296
Techniques to measure dynamic surface tension
Elias I Franses*t# I Osman A Basaran'I and Chien-Hsiang Chang§
Recent developments of techniques used to measure dynamic
surface tension aim at incorporating measurements during
area changes, and improving speed of measurements,
automation, and range of time scales (~1 rns), New
techniques incorporate better definition of surface age and
of the flow field , before or during measurements. They point
to truly dynam ic measurements, where the trans ient interface
shape is rigorously analyzed in terms of the flow, pressure,
and concentration fields.
Address
'School of Chemical Engineering, Purdue University, West Lafayette,
IN 47907-1283 , USA
[e-mail: franses@ecn.purdue.edu
te-mail: obasaran@ecn.purdue.edu
§Department of Chemical Engineering. National Cheng
Kung University; Tainan,Taiwan 701, Republic of China;
e-mail: changch@mail.ncku.edu.tw
#Aulhor to whom correspondence should be sent
Current Opinion in Colloid & Interface Science 1996, 1:296-303
© Current Science Ltd ISSN 1359·0294
Abbreviations
-y(t) dynamic surface tension, or DST
G gas
L liquid
L' second liquid phase
MBPM maximum bubble pressure method
S solid
Introduction ,
Equilibrium surface, or interfacial, tension of gas/liquid
(G/L) or liquid/liquid (L/L) interfaces is defined as the
surface excess stress integrated over the interfacial zone
[1-5]. Solutions or dispersions containing surface active
molecules (surfactanrs, amphiphiles, lipid s, proteins etc.)
usually exhibit a decrease in the equilibrium surface ten -
sion, "Ie (mN/m), because of adsorption at the interfaces.
The relation of the equilibrium surface excess density
or adsorbed density (densities) ri,e (mol/m l , for solutes
i = 1,2,...) to "Ie is called the equilibrium surface equation
of state. For soluble surfactants, ri,e is related to the bulk
concentrations Cj (j = 1,2,...) by the adsorption equilibria.
The Gibbs adsorption isotherm of surface thermodynamics
relates "Ie to Cj. The drivin g force for adsorption is usually
minimization of the surface Gibbs free energy. Molecular
mechanisms include the hydrophobic effect, electrostatic
attraction, and stereospecific, or other, binding. The
equilibrium surface tension "Ie (Cj) can be measured using
various techniques [2-4).
Establishing the equilibrium adsorbed density takes time,
from approximately IO~ s to hours or day s, during which
the dynamic adsorbed densities, rj(t) (where t is time)
and n,e are not equal. The transient surface tension is
usually different from "Ie and is defined as the dynamic
surface tension , J<t), or DST [6]. Once certain molecules
adsorb, they may reorganize further (i.e. reorient, change
conformation, change domain size etc.) without changing
rj(t). The relationship between J<t) and n(t) is the
dynamic surface equation of state, which mayor may not
be unique, because of surface relaxation effects, and which
may be the same or different from the equilibrium surface
equation of state, "Ie(rj,e)'
Measuring J<t) is important for its own sake , for inferring
Ij(t), and for understanding other dynamic interfacial
phenomena, such as foaming, emulsification, surface
rheology, coating flows, etc. These phenomena affect
many technological, biological, and medical applications,
such as foam-based separations; agricultural chemicals,
fermenta tions, photographic film, polymer blending, and
lung surfactants [7-9,10·,11,12]. The subject has received
much attention recently, as shown by several reviews and
books [13··,14·,15·,16,17·].
This art icle focuses on three areas: reviewing and evaluat-
ing the most important techniques for measuring dynamic
surface tensions; providing guidelines on how to evaluate
literature methods and data; and helping research workers
to select th e method(s) best suited to their needs.
Perspective and key points
Many interfacial phenomena involving drops, bubbles,
menisci, liquid jets, and thin films are affected by the
equilibrium, or dynamic, surface tension. In principle, any
of these phenomena, properly analyzed and interpreted,
may be used to infer the value of surface tension. Most
equilibrium methods may be used to measure J<t), and
there are certain methods by which one can measure solely
dynamic tension. Most methods involve measurement of
forces, interface shapes, pressure differences, or flow rates
[1-4,13 ••,14.,15.,16,17°]. Optical methods are beyond the
scope of this review, but interested readers can refer to [18]
for further information.
The choice of method depends on the nature of the
interface (G/L, L/L), the rheology of the liquid(s), the
range of tensions, the range of temperatures and pressures,
the needed range of surface age required, ease of analysis,
accura cy, precision, speed, and practical considerations of
con venience, cost, and combination with other surface
probing techniques. Impurities may affect the tension
substantially. Issues of surface chemical purity, which may
affect the interpretation of tension measurements, have
been discussed [17·,19,20).
 Techniques to measure dynamic surface tension Franses, Basaran and Chang
Measurements of DST usually start (at t =0) from a clean
('nascent') interface (li[O] =0) or from an equilibrium
interface. In the former case, the formation of the interface
involves some flow, which in turn affects y(t) for some
