JOURNAL OF COLLOID AND INTERFACE SCIENCE

ARTICLE NO.

196, 136147 (1997)

CS975214

Axisymmetric Drop Shape Analysis: Computational Methods

for the Measurement of Interfacial Properties from the Shape
and Dimensions of Pendant and Sessile Drops
O. I. del RB o and A. W. Neumann 1
Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario M5S 3G8, Canada
Received September 27, 1996; accepted October 9, 1997

State-of-the-art axisymmetric drop shape analysis (ADSA)

techniques for the computation of interfacial tensions and contact
angles by fitting the Laplace equation of capillarity to the shape
and dimensions of pendant and sessile drops are presented. More
accurate, efficient, and reliable versions of the technique for the
measurement of contact angles from the volume and diameter of
sessile drops [axisymmetric drop shape analysisdiameter
(ADSA-D)] and for interfacial tension measurements from a series of arbitrary profile coordinates of sessile and pendant drops
[axisymmetric drop shape analysisprofile (ADSA-P)] have
been developed. Advanced numerical methods have been used to
improve the numerical stability and global convergence, for more
accurate results and a wider range of applicability of the methods.
A new technique called axisymmetric drop shape analysisheight
and diameter (ADSA-HD) has been developed to estimate interfacial tensions from the height and diameter of sessile and pendant
drops. Numerical simulations using numerically generated drop
profiles were used to evaluate the accuracy and applicability of
the methods. q 1997 Academic Press
Key Words: interfacial tension; surface tension; contact angle;
drop shape analysis; pendant drop; sessile drop.

1. INTRODUCTION

In recent years, the use of automated computer software

for the measurement of interfacial properties of fluids, i.e.,
surface tensions g and contact angles uc , has not only improved the accuracy of the measurements considerably (1
4) but it has also permitted the study of phenomena that
were not possible or difficult to investigate in the past, such
as ultralow interfacial tensions (5), the relaxation of adsorption layers (6), and dynamic surface tensions (7). Using a
desktop computer, the time required for a single interfacial
tension measurement has been reduced from hours of dedicated work to just a few seconds, allowing thousands of
time-dependent measurements to be performed, unattended,
in a single day.
1

To whom correspondence should be addressed.

136

0021-9797/97 $25.00
Copyright q 1997 by Academic Press
All rights of reproduction in any form reserved.

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Numerous methodologies have been developed for the

measurement of interfacial tensions and contact angles,
as outlined in Refs. ( 8, 9 ) . Of these, axisymmetric drop
shape analysis ( ADSA ) methods are considered to be the
most powerful because of their accuracy, simplicity, and
versatility ( 3, 10 ) . They are also very suitable for automated computer implementation by means of digital image analysis ( 2 ) .
ADSA methods are based on the numerical fit between
the shape of experimental drops (or bubbles) and the mathematical model given by the classical Laplace equation of
capillarity. They are applicable to pendant and sessile drops
in a very wide range of surface tensions, for any fluidliquid
system that can be represented by the Laplace equation of
capillarity. Early efforts in the analysis of axisymmetric
drops to determine surface tensions were those of Bashforth
and Adams (11) and Maze and Burnet (12), who developed
the numerical strategy on which modern methods are based,
i.e., the numerical integration of the Laplace equation and
the use of nonlinear least-squares optimization techniques.
The most powerful and widely used method to date is that
of Rotenberg et al. (1), called axisymmetric drop shape
analysisprofile (ADSA-P). Jennings and Pallas (10) developed a similar method, built on Rotenberg and colleagues work, in an attempt to make the method computationally more efficient, but they introduced numerical simplifications that affect the accuracy of the method.
Another advantage of ADSA methods is that contact
angles, as well as volume and surface area, can be computed
simultaneously. This led to the development of axisymmetric
drop shape analysisdiameter (ADSA-D), which computes contact angles based on the volume and diameter of
sessile drops with known surface tension (13, 14). ADSAD is particularly powerful for low contact angles (e.g., uc
207 ) where other methods present difficulties.
Another popular method for estimating surface tensions
is the one developed by Malcolm and Elliott (15), which
uses a semiempirical equation to approximate surface ten-

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AXISYMMETRIC DROP SHAPE ANALYSIS

dV
px 2 sin u,
ds

[1d]

dA
2px,
ds

[1e]

x(0) z(0) u(0) V (0) A(0) 0,

FIG. 1. Coordinate system used in the numerical solution of the Laplace

equation for axisymmetric liquidfluid interfaces.

sion from the total height H and maximum diameter D of a

sessile drop or captive bubble with a 1807 contact angle.
Although this method is limited to a particular case, their
approach has been extended to sessile drops of any contact
angle (16) and can be further generalized to pendant drops.
This approach has been applied to measure low interfacial
tensions that can be generated in pulmonary surfactant by
compressed captive bubbles (1720) and other systems with
ultralow interfacial tensions (5).
This paper describes recent developments in the ADSAP and ADSA-D methodologies and introduces a new technique, axisymmetric drop shape analysisheight and diameter (ADSA-HD), to determine surface tension based on the
height and diameter of sessile and pendant drops. Efficient,
general-purpose numerical algorithms that make use of recent developments in numerical analysis have been implemented, and a numerical library of ADSA algorithms has
been created to facilitate implementation and further development of the methodologies. Emphasis has been given to
the numerical accuracy, efficiency, flexibility, and stability
of the methods. The only assumptions made are that the
drops or bubbles are Laplacian and axisymmetric.
2. NUMERICAL SOLUTION FOR AXISYMMETRIC
LIQUIDFLUID INTERFACES (ALFI)

