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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 and n,e are not equal. The transient surface tension is
surface tension aim at incorporating measurements during usually different from "Ie and is defined as the dynamic
area changes, and improving speed of measurements, surface tension , J<t), or DST [6]. Once certain molecules
automation, and range of time scales (~1 rns), New adsorb, they may reorganize further (i.e. reorient, change
techniques incorporate better definition of surface age and conformation, change domain size etc.) without changing
of the flow field , before or during measurements. They point rj(t). The relationship between J<t) and n(t) is the
to truly dynam ic measurements, where the trans ient interface dynamic surface equation of state, which mayor may not
shape is rigorously analyzed in terms of the flow, pressure, be unique, because of surface relaxation effects, and which
and concentration fields. may be the same or different from the equilibrium surface
equation of state, "Ie(rj,e)'

Address
'School of Chemical Engineering, Purdue University, West Lafayette,
Measuring J<t) is important for its own sake , for inferring
IN 47907-1283 , USA Ij(t), and for understanding other dynamic interfacial
[e-mail: franses@ecn.purdue.edu phenomena, such as foaming, emulsification, surface
te-mail: obasaran@ecn.purdue.edu rheology, coating flows, etc. These phenomena affect
§Department of Chemical Engineering. National Cheng
Kung University; Tainan,Taiwan 701, Republic of China;
many technological, biological, and medical applications,
e-mail: changch@mail.ncku.edu.tw such as foam-based separations; agricultural chemicals,
#Aulhor to whom correspondence should be sent fermenta tions, photographic film, polymer blending, and
Current Opinion in Colloid & Interface Science 1996, 1:296-303
lung surfactants [7-9,10·,11,12]. The subject has received
much attention recently, as shown by several reviews and
© Current Science Ltd ISSN 1359·0294 books [13··,14·,15·,16,17·].
Abbreviations
-y(t) dynamic surface tension, or DST This art icle focuses on three areas: reviewing and evaluat-
G gas
L liquid
ing the most important techniques for measuring dynamic
L' second liquid phase surface tensions; providing guidelines on how to evaluate
MBPM maximum bubble pressure method literature methods and data; and helping research workers
S solid to select th e method(s) best suited to their needs.

Introduction , Perspective and key points


Equilibrium surface, or interfacial, tension of gas/liquid Many interfacial phenomena involving drops, bubbles,
(G/L) or liquid/liquid (L/L) interfaces is defined as the menisci, liquid jets, and thin films are affected by the
surface excess stress integrated over the interfacial zone equilibrium, or dynamic, surface tension. In principle, any
[1-5]. Solutions or dispersions containing surface active of these phenomena, properly analyzed and interpreted,
molecules (surfactanrs, amphiphiles, lipid s, proteins etc.) may be used to infer the value of surface tension. Most
usually exhibit a decrease in the equilibrium surface ten - equilibrium methods may be used to measure J<t), and
sion, "Ie (mN/m), because of adsorption at the interfaces. there are certain methods by which one can measure solely
The relation of the equilibrium surface excess density dynamic tension. Most methods involve measurement of
or adsorbed density (densities) ri,e (mol/m l , for solutes forces, interface shapes, pressure differences, or flow rates
i = 1,2,...) to "Ie is called the equilibrium surface equation [1-4,13 ••,14.,15.,16,17°]. Optical methods are beyond the
of state. For soluble surfactants, ri,e is related to the bulk scope of this review, but interested readers can refer to [18]
concentrations Cj (j = 1,2,...) by the adsorption equilibria. for further information.
The Gibbs adsorption isotherm of surface thermodynamics
relates "Ie to Cj. The drivin g force for adsorption is usually The choice of method depends on the nature of the
minimization of the surface Gibbs free energy. Molecular interface (G/L, L/L), the rheology of the liquid(s), the
mechanisms include the hydrophobic effect, electrostatic range of tensions, the range of temperatures and pressures,
attraction, and stereospecific, or other, binding. The the needed range of surface age required, ease of analysis,
equilibrium surface tension "Ie (Cj) can be measured using accura cy, precision, speed, and practical considerations of
various techniques [2-4). con venience, cost, and combination with other surface
probing techniques. Impurities may affect the tension
Establishing the equilibrium adsorbed density takes time, substantially. Issues of surface chemical purity, which may
from approximately IO~ s to hours or day s, during which affect the interpretation of tension measurements, have
the dynamic adsorbed densities, rj(t) (where t is time) been discussed [17·,19,20).
Techniques to measure dynamic surface tension Franses, Basaran and Chang 297

