Colloids and Surfaces A: Physicochem. Eng.

Aspects 250 (2004) 367384

Hydrodynamic effects on the oscillations of supported bubbles:

implications for accurate measurements of surface properties
Ying-Chih Liao, Osman A. Basaran, Elias I. Franses
School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, IN 47907-2100, USA

Received 21 January 2004; accepted 6 April 2004

Available online 26 October 2004

Abstract
Oscillating bubble techniques are commonly used to infer dynamic surface tensions (DST) from the measurements of the dynamic pressure
differences across an interface. In inferring DST from such measurements, it is assumed that hydrodynamic efects either are negligible or can
be approximated. In virtually all previous studies, the dynamic bubble shapes, which are set by the requisite balance of forces at the bubble
surface, are taken to be nearly spherical and assumed to be governed by the static YoungLaplace (YL) equation alone. To examine these
assumptions, the NavierStokes and continuity equations governing the flow of a liquid outside an axisymmetric bubble supported by a narrow
capillary are solved simultaneously by a rigorous finite element method. Cases of constant surface tension (pure liquids or solutions with very
fast adsorption) are tested to focus on understanding the effects of fluid motion on surface tension measurements. To test the capability of
the computational algorithm on describing the hydrodynamics, computed and experimental velocity profiles are compared and found to be
consistent, as are the apparent surface tensions. Parameters such as forcing frequency, forcing amplitude, chamber dimensions, and surface
tension and viscosity of the liquid are varied to find the limits where pulsating bubbles depart from spherical and where hydrodynamic
effects impact the determination of surface tension. In the commercial pulsating bubble surfactometer (PBS), the bubble shapes remain nearly
spherical for low pulsation or oscillation rates (100 Hz) with moderate volume amplitudes. Under these conditions, however, two major
hydrodynamic effects, due to the inertia of the bulk liquid, or to the liquid viscosity and the viscous forces acting on the chamber walls, are
found to be important and can cause large errors in the surface tension measurements. For measurements of low surface tensions (5 mN/m)
in a PBS, oscillating bubble methods that do not take into account shape deformations from the spherical are found to be inaccurate, and the
results from dynamic bubble shape analysis (solving the YL equation for a nonspherical axisymmetric surface) are shown to provide another
approach to obtain accurate results provided that hydrodynamic effects can be neglected. At higher frequencies (200 Hz), because of strong
convection around the surface of the bubble, the bubble shapes become highly deformed. Further extensions of this algorithm are needed, to
include the surfactant diffusion and adsorption effects by which the surface tension may change with time.
2004 Elsevier B.V. All rights reserved.

Keywords: Supported bubble; Hydrodynamics; Surface tension measurements; Oscillating bubble method for tensiometry ; Finite element method; Free surface
flow; YoungLaplace (YL) equation; Pulsating bubble surfactometer (PBS)

1. Introduction port can be studied by measurements of DST. DSTs un-

The dynamic surface tension (DST) is important in many
applications involving lung surfactants [118], drop and jet
breakup [1924], foams [25,26], and coatings [27,28]. The
adsorbed surface density of surfactant and the DST at an
interface are related to each other [7]. Thus, interfacial trans-
Corresponding author. Tel.: +1 765 494 4078; fax: +1 765 494 0805.
E-mail address: franses@ecn.purdue.edu (E.I. Franses).
der constant area conditions can be measured with various
methods [29]. Some of these methods, such as those in-
volving drops or bubbles, can be also used under pulsat-
ing area conditions. Then, DSTs and dynamic surface rheo-
logical properties can be inferred [30] from measuring dy-
namic shapes or dynamic pressure differences under area
pulsation.
One of the most important and popular techniques for mea-
suring DST is the oscillating bubble method [218,29]. A
commonly used and commercially available instrument that

0927-7757/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.04.101
368 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384
uses this method is the so-called pulsating bubble surfactome-
ter, or PBS, which can be used under constant or pulsating
area conditions. When DST is measured with a PBS, it is
normally assumed that fluid mechanical effects can be either
totally neglected [2] or estimated from simplified conditions
[3,8]. A major reason that hydrodynamic effects have not rig-
orously been assessed to date in making such measurements
is because doing so would require the numerical solution of a
complicated free surface flow [31]. Such a rigorous approach
would entail the simultaneous determination of the a priori
unknown transient profile of the bubble and the flow field
in the irregularly shaped and continuously changing domain
outside the bubble. Recently, however, the closely related
problem of oscillations of pendant drops has been solved with
the finite element method (FEM) [3235]. In these studies,
the FEM used is based on a technique of domain discretiza-
tion known as the method of spines [36]. This method has
been shown to be highly accurate [31] but can be cumber-
some to use [35]. More recently, Notz et al. [37] and Chen
et al. [38] have shown that such problems can be analyzed
with equal accuracy using an FEM algorithm in which the
domain discretization is more conveniently achieved with el-
liptic mesh generation [39]. Therefore, the goal of this paper
is to analyze rigorously for the first time the fluid mechani-
cal effects in a PBS by using techniques which are similar to
those described in [35] and improved upon in [37,38].
The schematic for a commercially available PBS is shown
in Fig. 1 [2]. A small amount (about 30 l) of a liquid solu-
tion or suspension is placed in the sample chamber (Fig. 2),
which has a square cross section of 1.76 mm 1.76 mm and
a length of 1 cm. A small capillary, with an inner diameter
of 0.58 mm, just protrudes into the chamber from its top, as
shown in Fig. 2. The capillary is open to the atmosphere at
its other end. The sample chamber sits on a gasket, which
has a movable metal rod in the center. A bubble is gener-
ated by moving the rod downward and remains continuously
attached to, or supported by, the capillary. Normally, the
bubble radius is forced to oscillate between 0.4 and 0.55 mm
by moving the bottom rod sinusoidally in time at a constant
frequency , which can vary from 1 to 100 rpm (0.017 to
1.7 Hz). The bubble area also oscillates nearly sinusoidally.
The bubble radius is normally obtained by pre-calibration,
with the bubble assumed to be spherical. During pulsation of
Fig. 1. Schematic of a pulsating bubble surfactometer. For a detailed photograph and schematic of the sample chamber, see Fig. 2.
the bubble, its instantaneous dimensions and shapes can also
be directly imaged by a camera for surface tension determi-
nation by axisymmetric drop shape analysis (or ADSA) [40],
if the bubble is sufficiently deformed by gravity, as it may
occur for low surface tensions [13,17].
The DST is obtained by measuring the pressure jump at
the interface. A pressure transducer is used for measuring
the pressure close to the bottom of the chamber, pL (Fig. 1),
with reference to the atmospheric pressure p0 (Fig. 1). If one
assumes that hydrodynamic effects are negligible, or uses the
quasistatic assumption, then the pressure jump across the
gas/liquid interface follows from hydrostatics:
p = ptip p0 = pL gh p0 , (1)
where ptip is the dynamic pressure of the liquid at the
gas/liquid interface, is the density of the liquid, g is the
gravitational acceleration constant, and h is the vertical dis-
tance between the bubble tip and the pressure sensor. If the
bubble is spherical and the quasistatic assumption holds, the
DST can be obtained from the pressure jump at the interface
and the radius using the YoungLaplace (YL) equation:
ri (t)p(t)
(t) = , (2)
2
where ri (t) is the bubble radius at time t.
For practical surface tension measurements [2] in the fre-
quency range of 1 to 100 rpm, Eq. (2), which is based on the
quasistatic and perfect sphere assumptions, is fairly accurate
[8,10]. Since the bubble is small compared to the capillary
length (2.7 mm for water), the bubble usually remains spher-
ical for 20 mN/m (Fig. 3(a)). Under certain conditions
of DSTs, however, the bubble can be deformed by gravity,
as shown in Fig. 3(b) [3,4,13,17]. Then, the assumption of
a spherical shape is clearly invalid. Moreover, the deforma-
tion of the bubble can also be a result from normal viscous
stresses, Marangoni stresses, or possibly surface rheological
effects.
The problem of a pulsating spherical bubble in contact
with an infinite amount of liquid, i.e. with no wall effects,
has been addressed by several authors, either with no
hydrodynamic effects [2], or with hydrodynamic effects ap-
proximated [6,41,42]. If these effects are important, then the
dynamic pressure in the liquid at the gas/liquid interface, ptip ,
 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384
Fig. 2. (a) Photograph and (b) schematic showing cross-sectional view and dimensions of the PBS chamber.
Fig. 3. Pictures of: (a) a spherical bubble ( = 50 mN/m from pressure jump
method) and (b) a deformed bubble ( 2 mN/m from shape analysis) in
dipalmitoylphospatidylcholine (DPPC) dispersions at 1 Hz. These results
have been obtained using systems and experiments that are similar to those
previously published [17].
369
is given by the following approximate equation [8,41,43],
which is valid for radial flow in an infinite amount of liquid
(no wall effects),
2(t) 4 4s
ptip = p0 r i 2 r i , (3)
ri (t) ri ri
where is the bulk viscosity of the liquid, r i dri /dt, and s
is the surface dilatational viscosity. The second term of Eq. (3)
is the pressure jump due to the surface tension as indicated
by the static YL equation. The third term is the normal vis-
cous stress exerted by the bulk liquid. The last term results
from the surface dilatational viscosity s , the precise mean-
ing and magnitude of which remain controversial [44,45]. It
is generally presumed that for pure liquids, s = 0.
If the wall effects are neglected, the liquid pressure pL
far from a bubble undergoing sphero-symmetric oscillations
can be obtained by integrating the r-component (in spherical
coordinates) of the NavierStokes equation as [8,41]