The classical Laplace equation of capillarity describes the

mechanical equilibrium conditions for two homogeneous
fluids separated by an interface. For axisymmetric interfaces
it can be written as the following system of ordinary differential equations as a function of the arc length s, as shown in
Fig. 1 (1):

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dx
cos u,
ds

[1a]

dz
sin u,
ds

[1b]

du
sin u
2b / cz 0
,
ds
x

[1c]

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[1f]

where b is the curvature at the origin of coordinates and c

( Dr )g/ g is the capillary constant of the system. u is the
tangential angle which, for sessile drops, becomes the contact angle uc at the three-phase contact line. Although the
surface area A and the volume V are not required to define
the Laplacian profile, they are included here because of their
importance and the fact that they can be integrated simultaneously with little computational overhead. It should also
be noted that since at the apex of the drop,
sin u
b
x

at s 0,

then Eq. [1c] becomes

du
b
ds

at s 0,

[1g]

which avoids a division by zero, and there is no need to use

analytical approximations to initialize the integration as done
by Dimitrov et al. (21).
For given values of b and c, a unique shape of a Laplacian
axisymmetric fluidliquid interface can be obtained by simultaneous integration of the above initial value problem.
However, there is no known analytical solution for this problem, except for very limited cases, and a numerical integration scheme must be used, as implemented in the axisymmetric liquidfluid interfaces (ALFI) computer program described below.
There exist several numerical methods to solve systems
of ordinary diferential equations for initial value problems
and considerable research is still devoted to this subject
(22). The three major types of methods most commonly
used are the RungeKutta, BurlischStoer extrapolation,
and predictorcorrector methods (23). For simple equations
and when efficiency is of no concern, fixed stepsize implementations are often used, but they are not suitable when
accuracy and computational efficiency are important. Hartland and Hartley (24) used a fourth-order RungeKutta
method with truncation error control to solve the Laplace
equation (1). Rotenberg et al. (1) and Jennings and Pallas
(10) implemented a second-order implicit Euler method.
After testing and comparing other methods, it was found that
the BurlischStoer scheme with adaptive stepsize control is

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DEL RIO AND NEUMANN

computationally efficient but it can fail for large drops with

very low surface tension.
A more efficient and flexible method is the fifth- and
sixth-order RungeKuttaVerner pair, as implemented by
Hull, Enright, and Jackson in the DVERK FORTRAN numerical routines (25, 26). Some important features of this
code are its defect-based error and stepsize control that
allows large integration steps with controlled accuracy, its
flexible design that allows the calling program to interrupt
and continue the integration after any step, and its capability
to produce continuous approximations to the solution on
each step using very accurate interpolations. These features
are important to improve the speed and accuracy of ADSA
computations, where numerous integrations are required, as
described later.
ALFI was written, implementing the HullEnrightJackson numerical integration scheme, to generate Laplacian profiles of pendant and sessile drops of any size and surface
tension by numerically integrating the initial value problem
[1]. The following are some of the features of ALFI:
The volume V and surface area A are computed simultaneously with the drop profile with negligible computational
overhead. These properties are useful in applications such
as the ADSA film balance (27).
The integration can be stopped when any given values
of s, u, x, z, V, or A are reached, allowing the computation
of drop profiles of any specified contact angle, volume, surface area, or size. The integration also terminates if u reaches
1807 (sessile drops) or becomes negative (pendant drops).
The inflection point of pendant drops is accurately computed, which is useful for testing and evaluating drop profile
methods.
The origin of the coordinate system can be translated
and rotated arbitrarily, and the coordinates can be scaled in
the horizontal and vertical directions. This feature permits
the comparison between theoretical and experimental drop
profiles which have generally an arbitrary origin of coordinates, can be vertically misaligned due to a vertical misalignment of the video camera, and have an arbitrary magnification.
The profile coordinates can be randomly perturbed in
the normal direction, allowing the simulation of experimental errors, which can be used to evaluate ADSA methods.

ALFI has been found very useful not only in producing

tables and plots of Laplacian data as done by Hartland and
Hartley (24) and by Bashforth and Adams (11), but it is
also a very important tool to test and evaluate drop shape
analysis methods, as described later.
As mentioned before, ALFI generates complete Laplacian
profiles from values of b and c by integrating the initial
value problem [1]. The inverse process of determining b
and c (from which g and contact angle uc can be easily

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computed) based on drop profile characteristics is a more

difficult task and forms the basis of the ADSA methods
described in the following sections.
3. CONTACT ANGLE MEASUREMENTS
FROM DIAMETER AND VOLUME
OF SESSILE DROPS (ADSA-D)

