across the spherically shaped merusci is
given by the same formula used under static conditions. For the simple steady flow
illustrated in figure 1, these assumptions imply that the pressure drop between
z = - LA in the advancing fluid and Z = L R in the receding fluid is given by

(1.1 )

where a is the radius ofthe capillary; fl.A and flR are the viscosities ofthe advancing and
receding fluids, respectively; U is the speed of the meniscus relative to the capillary;
'}' is the surface tension of the fluid-fluid interface; and 8 w is the dynamic value of the
contact angle.
U ndoubtedly, there is a certain amount of error associated with the aboye approach;
fol' example, end effects and the influence of the viscous forces on the shape of the
meniscus have both been ignored. However, this approach has pro ven to besurprisingly
t Present address: E. L Du Pont De Nemairs & Company, Experimenta! Station-B/304. Witmington,
DE 19898.

0022-1120/79/4290-7360 802.00 1979 Cambridge University Press

540 F. Y. Kafka and E. B. Dussan V.

.. u

.... -- LA ----------~---------- LR --------~

FIGURE 1. The receding fluid is being displaced by the advancing fluid. The frame of reference la
at rest with respect to the contact line; consequently, the cap illary is rnoving from right to left.

good when Uapj and Uj"1 are small. By measuring the speed of entrapped mercury
indices of known length and su bject to known pressure drops in capillaries of various
radii, West a,nd Yarnold (1938) were ab le to determine the viscosity of mercury to
within 7%. t Another way of assessing the accuracy of this approach is to compare
the values of the cont ad angle which (1.1) predicts from experimentally measured
values of the pressure drop, U, , a, L and y, with that measured directly by
optical means. Rose & Reins (1962), upon observing an index of oil moving thTough
a glass capillary, found good agreement, although the scatter in their data is COll
siderable. Blake (1968) found that the two methods always agreed to within his
experimental error of 2 for both benzene disp lacing water and water clisplacing
benzene thTough a glass capiUary (his experiments were restricted to very smaH U,
10- 6 .:S UIr .:S 10-3 ) .
Besides its direct app1ication to technology, for which WeBt's approach of deter
mining the volumetric flow rate seems to be sufficient, there remains an important
scientific reason for studyi ng the displacement ofimmiscible ftuids through a capillary.
Due to its compactness and symmetry, it is a convenient system for studying the
dynamic behaviour ofthe contact angle. Hansen & Toong (1971 ), based on an interest
ing though ad hoc hydrodynamic analysis, were the first to point out that the contact
angle everyone measures in the capillary is probably not its actual value due to the
fact that viscous forces may severely deform the shape of the fluid-fluid interface so
close to the moving contact line that it cannot accurately be Ilwusured by low-magnifi
cation optical techniques . Instead of attempting to measure the actual contact angle
with a protractor and an enlarged photograp h of the meniscuti (the technique used by
Rose & R ens, 1962 ), they report their experimental findings (Ransen & Toong
1971a) in terms of an apparent contact angle, B:f[, which is unambguously defined in
terms of H, the distance between the apex ofthe meniscus and the plane containing the
moving contact line:
_ -i[
BN = cos
-2H j
1 + (H ja) 2 .
a] (1.2)

If the interface were shaped like a portion of a sphere of radius aj cos B]vI aH the way up
to the contad line, then the angle formed between it and the capillary would be B.J./'
Using his own data and that of others for the displacement of air by various oi18
thTough a glass capillary, Roffman (1975) has demonstrated graphically that t,he

t Yarnold includes a n extra term in his analysis to accoun t for so rne of the end effects ; ho',\'
ever, it does not improvu the accuL'acy.
L V.
ZZZZZZZ
ji ng fluid
ZZZZZI/ Z/
LR
19 fluid. Tito frame of reference is
lary is m oving from right to left.
e . peed of entrapped mercury
dr ps in capillaries of various
~ t he viscosity of mercury to
this a pproach is to compare
om exper imentally measured
1 tha t measured directly by
index of oil moving through
. scatter in their data is con
alw ys agreed to within his
':1 wa t er an d water displacing
~e r stricted to very small U,
eh We t 's approach of deter
, there remaina an important
!ible fiuids through a capillary.
Lent system for studying the
\g (197 1), based on an interest
t t o r oint out that the contact
lOt it actual value due to the
! of the Huid-Huid interface so
y b measured by low-magnifi
!a5ure t he actual contact angle
eniscus (the technique used by
Ll findings (Ransen & Toong
;h is una.mbiguously defined in
as and the plane containing the
(1.2)
[ ra ius a jcoseJl{all thewayup
nd the c!:Lpillary would be e JIl'
lccment of air by various oils
mstrated graphically that the
lt fo l' sorne of the end effects ; how -
Interpretation 01 dynamic contact angles in ca.pillaries 541
parameters 8.1[' UIJfr, and the static contact angle, es' can be related by a single curve.
Jiang, Oh & Slattery (1979) have found that the following function best fits this curve:
cos es - cos ev = tanh 4-96Ca o 702
1 + cos es
Even though Hansen & Toong and Hoffman realized that 8 111 was not the actual
contact angle, they did not recognize the fact that such an angle might not be a
material property ofthe system, i.e. it might depend explicitly on the overall geometry
ofthe Huid. Ifthis is the case, then the usefulness of their experimental data is limited.
e
For example, it would not be possible to use M for studying the spreading of the same
liquid over the same solid in any geometry other than the capillary. Hence, in order to
extract matmial invariant information from these experiments, it is essential to
perform a detailed analysis of the motion of the fiuid in the immediate vicinity of the
fluid-fluid interface and the moving contact lineo
Unfortunately, this is not a straightforward task. Dussan V. & Davis (1974) have
shown that the fiow field surrounding a moving contact line, modelled as a continu um
with the no-slip boundary condition imposed at a rigid solid wall and with an imper
meable fiuid-fiuid interface, is singular; fiow fields having those properties must exert
an unbounded force on the solido Since this impli cation is unphysical, it is necessary to
change at least one of the basic modelling assumptions in order to analyse the motion
of the fiuid. Several possibilities exist; however, those explored to date all involve
introducing a boundary condition which permits the fiuid to slip along the wall.
Hocking (1977) and Huh & Mason (1977) have successfully analysed the fiow fieId
associated with the dispacement of immiscible fiuids through a capillary by using
various slip boundary conditions to remove the abovementioned singularity . Both
have obtained a solution valid for an almost fiat fiuid-fiuid interface near the singular
limit, LJa-+ 0, by the method of matched asymptotic expansions. Roughly speaking,
Li denotes the size of the region near the contact line within which the fiuid slips along
t,he wall; the no-slip boundary condition, corresponding to LJa == 0, represents the
singular limito Hocking analysed the case of two immiscible fiuids with arbitrary
viscosities in which the relative speed of the fiuid at the wall is assumed to be propor
tional to the shear stress exerted by the fluid on the wal\. His main conclusion, based on
a seemingly reasonable guess for the size of the unknown slip coefficients appearing in
his analysis , was that the magnitude of the force exerted by the fiuid near the moving
contact line is small when compared with the total drag on a capillary over 100 radii in
length. However, a detailed analysis was not necessary to come to this conclusion. We
already know from (1.1) that the maximum effect that the dynamics of the fiuid near
the moving contact line can have on the pressure drop down the capillary is 2yja.
Hence, an estimate of its relative importance is given by the expression
(2yja) (8U[,uA LA +,uR L R]ja 2 ) - \
the evaluation of which does not require guessing the value of any unknown para
meters. Hocking neither analysed the first correction to the shape of the interface nor
cIid he present his solution for the velocity and pressure fields. Huh & Mason (1977)
carried Hocking's a.nalysis one stcp further by solving for the shape of the fluid inter
face when viscosity of one of the fluids is negligible. They investigate two slip boundary
conditions: that used by Hocking, plus a second wherein the fiuid exerts no tangential
542 F. Y. Kafka and E. B. Dtlssan V.
stress on the solid \Vithin a given small distance from the contact line, and does not
slip on the solid elsewhere. Their major difficulty arises from the fact that the expres
sion they derive for the apparent contact angle contains two unknown parameters: the
slip coefficient and the dynamic value of the actual contact angle. Consequently, when
comparing their results with experiments they make two unjustified assumptions: the
coefficient is 10-9 m; and the actual contact angle, under dynamic conditions, does not
differ from its value at static equilibriumot
In 2 it is pointed out, based upon results of existing analyses offlow fields containing
moving contact lines, that the motion of the fluid in the outer region, the regio n of
major concern to fluid-mechanicians, can be completel)' determined in terms of only
one experimental1y measurable parameter. This parameter can be used for the same
fluids spreading on the same solid material in any geometry. In 3 the lowest-order
outer problems are formulated, \Vith this in mind, fOl" immiscible fluid displacement
tbrough a capillary. Solutions are obta ined in 4 and 5 for the lowest-order velocity
and pressure field and shape of the fluid-fluid interface for the case of two immiscible
fluids with arbitrary viscosities using a technique particularly well suited for moving
contact line problems, which differs from that used by Hocking. In 6 expressions are
derived for the various dynamic contact angles which have appeared in capillary flow FIGURE 2. Tw(