2
pL = ptip ri r i + 23 r i + gh, (4)
where r i d2 ri /dt 2 . The second term of Eq. (4) is due to the
inertia of the liquid. The last term is due to the gravitational
force. Combining Eqs. (1)(4), the apparent dynamic surface
tension exp as estimated from the experiment is
 
2 3 2 2s
exp = (t) + 2r i +
ri ri + ri r i +
r i . (5)
2 2 ri
Hence, the measured dynamic surface tension exp is dif-
ferent from the actual value (t) due to viscous forces, the
inertia of the liquid, and possibly the surface dilatational vis-
cosity. From comparing the order of magnitudes, Chang and
Franses [8] concluded that only the surface dilatational vis-
cosity could be generally important, but that it has a minor
effect for the standard PBS operation at frequencies lower
370 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384
than 100 rpm. Although with Eq. (5) one can obtain a rough
estimate for the DST measurement error, one neglects the
wall effects and assumes that the velocity only varies radially.
In actual measurements, the bubble oscillates in a confined
liquid, and the wall effect can lead to significant flow circu-
lation and viscous stresses. To analyze these effects, a more
rigorous model is needed.
To understand the causes of bubble deformation and eval-
uate the reliability of DST measurements under these cir-
cumstances, a three-dimensional but axisymmetric computa-
tional algorithm is developed to elucidate the fluid dynamics
in the liquid outside the bubble. In the computations, the
sample chamber is simulated as a long cylinder (with a circu-
lar rather than a square cross section used in typical sample
chambers) within which the bottom rod is driven to oscillate
sinusoidally in time. The bubble is in contact with an incom-
pressible Newtonian liquid and is open to the atmosphere as
shown in Fig. 1. In this article, the bubble will be taken to
oscillate in pure liquids of various surface tensions, to focus
on developing an understanding of the effects on DST mea-
surements of the forcing frequency, forcing amplitude, and
the presence of having a solid wall at a finite distance from
the bubble. Algorithms have also been developed to analyze
situations where DST varies with the presence of insoluble
or soluble surfactants [46]. A discussion of surfactant and
variable DST effects is set aside in this paper, to focus on the
effects of liquid motion on the measurements in the complex
geometry of a PBS instrument. Conditions for low surface
tension fluids are presented and discussed, in order to eval-
uate the effect of bubble deformation on the measurements
without added complications due to dynamic adsorption or
surface convection and diffusion of surfactants.
The paper is organized as follows. First, experimental de-
tails are presented in Section 2. The computational algorithm
for solving the set of two-dimensional evolution equations
is presented in Section 3. The code based on the algorithm
is tested and validated in Section 4. To show the reliabil-
ity of the computations, the predicted velocity profiles and
the pressure jumps across the air/water interface, and the ap-
parent surface tensions from computations are compared to
those from measurements in Section 5. Then, the effects of
the forcing frequency, the forcing amplitude, the chamber
dimensions, and the viscosity and surface tension of the liq-
uid are examined with detailed simulations. In Section 6, the
conclusions are presented.
2. Materials and experimental methods
The water used for all samples was first distilled and then
passed through a Millipore four-stage cartridge system, re-
sulting in a water resistivity of 18 M cm at the exit port.
Dispersions of 2.5 wt% polystyrene particles of 6 m diame-
ter were purchased from PolySciences Inc., Warrington, PA.
The particles dispersion was diluted with water to 0.06 wt%
before it was used. The equilibrium surface tension of the
dilute dispersion, measured by the PBS under constant area
conditions, was 70 mN/m.
The pulsating bubble surfactometer (PBS), purchased
from Electronetics Company (Amherst, NY), was used for
surface tension measurements. The measurement procedures
have been described in Section 1. The bubble shape was moni-
tored continuously by using a CCD camera (Model MN401X,
from ELMO Corp., Plainview, NY) and the images were dig-
itized with a frame grabber (Model ALL-IN-WONDER 128
PRO, from ATI Technologies Inc., Marlborough, MA).
The velocity fields around a pulsating bubble in water were
obtained by particle image velocimetry (PIV) [47], with the
polystyrene particles used as tracers. The images of the dis-
persed particles and the bubble were recorded by the CCD
camera every 1/30 s during the bubble pulsation. The veloc-
ity profiles at different times were obtained by tracking the
particles displacements between pairs of consecutive images
using a correlation method as described by Gui and cowork-
ers [4850].
3. Mathematical formulation and solution method
3.1. Problem statement
The liquid surrounding the bubble is incompressible and
Newtonian with constant density , viscosity , and surface
tension 0 . Since the bubble is open to the atmosphere through
a capillary tube with a radius R = 0.29 mm and the viscos-
ity of air is quite small [8], the pressure in the gas phase
is assumed to be uniform and constant (equal to p0 ) during
the pulsation. To avoid the further complication of a three-
dimensional problem with the actual square cross section of
the container, the sample chamber is taken to be a circu-
lar cylinder. Moreover, both the bubble shapes and the flow
around the bubble are assumed to be axisymmetric. Thus, it
is convenient to adopt a cylindrical coordinate system with
its origin located along the centerline of the chamber (cf.
Fig. 4(a)). The governing equations and boundary condi-
tions in the following section have been normalized by using
as reference the tube radius R and the capillary time scale

tc R3 /0 . The dimensionless time, spatial coordinates,
velocity and pressure, are
t r z vtc p p0
t , r , z , v , p ,
tc R R R /tc
(6)
where r and z are the radial and axial coordinates, respec-
tively, v is the velocity, and p is the liquid pressure. In Eq. (6)
and what follows, variables without tildes over them are the
dimensionless counterparts of those with tildes.
The dimensionless continuity equation and equation of
motion for an incompressible Newtonian liquid in a chamber,
the walls of which remain stationary, are
v = 0, (7)
 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384 371

