Surface tension measurement technique by differential phase detection of capillary

waves in liquids
F. Marinozzi
Citation: Review of Scientific Instruments 71, 4231 (2000); doi: 10.1063/1.1315349
View online: http://dx.doi.org/10.1063/1.1315349
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REVIEW OF SCIENTIFIC INSTRUMENTS

VOLUME 71, NUMBER 11

NOVEMBER 2000

Surface tension measurement technique by differential phase detection

of capillary waves in liquids
F. Marinozzi
Mechanical and Thermal Measurements Laboratory, Department of Mechanics and Aeronautics,
University of Rome La Sapienza, via Eudossiana 18-00184 Rome, Italy

Received 20 December 1999; accepted for publication 2 August 2000

A simple device was developed for measuring surface tension of liquids typically water solutions
based on the mechanical generation of capillary waves on a sample surface. The detection of the
phase shift among two laser beams reflected by the liquid surface excited with a sinusoidal
mechanical perturbation allows the calculation of the sample surface tension. Preliminary
experimentation using a prototype of the instrument with water and water plus surfactant has been
successfully performed. Some theoretical considerations are also pointed out to show the main
design issues for proper operation mode. The proposed prototype appears innovative and suitable for
online or field operation. 2000 American Institute of Physics. S0034-67480002511-9

I. INTRODUCTION

Surface tension is an extremely sensitive indicator providing information on washability, wetting, emulsification,
foaming, and other surface related processes. The progress of
various chemical reactions and presence of solvents or surfactants in a liquid system can be monitored by surface tension measurement. Surface tension also provides information
about the quality of water-repellent finishes, stability of
emulsions, oxidation, polymerization, etc.
Another important feature of measuring surface tension
is given by the opportunity for monitoring water pollution or
evaluating some kind of food adulteration, e.g., methanol
versus ethanol in wine. Furthermore, in biomedical applications, pulmonary surfactant as well as artificial lung surfactant properties can be studied through surface tension
behavior.1,2
The most common way of measuring the surface tension
is with the Du Nouy ring method. A platinumiridium ring is
first immersed into the liquid and then carefully pulled up, by
lowering the sample cup, through the surface of the liquid. A
microbalance records the force applied on the ring while
pulling through the surface. The surface tension is the maximum force needed to detach the ring from the liquid surface.
Another way is given by the Wilhelmy plate method that
uses the same hardware as the ring method. In the dynamic
plate method the platinumiridium plate with a defined perimeter is hung from the microbalance and the plate is immersed in the sample liquid. The plate then is pulled through
the surface of the liquid until the maximum force is reached
and the plate breaks away from the surface.
In the static plate method, the dry plate is lowered to the
surface until its lower edge nearly touches the surface. At
this point the liquid jumps onto the edge of the plate. The
liquid wets the plate perimeter and increases its total mass to
some maximum point which is proportional to the surface
tension of the liquid.
As described, these methods need delicate force measurements by means of a high accuracy microbalance, a

platinumiridium ring or plate with defined geometry and a

precision mechanism to vertically move sample liquid in a
glass beaker. The related instrumentation, the Tensiometer,
does not allow easy operation and field measurements.3
Other traditional measuring systems adopt the bubble
pressure method or the drop volume method. The first calculates the surface tension from the maximum pressure in a
bubble of gas formed in the liquid sample; the latter measures the drop volumes immediately before it detaches from
a pipette orifice.4
In the literature, various techniques are reported for measuring mechanical properties of liquid films by means of
mechanical oscillations induced on the sample. Though these
are very interesting methods, they are mainly related to the
investigation of a particular samples physical properties,
performed with custom designed instrumentation for laboratory use.57
An interesting method for surface velocity measurements in liquids is based on the phase detection of a high
frequency continuous ultrasonic probe beam reflected from
the moving surface.8
The basic purpose of the proposed method is the design
of a new simple instrument for measuring the surface tension
of a wide range of liquids. The operation principle here described allows for easy determination of surface tension
without the need for expensive parts. Both the technique and
the relatively simple design make it suitable for online monitoring and/or field application.
The so-called oscillatory techniques, together with an
optical detection system, have been adopted in investigating
the capillary wave gas exchange, also in the presence of
surfactants.9,10 Another optical technique has been utilized
for measuring the height, slope, and frequency of winddriven capillary waves.11 Techniques similar to the one proposed have been utilized to study surface properties in the
frequency domain,12 and the adsorption of surface active materials at air/liquid interface.13
Furthermore, an apparatus proposed within a consortium