studies. Finally, in 7, it is shown how the parameter introduced in 2 can be deter plane tangent 1
wall i8 denoted
mined from existing data of the dynamic behaviour of the apparent contact angle
measured in capillaries.
tion is used,
Scriven (197 J
2. Approach not directly b
the fluid -flu<
One of the major contributions of Hocking and Huh & Mason is the demonstration
constant of i
that flow fields containing moving contact lines can be analysed near the singular
angle of incliJ
limit, LdL.p -+ 0, by the method of matched asymptotic expansions. Two regions
refer to figurE
emerge: the nner regon, located in the immediate vicinity of the moving contact
Ifthe outer
line and scaled by L i , within which the details of the tiow field are ver)' sensitive to the
mentioned ce
form of the slip boundary condition; and the outer regon, everywhere el se and scaled
contact angle
by L,p, within which, to lowest order, the fluid satisfies the no-slip boundary condition
constant mus
and the geometry of the fluid plays an important role. Although these analyses can
of the interfa
predict the behaviour of experimentally measurable quantities, for example the
fluids in the o
pressure drop across the capillary and the dynamic behaviour of the apparent contact
the abovemer
angle, they have two principal drawbacks: (i) no model for the slip boundary condition
In other we
has been demonstrated to date to be correct for any given circumstance, (i) the
calculated co
dynamic behaviour of the actual contact angle is unknown . The key to proceeding regan, the re
further in a quantitative fashion les in identifying the mechanism by which the inner
property that 1
a nd outer solutions affect each other . denote the va
Upon examining the analyses of H ocking (1977), Huh & Mason (1977), Dussan V. proper model
(1976) and Greenspan (1978), we find two features in common. (i) The velocity fields then the val UE
are' prematched', i.e. to lowest order in LdL.p there are no non-zero constants to be such knowled i
determined by matching the inner and outer velocity fields [when domain perturba- lllain objectiv
t Hocking's results contain only one parameter , the slip coefficient, because he makes the ad i(lians interes1
hoc assumption that the actual contact angle is exactly 90. hOwnhowto
:j: Even though the analyses of Dussan V. and Greenspa n do not involve a perturbation in
fluid displacel
LjL.p, the following rema.rks are true if their analyses are v iewed from this perspective.
n V.
,he contact line, and does not
from t he fact that the expres
two unknown parameters: the
lct angle. Consequently, when
) unjustified assumptions: the
. dynamic conditions, does not
lalyses offlow fielrls containing
he onter region, the regon of
{ determined in terms of only
eter can be used for the same
netry. I n 3 t he lowest-ordel'
.m.miscible fluid displacement
for the lowest-ordel' velocity
for the case of two immisci ble
ularly well suited for moving
Iock ing. In 6 expressions are
ave a.ppeared in capillary flow
ntroduced in 2 can be deter
f the apparent contact angle
& l aso n is the demonstration
,e analysed near the singular
ltic expansions. Two regions
cinit y of t he moving contact
r fieId are very sensitive to the
IZ , verywhere else and scaled
he no-slip boundn,ry condition
Although these analyses can
quantit ies, for example the
~viour of t he apparent contact
0 1' the slip boundary condition
. given circumstance, (ii) the
nown. T he key to proceeding
nechanism by which the inner
Ih & Mason (1977), Dussan V.
: nunon. (i) The velocity fields
~ no non-zero constants to be
i los [when domain perturba
~ ffi o i e n t, because he m akes the ad
d o no t involve a perturbation in
d from this perspective.
1nterpretation 01 dynamic contact angles in capillaries 543
Receding Ouid
z
r
Advan cing Ouid
FIGURE 2. Two co-ordinate systems are used : (r, z) and (Rla. <P). The angle form ed between the
plane tangent to the in terface at a distance R from the contact line and the plane tangent to the
wall is denoted by 7J.
tion is used, the velocity field in the intermediate region is that given by Huh &
Scriven (1971)]. In this sense, one can say that the velocity field in the outer region is
not directly affected by \vhat happens near the moving contact lineo (ii) The slope of
the fluid-fluid interface in the outer region can be completely determined except for a
constant of integration. Knowledge of this constant is equivalent to knowing the
angle of inclination of the interface, 7), at a specific distance f1'om the contact line, R;
refer to figure 2.
Hthe outer solution is valid in the neighbourhood ofthe contact line then the above
mentioned constant can be determined from the dynamic behaviour of the actual
contact angle (e is the actual contact angle when R = O). Howeve1', it is not; hence the
constant must be determined by matching the inner and outer solutions for the slope
of the interface. It is only through the slope of the interface that the motion of the
fluid s in the outer region is affected by the dynamics of the fluids in the inner region in
the abovementioned analyses .
In other words, if 7J at R is known then the entire solution in the outer region can be
calculated completely. 11 R is chosen to be a specific position within the inte1'mediate
regan, the region where both inner and outer solutions are valid, then 7J must have the
property that it is independent 01 the overall geometry 01 the outer region (el and Rl wiIl
denote the value of 7J and R at a specific position in the intermediate region). If the
proper model for the dynamic behaviour of the fluids in the inner region were known,
then the value of el could be calculated by first principIes through matching . However,
such knowledge do es not seem to be forthcoming in the foreseeable future. One of our
main objectives is pointing out that this do es not present an obstacle to fluid-mech
icians interested in predicting the spreading of liquids on solid surfaces. It wiIl be
shown how to determine el empirically from experimental measurements ofimmiscible
fluid displacement through a capillary. The capillary can thus be viewed as a device
544 F. Y. Kafka and E. B. DU8san V.
from which basic iruormation can be obtained that characterizes the spreading of
liquids on so lid surfaces.
The key to the correctness of using this procedure to solve the outer problem in
terms of el lies in the assumplion that all models of the inner region, not just the ones
cited at the beginning of this section, give rise to a velocity field in the inner region that
'prematch' that of the outer region. Although the models of the inner region froIn
andl
which this assumption has been abstracted all involve introducing a slip boundary
surfa
condition, they do in fact reflect vastly different physical mechanisms (refer to Dussan
V. 1979, for a detailed discussion).

3. The outer region

The geometry and co-ordinate system are shown in figure 2. The frame of reference
is choscn so that the fluid-fluid interface is stationary, the walls of the capillary moving Thet
with a velocity of - Uzo It is assumed that the dimensionless Navier-Stokes equations
are satisfied within both fluids:

wherE
of the
numb
fluid (
ties,
where K = A, R denotes the advancing and receding fluids, respectively; 1t and ware are
the radial and axial veloty components; and p + pga 2 z/y is the pressure within the
vertical capillary. Each fluid must also satisfy the continuity equation:
We
1 o
--(m K
r or )+-+ ow K
oz =0.
B, Re~
where
fiel d, o
The outer flow field satisfies the no-slip boundary condition along the moving wall, atz =
so that
1t
K = O, w K = - 1 at r = 1, Izl < 00
portur
intcrfa
and if the height of the fluid-fluid interface is given by a radial function, h(r), then the
normal component of the velocity must be zero :

Th us a
z == O. r
while the tangential component of the velocity is the same in both fluids: l t is
de crib
[1t+w~;]=o at z = h(r), r~ 1,
approa,

where the brackets are defined by

[ g(r)] == lim {g.d(r,h-)-gR(r,h+)} ,

c~o

g(r, z), represents any scalar field which characterizes the behaviour of the advancing This ex
and receding fluids such as pressure and either component of the velocity vector. The create a
:an V. Interpretation of dynarnic contact angles in capillaries 545
characterizes the spreading of dynamic boundary condition requires first that the tangential stress exerted by either
fl~id upon the meniscus be the same,
to salve the outer problem in
3 inner region, not j ust the ones dh (OW _OU) + (1 _ (dh) 2) (OU + OW)] = O l' ~ 1,
[ dr OZ or dr OZ 01' at z = h(r),
:ity field in the inner region that
lOdels of t he inner region from and second that the interface have a shape such that the product of its curvature and
re in troducing a slip boundary surface tension balance the normal stress difference,
'al mechanisms (refer to Dussan
~:~ I(1 + (~~rr + ~ ~:~ / ( 1 + (~~rr = - [p TI + B z