Fig. 4. Schematics for the computational domain (left) and mesh (right) used for the FEM computations.

v where vrod is the velocity of the rod. The rod performs time
+ v v = Oh T Gez ,
t periodic oscillations in the axial direction, so that the bubble
volume varies from the initial value V0 to a maximum value
T pI + [v + (v)T ]. (8)
Vmax . The instantaneous position of the rod, with respect to

In Eqs. (7), and (8), the Ohnesorge number Oh / R0 the fixed origin, is
is a measure of the relative importance of the viscous forces V0
to the inertial forces, i.e., it is the reciprocal of the Reynolds zrod (t) = [cos(2t) 1], (12)
2W 2
number. The Bond number G gR2 /0 measures the im-
portance of the gravitational forces relative to the surface where (Vmax V0 )/V0 is the volume pulsation ampli-
tension forces, and ez is a unit vector in the z-direction par- tude, tc is the dimensionless frequency, and W is the
allel to gravity. T is the stress tensor and it too is measured dimensionless chamber radius (Fig. 4). The velocity of the
in units of /tc . rod is
Initially, the bubble has a volume V0 and is at equilibrium V0
vrod = 2 sin(2t)ez . (13)
with a stagnant liquid, i.e., W
Along the moving and deforming liquid/gas interface or the
v=0 at t = 0. (9)
bubble surface S(t), the kinematic and traction boundary con-
The initial bubble shape can be determined from the static ditions are applied:
YL equation along with a volume constraint [51], and the
n v = n vs , (14)
pressure in the liquid is determined by hydrostatics.
Because of axial symmetry, the following boundary con- Oh n T = (s n)n, (15)
ditions are used along the centerline of the chamber:
where n is the unit normal to S(t) pointing into the bubble, vs
er T ez = 0 and v er = 0 at r = 0, (10) is the velocity of points on the interface, and s (I nn)
is the surface gradient operator [52]. At the gas/liquid/solid
where er is the unit vector in the radial direction. On the solid contact line LS , the bubble is assumed to be pinned (i.e.
wall boundary, liquid neither penetrates nor slips on SW . This not moving) at the tip of the capillary,
adherence condition requires that
 r=1 at LS . (16)
vrod , at the rod,
v = vwall = (11) The model described above is complete and involves no
0, elsewhere on SW ,
other simplifying assumptions or approximations. The evolu-
372 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384

tion in time of the bubble shapes, and the velocity and pres- S(t):
sure fields in the surrounding liquid are governed by nine 
dimensionless groups. Two key dimensionless groups, Oh i (v vs ) n dA = 0. (21)
and G, provide measures of the importance of the viscosity S(t)
and gravity. The chamber dimensions are specified by the
dimensionless chamber radius W and the height H. The con- 3.3. Mesh generation and time integration
nection between the capillary and the sample chamber is a
circular ring and is described by two parameters W1 and H1 An elliptic mesh generation technique [39] is appropri-
(Figs. 2(b) and 4(a)), which are not varied in the following ately combined with an algebraic mesh generation technique
calculations. In the bubble pulsation, the initial bubble size to generate the computational grid and account for the pres-
V0 , the forcing frequency , and the forcing amplitude af- ence of the moving boundaries. As shown in Fig. 4(b), the
fect substantially the dynamic shapes and the liquid pressure computational domain is divided into seven regions. Regions
distribution. 1 and 2, which are far from the free boundary S(t), are tessel-
lated (divided into elements) using algebraic mesh generation
3.2. FEM analysis [31,32,34,55]. In these two regions, the element size in the
r-direction is held fixed, and that in the z-direction is varied
The governing equations are solved numerically by a with time in proportion to the distance between the instanta-
method of lines using the Galerkin finite element method neous location of the rod and a fixed axial coordinate, which
[53] for spatial discretization and an adaptive finite difference divides the domain into one part where the algebraic mesh
method for the time integration [54]. Under mixed interpola- is used and another part where the elliptic mesh is used (cf.
tion, the Galerkin weighted residuals of the continuity Eq. (7) Eq. (11)). Regions 37 are tessellated using elliptic mesh gen-
and momentum Eq. (8) are eration [3739]. Since the problem is solved at moving mesh
 locations, the time derivative v/t in Eq. (18) is evaluated
Ri,C = i v dV = 0, i = 1, . . . , M, (17) by accounting for the movement of the mesh:
V (t)
v
= v x v (22)
 t
Ri,r where v denotes the time derivative at a mesh point and x is
Ri,M =
Ri,z the velocity of this mesh point.

 The Galerkin weighted residuals (1721) and the mesh
v
= i ek + v v Oh T + Gez dV generation equations result in a large set of nonlinear
V (t) t differential-algebraic equations in time. The time derivatives
= 0, i = 1, . . . , N, (18) are discretized with either the backward difference method
or the trapezoidal rule over a time interval tp = tp tp1 .
where ek is either er or ez and Ri,r and Ri,z denote the r- The final system of nonlinear algebraic equations is solved by
momentum and z-momentum residuals. Here, M is the num- Newtons method. Integrals that arise in the residuals and the
ber of bilinear basis functions i used in representing the Jacobian matrix are evaluated by Gaussian quadrature [53].
pressure Initially, four backward difference time steps with a fixed
M time step size t = 102 are used to provide the necessary

p(r, z; t) = pi (t)i (r, z), (19) smoothing upon setting the rod into motion from rest [56]. In
i=1
the subsequent steps, a second-order AdamsBashforth pre-
dictor is used with the trapezoidal rule to evaluate the relative
where pi is the nodal values of the pressure, and N is the time truncation errors and determine time step sizes adap-
number of biquadratic finite element basis functions i used tively. A relative error of 0.1% per time step is prescribed in
in representing the velocity the computations [54]. The maximum time step size tmax

 N
is set to be Tc /20, where Tc 1/. Furthermore, following
vr (r, z; t) 
v(r, z; t) = = vi (t)i (r, z) Chen and Tsamopoulos [57] and Wilkes and Basaran [33],
vz (r, z; t) whenever the rod reverses its direction, two backward differ-
i=1