The ADSA-D methodology to compute contact angles uc

from the contact or maximum diameter D (usually measured
from a picture of the drop looking from above) and volume V
of sessile drops with known surface tension g was originally
developed by Skinner et al. (13) and Moy et al. (14). The
basic scheme of their implementation was to generate Laplacian profiles by integration of [1] for different values of b,
comparing the measured and the computed volumes at the
given diameter, until convergence, employing a Newton iteration. However, this approach, also known as single shooting, has numerical deficiencies and can fail if the initial
values are distant from the solution. In this section, a boundary-value-problem approach to ADSA-D is described, which
is numerically more stable and easier to implement.
As in the original ADSA-D, there are two cases to consider(1) uc 907 and (2) uc 907 which represent
two separate boundary-value problems since in the first case
the maximum diameter corresponds to the equatorial diameter of the drop (at u 907 ) and in the second case the
maximum diameter corresponds to the three-phase contact
line (at u uc ) (see Fig. 2).
a. Contact Angle Greater than or Equal to 907
Rewriting equations [1a] [1c] as functions of x, considering the curvature b as a new variable, and with the boundary conditions as seen in Fig. 2a, the Laplace equation can
be written as the following boundary-value problem for uc
907:
du
1

dx
cos u

2b / cz 0

sin u
x

[2a]

dz
tan u,
dx

[2b]

db
0,
dx

[2c]

z(0) u(0) 0,

u(R)

p
2

[2d]

where R D/2 is the maximum (equatorial) radius. Problem

[2] completely defines the Laplacian shape; its solution
gives directly the profile shape for 0 x R, and the
constant value of the apex curvature b. The contact angle

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AXISYMMETRIC DROP SHAPE ANALYSIS

FIG. 2. Boundary conditions for ADSA-D boundary-value problems

[2] and [3]. (a) Contact angle greater than or equal to 907; (b) contact
angle less than 907.

uc can then be computed by integrating Eq. [1], for the

known values of b and g, past the maximum diameter, stopping when the computed volume reaches the drop volume,
Vc . This problem thus requires a boundary-value problem
solver plus a numerical integration.

b. Contact Angle Less than 907

Similarly, as seen in Fig. 2b, the Laplace equation for
uc 907 can be written as the following boundary-value
problem:
du
1

dx
cos u

2b / cz 0

sin u
x

[3a]

dz
tan u,
dx

[3b]

dV
px 2 tan u,
dx

[3c]

db
0,
dx

[3d]

z(0) u(0) V (0) 0,

V ( R) Vc .

[3e]

Here Vc is the total volume of the drop. Problem [3] completely defines the Laplacian shape. There is no need for an

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139

additional numerical integration since the contact angle can

be obtained simply from uc u(R).
To initialize ADSA-D it is necessary to determine, for
given values of Vc and R, whether uc 907 (problem [2])
or uc 907 (problem [3]). On occasion, the user can give
this information as input, but in many cases, especially for
uc near 907, it is not known. The approach implemented in
the program is (1) if the user knows whether the drop is
wetting ( uc 907 ) or nonwetting ( uc 907 ), solve the
respective problem and exit; otherwise, (2) assume uc 907
and solve problem [2] for the given R, and compute volume
V90 at u 907 by numerically integrating [1]. If V90 Vc
the initial assumption was correct, compute uc , and exit;
otherwise, (4) solve problem [3] for uc 907.
The nonlinear problems [2] and [3] must be solved numerically. Numerical methods to solve boundary-value problems can be divided into two main categories (28, 29):
initial value or shooting methods, and finite difference or
collocation methods. The original implementation of ADSAD used a variation of the single shooting method, which is
known to have stability drawbacks. Multiple shooting methods are more stable but, after some tests, they were found to
be inefficient for Laplacian problems, particularly for welldeformed drop shapes. A more efficient approach is the use
of finite-difference methods with collocation formulas, as
implemented in the COLSYS FORTRAN library by Ascher
and Bader (28), which uses collocation at Gaussian points
to approximate the solution.
COLSYS, as well as any other nonlinear numerical
method, requires initialization with approximate values of
the solution. For the case of uc 907, the profile and the
curvature are initialized with an elliptical approximation,
and for uc 907 the solution is initialized with zero values
and the curvature with 1/R. It was found that these rough
approximations are sufficient for COLSYS to converge.
Nevertheless, a continuation algorithm (subdividing the
problem into several easier-to-solve steps) was implemented
to guarantee convergence to a solution in case of an initial
failure of COLSYS, using the capillary constant c as the
continuation parameter.
4. SURFACE TENSION MEASUREMENTS FROM
HEIGHT AND DIAMETER OF SESSILE
AND PENDANT DROPS (ADSA-HD)

Several methods to approximate g from the height H and

diameter D of sessile drops, based on semiempirical equations and/or Laplacian tables, have been developed in the
past (15, 16). However, these methods are restricted to special cases (e.g., sessile drops with uc 1807 ) and their
accuracy is limited for a certain range of height/diameter
ratios (20), even when perfect numerical data are used.
In this section a boundary-value-problem approach to this

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DEL RIO AND NEUMANN

case, problem [4] is a three-point boundary-value problem;

if H and D are measured at the same location, i.e., u1 u2 ,
it becomes a two-point boundary-value problem.
As in the ADSA-D implementation (see above), the COLSYS library can be used to solve problem [4], taking advantage of its ability to handle multiple-point boundary conditions. The algorithm in this case is initialized using an elliptical fit that satisfies the boundary conditions [4e], an initial
curvature equal to the curvature of the fitted ellipse at the
origin, and the capillary parameter is initialized with a usersupplied value, which can be a very rough estimate, as seen
in Section 9. A continuation algorithm has also been implemented in case COLSYS fails initially.

