13242 Langmuir 2007, 23, 13242-13242
Comments
Comment on How Wenzel and Cassie Were Wrong
by Gao and McCarthy
In a recent article, Gao and McCarthy1 explored the possibility
that the theories due to Wenzel2 and Cassie3 may be more
restrictive than previously envisioned or even being utilized today.
The importance of the behavior in the vicinity of the three-phase
contact line has been acknowledged in the literature.4-6 By this
comment, we wish to delineate the progression of thought in
Cassie’s3,7 work to demonstrate that his theory is not in
contradiction with the experiments of Extrand8 and Bartell and
Shepard.9 In addition, we wish to demonstrate that surface energy
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minimization arguments that form the basis of Cassie theory are
essentially analogous to contact line kinetics in the absence of
hysteresis.
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Cassie’s3 analysis of drop contact angles on a general
heterogeneous surface consisting of two materials is based on
the energy minimization principle. Beginning his derivation, he
writes,3 “If a unit geometrical area of a surface has an actual
surface area σ1 of contact angle θ1 and an area σ2 of contact angle
θ2, the energy E gained when the liquid spreads over the unit
geometrical area is E ) σ1(γS1A - γS1L) + σ2(γS2A - γS2L),
where γS1A and γS1L are interfacial solid-air and solid-liquid
tensions for the σ1 areas, and γS2A and γS2L are interfacial solid-
air and solid-liquid tensions for the σ2 areas.” For a smooth
heterogeneous surface, σ1 + σ2 ) 1. It must be noted that E in
the above statement refers to the net change δE in the system
free energy during the advancing event (and not the absolute
value of the drop free energy), given by the difference between
the energy σ1γS1A + σ2γS2A which “is gained by the destruction
of the solid-air interfacial area”, and the energy σ1γS1L + σ2γS2L
which “is expended in forming the solid-liquid interface over
the same area”.7 The well-known Cassie equation for a
heterogeneous surface follows from this statement. The contact
angle predicted by this equation requires the surface area fractions,
σ1 and σ2, of the solid heterogeneous surface that is about to be
wetted by the advancing three-phase contact line as inputs and
not those of the entire drop footprint.
* To whom correspondence should be addressed. Telephone: (931) 372
6143. Fax: (931) 372 6340. E-mail: mvp@tntech.edu.
† Tennessee Technological University.
‡ National University of Singapore.
(1) Gao, L.; McCarthy, T. J. Langmuir 2007, 23, 3762-3765.
(2) Wenzel, R. N. Ind. Eng. Chem. 1936, 28 (8), 988-994.
(3) Cassie, A. B. D. Discuss. Faraday Soc. 1948, 3, 11.
(4) Nosonovsky, M. Langmuir 2007, 23, 9919-9920.
(5) de Gennes, P. G. ReV. Mod. Phys. 1985, 57, 827.
(6) McHale, G. Langmuir 2007, 23 (15), 8200-8205.
(7) Cassie, A. B. D.; Baxter, S. Trans. Faraday Soc. 1944, 40, 546-551.
(8) Extrand, C. W. Langmuir 2003, 19 (9), 3793-3796.
(9) Bartell, F. E.; Shepard, J. W. J. Phys. Chem. 1953, 57, 455.
(10) Vedantam, S.; Panchagnula, M. V. Phys. ReV. Lett. 2007, 99, 176102.
10.1021/la7022117 CCC: $37.00 © 2007 American Chemical Society
Published on Web 11/15/2007
In their article, the authors cite experiments from Extrand8
and Bartell and Shepard9 to suggest that Cassie theory predictions
based on the overall surface area fractions of the component
materials “are meaningless” and that it is due to a fault with
Cassie theory. Let us consider the case of the experiments
presented by Extrand8 with an island of etched Perfluoroalkoxy
(PFA) (material 2) on a smooth PFA (material 1) surface. (Similar
arguments can also developed to explain the experiments of
Bartell and Shepard.9) When the contact line is wholly resident
on the smooth PFA surface (with the etched PFA island en-
tirely under the drop footprint) and acquires an incremental
unit geometrical wetted area by advancement, all of the area
acquired by the drop footprint is of material PFA. The net
energy change for this event is E ) γS1A - γS1L. Comparing this
to the general equation for E from Cassie,3 σ1 ) 1 and σ2 ) 0.
When these values are used, the Cassie equation yields the
expected contact angle which is the advancing contact angle of
smooth PFA. In contrast, an inappropriate choice of surface area
fractions for this case would be based on the total geometric
surface area fractions under the drop, given by σ2 ) (area of
etched PFA)/(total solid-liquid interfacial area) and σ1 ) 1 -
σ2 (as in Table 1 in ref 1). The disagreement between Cassie
theory and Extrand’s8 experiment does not arise from a fault
with Cassie theory but from an incorrect choice of surface area
fractions.
As a general rule of how the Cassie equation can be used, we
would like to propose that, in keeping with the intent of the
energy minimization principle, surface area fractions that the
contact line will experience as it advances need to be used with
the Cassie equation. In instances where agreement with the Cassie
equation has been reported, it arises from the fact that the contact
line experiences the same area fractions as the overall surface
area fractions.10 The authors write, “We do not advocate never
using Wenzel’s or Cassie’s equations, but they should be used
with the knowledge of their faults.” We wish to point out that
a correct application of Cassie’s equation in terms of area fractions
in the neighborhood of the advancing three-phase contact line
yields the desired results.
Mahesh V. Panchagnula*,† and Srikanth Vedantam‡
Department of Mechanical Engineering,
Tennessee Technological UniVersity,
CookeVille, Tennessee 38501, and
Department of Mechanical Engineering,
National UniVersity of Singapore, Singapore 117576
ReceiVed July 21, 2007
In Final Form: September 7, 2007
LA7022117