 ence steps with fixed t = 102 are taken before reverting
N
 vr,i (t) to the use of the trapezoidal rule.
= i (r, z), (20)
vz,i (t)
i=1
4. Code validation
where vr,i and vz,i are the nodal values of the radial velocity vr
and axial velocity vz , and vi are the nodal values of the veloc- The code implementing the FEM analysis has been writ-
ity. Galerkin weighted residuals of the kinematic boundary ten in FORTRAN. The calculations have been carried out on
condition Eq. (14) are used to determine the bubble shape a LINUX cluster with PIII 550 MHz processors at Purdue
 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384
University. The code has been validated in many aspects, in-
cluding strict mesh refinement tests in which the number of
elements is systematically increased. Thus, the solutions re-
ported in this paper are insensitive to the further increase in
the number of elements used. In the calculations, the volume
of the liquid is monitored and always found to be conserved
within 0.01%. Moreover, the correctness of the code for solv-
ing the NavierStokes equations with a moving interface has
been verified by analyzing the oscillations of a free bubble in a
slightly viscous liquid [58,59]. As shown in the Appendix A,
the calculated oscillation periods for small-amplitude oscilla-
tions agree to within an error of 103 with the analytically ob-
tained periods of oscillation of bubbles in an inviscid liquid.
More than 200 sample computations for pulsating bubbles
were carried out to evaluate the effects of each dimensionless
group on the surface tension measurements. For each com-
putation, the code solves simultaneously more than 20,000
nonlinear algebraic equations during each of the 24 Newton
iterations required at each time step. It takes about 20 h of
CPU time to simulate ten cycles of bubble oscillations.
5. Results and discussion
5.1. Experimental results and tting to the model
The computed and measured flow fields when a bubble is
pulsating in pure water at 1 Hz are compared in Fig. 5. In the
Fig. 5. (a) Measured and (b) computed velocity fields for a pulsating bubble in pure water at 1 Hz at time (1) t = 0.15 s after the start of the pulsation, bubble
expanding, and (2) t = 0.75 s, bubble shrinking. In this and similar figures, each velocity vector shown indicates the velocity at its base point.
373
experiments, while the bubble is growing, the velocity has a
maximum in the vicinity of the bubbles tip. Moreover, the
liquid velocity is nearly zero near the top corner of the cham-
ber. While the bubble is shrinking, the maximum velocity
also occurs at the bubbles tip, and there is little liquid motion
near the top corner of the chamber. The computed velocity
fields show similar qualitative patterns and agree well with
the experimental data within 5% or better. Since the predicted
velocity fields are accurate, the pressure fields obtained from
the same computations should be reliable, as incompressibil-
ity is satisfied well in the calculations (cf. Section 4).
The computed bubble shapes and pressure contours for the
conditions of the commercial instrument are shown in Fig. 6,
where the standard parameters are used: V0 = 10.28, =
1.74, H = 34.5 and W = 3.03. For a bubble of the given size
in pure water, the Bond number G and the Ohnesorge number
Oh are small, 0.011 and 0.0069, respectively, indicating neg-
ligible gravitational forces and viscous forces in the liquid
(except near the solid/liquid boundary and the gas/liquid in-
terface). Thus, the bubble shapes should remain nearly spher-
ical under these conditions. One measure of the bubble shape
is the shape factor
ra
fs , (23)
ri
where ra is the maximum radial position of the liquid/gas
interface (Fig. 6) and ri is the volume-average radius of
374 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384

Fig. 6. A pulsating bubble surrounded by water at 1 Hz in a standard PBS

chamber: (a) computed shapes at different times, as indicated, during one Fig. 7. Computed shapes for pulsating bubbles surrounded by water in a
period of oscillation; (b) selected pressure contours when t = 0.25; 100 standard PBS chamber at different times, as indicated, during one period of
dimensionless pressure units corresponds to 1.75 cm H2 O or 1.29 mm Hg. oscillation at a forcing frequency of: (a) 100 Hz, (b) 200 Hz, (c) 500 Hz, (d)
1000 Hz.
direction, and the pressure gradient dp/dz is constant at any
the pulsating bubble. When the bubble is spherical, fs = 1.
time instant (Fig. 6(b)). When the bubble pulsates at 1 Hz, the
When fs > 1 or fs < 1, the bubble is an oblate or a prolate
velocity profile in the central part of the chamber is parabolic
spheroid, respectively. The maximum and minimum values
(Fig. 8(a)). When > 1 Hz, the velocity profiles become ra-
of fs for a pulsating bubble surrounded by water in a stan-
dially more uniform and close to that of plug flow with a
dard PBS chamber at various frequencies are listed in Table 1.
thin boundary layer near the wall (Fig. 8(c)). This behavior
For 100 Hz, |fs 1| < 0.04, indicating that the bubble
indicates that inertial effects become more pronounced as the
shapes are close to spherical. Thus, at these conditions, the
forcing frequency increases, because as increases the time
assumption of a spherical bubble surface for the standard
scale for vorticity diffusion from the side wall of the cham-
PBS measurement is fair. For > 100 Hz, the bubbles can
ber becomes long compared to the period of oscillation of the
be deformed substantially (Fig. 7). For = 1000 Hz, in the
rod. The apparent surface tension is determined in the calcu-
first cycle when the rod reverses its direction (t = 0.5), the
lations similarly as in the measurements. First, the pressure
fast fluid motion near the centerline causes a dimple at the tip
sensor is assumed to be located in the center of the bottom
of the bubble, and the dimple gradually forms an overturn.
rod. After correcting for the hydrostatic pressure, the dimen-
When the second cycle begins, the rod changes its direction
again. The fluid around the bubble moves downward, except
Table 1
for the overturned portion. This flow pattern can eventually Shape factors for a pulsating bubble surrounded by water (Oh = 0.007,
lead to a satellite drop formation (not shown here). G = 0.011) in a standard PBS chamber
At low frequencies, 100 Hz, since the standard cham- (Hz) fs,max fs,min
ber is a long slender cylinder, far from both ends the flow is
1 1.003 1.000
unidirectional and the radial velocity is zero, except during 10 1.003 1.000
the short periods of time when the rod reverses direction (see 20 1.003 1.000
Section 5.5); an example is given in Fig. 8. The flow profile 50 1.007 1.000
in the central part of the chamber is quite similar to Poiseuille 100 1.037 0.969
flow in a circular tube: the pressure varies only along the z- 200 1.709 0.873
 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384 375

Fig. 8. Velocity fields in the central part of a standard PBS chamber for t = 0.25 at different forcing frequencies : (a) 1 Hz, (b) 10 Hz, and (c) 100 Hz. The
flow is essentially unidirectional. With increasing frequency, the axial velocity distribution becomes more radially uniform with a thin boundary layer near the
wall.

sionless calculated pressure jump across the interface, if the

hydrodynamic effects are neglected, is (cf. Eq. (1))

G
p(t) = prod + (zrod ztip ), (24)
Oh

where ztip is the axial position of the bubbles tip. From the
YL equation for a spherical interface, the apparent dimen-
sionless surface tension is (cf. Eq. (2))

ri (t)p(t)
app = Oh . (25)
2

For a bubble pulsating in water at = 1 Hz, the computed and

preset radii overlap (Fig. 9(a)). The radii measured from the
images, shown as square symbols, differ from the preset radii
by less than 5%. The computed pressure differences p dif-
fer by less than 5% from the measured values. Although the
computed apparent surface tension app 0 app is nearly
constant (0.5 mN/m), the measured surface tension shows
a larger amplitude of 4 mN/m. This experimental error is
due to the difference between the actual and the preset stan-
dard radii. This difference is caused by the movement of the
pressure sensor, and has been identified before [2]. While
the bubble is growing (Fig. 1), the increase of pL makes the
sensor to move toward the meter and causes some liquid to
leak out of the sample chamber because of the incomplete
seal. Therefore, the bubble becomes larger than the preset Fig. 9. Comparison between computations and experiments: (a) radii mea-
value and the measured pressure is larger than the value at sured from experimental pictures (
), preset radii curve (solid line), and
the preset bubble size, resulting in a smaller apparent surface predictions from simulations (dashed line); (b) measured (solid line) ver-
sus predicted (dashed) pressure difference (p in Eq. (1)); (c) comparison
tension. While the bubble is contracting, the sensor moves of apparent surface tensions calculated from measured p and preset radii
away from the meter and some liquid below the rod is pushed curve (solid line) to the values calculated from predicted p and predicted
into the chamber, making the bubble smaller and resulting in radii (dashed line).
376 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384

be safely neglected. If one ignores viscous forces and assumes

that all of the liquid in the chamber accelerates exactly as the
rod, the z-component of the NavierStokes equation becomes
vz dvrod V0 p
= 22 2 cos(2t) = Oh G.
t dt W z
(27)