+ 2C [- {(dh)2 O
U_ dh (OU + OW) + OW1']/(1 + (dh) 2) at z = h(r).
a dr or dr OZ 01' OZ J dr
fig: 41'e 2. The frame of reference
The boundary conditions on h(r) are
thc walls of the capillary moving
ionleas ja ier-Stokes equations
h(l) = O and ~; = tan (i- er) at r =
Rr
1-
a'

where er and Rr have already been defined in 2. We shall treat er as a known property
of the system. Other parameters appearing in the aboye equations are : the capillary
number, Ca == U ,c1 /Y; the Bond number, B :=: (P A -Pn)ga 2 /y, where PA and PR are
[
,' r ur
~~
':\ r '.l
ur
02W~
(OW K ) +" 2
uZ '
fluid densities; the Reynolds nnmbers, Re K == UaPK//K; and the normalized visco
sities,71K == ,u K / A' The dimensional form of the dependent and independent variables
fluids, respectively; u and w are are
la 2zjy is the pressure within the py/a; (uU, wU); (ra, za); R-, ha.
ntinuityequation: We shall only be concerned with the case wherein the fi\'"e parameters (e r - t 7T , Ca'
B,Re A , Re R ) are small. Dnder these circumstances it is anticipated that h(r) is every
). where close to the plane z = O. It is reasonable to expect that the velocity and pressure
lield, or the continuation of each field, has the property that a Taylor series expansion
Jndition along the moving wall, at z = O can be used to express valnes of the dependent variables at z = h(r) (domain
perturbation). For example, the kinematic boundary condition at the fluid-fluid
\z\ < co interface becomes
ya radial function, h(r), then the
at z = h(r).

Thus al! the boundary conditions at the meniscus are tra,nsformed to conditions at
:r), r ~ 1,
z = O. The fluid-fluid interface remains at z = h(r) .
It is assumed that the dependent variables (u K , w K , pK, h) can everywhere be
: SLme in both fluids:
described by an asymptotic expanson valid in the limit that the five parameters
approach zero :
" r ~ 1,

(r, h + e)},
(1~:) ~ (:r}
P
h
Po
ho
+ (}7T- er) {:;}
Pe
he
+Ca{:~} +B{:!} +Re
Pe,.
he,.
PB
hB
A {:;::}
PReti
hRetJ.
+ReR{~;:} PReR

hReR

+ ... .

s t h behaviour of the advancing This expansion is substituted into each governing equation and boundary condition to
lonent of the velocity vector. The create a sequence ofwell-posed boundary valne problems.
546 F . Y. Kaflca and E. B. Dussan V.
To lowest order, the preSSUI'e field and interface shape must satisfy
Vpf = O;

~~
r dr
(r
dho
dr
) = pr;-pt at z = O;
It is co
dh o = O at r = 1- RIla; and ho = O at r = 1.
dr
The solution to the above is
In terrr
ho == O and pt == pr; (constant). the low
In a similar manner it can be shown that
{P1 = p!i = ha. = O la = B,Re 4 , Re R }
The terms pf and he must satisfy
Vplf = O;

~~
r dr
(r
dhe
dr
) = p~-pf at z = O;

dh o It is als
1 at r=l-Rrfa; and ho=O at r=1.
dr
The solution is
he = t(r 2 - 1) and pf = p7} 2 (constants)t
with th
This mode, while free of viscous effects in the outer region, nevertheless represents a
dynamic contribution to the interfacial shape and pressure fieId since the value of O]
depends on the speed of the contact lineo The lowest-order mode in which
effects are important is described by

_ -----;r
O- - ;. (1; or
oPa + /1_K [O o (ruoK) + 8Z2
02 u f ]
'
OPa
0= ----az +#K
_ [1;;.o (OW f ) 02 wf ]
r T + OZ2 '
and

with boundary conditions

uf = O and w{f = 1 at r = 1,
_ out
_ our;
w{f = 0, ut = ur;, and az #Raz
#4 at z = 0,
=

~ ~ (r dh ca ) _ R _ A + 2 [ owt _- Ow~] at z = O,
rdr dr -Pca PCa #4 #R OZ 0z

and dh c ) dr = at r = 1 - Rrfa, and hc. = at r = 1. In the next section, a solution is g ener.
obtained for u{f and w{~ which is then used to obtain Pla and hCa'
t A negligible error has been introduced by neglecting terms involving Rrla.
'san V. 1nterpretation of dynamic contact angles in capillaries 547
lpe must satisfy
4. 1'he outer velocity field
4.1. Solution
Itia converuent to introduce a stream function, fK:

= at r = 1. (nlf,wf) =
lofK
( -r - -uZ" , ,
1 01 'r K)
---'
r r
.

In terrns of the stream function, the governing equation and boundary conditions for
.stant). the lowest-order mode in which viscous effects are important become
o 1 o 02 J2
[ r orr or + OZ2 fK = O;

ofK
fK = 0, --= 1 at r = 1,
or

fK = 0, at z = 0,

It is also convenient to solve this system by superposition :

,= O at r = 1.
f K = fK + _1 Ti,TiR fK
1 #K#,+/i R 11
(constants)t
with the non-homogeneous boundary condition at r = 1 absorbed in ff:
l'gion, nevertheless represents
~ess ure field since the value of
ff = 0, at r = 1
st-order mode in which V1ScOUS '~.'

ff = 0, at z = O.

,.... ""'SoIution for f'f was obtained by Bhattacharjii & Savic (1965) using a sine trans

that this flow exhibits no tangential stress at z = O. The functions 10 and 11 are
momfied Bessel functions as given in Abramowitz & Stegun (1964).
The function ffr. has boundary conditions

at z = 0, Vtfi = and offi.

or
= at r = 1;

at z = 0, and at z = 0,

. I n the next section, a solution is Ageneml solution for fut in either fluid can be found by separation of variables or in
p!a and hca
o~ing terma involving Rrla.
t It will b es tablished shortly that the superscript K is not necessary for ff1I'
t Where (- l)A-l == - 1 and (- l)R-l == + 1.
548 F. Y. Kafka and E. B. Dussan V.

n Res n 1m8 n Re 0(8,,) 1m 0 (8,,)

O 00 00 00 00

1 146746 446630 - 99816 - 05600

2 172697 769410 -173266 -4,1056

3 189494 1087457 - 244043 -7 9430

4 202006 1403889 -31 3717 - 119077
5 211995 1719556 - 38280 1 -159442
where
6 220312 2034795 -45'1530 - 200260

7 227440 2349770 - 520046 - 241381

8 233678 2664571 -588325 -282742

9 239222 2979247 - 656508 - 324293

10 244212 32 938 31 -72,4559 - 36593 8

11 2'48750 3608350 -792564 -407747 exhibiti
12 252911 3922815 - 86 0456 - 44960 1 can be ~
13 256752 4237238 - 92,8238 -49 , 1582
14 260319 4551630 -996144 - 533514

15 263648 4865990 -1063922 -575685

16 266769 5180330 -113,1692 - 617704

17 269706 54 94652 -119 9416 -6.59903

are id en
18 272481 5808954 -126'7092 -702071
19 275110 6123247 -133 ,4834 -74,4356
20 2' 77609 6437526 -1402406 -786654

TABLE 1. Eigenva.Jues and oigenfunction coefficients.

where tl
onz =
onz = O.

terms of a Green's function. Work by Smith (1952) and, later, Yoo & Joseph (1
suggests a separation of variables of the form
!rOID !frrr
All th
that T rol

where the sets {s} and {p} are eigenvalues and eigenfunctions determined by
boundary conditions at r = 1 and the requirement of a bounded velocity field at r ==
Each element of {s} must be a zero of the characteristic function g(s):
g(s) == 2Io(s)Il(s)-sI5(s)+sIi(s) .
Those elements \vith non ~ negative real and imaginary parts are ordered with i The first
roagnitude to forro {sn}, where So = O; the complete set of eigenvalues which has '1I.gular 1
required property that eislzl is bounded for ]f\.rge z consists of {sn} U { - sn}' It can field in th
shown for large n that sn "" lln 47T(n + l) + 7Ti(m + ~.). The values of {sn: n = 1, ... , Theset:
were found by the secant method applied to the analytic function g(s) and the aubstituti
twenty-one are listed in table 1. Zeros near the origin were counted by numeri
integrating g' / 9 abou t closed contours to confirm that no element of {sn} was missed.
A sequen ce of functions, {o(r; s)}, biorthogonal to {p(r ; s )} have been found with lb!
propel'ty that if s and s' are any two eigenvalues then