time, during which measurements are not possible or
meaningful. The 'dead time', td, affects the definition
of the actual surface age, which may differ from t in
ways which are difficult to quantify without elaborate
computations. Moreover, when an interface forms, the
surface age may not be uniform across the interface,
possibly resulting in Marangoni flows [21] (flows driven by
a surface-tension gradient), which should be accounted for
when interpreting measurements.
Many techniques use the so-called quasistatic approach,
in which it is assumed that y(t) affects the dynamic
interface shape (or pressure, or force) just as "Ie affects
the equilibrium shape. A more rigorous approach would be
the dynamic approach: calculating the shape exactly based
on y(t), and understanding the 'direct problem', before
the 'inverse problem' of inferring y(t) from the dynamic
shape is addressed. This latter approach has been applied
recently and bodes well for more rigorous and precise
measurements in the future. In the following section,
several important techniques are reviewed and evaluated
using the above and other criteria. Even though they are
classified as force, shape, pressure, or flow methods, they
may involve a combination of these probes.
Description and review of the most important
methods
Force methods
When a solid substrate is inserted at a fluid/liquid inter-
face, a meniscus forms (Fig. 1). At the fluid/liquid/solid
contact line, with wetted perimeter, I, an unbalanced force
F(t) is generated by the surface tension forces (3):
F(t) = ){t) l cos aCt) ( 1)
where 8(t) is the dynamic contact angle [4,22·,23). The
concomitant capillary rise (hjtl) at the wall can be
estimated from the equilibrium equation as follows [4,24):
htt) = 2"1(t)(1_cosa(t») (2)
6pg
where 6p is the density difference and g is the acceleration
of gravity. If 8(t) were independently known (or 8[t) =0),
y(t) may be determined from either equation, from meas-
urements of Fft) or of hu), Otherwise, both measurements
and equations would be required. These principles form
the basis of the Wilhelmy plate method, which is best
used for gas/liquid interfaces with a static plate, and the
DuNoiiy ring method, in which the ring is continuously
pulled until the meniscus breaks. The former method
is also used in Langmuir troughs in which the surface
area is varied via surface barriers. The Wilhelmy plate
method with a Langmuir trough is simple, convenient, and
297
popular, allowing i1J situ surface purification by sweeping
away (Of aspirating) the surface layer [19,20,25·).
A major uncertainty of force methods is the non-unique
value of 8(t), which depends on meniscus velocity, prior
wetting history, and adsorption at, and surface energies
of, all three interfaces (G/L, LIS, G/S) [4,23]. Moreover,
the above equations are really rough approximations of the
fluid physics: they ignore the dynamic nature of the capil-
lary rise, namely the finite time required for the meniscus
and the underlying liquid to flow after a change in y(t).
Measurements from "1= 1000 to -1 mN/m are' possible
(with an uncertainty of 0.1 mN/m or better), every 0.1 s
or faster. Dead times of 10-100 s preclude measurements
at lower time scales. Recent developments {26·] include
more precise, automated, and fast measurements, but not
improvements in interpretation despite advances in the
fluid mechanics of dynamic meniscus rise [27,28].
Shape and pressure methods
The well known Laplace-Young equation relates y(t) to
the pressure jump 6p across the interface [1-5):
6p = y(l.. + l..)
r1 rZ
(3)
where fJ and r2 are the principal radii of curvature. If the
drop or bubble dimensions are lower than the capillary
length a, where a,. ~2y / <1pg. then f1 = r2= R, and the
interface is a section of a sphere. When 6p is measured
directly, one has a 'pressure method'. Examples are the
maximum bubble pressure method (MBPM) and other
bubble methods (see below). If R~a, the drop or bubble
is deformed by gravity forces. The resulting shape can be
calculated, or the direct problem can be solved, most easily
for planar or axisymmetric interfaces [1-9,24). Examples
that are based on solving the inverse problem include the
pendant drop method, the emerging (or pendant bubble)
method, the sessile drop method, the captive bubble
method, Schurch's special captive bubble method (see
below), and the spinning drop (or bubble) method (Fig. 1).
Recently the pendant drop (or bubble) method has been
used extensively, with dead times of 2-4 s and automated
image analysis approximately every 0.1 s or so [29-33)
(DO Johnson, KJ Stebe, personal communication). The
method is convenient and generally reliable. Uncertainties
in interpretation include the quasistatic character of
Equation 3, which ignores effects of fluid viscosity and of
non-uniformity in surface tension [4,21). Recent advances
include the rigorous solution of the dynamic shape for
constant "I(OA Basaran, X Zhang, t\IT Harris, paper 51k,
Winter Annual Meeting of the AIChE, St Louis, 1993),
with possible future extensions to y(t). This work also
examines the validity of the simple static Laplace-Young
equation, Equation 3, in dynamic situations and quantifies
the departure of the real flow inside a pendant drop
from a simple radial flow. The captive bubble method
of Schiirch and co-workers has been applied successfully
298 Imaging and other techniques