Integrating this equation along the z-direction and assuming

that it holds for zrod < z < ztip , one obtains the following
expression for the dimensionless pressure difference between
the tip of the bubble and the rod
 
ztip zrod 2 V0
ptip prod = 2 cos(2t) G .
Oh W2
(28)

Fig. 10. The effect of forcing frequency on the dimensionless apparent

surface tension for a bubble pulsating in water. Standard parameters are
used: Oh = 6.92 103 , G = 0.012, V0 = 10.28, = 1.74, W = 3.03,
and H = 34.5. Values of used are indicated in the legend in the figure.
For 20 Hz, app starts from the unphysical value of 1.05 or more, and
can range between 1.22 and 0.65 (8847 mN/m) due to hydrodynamic ef-
fects.
a larger apparent surface tension. This effect is more pro-
nounced when the pressure pL varies over a wider range [2].
5.2. Effects of inertia on surface tension measurements
for low-viscosity uids
5.2.1. Effect of the forcing frequency on the apparent
surface tensions
When the bubble pulsates at = 1 Hz ( = 5.82 104 ),
app is virtually constant and equals to the theoretical value
of 1 (Fig. 10). For = 20 Hz, app starts with an unphysical
initial value of 1.04 and varies between 1.04 and 0.94. This
fluctuation amplitude increases with increasing frequency.
Thus, to have an accurate standard PBS measurement with a
maximum error less than 5%, one needs to use frequencies
of less than 20 Hz. The unphysical initial value and the fluc-
tuation of app are plainly artifacts due to the hydrodynamic
effects.
5.2.2. Approximate apparent surface tensions for
low-viscosity uids
Since the velocity field in the central part of the sample
chamber is unidirectional (Fig. 8), the continuity equation
and the r-component of the NavierStokes equation lead to
vz p
=0 and = 0, (26)
z r
indicating that the axial velocity does not vary along the z-
direction (Fig. 8) and the pressure depends only on z and t
(Fig. 6(b)). Moreover, for low-viscosity liquids, such as water,
the Ohnesorge number is quite small, indicating that viscous
stresses away from the solid walls and the fluid interfaces can
For a spherical bubble pulsating with a time dependent radius
ri (t), the pressure at the bubble tip is approximately [8]
2 4ri
ptip . (29)
ri Oh ri
Combining Eqs. (28) and (29) yields:
2 4ri ztip zrod
prod =
ri Oh ri Oh
 
2 V0
2 cos(2t) G . (30)
W2
The apparent surface tension can be obtained by combining
Eqs. (25) and (30) as follows:
ri
app = [Oh prod + G(zrod ztip )]
2
V0
= 1 + 2 Oh ri + ri 2 2 (ztip zrod ) cos(2t).
W
(31)
The apparent surface tension in Eq. (31) is comprised of three
parts: the theoretical value of 1 (app = 0 ) without any hy-
drodynamic effects, the effects of the normal viscous stresses,
and the effects of the inertial forces in the bulk liquid. The
dimensionless interfacial velocity ri is of the same order as
. For conditions in which the spherical shape assumption
holds, Oh and or ri are much smaller than unity; hence, the
normal stress effect on app is very small (104 for water).
The second term in Eq. (31) is the same as the second (vis-
cous normal stress) term in Eq. (5). The third term (hereafter
called inertial deviation) in Eq. (31) is different from the third
(inertia) term in Eq. (5). This is because Eq. (5) deals with a
radial flow with a different geometry from that in the PBS.
The inertial deviation, is out of phase with the pulsating
radius ri , i.e. for a minimum (t = 0) radius or a maximum
(t = 0.5) radius, the apparent surface tension app from
Eq. (31) shows instead a maximum or a minimum, respec-
tively. The amplitude of the inertial deviation decreases as the
chamber radius W increases or as the forcing frequency , the
 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384
Fig. 11. Comparison of apparent surface tensions app from computations
(solid lines) and approximated (dotted lines) values from Eq. (31) with the
normal stress term set to zero at: (a) 100, (b) 50, and (c) 20 Hz. Parame-
ters used are the same as in Fig. 10. The approximated app values overlap
with the computed values, indicating that the inertial forces dominate the
hydrodynamic effects.
volume amplitude , or the chamber height H (ztip zrod )
decrease.
Since H is much larger than 1 because a long slender cham-
ber is used, the inertial deviation is quite large: the maximum
value of the inertial deviation for a bubble pulsating in water
at 20 Hz in a standard chamber is around 0.05. Moreover,
Eq. (31) makes plain that at t = 0, or at the beginning of each
cycle, app starts from a value greater than one and increases
with frequency , as observed in Fig. 10. When Eq. (31) is
applied without the normal stress term for 20 Hz, the
approximate and computed solutions are almost the same
(Fig. 11), indicating that inertial forces, in accord with intu-
ition, dominate when the liquid has a low viscosity.
5.2.3. Effect of the forcing amplitude
As the forcing amplitude increases, the dimensionless
apparent surface tension app can deviate greatly from 1.0
(Fig. 12). Indeed, for the standard value of = 1.74, app can
even be negative for = 100 Hz, as shown in Fig. 12. When
decreases, the deviation of app from 1.0 decreases sig-
nificantly, indicating a major reduction of the hydrodynamic
effects and of the artifacts in the surface tension measure-
ments. The deviation amplitude of app is nearly proportional
to (app,max 1 = 0.9, 0.45, and 0.23 for = 1.74, 0.87,
and 0.425). The linear dependence is consistent with the ap-
proximate equation, Eq. (31). Hence, hydrodynamic effects
in aqueous solutions are minimal for very small forcing am-
plitudes, as would be expected.
5.2.4. Effects of chamber dimensions
The predicted maximum and minimum of app of a bubble
pulsating in water at 100 Hz in chambers of different radius
W and height H are shown in Fig. 13. For a chamber which
377
Fig. 12. Dimensionless apparent surface tension app of an oscillating bubble
at a frequency of 100 Hz for various forcing amplitudes = V/V0 ; other
parameters used are the same as in Fig. 10. For the large amplitude = 1.74
(solid line), app ranges from 0.3 to 2, indicating major hydrodynamic
effects and a major failure of the quasistatic assumptions. For = 0.87
(dashed line) and 0.435 (dotted line), app remains positive. The amplitude
of app decreases as decreases.
is long and narrow (W < 3 mm), the predicted variations in
app are quite close to the values approximated from Eq. (31).
If one uses a longer chamber, the fluctuation of app is larger
because of increased inertial effects, as shown in Eq. (31).
When W increases, the fluctuation of the computed app be-
comes smaller, indicating that the wall effects are smaller. For
H = 1 cm, the maximum and minimum app reach plateaus
of 1.05 and 0.95, respectively, for W 6 mm. By contrast,
Eq. (31) predicts values (solid lines in Fig. 13) that tend to
1.0 as W grows without bound.
This discrepancy between the rigorous computational re-
sults and the approximate results from Eq. (31) can be ex-
plained as follows: as the chamber gets wider, the radial flows
around the bubble become more pronounced and the liquid
motion becomes close to that of a bubble pulsating in an in-
finite amount of liquid (this case was also examined in the
simulations, but is not shown here). Then, Eq. (31), which is
derived based on a unidirectional flow assumption, is inaccu-
rate. For a pulsating bubble in an infinite expanse of liquid,
the apparent surface tension is given by Eq. (5) [8], or in
dimensionless form


app = 1 + 2Oh ri + 21 ri2 ri + 23 ri ri2 . (32)
The maximum and minimum values of app from Eq. (32)
(dotted lines in Fig. 13) are the limits for no wall effects, or
for W . Thus, as W (or W) rises, the predicted fluctua-
tion in app approaches the values from Eq. (32). The larger
the value of H, the larger is the value of W needed to reach
the limit of an infinite amount of liquid. These results may
provide useful guidelines for designing improved versions of
supported bubble instruments.
378 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384