[01 - 1]2 p(r;s), dI nr= {Ok(s)if ifs =l=s=s'.

f 1
o or;s
( ) s', The differ
Oontinuitj
'Jussan V. 1nterpretation al dynamic contact angles in capillaries 549

constants C(sn) are then determined by

Re C(snl
1m C(snl

C(,.) ~ k(:.J: [~ !1r:~'('~ &V 1 d

00 00

- 9 98 16
- 05600
a(r ; s.) - n) lnr , (4.3)
- 173266
-24404 3

- 31371 7

-41056

- 79430
- 119077

l or r or z=o

- 38 280 1
-1 59442 a = (0'1,0'2) = (2pl(r; s) + P2(r; s), Pl(r; s)),
-4515:l 0 - 200260

- 52004 6
-24,1381 PI) (r11(rs)/ 11 (s) - r 210(rs)/ 10 (s) )

- 282142
- ;38 8325
p = ( pz = 2rIl(rs)/s10(s)-r11(rs)/11(s)+r210(rs)/10(s) ,
- 656508 - 324293

- 724559
- 36,.5938
ex;hibiting the properties that p(r; s) = p(r; - s) and p(r; s) = p(r; 8). In addition, it
- 79 2564 - 407147
- 86045 6 - 44960 1
be shown that k(s) = -1i(s)/S21~(s) for s = Sn ' For the problem at hand, frn and
-9 28238
-491582

- 99614 4

-1 06, 392 2
- 533514
- 51568 5
r ~ (~ ofr
or r or
n)
- 113-1692 - 617104

- 11994 1 6 - 659903 identically zero on z = O, so that (3.2) can be integrated to give

- 126,7 09 2 -702071

~
- 133483 4
-744356
- 786654 frn = - 2 Re {C(!n) Pl(r; sn) eianlzl}, (4.4)
- 1402406 m =l Sn
llction coefficients.
the C(sn ) can be calculated for any specified 02frn /oz2Iz=0' Since 02frrfOZ2 = O
z.= O, the function 7(r) = (1/r)02frn /oz2Iz=0 represents the entire tangential stress
z = O. This is the same in both fluids, wrnch justifies the removal of the superscript
,2) and, later, Yoo & Joseph (
fr JI'
AH that remains is to calculate 7. Upon combining (4 .2), (4 .3) and (4.4) it is found
7 must satisfy:
R
2 o'/e
A(r; 7) = __ \
'1'_1 , (4.5)
r OZ z=o

eigenfunctions determined by
,o a bounded velocity freId at r 1 ~'QU 9"tlcm (4.5) is solved approximately by assuming 7 has the form
~risti c function g(s):
7 == 7M (r) = --
- 32 (
--
r) + lvI
}:; a M r 2m - 1.
:) + sI(s). 1T 2 - 4 1- r2 m=1 m

i,r y parts are ordered with . the right-hand side of tbe equation represents the anticipated
}te set of eigenvalues which has behaviour which 7 must have near the contact line in order for the velocity
z consists of {sn} U { - sn}' It can 1I1-"'filrl in the outer region to 'prematch' that of the inner as discussed in 2.
i ). T he values of {sn: n = 1, .. . , Thesets of coefficients {a~: m = 1, ... , M} for different values of 111 wereobtained by
an alytic function g(s) and the bstituting the above expression for 7 into (4.5) and minimizing a numerical approxi
origin were counted by to the 2 2 norm of the residue:
hat no element of {sn} was m
to {p(r;s)} have been found with ' 39 {0.02-P-
') oM}:; 2 ofrr
') I- A(0025P; 7) }2= O for m = 1, .. . ,111. (4.6)
uam p= 1 .') uZ z=o
then r=O'025P

O if s 9= s', Tb difference between the left- and right-hand sides of (4.5) corresponding to a dis
= { k(s) if s=s'. e,ontinuity in the radial component of the velocity at Z = O, ['Uo~ Iz=o, for 111 = 1,2,3,4
550 F. Y. Kafka and E. B. Dussan V.

00015

00010

00005

- 00005

- 00010

O 02 004 06 OS 10

FIGURE 3. The magnitude of the discontinuity in the tangent component of the velocity at
interface, [ uo] \' _o' decreasea in value as the number of trial functions increases in number;
6, O and correspond to two, three and four trial fun ctions, respectively.

is illustrated in figure 3. As )J1 increases in value, the error uniformly approaches

This is also illustrated by the behaviour of 7 111 - 7 4 in figure 4, where

- 5452r
1 2 -4860r+ 1336r 3 + 1063r5 -O348r7
-r

The corresponding values of {C(sn)}' which are the same for both fluids,
table 1. The radial velocity of the fluid at z = O, 1.I.f(r, O), can readily be calculated
its defin.ition:
1 o,/r R
ut"(r,O)=u5'(r,O)=-_'f'_I I -
+ JA _~ 1 o,/rR I
r o Z Z~O fiA +fiR r oZ 2 ~O
along with the identity
. Dussan V. 1nterpretation of dynamic contact angles in capillaries 551

o -~_~=-- __ ===-~ ______ --=-.l..,~:.-- __~___ _

" -'-- ,
,
t " \
\

-os - 50 "
\
\
\
\
\
- o \
\

' 11
:;
- 5 '"
<>
'"
111

'"'' ""
'1
"
<> '11
o o

4. The solid Ene - corresponds to the tangent component of the surface traction vector
" '''''-'.P'' at the fluid-fluid interface when fOUT trial functions are used, 7 4 ; ---, 7 1 - 74; - ---,
_ ~; - - - - - , 7 3 - 7 4

0 6 10
t an gcnt component of the velocity at
bria l f unc tions i.l.1creases in number;
fU.I.1c t ions, respectively .
, t he error uniformly approaches
74. in figu.re 4, where
) the sa me for both fluids, appear
~o1(r, O) , can readily be calculated
an evaluation of 8Vrr!8zlz=o obtained from (4.1):
18#1
--- ..:..10168r-O3206r3 -O0561r 5
r 8z z=o
+ 0'0225r' 00259r9
aboye expression is accurate to within an absolute error of 0,0003, or 005 % of its
um value.
An integral representation of Vrn was also obtained by finding the Green's function,
appendix A. This form, though somewhat cumbersome, was useful in evaluating
of the solution at z = O, where the sum of the eigenfunctions shows poor
ce. In addition, a grid of Vrr and Vrn values is displayed in table 2; this may
llsed to estimate velocities at any point within the two fluids.

4.2. Discussion
streamlines within the rececling fluid are shown in figure 5 for both large and small
of ;URo It is interesting to note that a stagnation point is preclicted within the
viscous fluid along the axis at a clistance Zs = O from the flat interface. Figure 6
the dependence of Zs on the viscosity ratio; note that its largest value, Zs == 0,25,
 <:Jt
<:Jt
~

tI
020 030 040 050 060 070 080 090 00
r z 010
-000274 - 0003 38 - 0003 90 -0 00426 - 000452 - 000469 - 000479 -000495
010 - 0001 00 - 0001 9:3
-001079 -001333 - 001526 -001 664 -001760 -001823 -001864 -001920
020 - 0003 96 - 000763
030 - 000876 -00168 1 - 002364 - 002904 - 0033 06 _- 0-03590 -0-03783 - 003908 - 0-03987 -004095 ~
- 004024 - 004910 - 0-055 44 -0 0598 1 - 006270 - 006455 - 0-06569 - 0-06720
0-40 -0 -01517 -0-02893 ~
- 005932 - 007125 - 007953 - 0-08502 -0 ,08855 - 009074 -009208 -009375
050 - 0-02286 - 004313
-0,05803 -0 -07808 - 0-09192 - 0-10099 - 010673 - 011028 -0,11243 -011370 -011520 ~
060 - 0-03132
-009230 -0,10555 -0-11362 -0-1184 2 - 0-12127 - 012294 -0-12388 -012495 ~
0-70 - 0-039 76 -007113 ~

-0-10353 - 0-10869 - 0-111.59 -0 -11324 -0,11417 -011468 -011520 ~

080 -0- 04650 -0 -07719 - 009424 ~
- 0-070 16 -007341 -007506 - 0-075 94 -0-07642 - 007 69 - 0'0783 -0-07695
090 - 0-04550 - 006316
~
I:>;j
tu
0-30 0-40 O-50 060 070 080 0-90 00 b:l
r z O-lO 020
0-00222 0-00186 000146 000109 000078 000054 O
010 0-00154 000227 0 00242
000291 000201 O b
0-00552 000409
020 000608 000886 000937 0-00854 000709
000396 O
~
0-01989 001783 001460 001121 000821 000579 <Jo
030 001329 001911 ~
002825 0-02263 001706 001230 000856 000579 O ;::;
040 002262 0-03178 0-03227
002892 002126 001502 001028 000685 O ""i
050 003318 0-04495 0-04397 003719
003101 002211 001524 001022 000670 O
060 0-04355 005565 005146 004148
002712 001864 001250 000820 000528 O
070 005127 005934 005041 003807
001745 001154 0-00751 000481 000304 O
080 0-05149 004969 003721 002588
000585 000373 000236 000148 000091 O
090 003333 002269 001439 0-00916
TAllLE 2. Stream fWlction component values.