Figure 1

@
L

,
L

@ G @ vzzzzzzzzzzzzzza @ ®

@
IZ~ZI
P~21
(j)
( G )
L
L
L
·tJ
,: G;,
\..... . -.....,." .: L
P
-(-G-or-b' ":JtJ. P2 2
L

@ @ iF
@ I

G
..__.....G or L'
G or L'
(not to scale)

Schematic of some experimental setups for measuring dynamic surface tension (1) Wilhelmy plate method (F [the force) is measured; h is the
capillary rise at the wall; and 0 is the dynamic contact angle); (2) DuNouy ring method; (3) pendant drop method; (4) emerging bubble method;
(5) sessile drop method; (6) captive bubble method; (6)' captive bubble method of Schurch and co-workers [34,35',36"); (7) spinning bubble
or drop method; (8) maximum bubble pressure method (PI is measured [where p denotes pressure)); (9) bubble method (Pl-r2 is measured;
constant area mode, solid line, and variable area or pulsating bubble mode, between the solid line and the dashed-solid lines); (10) growin9
drop method; (11) drop weight or volume method; (12) osc illating jet method (a and c represent cross-sections that are ellipses with their major
and minor axes interchanged; band d represent cross sections that are circles, and 1.. is wavelength); (13) inclined plate method (tension is
measured with a Wilhelmy plate).

using high temperatures and pressures, and under variable
or pulsating area conditions [34,35-,36--J,
In the above methods the drop shape is determined by a
balance of gravity and surface tension forces, whereas in
the spinning drop method the drop (or bubble) shape is
governed by a balance of centrifugal (or, more precisely,
centripetal) and surface tension forces [3,4,37,38]. The
spinning drop method was applied to variable area
conditions and very low surface tensions « 10 mN/m) and
interfacial tensions (as low as 10-4 mN/m), but only in
the quasi static mode [25,39]. The solution of the dynamic
shape, at constant y, was reported recently [40,41-].
Extension to a time-dependent y may result in a truly
dynamic system.
The bubble method was used under constant or pulsating
area conditions, for R = 0.050cm < a, with pressure meas-
urements [42,43,44-,45-]. Very low surface tensions were
reported under dynamic area compression. The conditions
under which Equation 3 is a good approximation were
defined recently [43,44-]. At low frequencies, bulk vis-
cosity effects are unimportant for low-viscosity liquids,
as are surface dilatational viscosity effects [16,21J. There
are conditions, however, for which the surface dilatational
viscosity, Ks may be the dominant factor affecting 6p(t);
then the method may be used to measure Ks, rather than
')'(t) [46]. For tensions y5, lOmN/m, the condition R<a is
no longer valid, and the surface tension is also inferred
from the bubble shape [43]. The oscillating bubble
method, in which small-amplitude area oscillations and
 Techniques to measure dynamic surface tension Franses, Basaran and Chang
bubbles (or drops) deformable by gravity (R2:a) are used,
was developed early [13--,17-,47,48] and recently analyzed
more rigorously [49-] (DO Johnson, KJ Srebe, personal
communication). Sometimes the results are reported in
terms of the surface elasticity dy/dlnA = (dy/dt)/(dNAdt).
The bubble methods have provided valuable information
at small time scales (from 0.1 s to minutes) and various
frequencies.
Flow methods and other methods
The maximum bubble pressure method (MBPM)
In this popular method for establishing ')'(t), one measures
the pressure needed to blow a bubble into a liquid from
a capillary tip [3,17-]. The surface age is estimated, at
interval times tj from the frequency of bubble formation,
and normally ranges from 0.1 s to minutes. Recent
developments have reduced the minimum surface age to
0.1-1 ms [50,51,5Z-,53-].
Growing drop methods
These relatively recent techniques will be reviewed in
more detail. They apply to gas/liquid and liquid/liquid
interfaces. A drop is grown from the tip of a capillary of
radius re with velocity U equal to flow rate divided by 1tfe2•
For a small «< 1) Bond number B := 6pg'~JY (rc«a) and
small capillary number Ca == JlUly, where Jl is the drop
viscosity, the drop shapes are virtually sections of spheres,
and Equation 3 should apply. The pressure is measured
via a sensitive transducer flash-mounted against the wall of
the capillary, upstream from the tip. Flow rates and drop
radii are also monitored.
Several versions of the technique are summarized in
Table 1 ([54-57-]; see also [58,59-,60,61,6Z-]). The work
presented in [55] and [56] is the first true implementation
of the growing drop technique for measuring DST. In
most versions, the drop radius Rtr) is not monitored,
either because it is not needed [55], or because it is
presumed that it can be calculated from the measured
flow rate [56]. The calculation relies on the assumption
that 6p(t) is maximum when Ru) is minimum. When the
surface tension varies with time, however, this assumption
may fail, as follows from differentiating Equation 3 with
respect to time [57-]. In principle, the method allows the
researcher to follow continually the whole time evolution
of ')'(t), in contrast to the interval-time used in the r-,1BPr-,1
and drop weight methods. The type of information gained
from the latter methods is also obtainable from this
method when the pressure is maximized or as the drops
detach. The range of surface ages is 20 ms to minutes.
Figure Z shows typical results obtained with the version
of the technique as practiced in [57-]. Following the
detachment of the previous drop, the rate of interface
dilatation increases rapidly as the new drop starts to grow.
This causes a depletion of the surfactant molecules on the
interface and a concomitant rise in the surface tension.
Once the drop volume exceeds that of a hemisphere, the
rate of interface dilatation slows, allowing the surfactant
299
molecules to repopulate the interface and thereby causing
the tension to fall. Faster measurements require theory
more advanced than Equation 3 (57-,63], because of
oscillatory behavior or aperiodic decay of 6P(t) and R(t)
after the previous drop detaches.
All three versions of the growing drop method for mea-
suring ')'(t) [55,56,57-] suffer, however, from an uncertainty
in the initial state of the system. Although in [55] one
starts at time t = 0 with an equilibrium interface, the
transient fluid motion ensuing the impulsive start of the
drop formation process (OA Basaran, X Zhang, MT Harris,
paper 51K, Winter Annual Meeting of the AIChE, St
Louis, 1993) may lead to tension inhomogeneities which
can cause Marangoni stresses and flow [Zl]. The transient
nature of the flow and pressure fields and the drop shape
that exists within -Z0-50 ms after the drop is set into
motion introduce uncertainty into the knowledge of the
initial state of the system. In the versions of the method
practiced in [56,57-], the state of the interface when
one drop detaches and another one starts growing is also
unknown due to oscillations in the .flow and pressure
fields and the drop shape following the rupture of the
liquid bridge connecting the former drop to the rest of
the liquid in the capillary (63]. The transients that arise in
the experiments of [55,56,57-] will violate the assumption
of radial flow; this is a problem for many of the other
techniques involving drops and bubbles for measuring jit).
These issues concerning the initial state of the system
may be elucidated if the problem of determining the drop
shape from a known ')'(t) is solved rigorously.
Drop weight (or volume) method
When drops of volume V form and fall from a capillary,
their average weight (w = V6pg is approximately balanced
(there is an empirical correction factor F) by the surface
tension force Z1tfcY [3,64]. The surface age (from 1 s to
hours) is estimated from the interval· time tj, as with
the r-,1BPr-,1. The factor F introduces much uncertainty
to this equation, which does not explicitly acknowledge
the intricate details of the flow and the drop breakup.
Recent developments include firstly, observations, at short
interval times, of irregular drop formation dynamics due
to 'wave effects' along the liquid bridge connecting the
drop to the capillary [65]; and secondly submillisecond
visualization of the dynamics that depicts formation of not
only primary drops but also of tiny satellite drops that are
directly produced by bridge breakup [63].
Oscillating jet method
When a liquid jet flows out of a thin orifice of ellip-
tical cross-section, the jet cross-section oscillates (nearly
harmonically) about a circular cross-section, because of
the action of surface tension forces. These stationary
oscillations continue until they are damped out by the
action of liquid viscosity or until the jet breaks up.
Such flows are important in spray formation, polymer
extrusion, and fiber spinning. The wavelength A and the
300 Imaging and other techniques