FIG. 3. Boundary conditions for ADSA-HD boundary-value problem [ 4 ] .

problem is presented, which is exact (to a specified numerical tolerance) and general: it is applicable to sessile drops
(wetting and nonwetting) and pendant drops, and it can be
used with any measured height and diameter, not necessarily
the equatorial diameter and maximum height.
The most general case, as shown in Fig. 3, can be defined
by the following boundary-value problem, written as a function of the tangential angle, with both the apex curvature b
and the capillary parameter c as unknown constants:

S
S

D
D

dx
sin u
cos u 2b / cz 0
du
x

01

dz
sin u
sin u 2b / cz 0
du
x

01

x(0) z(0) 0,

[4a]

[4b]

db
0,
du

[4c]

dc
0,
du

[4d]

x( u1 ) R,

z( u2 ) H. [4e]

Here R D/2. Problem [4] completely defines the drop

shape; its solution determines the profile coordinates for any
u, as well as the (constant) values of b and c from which
g and other drop properties, e.g., uc , V, and A, can be readily
computed by the numerical integration of [1]. The same
definition of the problem can be applied to pendant and
sessile (wetting and nonwetting) drops. The only limitation
is that, for pendant drops, the boundary conditions at u1 and
u2 must be measured before the inflection point ( uinf in Fig.
3) for the problem to have a unique solution. In the general

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5. SURFACE TENSION MEASUREMENTS BY

DROP PROFILE FITTING OF SESSILE
AND PENDANT DROPS (ADSA-P)

The ADSA-P methodology to determine interfacial properties by means of a numerical fit of several arbitrary drop
profile coordinates to the Laplace equation was originally
developed by Rotenberg et al. (1) using a four-parameter
nonlinear least-squares fit with a Newton optimization
scheme and incremental loading or parameter continuation.
This method has been used successfully to measure interfacial tensions in a variety of systems for several years (4)
but it has presented convergence problems for some systems
with ultralow interfacial tension and very flat drop shapes
because of the limitations of Newtons method when the
initial parameters are distant from the solution. A new version of ADSA-P is presented in this section, implementing
additional optimization parameters and more efficient and
globally stable numerical methods. Also, the original optimization parameters have been redefined, using the curvature
at the apex b instead of the radius of curvature (R0 b 01 )
and making the parameters independent of each other, which
simplifies the algebra and the numerical analysis.
Similarly to the original ADSA-P, the strategy used is to
construct and minimize an objective function E, defined as
the sum of the weighted squared normal distances between
any N profile coordinates and the Laplacian profile (problem
[1]), as seen in Fig. 4:
N

E wi ei ,

[5a]

i1

ei 12 d 2i 12[(xi 0 Xi ) 2 / (zi 0 Zi ) 2 ].

[5b]

Here, wi is a weighting factor, (Xi , Zi ) are the measured

drop coordinates, and (xi , zi ) are the Laplacian coordinates
closest to (Xi , Zi ). Currently, wi is set equal to 1.0 until
more studies are available on the effect of weighting factors.
By introducing the generally unknown origin (x0 , z0 ) and

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AXISYMMETRIC DROP SHAPE ANALYSIS

tance from the Laplacian curve to each experimental point.

This is done using a one-dimensional NewtonRaphson iteration to solve, for each ith point,
f (s)

FIG. 4. Definition of error function parameters for ADSA-P optimization problem [5].

angle of rotation of the system of coordinates a, and scaling

factors on both coordinates (Xs , Zs ), the individual error can
be written (dropping the subscript i) as
e 12 (e 2x / e 2z ),

[5c]

ex x 0 x0 0 Xs X cos a / ZsZ sin a,

[5d]

ez z 0 z0 0 Xs X sin a 0 ZsZ cos a.

[5e]

The objective is therefore to compute the set of M optimization parameters a that minimizes [5], where a [b c x0 z0
a Xs Zs ] T or any subset of it. This definition is more general
than the four parameters used by Rotenberg et al. and is
similar to the parameter set used by Jennings and Pallas
(10). It should be noted though that only one of the scaling
factors, Xs or Zs , can be optimized simultaneously with b
and c for the solution to be unique. Generally one of the
scaling factors is known from the experimental setup and
can be held constant while optimizing the other to correct for
the aspect ratio to calibrate the optical system. The rotational
angle a can also be optimized to correct for the rotational
misalignment of the camera for calibration purposes, but it
can be held constant once the system has been calibrated,
provided the camera has not been moved.
The optimization problem can be written as
N

min E(a) wi ei (a).

a

[6]

i1

Problem [6] is a multidimensional nonlinear least-squares

problem that requires an iterative optimization procedure.
When the minimum has been found, the optimization parameters determine the Laplacian profile that best fits the given
profile, from which g and other properties can be readily
computed.
Evaluating E for a trial set of a, i.e., for each optimization
iteration, involves determining the minimum (normal) dis-

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de
ex cos u / ez sin u 0.
ds