Measurements of DST usually start (at t =0) from a clean popular, allowing i1J situ surface purification by sweeping
('nascent') interface (li[O] =0) or from an equilibrium away (Of aspirating) the surface layer [19,20,25·).
interface. In the former case, the formation of the interface
involves some flow, which in turn affects y(t) for some A major uncertainty of force methods is the non-unique
time, during which measurements are not possible or value of 8(t), which depends on meniscus velocity, prior
meaningful. The 'dead time', td, affects the definition wetting history, and adsorption at, and surface energies
of the actual surface age, which may differ from t in of, all three interfaces (G/L, LIS, G/S) [4,23]. Moreover,
ways which are difficult to quantify without elaborate the above equations are really rough approximations of the
computations. Moreover, when an interface forms, the fluid physics: they ignore the dynamic nature of the capil-
surface age may not be uniform across the interface, lary rise, namely the finite time required for the meniscus
possibly resulting in Marangoni flows [21] (flows driven by and the underlying liquid to flow after a change in y(t).
a surface-tension gradient), which should be accounted for Measurements from "1= 1000 to -1 mN/m are' possible
when interpreting measurements. (with an uncertainty of 0.1 mN/m or better), every 0.1 s
or faster. Dead times of 10-100 s preclude measurements
Many techniques use the so-called quasistatic approach, at lower time scales. Recent developments {26·] include
in which it is assumed that y(t) affects the dynamic more precise, automated, and fast measurements, but not
interface shape (or pressure, or force) just as "Ie affects improvements in interpretation despite advances in the
the equilibrium shape. A more rigorous approach would be fluid mechanics of dynamic meniscus rise [27,28].
the dynamic approach: calculating the shape exactly based
on y(t), and understanding the 'direct problem', before Shape and pressure methods
the 'inverse problem' of inferring y(t) from the dynamic The well known Laplace-Young equation relates y(t) to
shape is addressed. This latter approach has been applied the pressure jump 6p across the interface [1-5):
recently and bodes well for more rigorous and precise
measurements in the future. In the following section,
several important techniques are reviewed and evaluated
6p = y(l.. + l..)
r1 rZ
(3)

using the above and other criteria. Even though they are where fJ and r2 are the principal radii of curvature. If the
classified as force, shape, pressure, or flow methods, they drop or bubble dimensions are lower than the capillary
may involve a combination of these probes. 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
Description and review of the most important maximum bubble pressure method (MBPM) and other
methods bubble methods (see below). If R~a, the drop or bubble
Force methods is deformed by gravity forces. The resulting shape can be
When a solid substrate is inserted at a fluid/liquid inter- calculated, or the direct problem can be solved, most easily
face, a meniscus forms (Fig. 1). At the fluid/liquid/solid for planar or axisymmetric interfaces [1-9,24). Examples
contact line, with wetted perimeter, I, an unbalanced force that are based on solving the inverse problem include the
F(t) is generated by the surface tension forces (3): pendant drop method, the emerging (or pendant bubble)
method, the sessile drop method, the captive bubble
F(t) = ){t) l cos aCt) ( 1) method, Schurch's special captive bubble method (see
below), and the spinning drop (or bubble) method (Fig. 1).
where 8(t) is the dynamic contact angle [4,22·,23). The
concomitant capillary rise (hjtl) at the wall can be Recently the pendant drop (or bubble) method has been
estimated from the equilibrium equation as follows [4,24): used extensively, with dead times of 2-4 s and automated
image analysis approximately every 0.1 s or so [29-33)
htt) = 2"1(t)(1_cosa(t») (2) (DO Johnson, KJ Stebe, personal communication). The
6pg method is convenient and generally reliable. Uncertainties
where 6p is the density difference and g is the acceleration in interpretation include the quasistatic character of
of gravity. If 8(t) were independently known (or 8[t) =0), Equation 3, which ignores effects of fluid viscosity and of
y(t) may be determined from either equation, from meas- non-uniformity in surface tension [4,21). Recent advances
urements of Fft) or of hu), Otherwise, both measurements include the rigorous solution of the dynamic shape for
and equations would be required. These principles form constant "I(OA Basaran, X Zhang, t\IT Harris, paper 51k,
the basis of the Wilhelmy plate method, which is best Winter Annual Meeting of the AIChE, St Louis, 1993),
used for gas/liquid interfaces with a static plate, and the with possible future extensions to y(t). This work also
DuNoiiy ring method, in which the ring is continuously examines the validity of the simple static Laplace-Young
pulled until the meniscus breaks. The former method equation, Equation 3, in dynamic situations and quantifies
is also used in Langmuir troughs in which the surface the departure of the real flow inside a pendant drop
area is varied via surface barriers. The Wilhelmy plate from a simple radial flow. The captive bubble method
method with a Langmuir trough is simple, convenient, and 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 The bubble method was used under constant or pulsating
or pulsating area conditions [34,35-,36--J, area conditions, for R = 0.050cm < a, with pressure meas-
urements [42,43,44-,45-]. Very low surface tensions were
In the above methods the drop shape is determined by a reported under dynamic area compression. The conditions
balance of gravity and surface tension forces, whereas in under which Equation 3 is a good approximation were
the spinning drop method the drop (or bubble) shape is defined recently [43,44-]. At low frequencies, bulk vis-
governed by a balance of centrifugal (or, more precisely, cosity effects are unimportant for low-viscosity liquids,
centripetal) and surface tension forces [3,4,37,38]. The as are surface dilatational viscosity effects [16,21J. There
spinning drop method was applied to variable area are conditions, however, for which the surface dilatational
conditions and very low surface tensions « 10 mN/m) and viscosity, Ks may be the dominant factor affecting 6p(t);
interfacial tensions (as low as 10-4 mN/m), but only in then the method may be used to measure Ks, rather than
the quasi static mode [25,39]. The solution of the dynamic ')'(t) [46]. For tensions y5, lOmN/m, the condition R<a is
shape, at constant y, was reported recently [40,41-]. no longer valid, and the surface tension is also inferred
Extension to a time-dependent y may result in a truly from the bubble shape [43]. The oscillating bubble
dynamic system. method, in which small-amplitude area oscillations and
Techniques to measure dynamic surface tension Franses, Basaran and Chang 299