0034-6748/2000/71(11)/4231/5/$17.00
4231
2000 American Institute of Physics
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4232

Rev. Sci. Instrum., Vol. 71, No. 11, November 2000

F. Marinozzi

led by NASA could be considered similar but, unfortunately,

no detailed information was retrieved.14 Moreover, several
reports exist about the so called Surface Tension Driven
Convection Experiment and Oscillatory Thermocapillary
Flow Experiment which investigate, in a microgravity environment, basic fluid physics and transport phenomena that
are fundamental to the understanding of the processing of
materials in space.1517
II. PRINCIPLE OF OPERATION

Surface tension is defined as the force per unit length

acting along the surface of a liquid at right angles to a line
that ideally separates two portions of the liquid surface.
A wave mechanically or thermally induced on a liquid
sample with a depth greater than /2 moves along its free
surface with a speed that depends on liquid density ,
wavelength , surface tension , and sample depth (h)
following the formula:18
u

g 2
2h

tanh
,
2

where g is the acceleration of gravity.

If h/2 and 2 / g, the related terms can be
neglected and Eq. 1 can be rewritten as
u

2
.

Under these conditions, the perturbation propagates

through capillary waves. In water at 25 C, if 17 mm the
gravity term can be neglected; so, for properly utilizing the
simplified formula 2, an excitation frequency greater than
about 10 Hz and a sample depth h/2 must be adopted.
The relationship among wave speed, wavelength, and
frequency of excitation is given by the well known formula:
u .
Under these assumptions, surface tension is expressed as
follows:

2 3
2

FIG. 1. Relationship between phase difference and surface tension at 280

and 2000 Hz, D1.79 mm.

Another method that could be adopted for surface tension involves an excitation frequency for which the two signals have exactly zero phase shift. The main advantage is
due to the great accuracy obtainable when utilizing a zero
phase detection system and thus the excitation frequency can
be servo adjusted to maintain 0.
In Fig. 2 the locus of the zero phase shift points in the
frequency-surface tension plane is traced.
III. DESCRIPTION OF THE INSTRUMENT

Referring to Fig. 3, a HeNe, 5 mW, laser beam LB

with nominal spot size of 0.8 mm is split by the 45 plate
beam splitter PB and fed to the liquid samples surface
LS. The beam splitter is a noncoated BK7 glass plate (n
1.515). The two beams are then reflected back by the
sample surface, bent by the mirror M and sent to the largearea photodiodes P No. 1 and P No. 2. The photodiodes
active area is partially screened by two blade edges E.
Waves on the surface of the liquid are excited by the
actuator Act that sinusoidally moves up and down the blade
B. Thus, the reflected beams oscillate with an amplitude
which depends on the intensity of the mechanical perturbation and the distance between the moving blade and the reflection point.

This latter expression states that the sample density

must be known.
The basic principle is to calculate the surface tension by
measuring the phase shift of a mechanically excited capillary
wave between two different points at distance D. If the
wavelength is , the phase shift is given by

D
1 .

Surface tension is then obtained, for a fixed frequency ,

calculating from Eq. 5 and solving Eq. 4.
Figure 1 shows the phase variation among the received
signals for two different frequencies, plotted versus the surface tension. It is evident that by increasing the excitation
frequency, a better sensitivity is obtainable, but this could
originate ambiguous phase detection within the measurement
range.

FIG. 2. Excitation frequency vs surface tension when phase shift among the
signals is maintained to zero. Distance between the laser beams is equal to
the wavelength of the capillary waves, that is D/1, D1.79 mm.
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Rev. Sci. Instrum., Vol. 71, No. 11, November 2000

Surface tension measurement

4233

FIG. 4. Projection of the oscillating beam reflected by the liquid sample

LS over the photodiode P. The output of the photodiode is proportional
to the portion of the Gaussian beam impinging the active area.