This procedure requires several numerical evaluations of the

initial value problem [1] for each data point, and in previous
versions of ADSA-P it required several numerical integrations of [1] (approximately 3N integrations) that made the
evaluation of E computationally expensive. With the implementation of the numerical integration package of Hull, Enright, and Jackson, DVERK, only one integration of [1] is
necessary to evaluate E for any given set of the parameters
a, and any intermediate values are computed with the inexpensive and equally accurate function approximation routine
of DVERK, called INTRP (26).
In the work of Jennings and Pallas the residuals are computed using a linear interpolation in an attempt to reduce
computational time. However, this approach introduces
larger errors on sections of the drop with larger curvature
and is not suitable for highly curved surfaces. The Newton
Raphson approach implemented in ADSA-P is exact, to the
given numerical tolerance, for all curvatures and drop profiles.
There exist several numerical methods to solve optimization problems. Among them, Newtons method is well
known for its second-order convergence if the initial values
are very close to the solution, but it is unpredictable otherwise, particularly for multidimensional problems. To overcome this problem, several Newton-like algorithms have
been developed with more advanced convergence strategies.
The original ADSA-P used Newtons method with incremental loading to approach the solution, but this approach
is computationally expensive and its convergence is not
guaranteed. Jennings and Pallas (10) used a modified
GaussNewton method with restricted step. Another method
commonly used for nonlinear least-squares optimization is
the LevenbergMarquardt algorithm which can be described
as a trust-region implementation of the GaussNewton
method (30).
In this version of ADSA-P, a combination of the Newton and Levenberg Marquardt methods were implemented. Very often, as in the case of time-dependent studies, the results from a previous run can be used as initial
values and Newtons method can be used to take advantage of its fast convergence. The FORTRAN linear algebra
packages LAPACK and BLAS were used to solve the
system of equations to compute the Newton iteration
steps. The Newton optimization is aborted as soon as divergence is detected or if the Hessian matrix is found to
be nonpositive-definite ( 27 ) .

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DEL RIO AND NEUMANN

If good initial values are not available or if Newtons

method fails, the LevenbergMarquardt method is used.
This method takes advantage of numerical properties particular to least-squares problems, is known to be globally convergent, and needs only first-order derivatives to build the
Jacobian matrix. The numerical implementation chosen here
is the LevenbergMarquardt with derivative (LMDER) routines from the FORTRAN MINPACK library developed by
More and Wright (31).
Both the first derivatives needed to construct the Jacobian
matrix used by LMDER and the second derivatives needed
to construct the Hessian used by Newtons method are computed with the same degree of accuracy as the objective
function by simultaneous numerical integration of the derivatives together with the integration of [1], as described in
Ref. (1). This involves the simultaneous numerical integration of a system of 11 first-order ordinary differential equations for the LMDER routines and 20 for the Newton
method.
Of the seven possible optimization parameters, the most
difficult one to initialize is the capillary parameter c. It can
be initialized with either a call to ADSA-HD, with results
from a previous run (e.g., time-dependent studies), or with
user-supplied values. The effect of this initial value on the
performance of the program is evaluated in Section 10. Good
initial values for b, x0 , and z0 can be found by a least-squares
elliptical fit of several points near the drop apex, and the
rotational angle a and the scaling factors Xs and Zs are generally known from the experimental setup.
6. TESTING AND EVALUATION PROCEDURE

The evaluation of ADSA methods requires that drop profiles of known surface tension and apex curvature be given
as input data, so the numerical results can be compared
with the known values of the parameters. Since experimental
values of surface tension and curvature are generally uncertain or unknown, the evaluation of ADSA numerical methods is best done by means of synthetic or theoretical
drops, obtained by numerical integration of the Laplace
equation. Another advantage of using synthetic drop profiles
is that the sensitivity of the methods can be easily measured
by perturbing the input data to simulate experimental errors,
and comparing the results with the known exact solution.
The following sections describe how the ALFI program
was used to generate synthetic profiles to test and evaluate
the ADSA methods presented above. The computational
times were measured on a Sun SPARCstation 10 (60-MHz
SuperSPARC CPU) and are presented here only as reference. Comparative or even faster performance can be obtained on other computer systems, e.g., Intel Pentium personal computers.

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FIG. 5. Sessile and pendant drop profiles generated with ALFI for
testing and evaluating ADSA program.

7. TESTING AND EVALUATION OF ALFI

The numerical profiles obtained with ALFI agree, within

a specified numerical precision, with those published by
Hartland and Hartley (24) and with other numerical integration schemes tested; they are not reproduced here. By tracing
the numerical integration steps, it was found that, as the
numerical integration routine DVERK automatically adjusts
the stepsize along the profile to control the estimated numerical errors, small steps are usually needed near the drop apex
and increasingly larger steps (compared to the total arc
length) afterward.
Several drop profiles, both sessile and pendant, were generated during the testing and evaluation of the programs.
Figure 5 shows some selected profiles with a variety of drop
shapes, with the corresponding parameters shown in Table
1. The capillary parameter c 13.45 cm02 used for some
of the profiles corresponds to a value typical of a waterair
system. The computational performance of ALFI is of the
order of 0.05 s to produce 100 plotting points for each drop.
A numerical tolerance of 10 08 was used to generate the drop
profiles.
8. TESTING AND EVALUATION OF ADSA-D

ADSA-D requires as input c, R, and V of a sessile drop,

and returns the contact angle uc . Table 2 shows the results
of running ADSA-D for sessile drops S1S5 with arbitrarily

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AXISYMMETRIC DROP SHAPE ANALYSIS

TABLE 1
Parameters of Sessile (S) and Pendant (P) Drop Profiles, Generated with ALFI, Used in the Testing and Evaluation of ADSA
Methods.a
S1
c (cm02)
b (cm01)

c (cm02)
b (cm01)

S2

S3

S4

S5

13.45
0.03

13.45
10.0

1.0
1.0

1000.0
1.0

P1

P2

P3

P4

P5

013.45
5.838

013.45
10.0

013.45
1.0

01.00
2.0

01000.00
50.00

13.45
0.734

a
c is the capillary constant (Dd)g/g and b is the curvature at the drop
apex.