bubbles (or drops) deformable by gravity (R2:a) are used, molecules to repopulate the interface and thereby causing
was developed early [13--,17-,47,48] and recently analyzed the tension to fall. Faster measurements require theory
more rigorously [49-] (DO Johnson, KJ Srebe, personal more advanced than Equation 3 (57-,63], because of
communication). Sometimes the results are reported in oscillatory behavior or aperiodic decay of 6P(t) and R(t)
terms of the surface elasticity dy/dlnA = (dy/dt)/(dNAdt). after the previous drop detaches.
The bubble methods have provided valuable information
at small time scales (from 0.1 s to minutes) and various All three versions of the growing drop method for mea-
frequencies. suring ')'(t) [55,56,57-] suffer, however, from an uncertainty
in the initial state of the system. Although in [55] one
Flow methods and other methods starts at time t = 0 with an equilibrium interface, the
The maximum bubble pressure method (MBPM) transient fluid motion ensuing the impulsive start of the
In this popular method for establishing ')'(t), one measures drop formation process (OA Basaran, X Zhang, MT Harris,
the pressure needed to blow a bubble into a liquid from paper 51K, Winter Annual Meeting of the AIChE, St
a capillary tip [3,17-]. The surface age is estimated, at Louis, 1993) may lead to tension inhomogeneities which
interval times tj from the frequency of bubble formation, can cause Marangoni stresses and flow [Zl]. The transient
and normally ranges from 0.1 s to minutes. Recent nature of the flow and pressure fields and the drop shape
developments have reduced the minimum surface age to that exists within -Z0-50 ms after the drop is set into
0.1-1 ms [50,51,5Z-,53-]. motion introduce uncertainty into the knowledge of the
initial state of the system. In the versions of the method
Growing drop methods practiced in [56,57-], the state of the interface when
These relatively recent techniques will be reviewed in one drop detaches and another one starts growing is also
more detail. They apply to gas/liquid and liquid/liquid unknown due to oscillations in the .flow and pressure
interfaces. A drop is grown from the tip of a capillary of fields and the drop shape following the rupture of the
radius re with velocity U equal to flow rate divided by 1tfe2• liquid bridge connecting the former drop to the rest of
For a small «< 1) Bond number B := 6pg'~JY (rc«a) and the liquid in the capillary (63]. The transients that arise in
small capillary number Ca == JlUly, where Jl is the drop the experiments of [55,56,57-] will violate the assumption
viscosity, the drop shapes are virtually sections of spheres, of radial flow; this is a problem for many of the other
and Equation 3 should apply. The pressure is measured techniques involving drops and bubbles for measuring jit).
via a sensitive transducer flash-mounted against the wall of These issues concerning the initial state of the system
the capillary, upstream from the tip. Flow rates and drop may be elucidated if the problem of determining the drop
radii are also monitored. shape from a known ')'(t) is solved rigorously.