FIG. 3. Experimental setup: LSliquid sample, Actelectromagnetic actuator, Bblade, LBlaser beam, PBplate beamsplitter, Eshielding
edges, Mmirror, P No. 1 and P No. 2photodiodes.

The phase relationship between the signals generated by

the photodiodes at a given excitation frequency depends on
the laser spot spacing D upon the surface of liquid sample.
Referring to formula 5, accurate determination of the distance D, is fundamental for measuring the phase shift . In
this case, D is related to the beam splitter thickness as
follows:

D ,n, 2 tan arcsin

sin
n

cos ,

where n is the beam splitter refraction index and the impinging angle of the laser beam. If the expected beam spacing equals the wavelength , no phase shift occurs. Variations of the parameters , n, , cause an error in the value
of D according to the expression:

D ,n,
.

For example, with 1.8 mm a systematic error of

about 1% could arise from: a a 30 m variation of the
nominal value of 2.4 mm; b a 0.7% variation of n BK7
glass1.5; c 2 of beam splitter tilt.
Furthermore, a bad value of the wavelength could derive from a nonexact zero phase condition among the received signals. Referring to Eq. 5, about 4 of phase shift
yields again a 1% error on the value of D.
Another possible error can originate from the lack of
parallelism between the line ideally passing through the laser
spot centers and the wave propagation direction. So, a nonzero angle yields an apparent beam spacing D
D cos( ); however, it is evident that gross misalignments
such as 10, cause only a 1.5% error.
Finally, all the reported errors should be referred directly
to the calculated value of the surface tension . From Eq. 4
can be shown that a 1% error on the nominal 1.79 mm
yields a 3% error on the surface tension .
By proper positioning of the screening edges (E) it is
possible to accurately shape the pulses generated by the pe-

riodical passage of the oscillating laser spot across the photodiode. Since the photodiode output is proportional to the
integral of the spot projected on the active area, different
situations can occur as depicted in Fig. 4. If the amplitude of
oscillation is small compared to the spot size, then a roughly
sinusoidal signal is obtained. On the other hand, large oscillations yield square patterns because the whole spot is alternately moving in and out of the active area. The duty cycle
of these signals is 50% if the oscillating spot is centered
along the knife edge when the mechanical excitation is off.
Generally, the normalized expression of the received signal versus time, corresponding to the shaded areas in Fig. 2,
has the following form:
s t

1
2 2

A sin t

exp

xm x 2 y 2

22

dx dy,
8

where A and are the amplitude and the pulsation of the

liquid surface oscillation, represents the diameter of the
Gaussian spot and m x represents its position with respect to
the blade edge E. Figure 5 shows the behavior of simulated
signals obtained with two different amplitude oscillations.
Also depicted is the duty cycle variation due to a noncentered laser spot.

FIG. 5. Effect of oscillation amplitude (A) on the shape of the signal: a

A /10, b A , square. Trace c shows the effect of shifting by m
2 the laser spot toward the active area.
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F. Marinozzi

FIG. 6. Phase matching obtained for a water sample with an excitation

frequency of 218 Hz. Signals are filtered and normalized.

If a small area photodiode has been adopted, the passage

of the spot back and forth would have caused a strong second
harmonic to appear, even larger than the fundamental one.
The use of a large area sensor together with the shielding
blade edge allows to obtain a pseudosinusoidal signal with a
small number of minor harmonic components, in order to

FIG. 7. Mismatch at 281 Hz with the sample surface touched with a pin tip
wetted with commercial dish soap. Signals are filtered, non-normalized.

ease the phase relationship measurement among the reflected

beams.
The phase was extracted from each photodiode signal
using the Hilbert transform. Assuming that a sinusoidal signal is obtained after passband filtering, then one can combine
the normalized photodiode outputs s 1 and s 2 as follows:

s 1 s 2 2 H s 1 s 2 2

2 arccos

sin t sin t 2 H sin t sin t 2

2 arccos

sin t sin t 2 cos t cos t 2

2 arccos

22sin t sin t 2cos t cos t

2 arccos

2 1cos

2 arccos

4cos2 /2

2 arccos

To minimize edge effects due to signal discontinuity, s 1

and s 2 were windowed; furthermore, for each of the two
signals, the first and last 200 samples points of the entire
3000 sample acquisition were eliminated. The standard deviation of the phase calculated in this manner from simulated
signals typically ranges between 0.01 and 0.3 with a mean
value of 0.15 which corresponds to a 0.12% spreading of
the calculated value of water surface tension.
IV. FIRST EXPERIMENTAL RESULTS

Some preliminary tests were performed to validate the

measuring principle proposed. A sample of distilled water
was analyzed at a temperature of 251 C; surface tension
of water against air19 at 251 C is 71.97E30.3E3
N/m.