selected contact angles. The input values were obtained from

the data generated by ALFI for the respective contact angles.
A numerical tolerance of 10 06 was used in the computations.
It can be seen that ADSA-D returns the correct contact angle
with negligible errors in all the cases. Table 2 also shows
the computational time t required to run ADSA-D. Its performance is always satisfactory, with better performance for
contact angles less than 907 (less than 0.5 s). In all the cases
tested, the method succeeded in the first call to the boundary
problem solver COLSYS; i.e., parameter continuation was
not required.
To evaluate the sensitivity of the method to experimental
errors, each input parameter can be perturbed by a small
amount d, comparing the resulting contact angles with the
original one. In practice, V can be measured with a micrometer syringe with an accuracy of 10 05 cm3 (0.01 ml), D can
be measured using digital image analysis with an accuracy
better than 0.15% (approximately one pixel on a 640 1 480
image), and c can be obtained with an accuracy better than
1.0%. These experimental errors would produce the contact
angle errors shown in Table 3, where each row shows the
error obtained by perturbing each input parameter (keeping
the others constant) and the last row is the maximum combined error obtained by perturbing all the input parameters.
The tests show that the method is not very sensitive to experimental errors for small contact angles, for which the best
results are obtained (e.g., an error of less than 0.57 for contact
angles less than 307 and less than 17 for contact angles less
than 907 ). For contact angles greater than 907 the method
is more sensitive and more accurate measurements are required for good results.
These results agree with the experimental results obtained
by Skinner et al. in the evaluation of the original ADSA-D
method (13). The effect of nonaxisymmetry of the drops
was also addressed by Skinner et al. The larger errors for
contact angles greater than 907 are due to the faster angular
change of the drop profiles below the maximum diameter,

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which causes larger changes in contact angle for small perturbations of any parameter, especially for large values of
c. Note that drop S5 with uc 1807, which produced the
largest errors, corresponds to a very large value of c. Also,
for drop S1 with uc 57 the maximum error is due to the
very small volume of the drop, but with a more accurate
volume measurement the error would be negligible.
9. TESTING AND EVALUATION OF ADSA-HD

The only input required by ADSA-HD is coordinate information (x, z, u ) of one or two arbitrarily selected profile
points, from which c (therefore g ) is computed. See Eq.
[4]. The points of maximum diameter and maximum height
are usually chosen since they are easier to measure, but the
method is not limited to any particular locations. In practice
these coordinates can be accurately measured from a digital
image.
Table 4 shows the results and performance of ADSA-HD
for the sessile and pendant drops of Fig. 5 using arbitrarily
selected boundary points. D, H, u1 , and u2 are the input
data, t is the computational time required to run the program,
c is the output capillary constant, and cerror is the output error.
A tolerance of 10 06 was used, and the initial value of c was
always given with an error greater than or equal to 25% of
the exact solution, e.g., cinit 0.1, 10, 500 for c 1, 13.45,
1000, respectively. Every run shown in the table converged
in the first iteration (i.e., no parameter continuation was
required) in less than 0.5 s, except for pendant drop P3
which required two continuation iterations, hence the longer
computational time. It can be seen that the method is not
very sensitive to the initial estimate of c. The program succeeded for all the sessile and pendant drops tested with relative numerical errors within the specified tolerance.
To evaluate the sensitivity of the method to experimental
errors, the input values of H and D were perturbed by 0.15%
TABLE 2
Computational Results of ADSA-D for Exact Values
of Input Dataa
Drop
S1,
S1,
S2,
S3,
S4,
S5,
S5,

57
1207
107
807
307
1807
457

c
(cm02)

R
(cm)

V
(cm3)

t
(s)

uc
(deg)

uerror
(deg)

13.45
13.45
13.45
13.45
1.00
1000.00
1000.00

0.1161
0.6562
1.1152
0.0965
0.4849
0.1401
0.1299

0.00011
0.4578
0.1236
0.0014
0.0486
0.0032
0.00089

0.19
1.16
0.23
0.38
0.30
1.50
0.26

5
120
10
80
30
180
45

2.11e-04
9.83e-06
6.40e-08
6.71e-07
5.33e-08
1.0e-08
5.63e-05

a
uc is the output contact angle and uerror is the numerical error. The error
values are expressed in standard scientific notation; e.g., 1.0e-05 is equal
to 1.0 1 1005.

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DEL RIO AND NEUMANN

TABLE 3
Maximum Contact Angle Errors (deg) from ADSA-D for Typical Experimental Errorsa

dc
dD
dV
Maximum

S1, 57

S1, 1207

S2, 107

S3, 807

S4, 307

S5, 1807

S5, 457

0.0006
0.022
0.468
0.489

0.508
0.520
0.0033
1.024

0.028
0.036
0.0008
0.065

0.0082
0.187
0.295
0.490

0.0031
0.122
0.0056
0.131

11.04
9.816
9.498
17.30

0.134
0.156
0.492
0.779

a
Each row represents the error obtained by perturbing the parameters c, D, and V, simulating typical experimental errors. The maximum error
corresponds to the worst-case scenario by perturbing c, D, and V simultaneously.