Several versions of the technique are summarized in Drop weight (or volume) method
Table 1 ([54-57-]; see also [58,59-,60,61,6Z-]). The work When drops of volume V form and fall from a capillary,
presented in [55] and [56] is the first true implementation their average weight (w = V6pg is approximately balanced
of the growing drop technique for measuring DST. In (there is an empirical correction factor F) by the surface
most versions, the drop radius Rtr) is not monitored, tension force Z1tfcY [3,64]. The surface age (from 1 s to
either because it is not needed [55], or because it is hours) is estimated from the interval· time tj, as with
presumed that it can be calculated from the measured the r-,1BPr-,1. The factor F introduces much uncertainty
flow rate [56]. The calculation relies on the assumption to this equation, which does not explicitly acknowledge
that 6p(t) is maximum when Ru) is minimum. When the the intricate details of the flow and the drop breakup.
surface tension varies with time, however, this assumption Recent developments include firstly, observations, at short
may fail, as follows from differentiating Equation 3 with interval times, of irregular drop formation dynamics due
respect to time [57-]. In principle, the method allows the to 'wave effects' along the liquid bridge connecting the
researcher to follow continually the whole time evolution drop to the capillary [65]; and secondly submillisecond
of ')'(t), in contrast to the interval-time used in the r-,1BPr-,1 visualization of the dynamics that depicts formation of not
and drop weight methods. The type of information gained only primary drops but also of tiny satellite drops that are
from the latter methods is also obtainable from this directly produced by bridge breakup [63].
method when the pressure is maximized or as the drops
detach. The range of surface ages is 20 ms to minutes. Oscillating jet method
Figure Z shows typical results obtained with the version When a liquid jet flows out of a thin orifice of ellip-
of the technique as practiced in [57-]. Following the tical cross-section, the jet cross-section oscillates (nearly
detachment of the previous drop, the rate of interface harmonically) about a circular cross-section, because of
dilatation increases rapidly as the new drop starts to grow. the action of surface tension forces. These stationary
This causes a depletion of the surfactant molecules on the oscillations continue until they are damped out by the
interface and a concomitant rise in the surface tension. action of liquid viscosity or until the jet breaks up.
Once the drop volume exceeds that of a hemisphere, the Such flows are important in spray formation, polymer
rate of interface dilatation slows, allowing the surfactant 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 (including Marangoni flows) in the vicinity of the orifice.
tension.The surface age is estimated from the position on The technique probes r{t) and surface ages of 1-500 ms,
the surface and the measured flow rate. A simple 'theory and more commonly 10-100 rns, and normally cannot reach
first developed by Bohr [66] considers the superposition equilibrium tensions.
of three analyses: firstly, the effect of viscosity on
small-amplitude, two-dimensional oscillations of the cross- Other methods
sections about a circle; secondly, effect of finite-amplitude The falling meniscus method [17",68] places a liquid in
two-dimensional oscillations of an inviscid fluid; and a conical container and allows exp ansion or compression
lastly, small-amplitude vibrations in three dimensions of of its surface area, while the surface tension is probed
an inviscid elliptical jet. With this approximate theory, with a Wilhelmy plate. The inclined plate method (Fig. 1)
physic ally unrealistic tensions (80-200 mN/m for aqueous uses a falling film whose tension is position dependent.
solutions) are normally calculated from the first one to The DST is monitored with a Wilhelmy plate, which
three wavelengths of the jet [25"]. An improved recent may introduce a disturbance that is difficult to calculate
theory aims at better precision for r{t) and simultane- in the film flow and the dyn amic adsorption [69]. The
ous me asurement of the bulk extensional viscosity of position gives an estimate of the surface age, the accuracy
non -Newtonian fluids, but still yields unrealistic tensions, of which depends on the ' accuracy of the analysis. The
which introduce a major element of uncertainty in the analysis ignores possible film-thickness non-uniformity,
technique [67"]. A more rigorous analysis is needed obstruction by the plate, and possible Marangoni flows.
to account for the three-dimensional free-surface flow 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
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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.
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Advan Chem Phys 1981, 49:357-454.
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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
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either their better defined flow field, or their clearer 9. Lemlich R: Adsorptive Bubble Separation Processes. New York:
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302 Imaging and other techniques

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