Figure 6 shows that the zero phase shift condition (D

) was reached with a beam distance D1.79 mm at 281
Hz. Calculating in the zero shift condition using Eq. 4
yields a surface tension value equal to: 75.5E3
3.2E3 N/m. The uncertainty introduced by the phase detection using the Hilbert filter is negligible. The positive offset of about 3.5 N/m is probably due to the low frequency
oscillations of the liquid free surface. In fact, the lack of
perpendicularity between the laser beams and the sample introduces an unwanted phase shift which yields a greater apparent wavelength and thus a greater surface tension value
see Eq. 4. The apparent wavelength is roughly equal to
app/cos( ), where is the mean angle formed by the
liquid surface between its horizontal and actual positions,
due to the low frequency oscillations. For example, a value
of 10, makes app1.82 mm and app75.5EN/m.

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Rev. Sci. Instrum., Vol. 71, No. 11, November 2000

Surface tension measurement

4235

However, a more detailed analysis of the nature of this error

exceeds the aim of this article.
To explore further capabilities of the proposed apparatus, a simple experiment was done. Figure 7 shows the effect
obtained by touching the surface with a pin tip of a commercial dish soap and then the water sample surface. The signals
are now out of phase. To reestablish the zero phase condition
the frequency was adjusted to 181 Hz. This latter experimental possibility suggests the utilization of the device as a tool
for studying the properties of surfactant layers, such as adsorption dynamics at the air/water interface.20

cillations of the free liquid surface. In the present work, a

digital filter, after signal acquisition and A/D conversion, has
been utilized. The phase behavior of the filter plays a minor
role since only the phase difference between two nearly sinusoidal signals is measured. A different approach can be
adopted by means of analog filtering and, e.g., synchronous
phase detection of the signals, using a phase locked loop
system.
Further investigations must be done to accurately characterize the instrument with various samples of known surface tension value.

V. DISCUSSION

ACKNOWLEDGMENTS

The aim of this work was to present an original technique for measuring the surface tension of liquid samples
against air.
The measurement principle together with some considerations relative to the practical realization have been described. The viability of an instrument designed in accordance with the proposed technique was pointed out.
The first experimental evidence confirms the effectiveness of the adopted method in performing surface tension
measurements with neither expensive parts nor complex apparatus.
The obtainable accuracy is influenced by that of the laser
spots spacing which in turn depends on the beam splitter
thickness, refraction index, and tilt with respect to the sample
surface. Nevertheless, all these quantities can be previously
determined by means of several standard techniques, and the
related systematic errors can be reasonably minimized.
Therefore, the measurement of the phase shift among the
reflected beams is actually the critical task in evaluating surface tension with this technique. With this simple experimental setup, without using any expensive instrumentation e.g.,
a lock-in amplifier, the zero phase shift condition was detected via software elaboration with a typical standard deviation of about 4.5. This value corresponds to a standard deviation of about 4% in measuring the surface tension of
water.
Actually, the dimension of the rectangular container
does not have any fundamental influence on the measurement result since capillary waves are subjected to a strong
decay due to the sample viscosity.18 In water, at a distance of
0.1 m, the wave amplitude decreases by a factor of 70, so the
choice of a relatively large container allows the control of
this source of error. Consequently, phase perturbations due
to frontally reflected waves tend to be canceled in virtue of
the differential nature of the measurement.
Furthermore, some care should be adopted when extracting the carrier frequency from the raw signal. Large low
frequency components are often present due to random os-

The author wishes to deeply thank Professor F. P.

Branca and Professor F. Scudieri for their support and constant encouragement in doing this work. A sincere acknowledgment goes to E. Pichini for her skilled collaboration and
loyal friendship. Thanks to Anne Nebel for the advice during
the revision of this article.
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