Fig. 13. Effects of chamber radius W and height H on the dimensionless Fig. 14. (a) Comparison of apparent surface tensions app for a bubble pulsat-
apparent surface tension app of an oscillating bubble at a forcing frequency ing at 10 Hz for = 1100 cP, as indicated in the figure. The parameters used
of 100 Hz. Other parameters used are the same as in Fig. 10. The lines are the are Oh = 6.92 103 for 1 cP, G = 0.012, = 5.82 103 , V0 = 10.28,
maximum app,max or minimum app,min of dimensionless apparent surface = 1.74, H = 34.5, and W = 3.03. As the viscosity increases, app deviates
tension predicted from Eqs. (31) and (32), as indicated in the figure. The open more from 1; the maximum deviation does not occur at the maximum radius
and solid symbols are computed values of app,max and app,min , respectively, (t = 0.5). (b) The phase angle difference between app and the volume-
for different W and H, as indicated in the figure. For a narrow chamber averaged radius ri in figure (a). As the viscosity increases, for this particular
(W < 3 mm), the variation of the dimensionless apparent surface tension set of parameters used here, the phase angle difference decreases and reaches
app is large and follows the prediction of Eq. (31). As the chamber gets a plateau at a value of 82 at 200 cP.
wider, the variation gets smaller and gradually approaches the prediction of
Eq. (32). Moreover, the higher the H, the larger is the fluctuation. For details,
see text.
When bubbles oscillate in a high viscosity liquid ( =
100 cP), the velocity fields in the central part of in standard
5.3. Effects of viscosity PBS chamber are unidirectional (Fig. 15), similarly to those
in a low viscosity liquid (Fig. 8). In the latter, the axial ve-
The critical values of the forcing frequency c , below locity distribution changes from a parabolic profile into a
which the bubble shape factor fs remains 1 0.05 during nearly uniform profile as the forcing frequency increases. In
the pulsation, for different values of Ohnesorge number Oh, the former, the axial velocity distribution remains parabolic,
are listed in Table 2. For Oh < 0.692 ( < 100 cP), c is with magnitudes varying with frequency, indicating that the
0.0582 (c = 100 Hz), and it drops to 0.00582 (c = 10 Hz) momentum transport in these flows is quite efficient. These
for Oh = 6.92 ( = 1000 cP). This decrease in c shows parabolic flows can be approximated by the HagenPoiseuille
that the viscous forces become an important factor in DST equation. For mass conservation, the average velocity is the
measurement in high viscosity liquids, and they may even same as the rod velocity vrod :
cause the bubble to become nonspherical. With increasing
 
liquid viscosity, the deviation of app from 1.0 for a bubble r2
pulsating at = 0.00582 ( = 10 Hz) is more pronounced vz = 2 vrod 1 2 . (33)
W
(Fig. 14(a)). Unlike the inertial effects for low-viscosity liq-
uids (Section 5.2), for which app starts from more than 1.0
at the beginning of each cycle, for high viscosity liquids, app Table 2
starts from 1.0. Moreover, the app curves for viscous liquids Critical frequencies for having essentially spherical pulsating bubbles when
are not in phase with the pulsating bubble radius ri . The phase they are surrounded by liquids of different viscosity in a standard chambera
angle difference between the maxima of app (t) and ri (t) de- Oh (cP) c b c (Hz)
creases gradually from 180 for = 1 cP to 90 for 100 cP, 0.007 1 5.82 102 100
and reaches a plateau of 82 for 200 cP. This is the first 0.035 5 5.82 102 100
report of such a phenomenon, which is not due to DST ef- 0.173 25 5.82 102 100
fects. The phase angle shifting shows a transition from the 0.692 100 5.82 102 100
3.46 500 2.91 102 50
inertia-dominated region (phase angle difference equals to 6.92 1000 1.16 102 20
180 ) to a viscous-force-dominated region, as explained be- a Parameters used are G = 0.012, = 1.74, V = 10.28, H = 34.5, and
low. The value at the plateau, here 82 , may vary depending
0
W = 3.03.
on the set of conditions considered. b : the dimensionless frequency below which |f 1| < 0.05.
c s
 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384 379

Fig. 15. Velocity fields around a pulsating bubble in a high viscosity fluid ( = 100 cP) for t = 0.25 at: (a) 1 Hz, (b) 10 Hz, and (c) 100 Hz. The parameters
used are Oh = 0.692, G = 0.012, V0 =10.28, = 1.74, H = 34.5, and W = 3.03. The flow is essentially unidirectional in the central part of a standard PBS
chamber. The velocity profiles are parabolic with magnitudes varying with the forcing frequency.

For this equation, the corresponding pressure gradient in the Eq. (36) and ri is about 82 , which is the same as the plateau
central part of the chamber is value for viscosity 200 cP in Fig. 14(b). The effects of
, , W, and H on the viscous deviation are similar to those
dp vrod G
= 8 2 , (34) discussed in Section 5.2.
dz W Oh When the approximate Eq. (36) is applied to a bub-
The pressure difference between the bubble tip and the rod ble pulsating at 10 Hz, the approximate and computed
can be obtained by integrating the above equation: app are almost the same for Oh = 0.692 ( = 100 cP)
  (Fig. 16), indicating that the pressure drop due to the viscous
vrod G
ptip prod = 8 2 + (ztip zrod ). (35) forces dominates the hydrodynamic effects. For Oh = 0.173
W Oh
From Eqs. (25), (29), and (35), the apparent surface tension
is
V0
app = 1 + 2 Oh ri + 4 Oh ri (ztip zrod ) sin(2t).
W4
(36)