Table 1
Growing drop method and variants.

Name of Method Pressure Expanding drop Growing drop Growing drop

derivative tensiometer tensiometer method
method

Authors and Passerone et al. Nagarajan and Wasan Macleod and Radke Zhang et al.
reference number (1991) [54) (1993) [55] (1993) [56) (1994) [57°)

What is Equilibrium Dynamic surface Dynamic surface Dynamic surface

measured? tension tension tension tension

Type of flow Continuous Started from rest Continuous Continuous

Is method based Only pressure, p, Both pressure, p, Same as [54) Both pressure,
on measurement is measured. It and initial drop p, and drop
of pressure alone is assumed that p radius are measured. radius, R, are
or both pressure is maximized when Thereafter, R is measured
and shape? Are radius, R, is determined from the
there any minimized. R is flow rate
quest ionable determined from
assumptions? the flow rate

Chief advantage H Data can (+) Data can be H Data can (+) Data can be
(+) and be acquired after acquired be acquired after acquired
limitations or the hemispherical continuously the hemispherical continuously
drawbacks H stage stage (but see text)
(+) Contact line H Contact H Contact (+) Because
position must be line position must position must be drop shape is
fixed throughout be fixed throughout fixed throughout monitored
the experiment the experiment. the experiment continuously,
H Current contact line
implementation position can
limited to slow change during
rates of interface experimentation
dilatation and
small times

Lowest surface Not relevant Not specified Approximately Approximately

age at which 50ms 20ms
measurements
can be made

Maximum rate of 50 ms (optimal) Not specified 20ms O.15ms

data acquisition

damping of the oscillation are me asured to infer the
tension.The surface age is estimated from the position on
the surface and the measured flow rate. A simple 'theory
first developed by Bohr [66] considers the superposition
of three analyses: firstly, the effect of viscosity on
small-amplitude, two-dimensional oscillations of the cross-
sections about a circle; secondly, effect of finite-amplitude
two-dimensional oscillations of an inviscid fluid; and
lastly, small-amplitude vibrations in three dimensions of
an inviscid elliptical jet. With this approximate theory,
physic ally unrealistic tensions (80-200 mN/m for aqueous
solutions) are normally calculated from the first one to
three wavelengths of the jet [25"]. An improved recent
theory aims at better precision for r{t) and simultane-
ous me asurement of the bulk extensional viscosity of
non -Newtonian fluids, but still yields unrealistic tensions,
which introduce a major element of uncertainty in the
technique [67"]. A more rigorous analysis is needed
to account for the three-dimensional free-surface flow
(including Marangoni flows) in the vicinity of the orifice.
The technique probes r{t) and surface ages of 1-500 ms,
and more commonly 10-100 rns, and normally cannot reach
equilibrium tensions.
Other methods
The falling meniscus method [17",68] places a liquid in
a conical container and allows exp ansion or compression
of its surface area, while the surface tension is probed
with a Wilhelmy plate. The inclined plate method (Fig. 1)
uses a falling film whose tension is position dependent.
The DST is monitored with a Wilhelmy plate, which
may introduce a disturbance that is difficult to calculate
in the film flow and the dyn amic adsorption [69]. The
position gives an estimate of the surface age, the accuracy
of which depends on the ' accuracy of the analysis. The
analysis ignores possible film-thickness non-uniformity,
obstruction by the plate, and possible Marangoni flows.
The dynamic capillary method [70] is another example of
 Techniques to measure dynamic surface tension Franses, Basaran and Chang 301