S O GD~O.o d'-O o
'1:I~ ~ .... gfE ..., Ef;;:;g
~ _
o>-1 -(J; ... g..~ ;;:.,...o;:r~
>-1 '-< _ ~ -o >-1
O"' e: S ro ::l. - ;; (Jq (J; rJ.

6- g: !:T> S~ ~ 00 P"' ~ 5'

 D ussan V . lnterpretation oi dynamic contact angles in capillaries 553

r---------------~--------------- l}i=0
(al

000000000
- 0005
- 001
- 002

..;< .... <,;>"'10 000..;<_ - 004

10 0 CF>t-OO t-C'l0CF>
OC'lMIO<O<OIO <o':lO
0000 0 0000 - 0 06
00 0 000000
66 6 666666 - 008

- 010
00 """"'Q)f.C OOC'l O ...... 00
t-"'t-IOC'l C'lC'loo"<l< - 012
O ~~OO OOOO~ ......
0 0 0 0 ............ 0 0 0

0000 0 0000
6 6 6666666

O':Im ~ o C'l~O~~
OO C'1M OC'lIOIO<o':l
-< ~OOC'lIO IOC'lt-C'l
00 0 '1"""'1 .-1 ............ 0 0
U=I
0 0 0 0 00000
6 6 6 6 66666
.---...--------,-------~-------------- l}i = O
(b)
(CIc-:&~
'<!ilQ ~
tOeo
OC'l
......
_<OIOt-
~-..:::I'iCf:)
l}i=0 _--------~ - 0005
...... ll') ...,...L- ....... C'lOO ....... M
_--------~- 00 I
O O ............. C'lC'l1""""! ....... O

00 0000000 _ - - - - - - 002
66 6 666666
_ _- - -004

- 006
c.JcnO..:t:l C'l ....... C'llC\O

00 0<0 "" 0>0-";<00 _----008

~r.-~C"1 00 ....... t-t-lQ
O O ....... C'lC'lMC'l ....... O

000000000 - O lO
666666666

C'I..,< <<:> IO CF>ool-oo<o

C'l\O aoC'l
e-l OO [- OOr- ...... OOlCO':I
O
0
O
00 000000
......
-t ~OOO

C'lC"')~MC'lO
.......

e- 012

66 6 666666

C'l t- cr.:> t- t- (O .............. O';l

"' M oo C'lO> "<I<"';<C'l<o':l FIGURE 5. Constant streamlines w ithin the receding fluid are given in (a) for
C"l~mc.:a~"""'Ot-~
O
' 000000000
O ...... M""dil.Ol..:":lM ......
flR ~ flA and (b) fOl'flR ~ flA"
' 6 6 66 66666
Oocurs in the limit as the v1scosity ratio approaches zero. An internal stagnation point
t-<:o-< oolOlO"<I<O>O> oftbis sort has been observed by Dussan V. (1977) for glycerine displacing mineral oil
C l 00 t- O';l (O CI") (O t.O
through a circular tube.
: ~ ~~~~:2~~~
00 0000000
' 6 6 6666666 It has been noted by Hocking (1977) that, when the two fluids have the same vis
cosity, the velocity at z = O is everywhere zero. The flow field is the same as that
occurring when a flat-headed plunger displaces a fluid out of a circular tube. This
'<!i 00 O> C'I 00 10 t- O> <o':l
LOOC'l(O ....... l.O~~M
problem has been sol ved numericaJly by 'Vagner (1975) who represents values of the
) o;g ~~~~8;;~ stream function for Re = 10. His values are consistently smaller in magnitude than
~ oo ooooooo
'666666666 ODrs, differing up to 23 % along r = 0,5, and 48 % along z = 0549 . This discrepancy
is probably due to the fact that our results correspond to R e = O; although his solution
0 00 000000
....... C\l('Q ~ l.Ocor-oom
- 6 66 6 66666
554 F. Y. Kafka and E. B. Dussan V.

030

025

020

Zs O 15

O 02 004 06 08 lO
(yA - i1R l!(i1A + i1R)
FIGURE 6. A stagnation point is located within the less viscous fluid at (O, z,) .

is clearly in error in the region where the face of the plunger meets the wall (he caleu
lates a finite drag on the wall wmch should clearly beinfinitesubjectto his assumptions).
Figure 7 gives the difference, at a distance R = O05a froID the contact line, between
the velocity field and its anticipated asymptotic form:
a a<p K " a<p K
u
K
= -JY-a; R+a aR $,
where

a
<p K 2 1
=-I<Plcos<P+= - -
fLAfLR 2
4 (4-1<PICOS<p+2<psin<p-7TSinl<Pl) (4.8)
R 7T fLK (fL A + fLR) (7T - 4) 7T F lOt
limit
This is the solution given by Huh & Scriven (1971); however, they did not recognize both
that it represented the velocity field of the fluids within the intermediate region. Upon
repeated evaluation of the difference at decreasing values of R, it is found to be O(R) whe
as R -+ O. It has also been established through numerical calculations that
-16 a
T(Rja) == 7T 2 -4 x"R-O'08+O(Rja) as Rja-+O ortb
and asyr
agre
~ a frp I
2
== 134 + O(R(a) as R(a-> O. \Vou
r ar oz Z~O

Hocking (1977) al so anticipates a solution in terms of {p} but do es not make use of
the dual {a} to evaluate his complex coefficients {O(sn)}' Instead, he makes the resid ue
of truncated sums for the stream function and radial velocity discontinuity at z == O
san V. 1nterpretation 01 dynamic contacl angles in capillaries 555

0015

0020 ~
/ 0010

0005

08 O

? les.' v iscous fluid at (O, z,l

- 0005

plunger meets the wall (he calcu

lfinite su bject to his assumptions).
5a from the contact line, between
n:
- 0010

- 10 - 08 -06 - OA - 02 o
)S~+ 2cpsin ~-7Tsin I~I). (4.8) 2q,/rr
FIGURE 7. The difference between the outer and the anticipated asymptotic expression in the
limit as r ~ 1 and z ~ 0, I1v R , can be eva.luated at a. distance R = 0050. from the contact line for
however , they did not recogniz c both components of the velocity vector using {[a, b]; a = r, z; b = l, II},
in the intermediate region. Upon
alues of R, it is found to be O(R) where I1v R = ([r, l] + ~ [r, II]) r + ([z, l] + ~ [z, II:I)Z.
'A+'R 'A+'R
'ical calculations that

as R/a~O orthogonal to a set of cylinder functions all zero at r = 1. His sole published result, an
asymptotic form for the integrated tangential stress on the solid wall, is in substantial
agreement with our findings. However, a more thorough presentation of his results
R!a ~O . would have been useful.

s of {p} but does not make use of

J}. I nstead, he makes the residue
~l velocity discontinuity at z == O
556 F. Y. Kafka and E. B. Dussan V.

tho
I \
,
1
I
I on
I cor
I
I abe
I
I wit
I
I
I
I
I
I Rla,_- ,
I \
L J L

l LA la ,1, L R la
FIGURE 8. The slope of the meniscus w ithin the intermedia te region is calculated by balancing
the forces acting on the flu id body enclosed by - - -o Thil
ditic