As mentioned in Section 5.2.2, the first term is the theoreti-

cal value without hydrodynamic effects, and the second term
results from the normal viscous stress, which is of the order
of 0.01 for Oh = 0.7 (100 cP) and  0.06 (100 Hz). The
last term in Eq. (36), unlike that in Eq. (31), results from the
pressure drop caused by viscous forces acting on the cham-
ber walls, and is called the viscous deviation term hereafter.
Since the chamber is slender, the term ztip zrod H is large
and the viscous deviation results in a larger variation for app
than the variation resulting from the normal stress close to
the bubble. The amplitude of the viscous deviation decreases Fig. 16. Comparison of apparent surface tensions app from computations
with decreasing Ohnesorge number Oh, forcing frequency (solid lines) and approximated values (dashed lines) from Eq. (36). (a) For
100 cP, the approximate app values overlap with the computed ones, indi-
, volume amplitude , and chamber height H, or with in-
cating that the viscous deviation dominates the hydrodynamic effects. (b)
creasing chamber radius W. When the viscous deviation is For 25 cP, the approximate app fits the computed app fairly well but with a
the only significant hydrodynamic effect, for this particular small phase angle difference, indicating that both viscous and inertial effects
set of parameters used, the phase angle between app from are important.
380 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384
Fig. 17. Effect of surface tension on the deformation of pulsating bubbles
at 1 Hz in simulations of the PBS chamber at different time stages. Standard
operating parameters are used: = 1.74, V0 = 10.28, H = 34.5, and W =
3.03. The time difference between two adjacent computed shapes is 0.05 s.
The apparent surface tension from calculations is shown in the figure as an
average with a fluctuation. The surface tensions calculated from the dynamic
shapes using the YL equation for nonspherical surfaces are the same as the
input surface tensions 0 .
( = 25 cP), although app from Eq. (36) and the computed
values are similar, they show a slight phase lag. Hence,
hydrodynamic effects other than simply the viscous devia-
tion are significant. For liquids of intermediate viscosities
(0.05 < Oh < 0.2), the fluctuation in app results from both
inertial and viscous forces, and should be obtained from the
rigorous numerical solutions.
5.4. Effects of surface tension
The time evolution of bubble shapes under standard PBS
conditions at 1 Hz is shown in Fig. 17 for four values of
the surface tension 0 . For 0 = 72 mN/m, the Bond Num-
ber is small, G = 0.01, and the dynamic shapes are close
to spherical (|fs 1| < 0.01). The apparent surface ten-
sion app , as computed from the pressure difference p
and the volume-averaged radius ri , is the same as the input
value of 72 mN/m with a variation of about 0.5 mN/m. For
0 = 20 mN/m, the dynamic shapes start to deform slightly
into oblate spheroids due to the larger gravitational effect
(G = 0.04), which causes the pressure jump at the tip of the
bubble to be smaller than that of a spherical shape. The aver-
age computed app is 19.3 mN/m, or about 3% smaller than
the input value of 20 mN/m. The deformation of the dynamic
bubble shape is more severe when 0 = 5 mN/m. The fluc-
tuation of app can be as large as 10% of the actual value,
and the tension measurement error is 20%. For still lower
surface tension, 0 = 2 mN/m, the bubble shapes start from
Fig. 18. Comparison of dynamic shapes (solid lines) and static shapes
(dashed lines) for 0 = 5 mN/m (Fig. 17). The static shapes are obtained by
solving the YL equation for static bubbles having the same volume as the
dynamic shapes. The dynamic and static shapes agree well, and they cannot
be distinguished in the figure, indicating that the surface tension measure-
ments from the ADSA analysis can be accurate so long as hydrodynamic
effects are negligible.
highly deformed oblate spheroidal shapes and are slightly
overturned (the bubble shape has a vertex higher than the
contact line) at the edge of the capillary at the onset of the
pulsations. The computation actually had to be stopped at
t = 0.35 because the strong overturning caused the bubble
to touch the chamber wall. In the actual experiments, such
touching of the wall by the bubble surface may cause a
contact line to move or jump, and the measurement would
be expected to fail. To prevent such situations, one should
use a smaller forcing amplitude or a smaller capillary
radius R.
For the case of 0 = 5 mN/m in Fig. 17, for which gravity
can deform the bubble even with no flow, the dynamic shapes
at different time stages agree well with the corresponding
static shapes (Fig. 18), which are obtained from solving the
YL equation for a static bubble of the same volume. Thus,
when one uses axisymmetric drop shape analysis (ADSA)
[40], for low surface tension (G > 0.1) measurements, the
accuracy is higher than using the pressure jump method for
a spherical interface. These results apply, of course, when
the forcing frequency is small and the bubble shape is not
distorted by the fluid motion (cf. Fig. 7).
 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384 381

Fig. 19. Streamlines at different times in the first oscillation cycle for a pulsating bubble in water at = 0.00582 or = 10 Hz. Parameters used are Oh =
0.00692, G = 0.012, = 1.74, V0 = 10.28, H = 34.5, and W = 3.03. The eddy near the corner of the chamber at t < 0.5 grows when the bubble increases
in size, and at t = 0.5 occupies the whole chamber. When the rod reverses its direction, the eddy vanishes; after the passage of certain time, the eddy forms
again but circulates in a different direction. This pattern is repeated in each cycle.

Fig. 20. Streamlines at t = 0.5 for bubbles pulsating at 10 Hz in liquids of increasing Ohnesorge number or bulk viscosity. Parameters used (except Oh as
indicated in the figure) are the same as those in Fig. 19. The vorticity is stronger in higher-viscosity liquids and can cause the formation of several counter
rotating eddies.
382 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384
5.5. Recirculating eddies and streamlines
For a pulsating bubble in water at 10 Hz, a recirculation
zone in the liquid is predicted to develop near the corner of the
chamber. The eddy grows when the bubble expands (Fig. 19),
and can occupy the whole chamber at t = 0.5 at which in-
stant the rod velocity is zero. Although the circulation appears
to dominate the whole chamber volume, the magnitude of
the maximum velocity is small ( 2 103 ). Hence, these
circulations affect only slightly the surface tension measure-
ments. When the rod starts moving in the opposite direction,
the eddy does not arise for t ranging from 0.55 to 0.7. When
the eddy reappears, the liquid circulation is in the opposite
direction. The eddy grows in size as the rod slows down and
ultimately disappears as the rod returns to its starting position
(t = 1.0). This pattern is repeated in each cycle.
For higher viscosity, the circulation pattern at t = 0.5
causes several eddies to form faster (Fig. 20). The pressure
fields are affected more significantly the higher the viscosity
is. For Oh = 6.92 ( = 1000 cP), the eddies near the bubble
surface seem to cause large normal stresses which might de-
form the bubble. Thus, the effects of the eddies on the surface
tension measurements can generally be significant, unless the
liquid viscosity is low.
6. Conclusions
The problem of a bubble that is supported by a small capil-
lary and oscillates in a Newtonian liquid with a constant sur-
face tension is solved for the first time with the complete set
of hydrodynamic equations by using a rigorous finite element
method. The only significant simplification in the computa-
tions is the use of an axisymmetric container with a circular
rather than a square cross section in the actual experimental
conditions. The model contains nine dimensionless groups.
The Ohnesorge number Oh and Bond number G provide
measures for the importance of viscosity and gravity, respec-
tively. The chamber is a long cylinder with a dimensionless
radius W and a height H. The chamber is open to the atmo-
sphere with a capillary. The connection between the capillary
and the sample chamber is a circular ring and is described by
two parameters W1 and H1 , which are kept constant in the
calculations as in the standard sample chamber. Three op-
erational parameters, the initial bubble size V0 , the forcing
frequency , and the forcing amplitude , are needed for
describing the bubble pulsation. The computed flow fields
agree fairly well with the measured flow fields from particle
image velocimetry. Moreover, the calculated pressure jump
p and apparent surface tension are fairly close to the mea-
sured values. The consistency between the computations and
the experiments indicates the correctness and accuracy of the
current model and the FEM algorithm used, which are used to
evaluate the measurement errors over wide parameter ranges,
and also the relevance of the computations to actual measure-
ments.
For a pulsating bubble in the standard PBS chamber
to remain nearly spherical, which is one essential assump-
tion of the PBS measurements, the forcing frequency has
to be smaller than 0.06 (or < 100 Hz) for Oh 0.7 (or
100 cP). The apparent surface tension for a liquid with a
constant surface tension from the pulsating bubble surfac-
tometer could still vary with time, even when the bubble
is nearly spherical, because of significant hydrodynamic ef-
fects.
For pulsating bubbles with nearly spherical shapes in low-
viscosity liquids (Oh < 0.05), such as water, hydrodynamic
effects cause errors in surface tension measurements, mostly
because of the inertial forces in the bulk liquid. The inertial
deviation, app 1, is out of phase with the volume-averaged
radius ri . At the beginning of each pulsation cycle, app starts
with an unphysical value of greater than 1.0. The inertial de-
viation term is proportional to the forcing amplitude , the
square of the forcing frequency , and the chamber height H,
and inversely proportional to the square of the chamber radius
W. For the commercially available experimental setup with
a preset forcing amplitude of = 1.74, frequencies lower
than 10 Hz are predicted to give accurate measurements. For
accurate measurements at higher frequencies (>10 Hz), to
diminish inertial effects, one needs to either reduce the forc-
ing amplitude or use a wider chamber. For W > 21 (or
W > 6 mm), app varies as app of a pulsating bubble in an
infinite amount of liquid, as has been modeled before [8].
For nearly spherical pulsating bubbles in high viscosity
liquids, errors in app are due mostly to the pressure drop
arising from the viscous shear stresses exerted by the liquid
on the chamber walls. The error due to the viscous forces in
app , or the viscous deviation term, for liquids in a standard
PBS sample chamber, has a phase angle difference of 82 ,
unlike the phase angle difference of 180 of the inertial devi-
ation term. The viscous deviation term is proportional to , ,
and H, and inversely proportional to W 4 . The phase angle dif-
ference between app and ri decreases gradually from 180 to
82 with increasing Oh, or viscosity . For Oh > 0.7, the vis-
cous deviation dominates the hydrodynamic effects for app .
For intermediate viscosities (0.05 < Oh < 0.7), the fluctua-
tion of app results from both inertial and viscous forces and
has to be evaluated numerically.
For the commercial PBS, which has a maximum frequency
of 1.7 Hz, the dynamic bubble shapes remain nearly spherical
for liquids with surface tension 0 greater than 20 mN/m. For
low frequencies and nearly spherical bubble shapes, errors
in PBS measurements are less than 5% for 0 20 mN/m.
At lower surface tensions (0 5 mN/m), pulsating bubbles
can and will be deformed by gravity. Thus, the apparent sur-
face tension from PBS, which is based on the static YL
equation for spherical bubbles, is less accurate. With ax-
isymmetric drop shape analysis (ADSA) one will be able
to determine accurately the surface tension for 0 5 mN/m
when the hydrodynamic effects can be safely neglected. For
0 2 mN/m, the bubble deforms more substantially and
could touch the chamber walls during the pulsation. Then
 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384 383