Figure 2 favorite, but perhaps with the pendant drop, growing drop,
emerging bubble, captive bubble, and bubble methods
having an edge.
73.0 . . . - - - - - - - - - - - - - - - - - - - - ,

The oscillating jet technique may remain unreliable until

65.0 the fluid mechanics at the jet entry is better understood.
Further progress is expected in techniques where the fluid
•••••• mechanical analysis is better developed. The Wilhelmy
57.0 ••• •• plate method should be used with explicit knowledge of
o

- - the contact angle. Although some approximate or reason-

49.0 - able data may be obtained with quasistatic approaches,

--
the most exact information may be obtained with truly
ODDCtJoO
00
C dynamic analyses. To avoid the uncertainties in the dead
4LO 0 •••••••••
D D •• - •• time, well defined initial conditions should be used,
a a •
a • preferably starting from an equilibrium interface.
33.0 -
Acknowledgements
ElF and C-HC thank the National Science Foundation (Grant # crs
25.0 L..---'--'-'-..L.L.......I.---'--'-'-..L.L.......I.-......L---I-'--I..L.u.u 93-0-B28) for partial support of this work. OAB acknowledges the
10-2 support received from the Division of Chemical Sciences, Office of Basic
1d Energy Sciences, US Department of Energy, New Directions in Chemical
TIME (s) Engineering Program of the School of Chemical Engineering of Purdue
University and its industrial partners,and the Exxon Education Foundation.
OA13 would like to thank X Zhang and MT Harris' (of Oak Ridge National
Evolution in time of the dynamic surface tension at the interface Laboratory), with whom he had developed the variant of the growing drop
technique reported in (570 ) . OAB also thanks them for their assistance in
between air and a growing drop of water containing 0.01 wt % Triton developing the results reported in Figure 2. Two of us, ElF and OA13. would
X-l00 at various liquid flow rates: open circles, 200mUmin, closed like to acknowledge the training received in interfacial phenomena,colloidal
circles, 100 mU min, open squares, 10 mU min, closed squares, science, and fluid mechanicsfrom our adviser I.E Scriven of the University
5mUmin. The horizontal line represents the equilibrium tension of the of Minnesota. For his unparalleled high standards and his demand for
drop solution/air interface measured with the pendant drop technique. excellence, we dedicate this article to him on the occasion of his 65th
birthday.
The capillary here is a stainless steel tube with inner and outer radii
of 0.0254 and 0.0397 em, respectively.

References and recommended reading

Papers of particular interest, published within the annual period of review,
a rather complex free-surface flow used to infer tensions have been highlighted as:
at small time scales.
- of special interest
-- of outstanding interest
Most of these methods have received limited use. A
more promising recent method involves hydrodynamic 1. Defay R, Prigogine I, Bellemans A, Everett DH: Surface Tension
analysis of a drop levitated in air and oscillating in shape and Adsorption. London: Longmans; 1966.