of the original values (approximately one pixel on a 640 1

480 digital image), and the resulting value of c was compared with the original one. These results are shown in Table
5. It can be seen that the sensitivity of the method varies
from drop to drop, with errors of less than 1% for some
drops but higher errors in other cases. This behavior depends
on the slope of the multidimensional topology of the given
problem and seems to be unpredictable, but it can be evaluated by perturbing the input data by the estimated measurement errors as described above. Further tests show that, for
a given drop, the error becomes smaller when the input data
are measured at larger angles u1 and u2 ; e.g., the error obtained using data points near u 1807 for drop S4 is approximately 1%.
10. TESTING AND EVALUATION OF ADSA-P

ADSA-P differs from the other ADSA methods in that it

requires as input an arbitrary number N M of profile
coordinates, where M is the number of optimization parameters. To test the accuracy of the algorithm, synthetic drops
S1S5 and P1P5 were given as input to the program, using
N 21 points and a numerical tolerance of 10 08 . The results
TABLE 4
Computational Results of ADSA-HD for Exact Values
of Input Dataa
Drop

D/2
(cm)

H
(cm)

u1
(deg)

u2
(deg)

t
(s)

c
(cm02)

cerror
(cm02)

S1
S2
S3
S4
S5
P1
P2
P3
P4
P5

0.6562
1.1152
0.0965
0.4849
0.1401
0.1860
0.1024
0.1839
0.4461
0.0217

0.4578
0.0503
0.0793
0.1278
0.0664
0.2705
0.2058
0.0166
0.2632
0.0250

90
10
80
30
90
90
90
10
60
90

120
10
80
30
180
100
140
10
60
90

0.35
0.47
0.35
0.35
0.45
0.50
0.32
1.33
0.33
0.44

13.45
13.45
13.45
1.0
1000.0
013.45
013.45
013.45
01.0
01000.0

1.0e-07
1.0e-07
4.0e-07
1.0e-07
9.8e-05
1.0e-06
3.2e-06
4.5e-05
1.0e-06
4.4e-04

c is the output capillary constant and cerror the numerical error.

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are shown in Table 6. It can be seen that the numerical errors

are negligible.
As mentioned earlier, the ADSA-P optimization algorithm
requires as input the initial values of the optimization parameters, which, except for the capillary constant c, can be
estimated using an elliptical least-squares fit. To evaluate
the global convergence and the sensitivity of the method to
the initial value of c, a wide range of initial values were
given as input to the program and the results are shown in
Table 7 for both Newton and LevenbergMarquardt optimization methods. It can be seen that the LevenbergMarquardt method succeeds for any initial value of c without a
significant increase in computational time, while the Newton
method succeeds only if the initial value is very close to the
exact solution ( {10% in this particular case). However,
when successful, the Newton method is considerably faster
than the LevenbergMarquardt method.
Figure 6 shows the computational performance of the
methods when different numbers of data points N are used.
For the Newton optimizations, initial values of 0.9 c were
used. It can be seen again that the Newton method is considerably faster but it failed to converge for drops S1, S4, and
S5, while the LevenbergMarquardt method succeeded in
all the cases.
TABLE 5
Capillary Constant Errors (% of Exact Solution) from
ADSA-HD for Typical Experimental Errorsa

dR
dH
Maximum

dR
dH
Maximum

S1

S2

S3

S4

S5

0.11
0.41
0.52

0.050
0.35
0.40

7.13
7.42
14.57

8.85
9.16
18.07

0.011
0.31
0.32

P1

P2

P3

P4

P5

0.71
0.41
1.12

1.01
0.71
1.71

5.29
5.0
10.33

6.95
6.65
13.62

1.11
0.81
1.92

a
Each row represents the error obtained by perturbing the parameters R
and H, simulating typical experimental errors. The maximum error corresponds to the worst-case scenario of perturbing both R and H.

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AXISYMMETRIC DROP SHAPE ANALYSIS

145

TABLE 6
Numerical Results of ADSA-P for Sessile (S) and Pendant (P)
Drops Using N 21 Points

c (cm02)
cerror (cm02)

c (cm02)
cerror (cm02)

S1

S2

S3

S4

S5

13.45
7.0e-08

13.45
7.6e-06

13.45
2.7e-04

1.0
8.1e-07

1000.0
8.3e-05

P1

P2

P3

P4

P5

013.45
2.4e-06

013.45
2.0e-06

013.45
1.3e-04

01.0
3.6e-06

1000.0
3.6e-03

To simulate the effect of experimental errors on ADSAP, ALFI was used to randomly perturb the Laplacian profiles
with a maximum normal perturbation of approximately one
pixel of a 640 1 480 digital image. Sessile drops of various
contact angles and pendant drops from the apex to the inflection point were used, as seen in Table 8. The inflection
points of the pendant drops were used only for convenience;
ADSA-P is not limited by nor needs information about the
inflection point. It can be seen that the larger errors correspond to sessile drops of low contact angle and pendant drop
P3, which does not have an equatorial diameter or a neck.
Otherwise, the accuracy is better than 1% for sessile drops
with uc 907 and better than 0.5% for pendant drops with
a neck, particularly when using N 50 points.
11. DISCUSSION

Recent advances in ADSA techniques have been presented in this paper: new versions of the ADSA-D and
ADSA-P methods that overcome the main limitations of
earlier versions, e.g., numerical instability and failure to converge for certain ultralow interfacial tensions and well-deformed drop shapes, and a new method called ADSA-HD
that computes surface tension from the height and diameter
of sessile and pendant drops. Advanced, general-purpose
numerical methods that are well known for their numerical
stability have been used, making the software more flexible
TABLE 7
Performance of ADSA-P for Initial Values
of c from 0.1c to 2.0ca

tN (s)
tLM (s)
cerror (cm02)

0.1c

0.5c

0.9c

1.1c

1.5c

2.0c

1.30
3.3e-06

1.30
2.4e-06

0.36
1.30
7.6e-07

0.27
1.22
9.7e-07

1.33
2.0e-06

1.41
1.9e-06

a
Drop P1 with N 21 points was used. tN and tLM are the computational
times required using the Newton and LevenbergMarquardt optimization
methods, respectively.