5. The pressure field and interface shape

The experimentally roeasurable quantities are : the pressure drop across a fixed
length of capillary necessary to create a given volumetric flow rate, and, assuroing th
capillary is transparent, the shape of the fluid-fluid interface. These quantities ar n cO)
related through the integral forro of the equation of conservation of linear roomentum. iate
The difference in pressure between any two points on either side of the fluid-fluiu Z= '
interface can be calculated by using (:3.1) along with the solution for the velocity appl
field presented in 4. If the points are located more than two diameters froro the tbe i
interface, then o ti
p (r, - LA) -
a
p~a (r, L R ) "" 8 (JiA L. + JiRLR) - l'96 5 (JiA + JiR) - 15.27 8 JiAJiR + ~Pc
A ~+~ a
,
where ~PCa denotes the pressure drop across the interface along the axis of the cap.
illary, Pa(O, O) - P~a(O , O). The constant term - 1.96 5 is due to that part of the solution
given by fr; hence, it was evaluated by performing a double integral numerically. The
second constant, - 15.27 8 , coming froro fu was evaluated by extrapolating to z = O
series representation whose convergen ce is very slow at the point (O, O). These
cients represent dviations froro the parallel flow pressure field in the vicinity of the
interface.
The constant ~PCa can be calculated by balancing the force s exerted on the body
fluid contained between the planes given by z = -LAja and z = LRja, excluding
fluid within a fixed distance R of the moving contact tine; see figure 8. It is CJ,:;OiU U''''''':
that R lies somewhere within the intermediate region. The force balance to WI
O(R) as R -> O becoroes

L
{87f ( JiA---.d+Jin-.B
a a 7f
R
L ) -7f(JiA+JiR) -ln-+4'62
a
(8
4) - 7fJi A Ji n (128
(2
'A+'n 7f7f-4
R
)ln-+6.57
a
6)}

1
+ { _ 8(Ji_ + .)
_ - - uR
128 lA, - 27T dh
~\ }
A R (7f2-4) ('A+'n) dr r=J-Rja

The first bracket gives the force exerted on the body of fluid by the walls of the
lary, where the constants were determined by extrapolation procedures similar
Dussan V. 1 nterpretation of dynamic contad angles in wpillaries 557

tho se of Hocking. The second bracket expresses the surface and viscous forces exerted
._--- - -- - --- -- --, on the body by the excluded flui.d within the are R, evaluated from an expression
I
I
correct to O( 1). The final bracket glves the force exerted upon the ends of the body. The
aboye equation can be interpreted as a representation of the shape of the interface
within the intermediate region

_________ _______ J
- -
+ /kA/kR ( - 64 ln-R + 0880) .
(5.1)
/kA+/kR 7T(7T 2-4) a
ediate r egio!l is calculated by U''''''''''''''lJ l~'. This can be used to evaluate the boundary condition (dhoJdr) Ir~l-Rlla = O. This con
mclos()d by ---o dition determines D.Poa:

~: the pressure drop across a

lli1etric flow rate, and, assuming

While ba.lancing the forces exerted. on the aboye material body of fluid has provided
Lu id interface. These quantities
a converuent method for calculating the tangent to the interface shape in the intermed
lf conservlLtion of linear m()melllGU
iate region; in order to determine dhoJdr elsewhere, the normal stress balance at
,ints on eit her side of the fl
z = O must be integrated. The part due to fr is obtained by inverting numerically the
, with the solution for the
appropriate sine-transform; the part due to fu is calculated both by extrapolating
'more than two diameters from
the integra.ted normal stress eigenfunction series to z = 0, and by the direct evaluation
of the Green's function, formulation at z = 0, Fitting polynomials with the desired
:)6 5(- + - )_ 15.27 8 fi A fiR + asymptotic form to these two components, we have
/kA /kR /kA+/kR
. interface along the axis of the dk
~={fiA+fiR} -
~
{4 (r l n2Ra- --ln(1
7T
I 1 - r ) +(1-r )(-1'583r-0'475r
r
2) 2 3

96" is d ue to that part of the sol

,g a double integral numerically.
valua ted by extrapolating to z = O
llow at the point (O, O). These
(5.2)

1 pressure field in the vicinity of

ing the forces exerted on the body
- L Ala and z = LRJa, excluding
ltact line ; see figure 8. It is
region. The force balance to wi
'rhe maximum error in the expression multiplying fiA + fiR is 0002 based on evalua
tion at r = (0 '05,0'10, ... , 0,95); for the fiAfiR/CfiA +fiR) part, the maximum differ
anee from the Green's function results at the same points is 0012.
Of course, the pressure drop and local shape of the interface given aboye represent
only the lowest-order mode in Ca. The complete expressions must include the other
small parameter terms:

pA(r), -LA/a)-pR(r2' +LR/a)

_ - 27T dh
__ oa \ ~ 2(8 l - t 7T ) + Ca[P~a.(r, - LA/a) - p[ja.{rz, LR/a)], (5.3)
}
n) drr= I-Rla
dh dh c
-d ~ r('~7T - 8l ) + Ca _ a . (5.4)
r dr

ody of fluid by the walls of the

extrapolation procedures similar
558 F. Y. Ka/ka and E. B. Dussan V.

6. Dynamic contact angles O' IC

Besides the actual contact angle, t), fom other contact angles have been introduced:
ew> defined by (1.1); ej1-l' defined by (1.2); eH&M' the angleintroduced byHuh & Mason,
defined by the relationship cos eH&M == - a.Y, where.Y is the mean cnrvature of the
fl uid-fluid interface evaluated at its apex; and el' the angle of inclination of the fluid
fluid interface at a distance R I from the contact line (refer to 2). We are now in a o' ~
posi tion, in the light of the results of 5, to examine their dynamic behaviom and to
o' C
calculate their interdependence. ...
:E 0,0:
In a static system all of the abovementioned angles are the same: however, when the
contact line is in motion we find

(6.1) FWURI
PR = f
RIla, =
upon combining (1.1) and (5.3); contac1

of the
excepl
upon combining (1.2) and (5.4); and

This di
value (
appear
The
upon combining the above-stated definition of eH & M with (5.2). Fo!" completeness, we measUl
present a relationship between el e
and based upon a solution of the motion of the mediat
fiuids in the inner region in which a particular slip boundary condition is assumed: behavi
inner r,
ism USE
a.nd (6.
mine t
nature ,
Thal
followi
refer to appendix B for details. The angles in the above expressions are in radians, ancl
the trigonometric functions have been linearized about -lIT.
It is interesting to note that the dynamic behaviour of al! three apparent contacu
e e
angles w , 111 and ()H&M - is influenced to sorne extent by the geometry of the outer
region as evidenced by the appearance of the parameter a in the bracketed expressions
on the right-hand side of (6.1), (6.2) and (6.3). Consequ ently, these angles do not
menisc
represent materi al properties ofthe system. This is not surprising when one recogn..izes
rnenisc
that each ofthese angles is calcu lated from a quantity which depends on the dynamic daahed
of the fluids in the outer reg on: ()w is calculated from the pressure drop down the
e
capillary; Mis ca lculated from H ; and {1U&lIf is calculated from the mean curvature t 'I
the meniscus at its apex. The dependence on geometry becomes explicit when any one :j: 'I
v.
angles have been introduced:
introduced by Huh & Mason,
- is the mean cnrvature of the
glc of inclination of the fluid
'efer to 2). We are now in a
lr dynamic behaviour and to ~
,the same: however, when the
(6.1)
h (5.2). For completeness, we
solution of the motion of the
_d ary condition is assumed :
,xpressioris are in radians, a,nd
t 7T
of all three apparent contact
by the geometry of the outer
t], in th bracketed expressio ns
quently , these angles do not
urprising when one recogruz es
hich depends on the dynamics
he pressure drop down the
d from the mean curvature of
I comes xplici when any one
Interpretation of dynamic contact angles in capillaries 559
0-10 ~ (a)
~ rl~~~~~~~:~~~~==============::=:::::::::::::,:----,---,-_L
o-os
O 01 02 03
~:--
04 0 -5
- =:'-r: ~I
06 07 0-8 0-9 10
(b)
015
0-10
fr --------- _
~ 0-05 L-~----' __'______'___~_____'___'______~,
_
01 02 03 04 0-5 0-6 07 08 09 10
FIOURE 9. The solid curve in (a) and (b) s the solution for the meniscus when ,Un ~ IA, and
}1Jl == A, respectvely. In both casos it is assumed U(A+R)/Y = 002 and (jI = 90 at
R!a == 0001_ The dashed curve is a segrnent of a circle pa-ssing through the apex, h(O), and the
contllct line o
of these apparent contact angles is evaluated for two systems identica.l in every way
except that the radius of the capillaries is different, for example,
This difference is due entire.ly to the independence of the size of the inner region on the
value of a_ Note that no parameter which depends on the model of the inner regio n
8.-ppears in the aboye expression.
The entire effect of the fluid motion in the inner region on the experimentally
measurable quantities 8w ' 8,11 and eH&M t appears in the dynamic behaviour of the inter
mediate angle, 81 , Two factors contribute to 81 , as illustrated by (6.4): (i) the dynamic
behaviour of the actual contact angle, e, and (ii) the bending of the meniscus in the
inner regio n due to hydrodynamic forces. The latter directly depends on the mechan
ism used to remove the singularity at the contact lineo It is evident from (6.1), (6.2)
and (6.3) that measurements of the pressure drop and H can, atmost, be used to deter
. -e the dynamic behaviour of 81 : they cannot be used to deduce anything about the
natv,re of the fluids in the inner region or the dynamic behavt:our of e.
T.hat the various contact angles can take on different values is illustrated by the
fOllowing exa,mple. Consider a capillary of radius a = 005 cm through which fluids
are moving at a speed of U('lA + f-tR)/Y = 002 with an intermediate angle (JI = 90 at a
distan ce Rr = 05 x 10-6 m from the contact line (this choice ofparameters is consistent
with Hoffman's correlation). Two cases are calculated, that of f-tR = O and f-tA = f-tR'
The solid lines in figure 9 (a, b) represent the solution of the shape of the interface.
The dashed lines represent scgments of spheres which pass through the apex of the
meniscus and the contact lineo Even for this low value of the capillary number the
meniscus deviates somewhat from a spherical segmento The angle formed between the
dashed ine and the wall, (JM' is 98 (102), while that determined by the pressure drop
t To our knowledge, experimentally measured values of eH..,,!. have yet to be reported.
t These correspond to N = O and R == A, respectively.
560 F. Y. Kafka and E. B. Dussan V.