[71--]. The oscillation frequency is affected by surface 2. Padday JF: Surface tension. Part I. The theory of surface
tension. Part II. The measurement of surface tensIon. Part
tension, and the decay rate is affected by surface (and III. Tables relating the size and shape of liquid drops to the
bulk) rheology. Generally, the simpler a flow method is to surface tension. In Surface and Colloid Science, vol 1. Edited by
Matijevic E. New York: Wiley; 1969:39-251.
analyze, the more reliable the results of DST.
3. Adamson SW: Physical Chemistry 01 Surfaces, edn 5. New York:
Wiley; 1990.
Conclusions 4. Miller CA, Neogi P: Interfacial Phenomena. Equilibrium and
The general principles and importance of measuring Dynamic Aspects. New York: Dekker; 1985.
dynamic surface tensions are discussed. The techniques 5. Davis HT, Scriven LE: Stress and structure In fluid interfaces.
Advan Chem Phys 1981, 49:357-454.
reviewed in this article include the Wilhelmy plate; Du
Noily ring; pendant drop; emerging bubble; sessile drop; 6. Defay R, Petre G: Dynamic surface tension. In Surface and
Colloid Science, vol 3. Edited by Matijevic E. New York: Wiley;
captive bubble; spinning drop (or bubble); maximum 1971 :27-81.
bubble pressure; bubble method; growing drop methods; 7. Valentini JE, Thomas WR, Sevenhuysen P, Jiang TS, Lee HO, Yi L,
drop weight; oscillating jet; and inclined plate. Techniques Yen S'C: Role of dynamic surface tensIon in slide coating. /nd
Eng Chern Res 1991, 30:453-461.
involving the Wilhelmy plate, the pendant, spinning and
growing drop, the emerging and captive bubble and the 8. Knoche M, Tamura H, Bukovac MJ: Stability of the
organosilicone surfactant silwet L-77 In growth regulator
bubble method seem the most promising because of sprays. Hortic Sci 1991, 26:1498-1500.
either their better defined flow field, or their clearer 9. Lemlich R: Adsorptive Bubble Separation Processes. New York:
or simpler theoretical interpretation. For time scales up Academic Press; 1972.
to one second, the bubble and growing drop methods 10. Schunk PR, Scriven LE: Surfactant effects In coating
processes. In Liquid Film Coating: Scientific Principles and Their
are recommended. For longer time scales the choice of Technofogicallmplications. Edited by Kistler SF, Schweizer PM.
method depends on the range of ,,/, T, and p, with no clear New York: Chapman & Hall; 1996, in press.
302 Imaging and other techniques
Adopts a rigorous state-of-the art approach to solve the direct problem in·
volving dynamic surlace tension effects in thin film and coating flows. Also
presents a good summaryof previous work done in the coating flows area
11. Notter RH, FinkelsteinIN: Pulmonary surfactant: an
Interdisciplinary approach. J Appl Physiol Respir Environ
Exercise Physiol 1984, 57:1613-1624.
12. Keough KMW: Physical chemistry of pulmonary surfactant in
the terminal air spaces. In Pulmonary Surfactant: from Molecular
Biology to Clinical Practice. Edited by Van Golde LMG, Batenburg
JJ. Amsterdam: Elsevier; 1992:109-164.
13 . Miller R, Joos P, Fainerman, VB: Dynamic surface and Interfacial
•• tensions of surfactant and polymer solutions. Adv Colloid
Interface Sci 1994, 49:249-302.
Review of several experimental techniques, key models, and data for con-
stant or pulsating area conditions. Contains direct comparisons of data by
different techniques.
14. Chang C-H, Franses EI: Adsorption dynamics of surfactants
at the air/water Interface: a critical review of mathematical
models, data, and mechanisms. Col/aid Surface A 1995,
100:1-45.
Review of thermodynamics and dynamics of adsorption for single surfac-
tants. Focuses on data and mechanisms- diffusion-controlled versus kinetic
or mixed kinetic-controlled.
15. Miller R, Wustnek R, Kragel J, Kretzschmar G: Dilational
• [dilatational! and shear rheology of adsorption layers at liquid
Interfaces. Colloid Surface A 1996, in press.
Important up-to-date review of theory, techniques, and data. including relax-
ation methods for surlace elasticity.
16 . Edwards DA, Brenner H, Wasan DT: Interfacial Transport
Processes and Rheology. Stoneham: Butterworth-Heineman;
1991. . elevated temperatures and pressures. Collo id Surface A 1995,
17. Dukhin SS, Kretzschmar G, Miller R: Dynamics of Adsorption at
Liquid Interfaces. Theory. Experiment; Application. Amsterdam:
Elsevier; 1995.
First comprehensive monograph on dynamic adsorption and tension. In-
cludes three chapters 'on theory and techniques for studying dynamic ad-
sorption and tension. Less detailed on fluid mechanics than [16], which has
a textbook format.
18 . Dorshow RB, Swofford RL: Adjustable resolution surface·
light scattering spectrometer and Its application to the
measurement of Interfacial tension and viscosity In crude oil
systems. Colloid Surface A 1990,43:133-149.
19 . Lunkenheimer K, Miller R: A criterion of judging the purity
of adsorbed surfactant layers. J Colloid Interface Sci 1987,
120:176-183.
20. Lunkenheimer K, Pergande H-J, KrOger H: Apparatus for
programmed high-performance purification of surfactant
solutions. Rev Sci Instr 1987, 58:2313-2316.
21. Scriven LE: Dynamics of a fluid interface: equation of motion
for Newtonian surface fluids. Chem Eng Sci 1960,12:98-108.
22. Good RJ: Contact angles and the surface free energy of solids.
In Surface and Colloid Science, vol 11. Edited by Good RJ,
Stromberg RR. New York: Plenum Press; 1979:1-29.
23 . Berg JC: Wet/ability. New York: Dekker; 1993.
24 . Hartland S, Hartley RW: Axisymmetric Fluid'Liquid Interfaces.
Tables Giving the Shape of Sessile and Pendant Drops and