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FIG. 6. Computational performance of ADSA-P for sessile and pendant

drops using Newton and LevenbergMarquardt optimization methods.
Computational times measured on a SPARCstation 10 computer (60 Mhz
SuperSPARC CPU). Similar results can be obtained on other computer
systems, including personal computers.

and easier to implement. No numerical simplifications were

made, to make the programs as accurate as possible. This
strategy has proven successful as can be seen by the wide
range of applicability of the methods, i.e., the wide range
of surface tensions, drop sizes, and variety of drop shapes
for which the programs succeed. Ultralow interfacial tensions and well-deformed drop shapes are no longer a limitation of the methods.
Numerical simulations, performed with the aid of a program that generates theoretical drop profiles (ALFI), show
the applicability of the methods. Contact angles can be measured with an accuracy better than 17 with ADSA-D from
the volume and diameter of sessile drops, and an accuracy
of 0.17 is readily obtainable for drops with low contact
angles, e.g., uc 307. However, more accurate measurements are required to obtain accurate contact angles for drops
near 1807 contact angle. ADSA-HD can be used to estimate
surface tension by measuring only height and diameter of a
pendant or sessile drop with an accuracy of about 2% for
drops with an equatorial diameter, i.e., sessile drops with uc
907 and pendant drops with a neck. ADSA-P can be used
for more accurate surface tension measurements, with which
an accuracy better than 0.5% is readily obtainable, with better results for pendant drops with a neck and sessile drops
with uc 907.
Since the input required by ADSA programs consists of only
a few drop profile coordinate measurements, they can be used
with any kind of data acquisition, although digital image analy-

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DEL RIO AND NEUMANN

TABLE 8
Computational Results of ADSA-P for Sessile (S) and Pendant (P) Drops after Perturbing Every Profile Coordinate by a Random
Normal Distance, with a Maximum Perturbation Equivalent to Approximately the Distance between Two Consecutive Pixels in a 640
1 480 Digital Image
N 21

S1,
S2,
S3,
S4,
S5,
P1,
P2,
P3,
P4,
P5,

1207
107
807
307
1807
1107
1437
187
1277
1097

N 51

N 101

c (cm02)

cerror (%)

c (cm02)

cerror (%)

c (cm02)

cerror (%)

c (cm02)

cerror (%)

13.419
13.428
14.371
1.146
991.76
013.432
013.425
013.179
00.995
0997.03

0.22
0.16
6.84
14.6
0.82
0.14
0.18
2.02
0.52
0.30

13.415
13.733
13.667
1.035
992.33
013.433
013.436
012.993
00.996
0996.66

0.26
2.11
1.61
3.54
0.77
0.13
0.10
3.40
0.35
0.33

13.407
13.700
13.679
0.953
991.99
013.428
013.447
013.077
00.997
0997.93

0.32
1.86
1.70
4.73
0.80
0.16
0.02
2.77
0.27
0.21

13.408
13.517
13.426
1.020
993.13
013.425
013.427
013.305
00.998
0998.06

0.31
0.50
0.18
2.03
0.69
0.19
0.17
1.08
0.21
0.19

sis is recommended for more accurate results and complete

automation. The software was designed to be used as
standalone programs or as a numerical library that can be easily
integrated with other modules such as image acquisition, image
analysis, and volume and surface area control.
All the programs were written in C, with FORTRAN interfaces to make use of the third-party FORTRAN numerical
libraries mentioned throughout the paper. They can be compiled on any computer system with C and FORTRAN compilers and can be obtained from the authors.
APPENDIX: ABBREVIATIONS

ADSA
ADSA-P

Axisymmetric drop shape analysis

ADSA based on profile coordinates of pendant
and sessile drops
ADSA-D
ADSA based on the maximum diameter of sessile drops
ADSA-HD ADSA based on the height and diameter of
pendant and sessile drops
ALFI
Axisymmetric liquidfluid interfaces
BLAS
Linear algebra package of the University of
Tennessee
COLSYS
Boundary-value problem solver by Ascher and
Bader (28)
DVERK
RungeKuttaVerner initial value problem
solver by Hull et al. (25)
INTRP
High-order interpolation routine of DVERK
LAPACK
Linear algebra package of the University of
Tennessee
LMDER
LevenbergMarquardt with derivatives subroutine of MINPACK
MINPACK Minimization package by More (31)

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ACKNOWLEDGMENTS
This work was supported by the Natural Science and Engineering
Research Council of Canada. The DVERK FORTRAN library was kindly
provided by W. H. Enright, Department of Computer Science, University
of Toronto. The COLSYS, MINPACK, LAPACK, and BLAS FORTRAN
libraries are available on the Internet at the Netlib Repository at the University of Tennessee, Knoxville, and the Oak Ridge National Laboratory
(http://www.netlib.org).

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