+ 0-0001
--~----

09990 09991 2 3 4 5
-- -._ -
6 7 - - - __

- 00001
FIGURE 10. The shape of the meruscus in figure 9( a) very close to the contact
line assuming LsJ. = 05 x 10- 6 cm.

down the capillary, ew ' is 96 (101).t Nevertheless, if a tangent to the interface is

drawn close to the contact line on figure 9, following the procedure of Rose & Reina
(1962), the angle measured with a protractor is approximately 94 (96). This is small r
than the apparent contact angles, but larger than the intermediate angle, er' For the
sake of demonstration, if we use the inner solution presented in appendix B
LSJ. = L~R = 5 X 10-9 m then the shape of the meniscusclose to the wal! is given
figure 10. The actual contact angle, given by (6.4), is 82 (76), wlUch differs quite
bit from the angle formed by the dashed lineo

7. Discussions and conclusions 'l'ABLE

An appropriate value for Rr has yet to be established. The only property which .
must have (refer to 2) 5s that it lie 'well within' the intermediate region, i.e .
region where both inner ana outer solutions are valido However, the size of tms T'ACn MI_' Tne ir
and the degree to which both solutions coincide depends on the value of LjLq,. If ih
assumed that fiow through a capillary with the inner region modelled as in a,uU<OUlJ
typifies fiow in any geometry with any model ofthe inner region, and that Li ,$ 10--11
and L", .G 10-5 m, then a good choice is Rl = 05 X 10-6 m. This is illustrated by
paring the values of the slope of the interface as predicted by the inner and ou
solutions for the example cited at the end of 6; refer to table 3. The two solu
differ by less than 0'5 for 5 x 10- 9 m < R < 5 x 10~ m (note that the minimum in
meniscus at R ~ 5 X 10-9 m (refer to figure 10) occ~rs in both solutions). It should
remembered that dynamic apparent contactangle measurements cannot be ~Q'~T'r ..... "

to better than 1 and 2" .

It can easily be seen how the displacement of immiscible fiuids through a
can be used as a device for obtaining basic modelling information that is necessary
solving boundary-value problems involving the moving contact lineo For a .
material system, two immiscible fluids and a solid, the dependence of H on the
of the contact line can be measured. This is sufficient, together with a detailed
mechanical analysis of the outer region, to calculate the dynamic behaviour of 0r
e
For the case in wmch H la ~ 1, r ( U) is obtained by substituting the experim
determined H(U) into the expression:

(}r~ 2H+~2+U{(4.+R)(~lnRr+2.10)+ 4.R (( ~4 )ln

Rr
+8'87)}.
a 'Y 7T a /,4. + R 1T 1T - 4 a
e
t It is interesting to note that Oro and M can ha.ve similar values even though they both
from e. Hence, Blake's repol'ted experimental agreement between these tWQ angles does not
tha.t he is measming the dyna.mic behaviour of the actual contact a.ngle.
:san V. lnterpretation of dynamic contad angles in capillaries 561

+ 00001 are tan

(_ d~;..,) t
~- - - -
90 + are tan -aretan

- 00001
RIL. r (a d;; 6T
t (
adhdR
illD",)

I(a) v ery close to the eontaet 002 09999998 8196 - 4 19

0-6em. 0 20 0999998 8249 - 149
10 099999 83 '72 -0'41
20 099998 84'50 - 019
1,if a tangent to the interface is 100 099990 8666 -0,02
g the procedure of Rose & 200 099980 8766 -0'01
1000 0999 90'00 -000
ximately 94 (96). This is smaller
2000 0998 9101 - 002
le intermediate angle, (JI' Fo!' 103 099 93'35 -010
n presented in appendix B with 20 x 103 098 94 36 -0'18
scusclose to the wall is given ' 10' 09 96'68 - 082
20 x 10' 08 9768 - 168
s 82 (76 ), which differs quite 40 x 104 - 505
0 6 9867
t Caleulated from (B 3).

:): Calculated froill (5 .4).

TABLE 3. The slopa of th e interface in the intermediate region for C. = 0,02, J.l R = O, a = 500 J.lill,

L, = 5 X 10-3 J.lm, R = 05 J.lm, (J = 90.

hedo The only propel'ty which

the intcr mediate region, .e.
l . H owever, the size of this
mds on the value of LJ Lrp. If it
, region modelled as in appendix
nnerregion , and thatLi;S 10-8
0- 6 m. Trus is illustrated by
)fedicted by the inner and
~fer to table 3. The two solu
-6 m (note that the minimumin
Lrs in Doth solutions). It should
~asurements cannot be
niscible fluids through a
~ i.nformation that is necessary
rroving contact lineo For a rrnrl~n.lil~
th dependence of H on the'
nt, together with a detailed
:} t he dynamic behaviour of el'
Iy substituting the
The implict dependenc of H( U) on a cancels the explicit dependence of the bracketed
expression on a. In order to predict the spreading of the same liquid on the same solid,
however, in a different geometry, for example a drop of liquid (!-lA) spreading over a
planar surface initially covered with fluid (!-lR), one need only solve for the dynamics of
e
e fluid in the outer region . The boundary condition that f3 = 1 ( U) at a distance RI
Iom the contact hne is sufficient for determining the shape of the meniscus in the
outerregion to O(Ca ); no ad hoc assumption need be made about the deformation ofthe
meniscus in the inner region (a case in point is Greenspan, 1978).
On the other hand, knowledge of the dynamic behaviour of el does not represent
lIufficient information for the physical chemist who is interested in identifying the
mechanism by which liquids spread on solids. Although it can be used to establish the
inadequacy of a given model of the inner region for a particular material system, it does
not contain sufficient information to identify either the dynamic behaviour of the
actual contact angle or the roechanism by which the singularity at the moving con
ct line is removed.
Until experimental techniques are discovered which can probe the inner region,
parameterizing the outer region in terms of the empirically measurable quantity el
a.ppears to be an adequate approach for fluid-mechanicians interested in analysing flow
fleids with moving contact hnes.

A!-lR ( 64 lnR1+8'87)}. The authors are grateful for the support received froro the N ational Science Founda
.+#R, 2
1T(1T - 4) a
tio n lmder grants ENG75-10297 and ENG77-10167.
ar va.l es even though thoy both

etw en these two angles does not

1 eontaet ang le.

FLM 95
562 F. Y. Kafka and E. B. DWJsan V.

Appendix A
An integral expression for 1/rn can be obta.ined by taking its sine-transformation
the z co-ordinate
1;n(r;s) == fo'" 1/rn(r,z) sin (sz) dz
and
1/rn(r, z) = - 2J"'-
7Ta
1/rn(r; s) sin (sz) ds

valid for < z < 00 and < r < 1. The transformed Stokes-Beltrami equation and
boundary conditions are.