External Menisci. with Examples of Their Use. Amsterdam:
Elsevier; 1976.
25. Coltharp KA, Franses EI: Equilibrium and dynamic surface
tension behavior of aqueous soaps: sodium octanoate and
sodium dodecanoate (sodium laurate), Colloid Surface A 1996,
in press.
Contains comparisons of data by Wilhelmy plate, spinning bubble, oscillating
jet, and bubble (via pressure measurement) methods.
26. Tsay R-Y, Yan SoC, Un SoY: A video-enhanced plate method for
simultaneous measurements of surface tension and contact
angle. Rev Sci Instr 1995, 66 :5065-5059.
Shows finite advancing contact angles. Contains lillie on dynamic tensions.
27. Young GW, Davis SH: A plate oscillating across a liquid
interface: effects of contaet-anple hysteresis. J Fluid Mech
1987,179:327-356.
28. Hocking lM: Waves produced by a vertically oscillating plate. J
Auid Mech 1987,179:267-281.
29 . Rotenberg Y, Boruvka L, Neumann AW : Determination of surface
tension and contact angle from the shapes of axisymmetric
fluid Interfaces. J Colloid Interface Sci 1983, 93 :169-183.
30. Cheng P, Li 0, Boruvka L, Rotenberg Y, NeumannAW:
Automation of axisymmetric drop shape analysis for
measurements of interfacial tensIons and contact angles.
Col/aid Surface A 1990,43:151-167.
31. Lin SoY, McKeigue K, Maldarelli C: Diffusion-controlled surfactant
adsorption studied by pendant drop digitization. AIChE J 1990,
36:1785-1795.
32 . Lin SoY, McKeigue K, Maldarelli C : Diffusion-limited
Interpretation of the induction period in the relaxation In
surface tension due to the adsorption of straight-chain, small
polar surfactants: theory and experiment Langmuir 1991,
7:1055-1066_
33. Lin S·Y, Lu T·L, Hwang W·B: Measurements of low interfacial
tension by pendant drop digitization. Langmuir 1994,
10:4703-4709.
34. Schurch S, Bachofen H, Goerke J, PossmayerF: A captive
bubble behavior reproduces the in situ behavior of lung
surfactant monolayers. J Appl Physio/1989, 67:2389-2396.
35. Schlirch S, Schurch 0, Curstedt T, Robertson B: Surface activity
of lipid extract surfactant In relation to film area compression
and collapse. J Appl Physio/1994, 17 ;974-986.
A method is set out here, and in more detail in [341. Size ofcaplive bubble,
and surlace area, are altered by changing the chamber pressure. Shows
stable low (-1 mN/m) tensions. Shows evidence of thick films connected to
the interlace layer. .
36 . Schramm LL, Fisher DB, SchOrch S, Cameron A: A captive drop
•• Instrument for surface or interfacial tension measurements at
94:145-159.
Describes new instrument for captive drops or bubbles. Reviews and com-
pares data with other methods.
37. Cayias JL, Schechter RS, Wade WH: The measurement of
low Interfacial tension via the spinning drop technique. In
Adsorption at Interfaces, vol 8. Edited by Millal KL Washington
DC: ACS Symposium Series; 1977:234-247.
38. Davis HT, Manning CD, Pesheck CV, Puig JE, Scriven LE, Seeto Y:
Measurement 01 Interfacial Tension. A Topical Report Issued by the
Bartlesville Energy Technology Center. Bartlesville, Oklahoma: US
Department of Energy; 1983.
39 . Chung 18, Shanks PC, Hannemann RE, Franses EI:
Spinning bubble tensiometry of aqueous dipalmitoyl-
phosphatidylcholine and lung surfactant dispersions. Colloid
Surface 1990. 43:223-240.
40. Joseph DO, Arney M, Gillberg G, Hu HH, Hultman 0, Verdier C,
Vinagre H: A spinning drop tensioextensometer. J Rheo/1992,
36:621-662.
41. Hu HH, Joseph DO: Evolution of a liquid drop In a spinning
drop tensiometer. J Colloid Interlace Sci 1994,162;331-339.
Method was developed [40) for incompatible polymersat high temperatures.
Theory defines roles of viscosity and tension in dynamic evolution of drop
shape.
42 . Enhorning G: Pulsating bubble technique for evaluating
pulmonary surfactant J Appl Physio/1977, 43 :198-203.
43 . Hall SB, Bermel MS, Ko YT, Palmer HJ, Enhorning G, Noller RH:
Approximations in the measurement of surface tension on the
oscillating [or pulsating] bubble surfactometer. J Appl Physiol
1993,75:468-477.
44. Chang C·H, Franses EI: An analysis of the factors affecting
dynamic tension measurements with the pulsating bubble
surfactometer. J Colloid Interface Sci 1994, 164:107-113.
Shows that the standard Laplace-Young equation is adequate for calculating
){t) from !>Ph), if the bulk and surlace dilatation viscosities are not too high.
Relies on [21) and agrees with [431.
45 . Chang C-H, Franses E1: Dynamic surface tension behavior of
aqueous octanol solutions under constant-area and pulsating
area conditions. Chem Eng Sci 1994, 49:313-326.
Comparisons of data with new model of the pulsating bubble. Model in-
cludes large area amplitude and radial flow and predicts (under surface
compression) non-equitibriumsurface tensions lower than equilibrium values,
as observed in [25',42,43,44'].
46 . Kao RL, Edwards DA, Wasan DT, Chen E: Measurement of
Interfacial dilatational viscosity at high rates of Interfacial
 Techniques to measure dynamic surface tension Franses, Basaran and Chang
expansion using the maximum bubble pressure method. J
Colloid Interface Sci 1992,148:247-256.
47. Wantke KD, Miller R, lunkenheimer K: Zur theorie radial
schwingeder blasen in grenflachen-aktiven losungen. Z Phys
Chem 1980 261 :1177-11 90. [Title translation: On the theory of
radially vibmting bubbles in interfacially active solutions.]
48. Wantke K-D, lunkenheimer K, Hempt C: Calculation of the
elasticity of fluid boundary phases with the oscillating bubble
method. J Colloid Interface Sci 1993, 159:28-36.
49. Johnson DO, Stebe KJ: Oscillating bubble tensiometry: a
method for measuring the surfactant adsorptive-desorptive