the measurement is expected to fail unless a smaller volume

amplitude or a smaller capillary radius is used.
The hydrodynamic effects on the surface tension measure-
ments with the pulsating bubble surfactometer for liquids of
constant surface tension are elucidated thoroughly. The rig-
orous finite element algorithm used here is found to describe
accurately the hydrodynamics with a complex geometry, a de-
formed bubble shape, and a moving interface. The algorithm
can be modified to include time-varying dynamic surface ten-
sions (DST) due to surfactant adsorption and surface con-
vection and diffusion. Then DSTs can be determined more
reliably than done previously by a better accounting of the
hydrodynamic effects. Before any conclusions can be drawn
for surface rheological properties of aqueous surfactant or
protein solutions by extracting DST data from pulsating bub-
ble experiments, the hydrodynamic effects must be fully ac-
counted for as in this article. This problem is addressed in
Fig. A.1. Schematic of a slightly deformed free bubble pulsating in a low-
[46]. viscosity liquid. The dashed line is a sphere of the same volume as the bubble
before the deformation.

Acknowledgements where is the polar angle. The frequencies of infinitesimal-

amplitude oscillation .  1 have been determined by
This research was supported in part by grants from the Rayleigh [58] (see also [59]) using a linearized analysis. For
National Science Foundation (Grant CTS 0135317) and the a bubble oscillating in an inviscid liquid, the linearized fre-
National Institutes of Health (Grant HL 54641-02) to Elias quencies of oscillation n0 are given by
I. Franses, and grants from the Basic Energy Sciences Pro-
gram of the US Department of Energy (Grant DE-FG02- n0 = [(n2 1)(n + 2)]1/2 , n = 2, 3, . . . (38)
96ER14641) and the Purdue Research Foundation to Osman The values of n0 and the periods of oscillation T 2/n0
A. Basaran. The authors would also like to thank Dr. Lichuan for n = 2, 3, and 4 are listed in Table A.1.
Gui and Professor Steve Wereley for discussions and help in Here, to test the code, the problem of a slightly deformed
the PIV measurements. We offer special thanks to Dr. Goran (. = 0.01) bubble in a low-viscosity fluid, Oh = 103 , is
Enhorning, and to Electronetics Corporation (Now General solved numerically. In the calculations, the infinite liquid do-
Transco Inc.), for the design of the commercial PBS instru- main has been truncated at a finite radius r = Rout (Fig. A.1)
ment, which allowed us and many others to obtain many valu- and the liquid far from the bubble surface, i.e. for r Rout ,
able data and inspired us to develop this and related models. is taken to be at rest or v = 0. The position of the bubble tip
We also thank Drs. Pat Notz and Alvin Chen whose pioneer- r( = 0, t), which executes sinusoidal oscillations, is plotted
ing uses of elliptic mesh generation in studies of oscillating against time, and the period of oscillation T is obtained by
and breaking drops were instrumental in expediting the de- the difference between successive times for which r( = 0, t)
velopment of the present algorithm. equals unity.
The resulting T for different modes of oscillation n are
listed in Table A.1. For n = 3, elements of the same size
Appendix A. Code validation for a bubble (N = 15; Nr = 5, 20 and 45 for Rout = 2, 5, 10; where N
undergoing small-amplitude oscillations in a
low-viscosity liquid Table A.1
Oscillation time periods of deformed bubbles with a small deformation of
An important accuracy check for the algorithm is pro- . = 0.01 in a low-viscosity fluid of Oh = 103
vided by analyzing the small-amplitude oscillations of a free n n0 T 2/n0 Rout N a Nr b Tcalculated
bubble immersed in a low-viscosity liquid. The computed 2 3.464 1.814 5 15 20 1.813
predictions are then compared to theoretical analyses of lin-
3 6.325 0.993 2 15 5 1.000
earized oscillations of a bubble in an inviscid liquid of infi- 2 30 10 1.000
nite expanse [58,59]. Initially, the bubble is perturbed from a 5 15 20 0.993
spherical shape (Fig. A.1) and the perturbation is described 5 30 40 0.994
by Legendre polynomials of order n Pn [cos()] with an am- 10 15 45 0.994
plitude ., i.e., the initial shape in spherical coordinates is 4 9.487 0.662 5 15 20 0.660
a N : number of elements in direction.
r = 1 + .Pn [cos()] (37) b Nr : number of elements in r direction.
384 Y.-C. Liao et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 250 (2004) 367384
and Nr are the number of elements in the and r direc-
tions) are used to find the value of Rout for approximating
Rout . The calculated time period Tcalculated is found
to differ by less than 103 (error criterion for the calcula-
tion) for Rout = 5 and 10. Hence, Rout = 5 is adequate for
approximating Rout . When the element size is dou-
bled (N = 30 and Nr = 40) for Rout = 5, Tcalculated varies
by less than 103 . Thus, the original number of elements
with Rout = 5 is sufficient for accurate computation for the
deformed bubble problem, and is used for perturbed shapes
with n = 2 and 4. Comparing Tcalculated for n = 2, 3, and 4
with the theoretical values of T, one finds an error less than
103 . Thus, the code does satisfy the test and provides addi-
tional confidence in the accuracy of the computations.
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