. d 1 d s 2] 2-
[ dr -d---:-
1- 1/rn -_ s3.
1/rn(r,0)-2s 2(r<>:---"
8 1 81/rn) 8 1/rn
-sCi'"2 I 2
I
r 1 u1 r ur z=o uZ z= o
and
-
1/rn =
r dr
1 d1;n
0, - - - = at r = 1.

At the plane z = the boundary conditions are

1821/rn
1/rn = 0, - Ci'"2 = T(r).
r uZ
It fo11ows directly that

1;n = - ~ {J: G(p, r; s) pT(p)dp + fl G(r,p; S)pT(p) dP}

where
G(p, r; s) = {11(ps) [210(s) + sI1(s)J [r11(s) Ko(rs) -11(rs) Ko(s)J
+ pI2(ps) [210(s) + sIl(s)] [11(rs) K 1 (s) -11 (s) K l(rs)J
+psI2(ps) 10(s) [1o(s) K 1(rs) -do(rs) K 1(s)]
+ sIl (ps) 10(s) [r10(rs) Ko(s) - r10(s) Ko(rs)]
+ [ps10 (ps) Ko(s) - sI1(ps) Kl(S)J [1o(s) 11(rs) - do(rs) 11(s)]}
x {210 (s) 11 (s) - sI0(s)2 + sI1(s)2}-1.
The modified Bessel functions Ka and K 1 used in the above expression are discussed
Abramowitz & Stegun (1964).

Appendix B
We sha11, for illustrative purposes, calculate the inner solution assuming that

axial velocity (from the moving reference frame) is given by

wK = - Izl at r = 1 for K = A, R,
Izl + LSK /a
where the parameters LM and L S R are slip lengths in the advancing and receding 1.1LU~-'A'"
respectively . This model was used by Dussan V. (1976) for a single liquid oGiven sucl\
model with its associated inner length scale Ls (L s, == maxL SK in this case),
m n K=A,R
appropriate inner problem can be generated by rescaling the independent variables
n V. lnterpretation of dynamic contact angle.s in capillaries 563
]l reduced to Stokes ftow in two dimensions, provided that LSm/ a is very small
& Mason 1977).
~;It;:l(p,,,,,l'.U"
as before in small parameters and using the polar co-ordinate system
ced in figure 2, the two-dimensional form of the inner interface shape is
z.) dz

'ill1Irn6l,t> h'1J: ee is determined by the zero-order inner veloeity field satisfying

sz) ds
1 () () 1 (}2] 2
[ R (}R R (}R+ R2 (}(p <pE = O;
" tok s- Beltrami equation
(}<P E _ (-l)E (R/a)2 _ K .
<p K = 0, ---a;- R/a+LsK/a on 4>-~(-1) rr,
ru)\
Or
_s (}2rn \,,- o
[~:]=O, [!l~:;]=0
2= 0 (}Z2
4>E = 0, and on 4>=0
. = 1.
dh inner
~
dR =. at R=O,

where ( - 1)..4 == - 1 and ( - 1) R == + 1.

.A 80lu tion for <p K is obtained in a straightforward manner using the Mellin transfor
JD.aMon. "VVe find the transformed steam function

<I>K
_ _ rr
= -2 ~
(L
)S+l cosecrrs
1
. .
[SIn (sl4>l) + SIn (s + 2)14>IJ
r,p;s)PT(P)dP} a cos~s

4( 1'(s) [{(s+1)tan!rrs+(s+2)coqrrs}sin(sl4>I)-cos(sl4>l)
rs) K o(s)J
s+l),uK

-11 (s) K 1 (rs)]

+ {(s + 1) tan ~srr + s cot tsrr} sin (s + 2) 14> 1+ cos (s + 2) 14>1 J,
where 1', which represents the transformed tangential stress on 4> = 0, is given exactly
1(s)]

by
>'s)]
1'(s) = !lA !lR [2rr(S + 1)2 ([L SA / a JS+1 + [L SR / a JS+l) cosec (rrs) sec trrs] .

11 (rs) - r Jo(rs) 11 (s)J) !lA +!lR (s + 1)2 tan }srr + s(s + 2) coqsrr

1'ob tain 4> E the inverse transform is used:

4> K =
1.
-2
rr~
f CTo +ioo
CTo-too
d) (s; 4 (!!.)
a
-8 ds for -2 < 0"0 < -1.

The radius of curvature of the interface within the inner region is equal to the sum
ofthe pressure and normal viscous stress differences a cross 4>= O. This is integrated
exactly to give
n r solution assuming that

ren by
dhinner
a d~
R
= -O; [pcJ-a 2
foR/a[!l {( R (}RR(}R+
() 1 () 2 ) (}<1> 1 (}3<P}]
R2 (}4> + R2(}4>3 dR/a, (B 1)

: K = ,R, where h, as before, represents the z location of the interface, though now as a function
of R/a, on 4> = O.
l advancing and receding fiuids, nee Our objective is to derive a relationship between e( U) and el' aH we need eval
for a single liquid. Given such. uate is dh~aDer /dR in the limit as R/ Ls-'r 00 because
== max L SK in this case), the inner
m K =A. R
el-~rr=addh
R I ~e(U)-!,Tr+Oaa dhdCRa I , (B 2)
ing th independent variables ~ R/a=RI/a R/a=Rr/a
564 F. Y. Kajka and E. B. Dussan V.
where Rr lies somewhere witmn the intermediate region. T. D.
1lr,i\KE.
Restating equation (B 1) in terros of the solution for <D K gives England.
!3~ , T.D.
dh mner R 3, 421.
a d~ = --;, [pcJlnner+/i.l.g (RjLSd) +/iRg(RjLsR ) pVSSAN V., E
1 665.
+-2 /i.l./iR {f(RjLsA)+j(RjLsRl} pVSSAL'< V., E
.l. +R linao A.I.'
where
pVSSAN V., E

J
ITO+iOO
g(x) == +i . [cosec(7Ts)sec~7Ts]x-(S+l)ds; lines. Am
0"0-1..00 pvasAN V., E
and surfaca. J
'fUO+iOO x-<s+l)(s + 1)2 cosec (7TS) sec 17TS ~,r.rOTT, G. E
j (x) = - 4~ 2 ds
- O'o-ioo (s+1)2+s(s+2)cot2t7Ts motion. J
for - 2 < (Jo < - 1.
GltEENSPAN,1
The function g has been evaluated in closed forro by Dussan V. (1976):
Mech. 84,
R. J
4
g(RjLs)~;lnLs+O R2lnLs
R (L; R)
i1WsEN,
another fl
If!NSEN, R. J
hydrodyn
Upon numerical evaluation of the functionj we found that !lClCKlNG, L. 1\
!lOCKING, L. 1\
64
j(RjLs) ~ 7T(7T2_ 4) ln Ls + O R2 ln Ls
R (L; R)
a slip ftov
KOFFMAN , R .

It is al so possible to show that .r. Colloid

HUR, C. & lVI
R mner 4 _ _ 64 /i.l./iR (L; R) .r. Fl-uid "
-;, [PcJ ~ - ; (.l. + R) - 7T(7T2 _ 4) (.l. + R) + O R2 ln Ls as HUR, C. & Se.
fluid cont
Upon substituting the aboye expressions into equation (B2) we get JANG, T. S.,
Colloid Ir.
81 ~ / i R . In -L SR +ln-
8 (U) + Oa { -4 (/i.l. +/iR) (1- R[) ROSE, W. &
7T A+R L Sl! L SA Col[oid Ir

/iA/iR 64
+ A + R 7T(7T 2- 4)
(1 + 1n (L RrL )}
SruTH, R. C.l
W.. GNER, M.]
Sd sR )! .
flow. J. ,
F~r the case of /iR == 0, the slope, dh~~ner jdR, has been sol ved exactly (Dussan VI
1 ~ 76) giving
Roy. SOCo
\ dh8 U 7T O {4RjL siJ. 4(RjLsA )3
YARNOLD, G.
adR~ ( )-2+ a 1 + (RjL sA )2-([1 + (Rj L SA)2]2
London 51
Yoo, J. Y. &,
12(RjL SA )2ln (RJLSA) + 4(RjL SA)2 8(RjL sA )41 n (Rj Ls) .r. Appl.
+ 7T[1 + (RjL Sd )2] - 7T[1+(RjLsA)2J2 .
VVe make use of the aboye expressions in 6 and 7.

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B~E , T. D. 1968 Ph.D. th es is, Department of Physical Chemistry, University of Bristol,
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~)
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; non. ewtonian behaviour in viscou!
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