kinetics and the surface dilatational viscosity. J Colloid Interface
Sci 1994,168:21-31.
Linearized theory for extracting adsorption rate information from tension re-
sponse to harmonic area variation.
50. Mysels K: The maximum bubble pressure method of
measuring surface tension, revisited. Colloid Surface A 1990,
43:241-262.
51. Fainerman VB, Miller R, Joos P: The measurement of dynamic
surface tension by the maximum bubble pressure method.
Colloid Polym Sci 1994, 272:731-739.
52. Rao P, Enhorning G: Surface tension determined with a
micromethod. Colloid Surface B 1995, 4:159-163.
Modification of the MBPM for low-volume (-1 Ill) samples.
53. Fainerman VB, Miller R: Dynamic surface tension measurements
in sub-millisecond range. J Colloid Interface Sci 1995,
7:118-121.
Improves the design of apparatus for making maximum bubble pressure
measurements by increasing the rate of both bubble formation and bubble
detection. Detection methods used include electrical as well as acoustic
ones.
54. Passerone A, Liggieri t, Rando N, Ravera F, Ricci E: A new
experimental method for the measurement of the Interfacial
tension between Immiscible fluids at zero Bond number. J
Colloid Interface Sci 1991,146:152-162.
55. Nagarajan R, Wasan DT: Measurement of dynamic interfacial
tension by an expanding drop tensiometer. J Colloid Interface
Sci 1993, 159:164-173.
56. Macleod CA, Radke CJ: A growing drop technique for
measuring dynamic interfacial tension. J Colloid Interface Sci
1993, 160:435-448.
57. Zhang X, Harris MT, Basaran OA: Measurement of dynamic
surface tension by a growing drop technique. J Colloid Interface
Sci 1994,168:47-60.
Presents the more accurate of the growing drop methods, in which the
liquid flows continuously through the capillary. Uses an ultrahlqh-speedvideo
system that makes it possible to monitor both pressure and radius with
submillisecond resolution. Also investigates and determines the limitations
of the technique.
58. Macleod CA, Radke CJ: Surfactant exchange kinetics at the
air/water interface from the dynamic tension of growing liquid
drops. J Colloid Interface Sci 1994, 166:73-88. .
59. Joos P, Van Uffelen M: Theory on the growing drop technique
for measuring dynamic interfacial tensions. J Colloid Interface
Sci 1995, 171 :297-305.
303
Presents a simplified but useful analysiswith a theory based on diffusion-con-
trolled adsorption kinetics of the growing drop method and puts experimental
measurements made to date with the technique on a firmer foundation.
60. Van Uffelen M, Joos P: Adsorption kinetics with surface
dilatation 3. Adsorption to a surface expanded with a constant
dilation rate. Colloid Surface A 1994, 85:107-118.
61. Van Uffelen M, Joos P: Adsorption kinetics with surface
dilatation 4. Peaktensiometry - adsorption to a linearly
expanded surface. Colloid Surface A 1994, 85:119-125.
62. Soos JM, Koczo K., Erdos E., Wasan DT: An automatic
apparatus for measuring interfacial and film tension
under static and dynamic conditions. Rev Sci Instr 1994,
65:3555-3562.
Presents an improved version of the apparatus described in [55] that is not
only automated but is also capable of studying film tensions and expanding
as well as contracting interfaces. However, neither [55] nor [62'] discusses
the effect of initial transients, due to the interface (or film) being set into
motion impulsively at time t=O, that render the use of the simple static
laplace-Young equation (Equation 3) impossible at early times.
63. Zhang X, Basaran OA: An experimental study of, dynamics of
drop formation. Phys Fluids 1995, 7:1184-1203.
64. Jho C, Burke R: Drop weight technique for the measurement
of dynamic surface tension. J Colloid Interface Sci 1983,
95:61-71.
65. Fainerman VB, Miller R: Hydrodynamic effects in measurements
with the drop volume technique at small drop times. 2. Drop
time and drop volume bifurcations. Colloid Surface A 1995,
97:255-262.
66. Bohr N: Determination of dynamic surface tension by the
method of jet vibration. Philos Trans R Soc Lon Phys Sci Eng
1909,209:281-317.
67. Bechtel SE, Cooper JA, Forest MG, Petersson NA, Reichard Dl,
• Saleh A, Venkataraman V: A new model to determine dynamic
surface tension and elongational viscosity using oscillating jet
measurements. J Fluid Mech 1995, 293:379-403.
Presents the most rigorous to date slender-jet asymptotic theory where the
small parameter is the ratio of the characteristic length in the transverse
(or jet.cross-section) direction to that in the axial direction. The analysis
produces a fully non-linear system of equations at leading order and sys-
tematically accounts for the effect of gravity.
68. Defay R, Hommelen J: Measurement of dynamic surface
tensions of aqueous solutions by the falling meniscus method.
J Colloid Sci 1959, 14:401-410.
69. Van den Bogaert R, Joos P: Dynamic surface tension of sodium
myristate solutions. J Phys Chem 1979, 83:2244-2248.
70. Van Hunsel J, Joos P: Steady-state dynamic Interfacial tensions
of 1-alkanols during mass transfer across the hexane/water
Interface. Langmuir 1987, 3:1069-1074.
71. Tian Y, Holt RG, Apfel RE: Investigations of liquid surface
rheology of surfactant solutions by droplet shape oscillations:
theory. Phys Fluids 1995, 7:2938-2955.
Method is attractive, despite its theoretical and experimental complexity,be-
cause of the absence of contact lines and the existence of rigorous analytical
or semi-analytical solutions of the underlying flow and surfactant transport
problems when the drops undergo linearoscillations. Acquiring a commercial
setup of an acoustic levitator has become easier recently.